Germanium Silicon:

Physics and Materials

SEMICONDUCTORS
AND SEMIMETALS
Volume 56
Semiconductors and Semimetals

A Treatise

Edited by R. K. Willardson Eicke R. Weber

CONSULTING PHYSICIST DEPARTMENT OF MATERIALS
SPOKANE, WASHINGTON SCIENCE AND MINERAL
ENGINEERING
UNIVERSITY OF CALIFORNIA
AT BERKELEY
Germanium Silicon:
Physics and Materials

SEMICONDUCTORS
AND SEMIMETALS
Volume 56
Volume Editors

ROBERT HULL
DEPARTMENT OF MATERIALS
SCIENCE AND ENGINEERING
UNIVERSITY OF VlRGINIA
CHARLO'ITESVILLE, VIRGINIA

JOHN C. BEAN
SCHOOL OF ENGINEERING
AND APPLIED SCIENCE
UNIVERSITY OF VIRGINIA
CHARLO'ITESVILLE, VIRGINIA

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Contents

......................................
LISTOF CONTRIBUTORS xi

Chapter 1 Growth Techniques and Procedures

John C. Bean
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
I1. Generichsues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
111. Common Growth Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1. Molecular Beam Epitaxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2. Rapid Thermal Chemical Vapor Deposition . . . . . . . . . . . . . . . . . . . . . . . . 13
3 . Ultra-high Vacuum Chemical Vapor Deposition . . . . . . . . . . . . . . . . . . . . . 16
4. Atmospheric Pressure Chemical Vapor Deposition . . . . . . . . . . . . . . . . . . . . 22
5 . GasSourceMBE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
IV. Comparison of Growth Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1 . LayerThickness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2. Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3 . Majority Carrier Transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4 . Photoluminescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5. Minority Carrier Lifetime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
V. Nonplanar Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1. Atomicordering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2. Islands and Wires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3 . Selective Area Epitaxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4. Strain-Relaxed GeSi and GeSi Pseudo-Substrates . . . . . . . . . . . . . . . . . . . . . 40
VI . Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

Chapter 2 Fundamental Mechanisms of Film Growth

Donald E. Savage. Feng Liu. Volkmar Zielasek. and Max G. Lagally
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
1. Equilibrium Growth Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2 . Kinetic Processes During Vapor Deposition . . . . . . . . . . . . . . . . . . . . . . . . 52
3. Kinetic Growth Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
XI. Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
1. Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ’ 37
2 . Growth of Si on Si(OO1) (Atomistic Mechanisms) . . . . . . . . . . . . . . . . . . . . . 62
3. Thermodynamic Properties and Equilibrium Surface Morphology . . . . . . . . . . . . 75

V
vi CONTENTS

111. Heteroepitaxial Growth: Ge on Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79

1. Growth of the Ge Wetting Layer on Si(OO1) . . . . . . . . . . . . . . . . . . . . . . . . 79
2 . Nucleation of Coherent ‘Hut’-Islands . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
IV. SiGe Alloy Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
1. Roughening and Coherent 3-D Island Formation in Alloys . . . . . . . . . . . . . . . . 92
2. Multilayer Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
V. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96

Chapter 3 Misfit Strain and Accommodation

in SiGe Heterostructures
R . Hull
I . Origin of Strain in Heteroepitaxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
I1. Accommodation of Strain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
1. Elastic Distortion of Atomic Bonds in the Epitaxial Layer . . . . . . . . . . . . . . . . 103
2 . Roughening of the Epitaxial Layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3 . Interdiffusion across the EpiIayedSubstrate Interface . . . . . . . . . . . . . . . . . . . 105
4 . Plastic Relaxation of Strain by Misfit Dislocations . . . . . . . . . . . . . . . . . . . . 107
5 . Competition Between Different Strain Relief Mechanisms . . . . . . . . . . . . . . . . 108
111. Review of Basic Dislocation Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
1. Definition and Geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
2 . Energy of Dislocations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3. Forces on Dislocations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4 . Glide and Climb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
5 . Geometry of Interfacial Misfit Dislocation Arrays . . . . . . . . . . . . . . . . . . . . . 113
6 . Motion of Dislocations: Kinks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
7 . Dislocation Dissociation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
8. Partial versus Total Misfit Dislocations . . . . . . . . . . . . . . . . . . . . . . . . . . 119
IV. Excess Stress. Equilibrium Strain and Critical Thickness . . . . . . . . . . . . . . . . . . . 120
1. introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
2. Matthews-Blakeslee Framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
3. Accuracy of the MB Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4 . Other Critical Thickness Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
5. Extension to Partial Misfit Dislocations . . . . . . . . . . . . . . . . . . . . . . . . . . 126
6 . Models for Critical Thickness iu Multilayer Structures . . . . . . . . . . . . . . . . . . 128
V. Metastability and Misfit Dislocation Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . 131
1. Basic Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
2 . Misfit Dislocation Nucleation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
3 . Misfit Dislocation Propagation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
4 . Misfit Dislocation Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5 . Kinetic Modeling of Strain Relaxation by Misfit Dislocations . . . . . . . . . . . . . . . 152
VI . Misfit and Threading Dislocation Reduction Techniques . . . . . . . . . . . . . . . . . . . 155
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
2 . BufferLayers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
3 . Threading Dislocation Filtering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
VII. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
 CONTENTS vii

Chapter 4 Fundamental Physics of Strained Layer GeSi: Quo Vadis?

M . J . Shaw and A4. Jaros
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
I1. Perfect Superlattice Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
1. Basic Concepts of Superlattice Bandstructures . . . . . . . . . . . . . . . . . . . . . . 174
2 . GeSi Bandstructures fromEmpirica1 Pseudopotential Calculations . . . . . . . . . . . . 182
111. Electronic Structure of Imperfect and Finite Systems . . . . . . . . . . . . . . . . . . . . . 189
1. Bandstructure of Ordered and Disordered Systems . . . . . . . . . . . . . . . . . . . . 189
2. Optical Transitions in a Finite Superlattice . . . . . . . . . . . . . . . . . . . . . . . . 193
IV. Luminescence and Interface Localization . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
1. Experimental Optical Spectra of SiGe Systems . . . . . . . . . . . . . . . . . . . . . . 195
2 . Impurities at Interface Islands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
V. Microscopic Signature of GeSi Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
1. First-Principles Calculations of SYGe Superlattices . . . . . . . . . . . . . . . . . . . . 200
2 . Interface-Induced Localization at Donor Impurities . . . . . . . . . . . . . . . . . . . . 203
3. Defect Perturbations to Conduction States . . . . . . . . . . . . . . . . . . . . . . . . 207
4 . Localization at Ge Impurities in Si Layers . . . . . . . . . . . . . . . . . . . . . . . . 211
VI . Microscopic Electronic Structure Effects in Optical Spectra . . . . . . . . . . . . . . . . . 212
VII . Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221

Chapter 5 Optical Properties

Fernando Cerdeira
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
I1. Forms of Differential Spectroscopy Based on Reflection or Absorption of Light . . . . . . . 226
1. General Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
2. On Pseudo-direct Optical Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
3. Other Optical Transitions in Si/Ge,Sil-, and Ge/Ge,Sil-, Microstructures . . . . . . 236
4 . Other Optical Transitions in Ge,Si, Quantum Wells and Superlattices . . . . . . . . . 243
I11. Raman Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
1. General Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
2 . Raman Scattering in Bulk Ge,Sil-, Random Alloys . . . . . . . . . . . . . . . . . . . 256
3. Raman Scattering by Optic Modes in Ge..Si, QWs and SLs . . . . . . . . . . . . . . . 258
4. Raman Scattering by Acoustical Phonons in Si/Ge Microstructures . . . . . . . . . . . 260
5 . Resonant Raman Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
6.Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
IV. Photoluminescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
2 . PL from Bulk Ge,Sil-, Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
3 . PL from Si/Ge,Si1-, Microstructures . . . . . . . . . . . . . . . . . . . . . . . . . . 280
4. PL from Ultrathin Ge,Si, QWs and SLs . . . . . . . . . . . . . . . . . . . . . . . . . 286
V. Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
viii CONTENTS

Chapter 6 Electronic Properties and Deep Levels in Germanium-Silicon

Steven A . Ringel and Patrick N . Grillot
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
I1. Deep Levels in Ge,Si .................................. 295
1 . DLTS Identification and Analysis of Extended Defect States in Ge,Sil-, . . . . . . . . 296
2 . Electron Traps in GexSil-, Alloys for x = 0 - 1 . . . . . . . . . . . . . . . . . . . . 303
3 . Hole Traps in Ge,Sil-, from x = 0 - 1 . . . . . . . . . . . . . . . . . . . . . . . . . 309
111. Influence of Defects on Electrical Properties of Ge,Sil_, Alloys . . . . . . . . . . . . . . 319
1. Doping Compensation in Relaxed Ge,Sil-, Layers . . . . . . . . . . . . . . . . . . . 319
2 . Carrier Generation-Recombination in Relaxed Ge, Sil -, Layers . . . . . . . . . . . . . 322
IV. Camer Transport Properties of Ge,Sil-, .......................... 326
1. Carrier Mobilities in Strained and Unstrained Bulk GexSil-, . . . . . . . . . . . . . . 327
2 . Two-Dimensional Carrier Transport in GeSi/Si Heterostructures . . . . . . . . . . . . . 334
3 . Minority Carrier Lifetimes and Diffusion Coefficients . . . . . . . . . . . . . . . . . . 339
V. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343

Chapter 7 Optoelectronics in Silicon and Germanium Silicon

Joe C. Campbell
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
11. Photodetectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
1. Avalanche and p-i-n Photodiodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
2. Resonant-Cavity Photodiodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
3. Metal-Semiconductor-Metal Photodiodes . . . . . . . . . . . . . . . . . . . . . . . . . 356
4 . Integrated Optical Receivers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
111. Light Emitters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
I . PorousSilicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
2. Erbium-doped Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
3 . Si]-*Ge, Quantum Wells and (Si),(Ge), Strained Layer Superlattices . . . . . . . . . 369
IV. Guided-Wave Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
1. Waveguides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
2 . Integrated and Active Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . 375
V. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380

Chapter 8 Sil-,C, and Sil-.-.Ge.C. Alloy Layers

Karl Eberl. Karl Brunner and Oliver G. Schmidt
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
11. General Remarks on the Material Combination of Si. Ge and C . . . . . . . . . . . . . . . 390
I11. Preparation of Sil_,C, and Sil_,_,,Ge,C, Layers by Molecular Beam Epitaxy . . . . . . 392
IV. Structural Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
1. Thermal Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
2 . Local Strain of Substitutional C in Si . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
V. Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
1 . Si1_,C, Alloy Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
2 . SiGeC Alloy Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
 CONTENTS ix

3. Si/Ge/Sil-yCy Quantum Wells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408

4 . Carbon-Induced Ge Quantum Dots . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
V1. Electrical Transport Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
VII . SummaryiDevices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 418
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419

INDEX. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
CONTENTS OF VOLUMES IN THISSERIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
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List of Contributors

Numbers in parenthesis indicate the pages on which the authors’ contributions begin.

JOHNC. BEAN(I), Department of Electrical Engineering, University of Virginia,

Charlottesville, Virginia
KARLBRUNNER (387), Ma-Planck-Institutfir Festkorperforschung, Stuttgart, Ger-
many
JOE C . CAMPBELL(347), University of Texas, Microelectronics Research Center;
Austin, Texas
FERNANDO CERDEIRA (226), Instituto de Fisica, Universidade Estadual de Camp-
inas, UNICAMP, S6o Paulo, Brazil
KARLEBERL(387), Max-Planck-Institutfur FestkBrpet$orschung, Stuttgart, Germany
PATRICKN. GRILLOT(293), Hewlett Packard Optoelectronics, Sun Jose, California
R. HULL(102), Department of Materials Science and Engineering, University of Vir-
ginia, Charlottesville, Virginia
M. JAROS(l69), Department of Physics, The University of Newcastle upon Tyne, New-
castle upon Tyne, United Kingdom
MAX G. LAGALLY (49), University of Wisconsin, Madison, Wisconsin
FENGLIU (49), University of Wisconsin, Mudison, Wisconsin
STEVENA. RINGEL(293), The Ohio State University, Department of Electrical Engi-
neering, Columbus, Ohio
DONALDE. SAVAGE (49), University of Wisconsin, Madison, Wisconsin
OLIVERG. SCHMIDT(387), Max-Planck-Institut fur Festkorperforschung, Stuttgart,
Germany
M. J. SHAW (169), Department of Physics, The University of Newcastle upon Tyne,
Newcastle upon Tyne, United Kingdom
VOLKMAR ZIELASEK(49), University of Wisconsin, Madison, Wisconsin

xi
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 SEMICONDUCTORSAND SEMIMETALS. VOL. 56

CHAPTER1

Growth Techniques and Procedures

John C. Bean
DEPARTMENT OF ELECTRICAL
ENGINEERING
UNIVERSITY OF VIRGINIA
CHARLOTTESVILLE. VIRGINIA

I . INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
I1 . GENERICISSUES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
111. COMMONGROWTH TECHNIQUES ............................... 6
1 . Molecular Beam Epitaxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2 . Rapid Thermal Chemical Vapor Deposition . . . . . . . . . . . . . . . . . . . . . . . . . 13
3 . Ultra-high Vacuum Chemical Vapor Deposition . . . . . . . . . . . . . . . . . . . . . . 16
4 . Atmospheric Pressure Chemical Vapor Deposition . . . . . . . . . . . . . . . . . . . . . 22
5. Gas Source MBE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Iv. COMPARISON OF GROWTHRESULTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1 . LayerThickness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2. Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3. Majority Carrier Transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4. Photoluminescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5. Minority Carrier Lifetime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
V. NONPLANAR GROWTH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1. Atomic Ordering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2. Islands and Wires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3. Selective Area E p i t q . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4 . Strain-Relaxed GeSi and GeSi Pseudo-Substrates . . . . . . . . . . . . . . . . . . . . . . 40
V L S U M M A R Y. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

I . Introduction

This chapter will focus on the actual growth of GeSi strained layers. Information will
be directed at users of GeSi and will provide candid information on what is possible
or most readily accomplished by crystal growth colleagues . Molecular beam epitaxy
Copynght @ 1999 by Academic Press
All nghts of reproductionin any form reserved.
ISBN 0-12-752164-X
0080-8784199 $30.00
2 JOHN C. BEAN

(MBE) will be described along with three types of chemical vapor deposition: ultra-
high vacuum (UHVCVD), atmospheric pressure (APCVD) and rapid thermal chem-
ical vapor deposition (RTCVD). All of these techniques produce high-quality crystal
growth at temperatures far below those used in traditional CVD. All were first used
for Si growth years or even decades before they were applied to GeSi growth. Their
use was driven by device requirements for very thin doped layers or layers with very
steep doping gradients. Ultimately, many of these requirements were met by alter-
nate, ion-implantation techniques. However, temperature did remain the key issue for
GeSi growth and, as such, all of these techniques have come to be identified with this
material.
Another historical point should be noted. In most discussions of GeSi, growth tech-
niques are presented ufier the theoretical framework has been established. This makes
for a clean and logical presentation. This book covers growth first. The reason is
simple: breakthroughs in growth came first and opened this field. In fact, earlier theo-
retical work “proved’ that useful strained layer GeSi growth would not be possible. It
was only after we had succeeded in growing material that was far in excess of predicted
limits that theories were revised and extended to account for experimental results. This
point is inserted to encourage other experimentalists who would attempt that which has
been “shown” to be impossible.
The development of GeSi growth techniques has been highly competitive. This has
produced rapid progress but has also led to an environment in which differences were
sometimes exaggerated and common features obscured. Many claims have been based
on measurements requiring esoteric apparatus or skills that are not widely available
and, indeed, it is extremely rare to find a paper that actually compares material from
different growth techniques, head-to-head. Other controversies, such as that concern-
ing Ge segregation, have been almost entirely divorced from any discussion of actual
technology requirements. Questionable data have been generated by groups with no
prior or subsequent history of quality growth in this admittedly challenging materials
system. Finally, while there has been intense discussion of the “device worthiness”
of material grown by various techniques, in the GeSi materials system, only very few
research groups have actually applied their work to fabrication of challenging devices.
This contrasts sharply with, for instance, AlGaAs growth where most efforts were es-
tablished with the exclusive aim of supplying material for device work. It has been
this author’s often humbling experience that there is no test anywhere so demanding
as fabrication of a successful minority carrier device. Until this challenge is success-
fully confronted, it is likely that material will not have been perfected and may not be
representative of a technique’s ultimate capabilities.
This chapter will address these issues and attempt to provide a more balanced, or
at least a more device-relevant view. At the outset, generic issues and concerns will
be discussed. In the second section, the apparatus and basic procedures for each tech-
nique will be separately detailed. A third section will compare material grown by these
techniques, including data on GeSi layer control, carrier mobility, lifetime, and lumi-
 1 GROWTH TECHNIQUES
AND PROCEDURES 3

nesence. The fourth section will describe unconventional or unexpected growth modes
including spontaneous atomic ordering, islanding and self-assembly, selective epitaxy,
and growth of thick, relaxed pseudo-bulk GeSi layers. Because many readers may be
motivated by the possible commercial application of GeSi, throughout the discussion
comments will be included on relevant strengths, weaknesses, or unresolved issues
relevant to various techniques.

11. Generic Issues

In its simplest form, crystal growth consists of the arrival and proper arrangement of
an atom at a solid surface. One GeSi growth technique, MBE, approaches this ideal as
closely as any other. Both Si and Ge evaporate from thermal sources as simple atoms,
a situation that does not occur in even 111-V MBE. At typical growth temperatures of
400-1O0O0C, these atoms have an overwhelming tendency to condense on the substrate
surface without re-evaporation. For materials such as GeSi, a fully coordinated cubic
crystalline site provides the lowest possible bonding state for the arriving atom. Thus,
for any temperature above absolute zero, it is simply a matter of patience: wait long
enough for thermally activated surface migration to move the atom to a proper site and
epitaxial growth will occur.
This simplified view makes two assumptions. The first is that the original atom will
not be buried or interfered with by a 2nd aniving atom in such a way that it cannot
reach a coordinated site. This condition can be crudely expressed by the requirement
that the surface migration time be shorter than the interval between arriving atoms
(with some constants taking areas into account). If one assumes that surface migration
velocity varies as a simple Boltzmann factor of e - E a / k T single
, crystal growth will
then be possible at all temperatures, provided that the maximum deposition rate is
limited by the reciprocal of that same factor. There is no absolute minimum growth
temperature.
The second, and implicit, assumption is that there are no other species
present-in particular, that there are no other species that will obstruct surface mi-
gration or disrupt the formation of an ideal crystal. The use of ultrahigh vacuum in
MBE is driven by this desire to reduce grossly the concentration of such interfering
species, and CVD techniques now emulate this feature. It is incorrect, however, to as-
sume that the use of an ultrahigh vacuum, alone, is sufficient. From kinetic gas theory
one can derive the rule of thumb that gas impingement rates vary as the gas partial
pressure. For a gas pressure of torr, that impingement rate is still approximately
1 atomic monolayer per s (- IOl5 toms/cm2-s). This is about the same rate at which
most epitaxy is grown. Clearly vacuum alone, even heroic, interstellar class torr
vacuums, would not produce hyperpure, interference-free epitaxy.
Most epitaxy, no matter how pure, thus relies on growth in temperature
windows to avoid the aforementioned impurity effects. These windows can be at-
4 JOHN C. BEAN

tributed to two thermal mechanisms: disassociation and desorbtion. A contaminant

arrives bound within a molecule. It requires some minimum substrate temperature to
disassociate that molecule and to adhere to the crystal surface. At a higher temper-
ature, if secondary reactions do not occur, re-evaporation increases to the point that
the impurity surface concentration again falls effectively to zero. One must avoid the
middle range for which surface impurity concentrations are significant. Different gas
impurities adhere over different temperature ranges. With luck, however, there will be
temperature gaps over which the most damaging impurities are absent.
For Si epitaxy, 0 2 begins to react and adhere at a very low temperature. However, the
Si-0 bond is relatively weak and re-evaporation occurs readily for temperatures above
600°C. On the other hand, at very high temperatures, gas species such as N2 begin to
decompose and bond with Si surfaces. These reactions suggest a growth temperature
range of 550-1000°C. This range is then somewhat narrowed by the realization that
in Si, common dopants begin to diffuse rapidly at temperatures above 800-900°C.
Together, these considerations yield the 550-850°C growth-temperature window used
for almost all of the techniques described in this chapter.
For CVD growth, one must deal with another high-concentration source of “impuri-
ties,” the reactant gas itself. The very low vapor pressures of atomic Si and Ge enable
MBE but at the same time make supply of Si or Ge “gas” to CVD impossible. Si and
Ge are, instead, generally supplied as molecules with hydrogen such as silane (SiH4),
disilane (Si2H6) or the Ge analogs. The simplicity of these molecules means that they
can be readily purified to rigorous semiconductor standards. Their shortcoming is that
when these molecules bond to the Si surface, they do so by releasing a single H atom.
Unlike molecular H2, this atomic H is highly reactive and will generally bond to an
adjacent Si atom. That Si atom will then only be freed for subsequent epitaxy when its
H combines with another to release H2 from the surface. This occurs only very slowly
-
at temperatures below 650°C and provides an additional low temperature constraint
for CVD processes that will be detailed here.
There is another particularly pernicious impurity: carbon. Carbon has an extremely
strong bond with silicon. This is evident in a comparison of pure Si’s melting point
-
of 1415°C and Sic’s melting point of 2700°C. It is also demonstrated by the hard-
ness of Sic. The Si-C affinity means that once C becomes bonded to a Si surface, it
is extremely difficult to remove. Indeed, early high-temperature heat treatments, once
thought to evaporate C from Si, are now known to function only by diffusing C from
the surface into the bulk of the crystal. To make things worse, S i c has multiple crystal
structures that are very different in spacing or arrangement from that of Si. In Si ho-
moepitaxy, a surface inclusion of S i c on Si will, therefore, nucleate a crystallographic
defect. For GeSi, where a combination of strain and chemical differences exists, even
smaller S i c clusters can provide sites that promote anomalous nucleation, nonplanar
growth, or premature strain relaxation.
For these reasons, carbon is a preoccupation for most Si crystal growers (as
AlGaAs growers are obsessed with the damaging affinity of aluminum for oxygen).
 1 GROWTHTECHNIQUES
AND PROCEDURES 5

This legitimate fear also accounts for the absence of organometallic Si growth tech-
niques parallelling those widely used for compound semiconductors. Even when
deliberate introduction of carbon is avoided, one must still deal with spontaneous con-
tamination due to ever-present oils and polymers. Fortunately, many of these species
are reactive or have fairly low vapor pressures. In the growth chamber and its plumb-
ing, they can generally be isolated by sorption or cryogenic traps, at least if they are not
produced in huge quantities through the misguided use of hydrocarbon-based pumps.
Thus, GeSi MBE is dominated by the use of oil-free cryogenic pumps. However, these
accumulation pumps are not suitable for the toxic and even explosive gases used in
CVD. There, turbo-molecular pumps, with their very minor use of bearing oil, are
employed.
Another generic growth concern relates to wafer cleaning. To promote epitaxy, one
must expose a perfect crystal surface. This, it would be expected, should be the goal
of the pregrowth cleaning technique. Initial ex situ Si cleaning steps are directed to-
wards impurity removal. This is greatly facilitated by the fact that Si is extremely
resistant to almost all acids and bases. Very harsh solutions can be employed to re-
move virtually all metallic and organic surface impurities. One of the oldest of these,
the so-called “RCA” (Kern and hotinen, 1970) clean employs a sequence of heated,
peroxide-charged hydrochloric acid and ammonia hydroxide baths. Variants of this are
employed in the “Henderson” (1972) or more recent “Shiraki“ (Ishizaka and Shiraki,
1986) recipes. As effective as the early steps of these recipes are at removing impuri-
ties, the final step is directed at adding one: oxygen. This strategy evolved because bare
Si will almost immediately react with and bind to impurities that are always present in
the air and in aqueous solutions. In contrast, an oxygenated silicon surface is quite in-
ert (witness the universal use of glass containers). A glassy surface thus protects the Si
and is readily produced by use of a chemical oxidant, such as peroxide. A hot peroxide
solution grows a 10-20 A-thick oxide that can then be evaporated within the crystal
growth reactor by briefly heating the wafer to 800-900°C.
More recently, chemical cleaning procedures have moved towards solutions produc-
ing a final hydrogen passivating layer. Surface hydrogen can be removed at somewhat
lower in situ annealing temperatures. Additionally, hydrogen simply desorbs. This
contrasts with glass evaporation, which occurs by the reaction Si02 + Si = 2 SiO (va-
por), which must consume some of the substrate Si. This miniscule Si consumption is
not in itself a problem. It has been shown, however, that with normal, slightly nonuni-
form Si02, the Si will be supplied at thin spots or pinholes and thus leads to pitting
of the underlying surface. Surface pits again provide attractive sites for nucleation of
defects or anomalous growth morphologies. Hydrogen surface passivation is generally
accomplished by a final etch in very weak HF solution, followed by a flowing rinse in
extremely pure DI water. Indeed, there is a growing consensus among many Si device
workers that the purity of the final chemicals (and cleaning environment) is far more
important in preparing a clean passivated Si surface than the exact chemical recipe
employed.
6 JOHN c. BEAN
The preceding issues must be addressed if one is to grow pure, high-quality GeSi.
For the vast majority of applications one must then go another step and add electrically
active dopant impurities. Doping is an often complicated and frustrating process for
low-temperature growth techniques such as those used for GeSi. Both Si and GeSi have
strongly bound lattices into which much smaller or larger atoms, such as B and As do
not readily fit. In the bulk of a crystal, dopant atoms have the “choice” of either being
incorporated as lone substitutional atoms or of forming second-phase precipitates. Both
alternatives carry energy penalties.
At the surface of a growing crystal, there is a third, often more energetically attrac-
tive alternative: segregation. Segregation is the process wherein a previously deposited
dopant atom that “should’ be buried by subsequent Si or Ge atoms instead switches
places to remain at the surface. This process is driven by that fact that the variety
of less constrained surface sites may more easily accommodate the mis-sized dopant
atom. This process may sharply limit maximum low-temperature dopant concentra-
tions or even lead to the build-up of surface dopant “reservoirs” that are only gradually
depleted, producing a blurring of intended doping profiles. For chemical vapor deposi-
tion techniques, surface processes are even more complicated and doping can produce
dramatic unexpected effects, such as radical changes in growth rate. Doping anomalies
will be described here for every growth technique. However, one must bear in mind
that many device applications call for only very simple doping profiles. Further, in
production, growth recipes are fixed and while those complications already mentioned
may make it initially difficult to define a recipe, in the long run, that inconvenience
may be inconsequential.

111. Common Growth Techniques

1. MOLECULAR
BEAMEPITAXY
Here MBE will be described first because of both its conceptual simplicity and its
historical priority in the growth of GeSi; GeSi MBE consists of the line-of-sight evap-
oration of atomic species onto a mildly heated Si substrate. In a vacuum, the mean free
path of a gas atom, between scattering events, varies as the reciprocal of the pressure
and has a value of 1 m for a pressure of about ton: The MBE chambers, with
dimensions on the order of a meter and base pressures of 5 lop9 torr, easily meet this
standard. The second requirement is that the evaporant itself not “reflect” off chamber
surfaces. If this is prevented, flux to the substrate can be controlled, simply and instan-
taneously, by inserting a “shutter” in the path between the evaporation source and the
growth substrate. This is the basis for the superb atomic level control of the MBE tech-
nique. For both Si and Ge, significant re-evaporation is extremely low for temperatures
below 1000°C and reflection is effectively absent, as intended.
Dopants do not behave in such an ideal manner. Many of the more readily evapo-
rated species can re-evaporate at the growth surface, somewhat compromising control.
 1 GROWTH TECHNIQUES
AND PROCEDURES 7
Others are prone to surface segregation and for simple evaporated dopants, maximum
doping level is generally limited to relatively modest peak concentrations on the order
of lO”/cm (Becker and Bean, 1977; Bean, 1978; Ishizaki and Shiraki, 1986.). This
constraint has been the basis for considerable research and has led to the use of dramatic
alternatives such as the dual low-energy dopant ion-implantation scheme developed by
the author (Bean et al., 1988). Ion implantation can insert dopants far enough from
a growth surface (e.g., 20-30A) that re-evaporation and surface segregation are effec-
tively eliminated. Upper doping limits can thus be extended towards 1020/cm3but at
an obvious penalty in the complexity of the apparatus.
Generic work on Si MBE centers on achieving the preceding, simple, atomistic pro-
cess. Base vacuums in the requisite to high lo-” torr range are achieved by a
now well-established combination of high-capacity closed cycle He cryopumps, baked
stainless steel chambers, and sample introduction load-locks. A modem system is
shown in Fig. 1. In such a system, there is no absolute vacuum requirement. Instead,
as indicated in the preceding, it is a question of ambient impurities competing with
deposition species. For the 1-10 Ah deposition rates typically used, very high crys-
talline quality is achieved for Si on Si growth at temperatures above 450°C with
a low torr base pressure. These rates are slow enough that the motion of me-
-
chanical shutters generally gives the desired atomic monolayer control of flux. For
GeSi, however, there is an additional tendency, detailed below, for nonplanar growth.
This is almost, but not entirely, suppressed at temperatures of 450°C. Experiments on

FIG. 1. Depiction of the author’s double-ended, dual-growth chamber MBE system based on a VG
Semicon “VG-90” design. This system handles wafers up to 150mm diameter, processing them individually
but loading up to 20 at one time. Si and Ge are evaporated from “e-gun” evaporation sources. Dopants
are depicted as being evaporated from conventional, resistively heated, Knudsen cells. In the actual system,
these have been replaced with a dual 3-keV dopant ion-implantation system that mates with the descending
flange at the right extreme of the system. (Used by permission of VG Semicon.)
8 JOHN C. BEAN

growth of single atomic monolayer structures are thus sometimes conducted at lower
temperatures and/or at lower growth rates, requiring even better base vacuums.
Much of the work on GeSi material has been directed at growth of layers for het-
erojunction bipolar transistors (HBTs). Minority carrier lifetime plays a key role in the
performance of such devices. For indirect bandgap GeSi materials, minority carrier
recombination occurs almost exclusively at metal impurity sites. State-of-the-art HBT
performance depends on carrier lifetimes in excess of 1 pS, which in turn dictates
residual metal impurity concentrations of less than 1 ppb. These low concentrations
are not easily achieved, particularly in ail-metal MBE chambers. This fact has been
overlooked by a majority of those growing GeSi MBE and this accounts for much of
the confusion and contention about ultimate MBE film quality. As such, its discussion
justifies a short digression.
Within a GeSi MBE chamber, most metal is introduced into the film by one of two
mechanisms. In the dominant commercial MBE system, substrates are heated by resis-
tively heated tantalum ribbons. Because these ribbons expand and droop upon heating,
they were given additional support from insulating rods. Unfortunately, red-hot tan-
talum reacts with the insulator to produce volatile metal oxides and nitrides that are
then incorporated in trace amounts into the epi. More recent designs either eliminate
the insulator supports or exchange the tantalum ribbons for rigid graphite serpentines.
However, these more advanced designs account for only a small fraction of those sys-
tems in use and MBE results are rarely correlated with the heater design.
A second metal contamination route occurs via the deposition sources and, to the
author’s knowledge, has not been addressed by any commercial MBE vendor. Because
Si and Ge have very low vapor pressures, they are generally sourced from high-energy
electron beam evaporators (Fig. 2). In these devices, the Si or Ge solid charge is seated

- 10 keV energy and -

in a grounded, water-cooled metal crucible and bombarded by an electron beam at
1 A current. The filament structure that emits the elec-
trons is generally hidden below the crucible and the emerging electron beam bent in
an arc, to the charge, by means of a magnetic field. Because the filament then can not
be seen by the substrate, metals evaporated from it generally will not find their way
into the deposit and these “guns” are a workhorse of the semiconductor industry. In
that industry, however, they are not expected to yield ppb deposition purity as they
are. in MBE. At those concentrations, one must fully appreciate the subtleties of such
sources. Even when they are used in ultrahigh vacuum, the effective vapor pressure
of the evaporant, immediately above the source, can be quite high. Indeed, it can be
so high that the mean free scattering path falls below 1 cm, creating a “virtual source”
in a spherical volume above the crucible. Evaporant atoms then follow paths from
this virtual source rather than from the melt surface. Further, this virtual source vol-
ume is traversed by the incoming electron beam, which will ionize some fraction of
the Si and Ge atoms. The ionized Si+ or Gef will be at ground potential but they
will be strongly attracted to the filament assembly with its -10 kV bias. From the
virtual source, the filament itself is usually not visible. However, most vendors route
 1 G R O W T H TECHNIQUES AND PROCEDURES 9

ELECTRON’ EMITTER
ASSEMBLY (-H.V.)

FIG. 2. Cross section through conventional “e-gun” evaporation source, such as the 40 cc and 150 cc
capacity models offered by Temescal and others. Emitter assembly is biased at - 10 kV such that emitted
electrons impact the charge of Si (or Ge) with 10 keV energy. The path of the electrons is bent by a permanent
magnet and pole pieces so that the “dirty” filament can be hidden below the body of the source with no line-
of-site to the substrate placed above this source. E-guns are commonly used with lower vapor pressure solids
for which very high temperatures ( i t . > 1000°C) must be reached to achieve significant evaporation rates.

the heavy copper leads to the filament in such a way that they are seen by the source
cloud. This can produce massive sputtering of those leads by the evaporant ions and
much of the sputtered surface is positioned such that material can flow into the epi
layer. A simple solution can be employed: the filament leads must also be carefully
tucked below the body of the e-gun where sputtering is grossly reduced and there is
no line-of-sight to the substrate. Attention to these details, and to rigorous substrate
cleaning, has produced MBE Si and GeSi with ,LLS lifetimes, suitable for fabrication
into high-performance devices. This has, however, involved a long and often frustrat-
ing learning process, which only a small minority of the workers in the MBE field have
mastered.
In the context of potential commercial application, a final equipment point should
be noted. Advocates of competing CVD techniques criticized MBE’s dependence on
load-locks and extended chamber bake-outs to achieve required vacuum quality. As
will be shown, it is ironic that CVD has now been compelled to adopt virtually iden-
tical practices. However, MBE does have one inherent weakness when it comes to
high-throughput growth. The issue is not throughput itself, for MBE systems do de-
posit on multiple wafers and even more ambitious schemes have been explored (Bean
and Butcher, 1985). The issue is with control of particulates. As already noted, MBE is
built on the use of evaporants that will deposit on all surfaces. These surfaces include
10 JOHN C . BEAN

the chamber walls where millimeter thicknesses of Si and Ge can eventually build-
up. These deposits can be removed when the chamber is vented for servicing but, for
high-throughput growth, venting will only occur after a large number of layers have
been deposited. In the interval between cleaning, wall deposits may reach sufficient
thickness that they will begin to peel off as fine particulates. This release can be ac-
celerated if the MBE system uses internal liquid nitrogen shrouds that were developed
for AlGaAs MBE but continue to be used in older Si MBE systems. In Si MBE SYS-
tems, wafers generally face downward but it has been shown that the pressure of the
evaporant itself can drive the particulates back up into the depositing layer where their
inclusion can nucleate defects (Matteson and Bowling, 1988).
In the mid 1970s, before many of the preceding issues were fully understood, Kasper
and co-workers first investigated growth of GeSi strained layers on Si (Kasper et al.,
1975; Kasper and Pabst, 1976; Kasper and Herzog, 1977). They found that high-
quality growth was possible only for temperatures above 750°C. Above 750°C GeSi
alloys grew as rough discontinuous films if the Ge fraction was increased above 0.15.
Further, within the 0-0.15 limit, crystallographic analysis indicated that strain-relaxing
defects formed whenever film thickness exceeded the equilibrium values calculated by
theories such as those described by Hull in Chapter I11 of this volume. The inter-
section of these constraints was that only very dilute thin films were possible. This
situation was worsened by the assumption that the bandgap of GeSi films would still
be described by data collected on bulk GeSi crystals in the 1960s (Braunstein et al.,
1958). These data indicated that the GeSi alloy bandgap did not change in a linear
manner between the 1.1 eV value of Si towards the 0.65 eV value of Ge. Instead, as Ge
was added, there was initially only a very slow reduction in bandgap until concentra-
tion exceeded 50%. These thin, dilute films would thus be expected to have bandgaps
only marginally smaller than Si, thereby precluding their use in heterostructure de-
vices.
After ten years of refinement, and with particular attention to the foregoing details, in
1984 we demonstrated growth of GeSi alloys on Si, at temperatures at or below 550°C
(Bean et al., 1984a; Bean et al., 1984b). This produced the first critical breakthrough,
the ability to grow smooth continuous films of all Ge fractions. Early morphology data
are presented in Fig. 3. It is seen that as Ge content is increased, lower and lower growth
temperatures must be used until, at 550"C, all alloys grow smoothly. These data are
consistent with the idea that as Ge content is increased, strain energy increases, driving
the deposit towards formation of isolated islands instead of continuous films. In three-
dimensional islands, strain relaxation occurs more readily and it has been shown that
islands can become the energetically favored morphology (Luryi and Suhir, 1986). The
temperature dependence of Fig. 3 then represents a competition between this islanding
driving force and the reduction in surface diffusion lengths as temperature is decreased.
That is, at higher Ge fractions, the larger islanding tendency can be frozen out by use of
lower growth temperatures where migration cannot occur over the distances required
to assemble islands.
 1 GROWTH TECHNIQUES
AND PROCEDURES 11

n - 0 0 0 0 0
1
I-

Bc3 ""1
400- 0 0
TWO DIMENSIONALGROWTH
(PLANAR)

0 0

I I I I I I I I I

FIG. 3 . Compilation of data from the earliest MBE GeSi experiments depicting the combinations of
GeSi composition and growth temperature that produce islanded (visually hazy) or smooth planar growth.
Boundaries are unexpectedly sharp with transition to rough growth occumng with very slight increases in Ge
content. Below 550"C, all compositions grow smoothly. Limited data on other techniques, such as RTCVD,
show an unexpectedly similar trend.

The aforementioned processes are thermally activated and can occur on different
length scales. One would therefore expect the boundary between smooth and islanded
growth to be a function of film thickness and for the transition to be gradual with a

at about 1 A l s to thicknesses of -
pronounced dependence on growth rate. Figure 3 is based on MBE data for films grown
1000 A. Subsequent MBE work directed towards
growth of single monolayer thickness films has indeed shown that to avoid islanding
on this much finer scale, growth temperatures must be decreased to temperatures at or
below 450°C.
Other details of the 2D to 3D transition are less expected. In the above experiments,
separate Si and Ge evaporation sources produced a gradation in composition across the
then 3-cm wide sample, such that one end had about 1.05 times the target composition
and the other end .95. In spite of this small variation, the transition from a smooth,
fully specular 2D morphology to a rough hazy 3D growth occurred within a band only
a millimeter or so wide along the sample length (that is, over a composition range
on the order of 1%). The other variable is growth rate. Within the relatively narrow
- 0.5-5 A l s range of MBE growth rate, significant morphological changes have not
12 JOHNC. BEAN

been reported. However, because morphology involves a competition between growth

rate and surface migration velocity, one would expect radically altered 2D to 3D curves
for CVD techniques with their often very different surface chemistries and reconstruc-
tions. Surprisingly, this does not appear to be the case and the limited available mor-
phology data for CVD appear to be remarkably consistent with the original MBE re-
sults of Fig. 3.
In early work, the goal was to avoid islanding. As boundaries were determined, and
they proved consistent with qualitative models, work turned towards application. More
recently, islanding has become a possible virtue as it is explored as the possible basis
for device “self-assembly” processes. Although these prospects are exciting, discrep-
ancies, such as the apparent insensitivity of morphology to growth technique, clearly
illustrate the limitations of current data and the need for a deeper understanding of
these processes.
In addition to overcoming morphology problems, lower MBE growth temperatures
produced two other related results, cementing the current interest in GeSi. First, TEM
images indicated that defect-free strained films were growing to thicknesses far greater
than then predicted by equilibrium theories. The early data and theory are shown by the
lower curve in Fig. 4. It is now known that as low-temperature growth tends to freeze

l V Misfit Dislocations
m r

0.0 0.2 0.4 0.6 0.8 1.0

x FOR Ge,Si,., ON Si

FIG. 4. Data for “critical layer thickness” below which GeSi layers grow on Si purely by strain ac-
commodation, with no misfit dislocations. Theoretical curve, based on assumption of equilibrium energy
configuration, shown at lower left. Earliest growth experiments supported those theoretical calculations in
the &15% Ge range. Subsequent, lower temperature MBE growth produced markedly thicker strained films
based on kinetic avoidance of dislocation formation.
 1 GROWTHTECHNIQUES
AND PROCEDURES 13
INDIRECT EANDGAP OF BULK Ge I x ) SI ( 4 - x ) ON <001> - S I
110 113

4 00 1 24

-f -tE
a
090 138 2
= I a
0
t
W
3
g 080
w
455
W
fj
2
W

070 177

060 2 07
0 20 40 60 80 1 00
MOLE 96 Ge-

FIG.5. Bandgap data for both “bulk” unstrained GeSi material (from Braunstein et al., 1958) and GeSi
strained layers on Si substrates (from Lang e l al., 1985). Bandgap for strained layers is markedly reduced
and falls sharply at even dilute Ge fractions.

out islanding, it also grossly suppresses the formation of strain-relieving defects. This
is particularly pronounced for dilute films where layers can be grown 10-100 times
beyond the point where relaxation becomes energetically favorable. This enhancement
is shown by the upper curve of Fig. 4, which defines the “metastable critical thickness”
for strained-layer growth of GeSi on Si. The strain in such films is surprisingly large,
on the order of that produced by pressures of 100,000atm. These pressures produced
a second key breakthrough: the pronounced alteration in the GeSi bandstructure as
shown in Fig. 5. Not only was the bandgap reduced below bulk unstrained values, but
the bandgap began to fall immediately as Ge was introduced. Thus, in contrast to bulk
GeSi data, useful heterostructures are produced when even dilute GeSi is grown on
Si. Metastable GeSi growth and strain effects on bandstructure are detailed by Hull in
Chapter 3 and Shaw and Jaros in Chapter 4 of this volume.

2. RAPIDTHERMAL
CHEMICAL
VAPORDEPOSITION

In industry, Si epitaxy has long been grown by CVD using reactants based on hy-
drogen, chlorine, or both. Typical Si precursors include S i c 4 and SiH4. Chlorides
+
have the advantage that the reaction S i c 4 = Si 2C12 can be more easily reversed to
facilitate in situ sample cleaning. The etching effect of the halogen can also be used to
facilitate selective area epitaxy. That is, single crystal Si will grow in a window through
14 JOHN c. BEAN
an oxide mask but the chlorine will etch away polycrystal Si that would otherwise de-
posit on that mask. This process is detailed in a subsequent section. On the other
hand, in classic CVD it was shown that hydride chemistries, particularly dihydrides
such as Si2H6, had the advantage of producing crystalline growth at significantly lower
temperatures (e.g., 950°C for SiH4 vs. 1100°C for SiC14). As already discussed here,
lower temperatures are a key to GeSi growth and much CVD work has thus focused on
hydride or mixed hydride-halogen chemistries.
In some of the earliest CVD GeSi work, the temperature question was addressed
indirectly. Low-temperature chemistry presents significant challenges as will be dis-
cussed in Section 111.3 on UHVCVD. Workers at Stanford realized that temperature
itself is not always the issue. More commonly, it is the time-temperature product. It
is this product that indirectly governs important parameters such as diffusion length,
which in turn control factors such as growth morphology and even defect growth. For
conventional high-temperature CVD, much of the time-temperature integral comes in
slow temperature ramps to and from the growth temperature. These ramps serve no
other purpose than getting the bulky and thermally massive reactors to and from the
desired reaction conditions. These investigators reasoned that if they could edit out
or “limit” these ramps, the remaining reaction time might be so short that high tem-
perature problems would be largely alleviated. This was accomplished by replacing
conventional CVD epi furnaces with single wafer reactors where the wafer was heated
by external infrared lamps. They named their technique “limited reaction processing”
(Gibbons et al., 1985), but the name did not stick and follow-up work is now generally
described as rapid thermal CVD (RTCVD).
An RTCVD reactor is depicted in Fig. 6. These reactors operate at deposition pres-
sures of 1-20 ton: While lower than some CVD systems, this reduced pressure opera-
tion is, in itself, not that unusual and it facilitates flow control and flow switching. The
very unusual feature of these reactors is their heating and cooling rates of 1-5ms/C (or,
200-1000°C/s!). More or less conventional SiH4 growth temperatures of 920-980°C
were initially used. However, by effectively eliminating heating and cooling times,
high-temperature thermal exposure could be limited to periods of a minute or less and
yet still produce useful epi thicknesses. These intervals are so short that gas switch-
ing cannot occur on this time scale. Thus, in RTCVD, reactant flows are established
before heat is applied, while the wafer is still at or near room temperature. There will
then be some reaction as the wafer rapidly warms to the desired temperature. If these
ramps were slow, that low temperature growth could result in polycrystalline or even
amorphous deposition. In RTCVD, however, ramps are so quick that growth during
the ramp is less than one atomic monolayer. These layers are both largely insignificant
and they are strongly driven towards a fully crystalline form by the proximity of the
substrate.
Several years after its initial development, RTCVD was applied to the growth of GeSi
layers for use in HBT device structures (King et al., 1989; Noble et al., 1989). Because
growth was narrowly targeted to this application, which requires only moderately dilute
 1 GROWTHTECHNIQUES
AND PROCEDURES
15

FIG. 6 . Schematic of RTCVD system developed at the Franhofer Institute for Solar Energy Systems.
This system resembles those used in early GeSi work in its use of a tubular furnace and a single bank of IR
lamps above the substrate. More modem production systems tend to be rectangular with the entire top of
the system lifting off for loading (reprinted with the permission of F. R. Faller, Franhofer Institute, Freiburg,
Germany)

1520% Ge layers, the data set is not as broad as the MBE work already mentioned.
However, the available data are strikingly similar to MBE results in one particular: the
trade-off between growth temperature and morphology. For 22% Ge films, smooth
growth compelled the use of a growth temperature of 625"C, a value consistent with
the MBE data of Fig. 3. Private communications with the authors confirmed this trend.
Because morphology should be controlled by surface migration, the results suggest
that, at least under these conditions, RTCVD surfaces must be largely free of hydrogen
reaction products. This will not be the case for the lower-temperature UHVCVD data
discussed in what follows.
Doping data for RTCVD are also somewhat limited. For Si on Si, where layer growth
occurs at more or less standard CVD growth temperatures, conventional hydride gases
work well for both N- and P-type dopants. There is one detailed report on B2H6 doped
Si films grown at 850°C, which demonstrates abrupt doping steps. Indeed, doping was
varied from the SIMS background detection limit up to extremely high levels in excess
of lO2'/crn3 (Gronet et al., 1986). GeSi doping data also confirm the successful use of
diborane but provides very little information of N-type doping. The paucity of data can
be attributed to the relatively limited use of the RTCVD technique and the very tight
focus, in the literature, on its application to HBTs with their single P-type GeSi layers.
Although RTCVD epi has found somewhat limited commercial application, rapid
thermal techniques, in general, are in heavy use. From this, at least one manufacturing
16 JOHN C. BEAN

issue can be identified. Not too surprisingly, it is how one achieves control of temper-
ature. Conventional CVD furnaces had been made thermally massive to address just
this issue. In the extremely nimble, lamp-heated RT systems, the challenge is how
to heat a wafer uniformly and ensure that it arrives at and holds the desired reaction
temperature. In the extreme, the wafer may be heated so nonunifomly that crystalline
slip defects form due to thermal stresses. This can be minimized by increasing the
lamp output at the generally cooler wafer edges. However, the balance of heating will
change as the temperature increases and wafer thermal emission varies. For this, and
for determination of the brief final reaction temperature, the challenge is not how to
tune the temperature but how to measure it. Thermocouples are not readily attached
to the wafers. While they could be embedded in underlying “susceptors,” the thermal
mass of these plates might seriously compromise rapid temperature cycling. For these
reasons, indirect, often noncontacting, temperature-measurement schemes are being
heavily investigated.
A second possible potential problem, wall deposition, is probably inhibited by
RTCVD’s use of chloride chemistries. Even if such deposition occurred, RTCVD
growth chambers could be opened for regular cleaning. Regular venting can be tol-
erated because at the higher (e.g., 9OOOC) growth temperatures, impurity incorporation
is less of an issue. Indeed, for growth at these temperatures, load-locks may not be
absolutely necessary.

3. ULTRA-HIGHVACUUM
CHEMICAL
VAPORDEPOSITION

The RTCVD largely sidestepped CVD temperature constraints by a combination of

editing and cycling between different growth temperatures for different layers. How-
ever, the above MBE data clearly demonstrated the desirability of a simple low-
temperature version of CVD. Conventional CVD epitaxy of Si had been limited to
temperatures above 900°C. Below this temperature heavily defective or polycrystalline
growth was produced. This occurred despite MBE data indicating that Si surface dif-
fusion lengths were still on the order of a micron at 500°C, considerably larger than
the distance an arriving atom would need to travel to find a crystalline site. This dis-
crepancy prompted a concerted effort to discover the mechanism that was disrupting
low-temperature CVD.
The key was identified in papers by Ghidini and Smith (1984) and Smith and Ghidini
(1982). Their work provided detailed data on the reaction of water vapor with clean
Si surfaces. Those data are represented in Fig. 7. The figure quantifies the balance be-
tween Si surface oxidation and oxide re-evaporation. It indicates that, as the Si temper-
ature decreases, water partial pressures must be driven ever lower if one is to maintain
an oxide-free surface. These general trends were understood, and were discussed in
the MBE section. However, the absolute numbers had not been fully appreciated, espe-
cially within the CVD community. An extrapolation of these data indicates that as Si
 1

-5
, ,
GROWTHTECHNIQUES

p
1
AND PROCEDURES

,I;,,,
TEMPERATURE (C)
10; 90; , 17

L OXIDE COVERED
10-1
t
W
K
3 10-2
3
w
E 10-3
s
I-
K
U
a 10-4
5 OXIDE-FREE
s t
I-
10-5
I
10-6
6.4 6.8 7.2 7.6 8.0 8.4 8.8

10000 I TEMPERATURE (K)

FIG.7. Equilibrium surface condition of silicon exposed to water vapor. Crystal growth requires essen-
tially no contamination of the substrate template. For Si, this will be achieved only for those water vapor
partial pressures falling at the bottom left of the figure. This requirement is the basis for the base vacuum
requirements in both MBE and UHVCVD, and for restrictions on CVD reactant gas purities. Data from
Ghidini and Smith.

temperatures are lowered from 900°C to 600”C, Si surfaces will be kept free of oxide
only if water partial pressure is decreased from torr to below ton. These are
equilibrium numbers. In fact, the initial oxide can be desorbed at higher temperatures
and then lowered quickly for growth. Nevertheless, these numbers demonstrate that
MBE paranoia about residual gases was not misplaced and, indeed, would have to be
shared by CVD growers if crystalline low-temperature films were to be produced. In
addition, CVD reactors would have to become every bit as leak tight as MBE systems
and similar measures would have to be taken to prevent their contamination during
sample loading.
Meyerson et al. (1986) first appreciated this point and designed a CVD reactor
to these stringent standards. He named his variant ultrahigh-vacuum CVD, which,
while literally a misnomer, nevertheless emphasized the basis for its success. That
is, although growth, in fact, occurred using reactant pressures in the “roughing vac-
uum” range of 1-10 mtorr, the background impurity gas pressures were maintained
at “ultrahigh-vacuum’’ values below torr. The UHVCVD apparatus is shown in
simplified form in Fig. 8. The deposition chamber is made of glass and heated by an
18 JOHNC. BEAN

GROWTH
FURNACE
m
1 LOAD-LOCK
n
FORE/G ROW1- L J
ROUGHING
PUMPS

lLzz2r ‘ ”“””‘ u
FORE PUMP

FIG. 8. Schematic of UHVCVD apparatus (after Meyerson, 1986). Turbo-pumped sample load-lock
with insertion arm at right. Multiple samples are loaded, stacked back-to-back in carrier. Growth chamber at
center consists of a vacuum tight tube enclosed by a furnace. In at least early experiments, an RF excitation
coil was included (not shown) to facilitate cleaning of this section. The left turbopump is used on initial
evacuation of the chamber to remove impurities and attain the requisite UHV background pressure. However,
during growth with reactant pressures above 1 mtorr, the turbopump is presumably either closed off or
throttled back with the bulk of the pumping provided by the roughing pumps of the left of the figure.

external furnace. It is pumped out using a turbopump and precleaned by inducing a

hydrogen plasma that, in effect, replaces the extended 150°C bake-outs used for MBE
systems. As with MBE systems, once it is pumped down and cleaned, it is kept at
vacuum for extended periods of time while samples are introduced using a separately
pumped load-lock.
Growth occurs by introduction of Si& and GeH4. If these gases are used at 10 mtorr,
Fig. 7 indicates that, to prevent 600°C surface oxide build-up, they must be free of
water vapor to a level of about 10 ppb. Not only are these gas purities extraordinarily
hard to produce, they can be very hard to maintain as gases pass from high-purity
tanks through mazes of piping into the growth chamber. Details have not been fully
disclosed but it is apparent, if only from the difficulty others had in reproducing results,
that particular care must be taken in preparing the reactor and its supply piping, and
it is probable that modern specialized point-of-use gas purifiers are used. This care
parallels that which be must employed in MBE to prevent metal contamination.
MBE can be modeled as a simple condensation process in which impurities are
treated only as second-order spoilers. However, with even the above precautions,
UHVCVD must confront immediate “impurity” effects in the form of decomposition
products. In a Si- molecule, hydrogen atoms are distributed at tetrahedral angles that
maximize their separation around the core Si atom. At typical 500--10OO0Ctempera-
tures, such a molecule will react with a bare Si surface in such a way as to begin the
 1 GROWTH
TECHNIQUES
AND PROCEDURES 19

deposition process. However, their geometry makes it very unlikely the S i b molecules
will, at least initially, release a pair of hydrogen atoms in such a way that a volatile H2
molecule can form. It is much more likely that at the Si surface, one Si-H bond will
be broken to give a tethered SiH3 molecule and the liberated H atom will then bond to
an adjacent Si surface atom. As already noted, surface hydrogen is in many respects
benign and, in cleaning procedures, is used to protect the Si surface from reaction with
other species. Unfortunately, the same blocking effect occurs in CVD as surface Si
atoms, which have become tethered to H, refuse to react with subsequent arriving SiH4
molecules. Thus, growth rate very quickly comes to depend not on reactant arrival rate
but only on the rate of H desorption. This available “site-limited” growth is depicted
at the right of Fig. 9. The experimental growth rate data of Fig. 10 confirm the transi-
tion from reactant limited to site limited growth as silane based growth temperature is
decreased.
Site-limited growth is a “good-newshad-news” proposition. As Meyerson et al.
1986 has pointed out, it means that deposition rate can be determined by a single ther-
mally activated parameter, completely independent of reactor and gas flow geometries.
This is, in effect, the antithesis of MBE where lines-of-sight are used to control the
deposition precisely on a limited number of substrates. Instead, for surface hydrogen
limited growth, if they are at the same temperature, all surfaces of all wafers will grow
at the same rate, as long as an undepleted gas flow can reach them. This will occur
even if 50-100 wafers are stacked back to back. For this hydrogen desorbtion limited
growth, reaction probabilities are indeed extremely small, and reactant gas depletion is
low enough that the aforementioned conditions are met. This gives UHVCVD a huge

REACTANT LIMITED SITE LIMITED

SiH4 SiH4 Sin4 SiH4

1 1
Si-Si-Si-Si-Si-Si-Si H H H H H H
I I I I I I I I I 1 1 . 1 1 . 1
Si-Si-Si-Si-Si-Si-Si Si-Si-Si-Si-Si-Si-Si
I I I I I I I
Si-Si-Si-Si-Si-Si-Si

FIG. 9. Schematic of Si surface upon exposure to silane reactant gas. At high growth temperatures,
silane readily decomposes at surface, depositing silicon and releasing two H2 gas molecules. Growth rate is
then limited by the arrival rate of silane reactant at the Si surface. At lower temperatures, silane molecule
instead breaks a single Si-H bond. It is then tethered to the Si surface but the liberated, reactive, H atom
attaches to a neighboring Si. Subsequent silane molecules cannot react at those H “passivated” sites and
growth is then completely limited by the thermal desorption rate of H.
20 JOHN C. BEAN

700 600 500 400

1000 , ,, \
I I

100

10

1
10 11 12 13 14 15
1000 / TEMPERATURE (K)

FIG. 10. Silicon growth rate as a function of temperature and S i b reactant gas pressure. Data are from
the RTCVD experiments of Liehr et al. (1990) but similar trends are expected for all CVD techniques using
this reactant. At higher temperatures, the growth rate is a function of reactant gas pressure, indicating that
growth is limited by the anival rate of the reactant at the substrate surface. At lower temperatures, growth
rate is a function of only substrate temperature, indicating the "site-limited' growth mode of Fig. 9. Slope
of the site limited curve provides the hydrogen surface binding energy to silicon of 46 Kcalimol or 2.0 eV
per atom.

advantage for multiwafer growth. This advantage is, however, somewhat moderated by
the fact that simultaneous deposition is facilitated by the low reaction probabilities at
temperatures below 600°C. These low probabilities also mean that growth rates are ex-
tremely low and, as shown in Fig. 10, fall to values of 0.1 to 0.01 A/s at typical growth
temperatures.
Surface hydrogen limited growth presents an additional challenge. Desorption is
controlled by a 2 eV thermal reaction barrier (46 KcaYmol). For this activation energy,
at 6OO0C,the hydrogen desorption rate will change by 5% with only a 1.25"C change
in Si temperature. Because the desorption process gates the SiH4 adsorption, growth
rate will vary in a similar manner. Devices frequently require epi layer control at or
beyond this level. The wafer temperatures within a UHVCVD reactor must, therefore,
be controlled to extraordinary accuracy both across the reactor and from growth run to
growth run.
Thermal chemistry is further complicated as one moves to growth of GeSi. At the
low 550-650°C temperatures necessary for growth of smooth strained GeSi layers,
 1 GROWTH
TECHNIQUES
AND PROCEDURES 21

there is the above very slow release of H from Si surfaces. It has been shown, however,
that H is much more weakly bound to surface Ge atoms and it will still rapidly desorb
from these sites. It is further evident that, while a Si atom will not release H to the
vacuum, it will readily transfer it to a neighboring Si atom, allowing H to migrate
freely along the surface. The net result is that Ge atoms catalyze the release of H
from the growing epi surface, ultimately freeing Si sites and dramatically increasing
overall growth rate. Figure 11 documents this complex effect for both UHVCVD and
APCVD (Racanelli and Greve, 1990, 1991a; Jang and Reif 1991). Dopant atoms can
also influence growth rate. Detailed boron data have not been presented for UHVCVD
but it has been shown that introduction of PH3 produces a mild inhibition of growth
(Greve and Racanelli, 1991). These effects mean that deposition becomes a complex,
coupled, thermally activated, problem. This contrasts with MBE where growth rates are
essentially linear, thermally independent, with no coupling between deposition species.
The complexity of low-temperature CVD processes does not, in itself, rule out growth

UHVCVD

I-
W
Q
610 C
I
600 C
0
c.3

0
0 0.05 0.10 0.15 0.20 0.25

Ge FRACTION

FIG. 1 1 . Effect of Ge content on growth rate for fixed SiH4 reactant pressure in both UHVCVD and
APCVD growth. APCVD data from Meyer and Kamins (1992). UHVCVD data at 500'C from Meyerson
(1988). Balance of UHVCVD data from Racanelli and Greve (1991). Initial growth enhancement (in all
but 750°C curve) can be attributed to low-temperature "site-limited" growth and tendency of bound surface
hydrogen to be released at Ge surface atoms sites. However, variations and ultimate downturn of most curves
clearly indicate more complex mechanisms.
22 JOHN C . BEAN

of a given doped GeSi structure. It may, however, affect reproducibility and certainly
increases the challenge of developing the recipe for a new structure.
For UHVCVD, diborane has proved to be an outstanding source for P-type films
and extremely high doping levels have been achieved (Meyerson et al., 1987). On the
other hand, the early sustained absence data on N-type dopant incorporation indicated
that this presented significant difficulties. However, data were ultimately published
indicating that N-type doping could be achieved with PH3 but that incorporation would
not exceed 5 5 x 10i8/cm3 (Greve and Racanelli, 1991). This might limit certain
applications of UHVCVD but it has not been a critical issue in the dominant HBT
application where UHVCVD has been used only for the growth of the single P-type
GeSi base layer (Patton et al., 1990).
Finally, it should be noted that while UHVCVD offers clear multiwafer
throughput advantages, a key manufacturing issue has not been publicly addressed:
SiH4 reactants will also produce deposition on the hot quartz walls of the
UHVCVD reactor, where those deposits should eventually produce the same particu-
lates seen in MBE. This could provide an ultimate limit on the crystallographic quality
of UHVCVD films or put constraints on the length of time such a system can be op-
erated between disassembly and cleaning. This might be sidestepped by periodic use
of alternate Si etching chemistries but if these, or other solutions, have been employed
they have not been disclosed.

4. ATMOSPHERIC
PRESSURECHEMICALVAPORDEPOSITION
Two final forms of CVD will be described. They are, however, variants on the fore-
going and discussion will be brief. The first is atmospheric pressure CVD (APCVD).
As the name indicates, unlike both UHVCVD and RTCVD, reduced reactant gas pres-
sure is not used. This, it is claimed, leads to simplifications in the apparatus that reduce
its cost. From the published system diagram, that simplification apparently comes
largely in the elimination of the turbopump. Otherwise, the system diagram looks re-
markably like that of the UHVCVD system presented here, right down to its use of a
valve isolated sample load-lock. Publications do not make it clear whether that load-
lock is purged, or if another simpler pump is used. The similarity to the UHVCVD
apparatus is not coincidental. To grow at reduced temperatures, APCVD must still take
extraordinary precautions to eliminate impurities.
Sedgewick and Agnello did work on APCVD that cites water partial pressures down
to lop6 torr in the reactor (Sedgewick and Agnello, 1992). As a fraction of the reactant
pressure, this is in fact better than that achieved in UHVCVD work. However, accord-
ing to the Ghidini data of Fig. 7, it is not low enough to prevent oxidation of Si surfaces
at the low, 625-700°C growth temperatures employed. The absence of such oxidation,
as indicated by film quality, is attributed, in part, to the addition of a hydrogen carrier
gas in the reactor. It is known that H2 can scavenge surface oxides and it is a standard
component in conventional CVD (but not in UHVCVD).
 1 GROWTH
TECHNIQUES
AND PROCEDURES 23

Another change is made in the processing environment: dichlorosilane (DCS) is

substituted for simple silane. As in RTCVD, the use of chlorides, with their tendency
to etch amorphous deposits, makes it possible for APCVD to deposit selectively on Si
exposed in oxide windows. Selective growth is not possible with MBE or the straight
hydride chemistries of UHVCVD, and is the topic of a separate section that follows.
The same selectivity should apply to the hot glass walls of the reactor. That is, although
it is not spelled out in the literature, it is probable that chloride-based APCVD is at
least partially free from the wall deposition and particulate formation problems that
can occur in both MBE and UHVCVD.
For APCVD, unusually complete data have been published on the effects of dopants
on growth rate (Sedgewick and Agnello, 1992; Sedgewick and Grutzmacher, 1995).
Some of these data are shown in Fig. 12. Both N- and P-type doping radically increase
the low-temperaturegrowth rate of Si. These changes are so large that it seems unlikely
that the isolated dopant atoms affect the capture of DCS molecules. It seems more prob-
able that the dopant atoms act in a manner similar to that of Ge in UHVCVD. That is,
they catalyze the release of a surface atom, in this case either H or C1, that would other-
wise block the reaction with the incoming Si molecule. While this analogy is plausible,
it should be noted that the strong PH3-induced enhancement of growth rate is very dif-

1000
+ B2H6

100

+PH3

10

1 UNDOPED
\
8.5 9.5 10.5 11.5 12.5
I0000 I TEMPERATURE (K)

FIG. 12. Acceleration of APCVD growth upon addition of dopants. Data from Sedgewick and Agnello
(1992) and Sedgewick and Grutzmacher (1995).
24 J O H N C . BEAN

ferent from the slight inhibition observed in UHVCVD. Workers in APCVD speculate
that this is due to the unique role of C1, but the complete mechanism is not currently
understood. In Fig. 12, the growth rate for undoped films falls sharply at low tempera-
tures, suggesting that in a manner similar to UHVCVD it is limited by H coverage of
the Si surface. For UHVCVD this coverage makes the growth rate independent of re-
actant concentration, and enables simultaneous deposition on large numbers of wafers.
The similarity of the data suggests that uniform multiple wafer deposition would also
be possible in APCVD, but this claim is not made in the literature.

5. GAS SOURCE
MBE

MBE has been combined with GeSi CVD precursors to produce so-called “gas-
source” MBE (GSMBE). For GeSi, it was developed primarily by Hirayama et al.
(1990a, 1990b, 1991) at NEC. Its use has spread to Shiraki’s group at the University of
Tokyo but it has otherwise been picked up by very few groups. For disilane precursors,
growth rates and dopant incorporation have been investigated and generally parallel
the results found in UHVCVD. Selective epitaxy has also been achieved, in contrast
to conventional MBE, and these results will be detailed later in this chapter. Further,
excellent device results have been obtained.
The limited use of GeSi GSMBE may be attributed to the fact that, while gas sources
can enhance MBE, as a production tool their use may also combine the least desir-
able features of MBE and CVD. Specifically, one brings together the complexity of
metal-sealed vacuum chambers with the tremendous safety precautions demanded by
the toxic and even explosive behavior of both Si and Ge hydride precursors. The overall
installation cost may thus be doubled. In conventional MBE, metal chambers provide
the space for sources, substrate heaters, and flow-controlling shutters, and yield unique
performance advantages. For GSMBE, it might be argued that because these functions
can be moved outside the main growth chamber (as they are in UHVCVD), the use of
a simple glass reaction tube makes more sense. In fact, it is the author’s experience
that the use of conventional MBE heaters within the growth chamber can lead to side
reaction of gas precursors that can complicate or damage growth quality. As a research
tool, GSMBE uses CVD chemistries in a high vacuum environment where powerful
gas and surface analysis tools can be easily employed. Thus, while its commercial
application may be uncertain, GSMBE could be a critical tool in reaching a detailed
understanding of complex CVD reaction mechanisms described in the foregoing.

IV. Comparison of Growth Results

This section will compare the quality and features of material grown by the different
techniques. Data are combined with the specific intent of adding a perspective that has
often been missing in GeSi literature that most often focuses on the development of a
 1 GROWTH TECHNIQUES
A N D PROCEDURES 25

single technique. To that end, this chapter will highlight figures of merit that have been
demonstrated for all or most of the foregoing techniques. Further, as already indicated,
I will weigh most heavily results relevant to the application of GeSi in devices such as
the HBT.
At the outset, it should be noted that all of the preceding techniques have been suc-
cessfully applied to the growth of fast, high-gain, minority carrier HBT devices. That
is not to say that all material, grown by all workers, by any technique, is up to this high
standard. In fact, there is strong evidence of a considerable range of quality in material
grown by most techniques. It does suggest, however, that most of the literature vari-
ability is in fact not indicative of the ultimate capabilities of each technique and that
selective citations can be very misleading. For each technique, only the best results
known to the author will be described.

1. LAYERTHICKNESS

The most basic figure of merit for all GeSi growth techniques is the ability to grow
with control the thin GeSi layers called for in present and future devices. The mildest
demand would be for the base layer of an HBT, which is generally 300-500 8, thick.
Tunneling devices then require barriers on the order of 100 A.Photodetectors, based on
tuned quantum wells, involve thicknesses of -20-100 A. The ultimate demand might
be in devices based on the changes in bandstructure that may occur in superlattices
with 1-10 atomic monolayer periods (1.5-15 A).
For conventional high-temperature CVD, growth rates can fall in a pndmin range
that would make all but perhaps the HBT application impossible. Growth rates for the
newer GeSi techniques are compared in Fig. 13. For all but MBE, these rates can be
strongly enhanced as Ge is added and, for simplicity, the rates for only pure Si growth
are given. In the temperature ranges used for GeSi growth, rates are from 1-100 A/min
(or -.Ol-IONS). Rates for CVD and gas-source techniques are thermally activated,
The rate for MBE can be varied arbitrarily within the capabilities of the e-gun sources.
All rates are low enough that flow or flux switching can occur fast enough to permit
growth of very thin layers.
Minimum layer thicknesses have been documented by a number of indirect tech-
niques. These have been employed because imaging techniques, such as TEM, average
over a significant sample thickness and may thus under-represent local roughness.
For MBE, continuous layers can be grown down to thicknesses approaching a single
monolayer. This was demonstrated by electroreflectance spectroscopy on a series of
samples with diminishing layer thickness. These optical signals varied in a systematic
and predictable manner as layers were thinned down to 2 atomic monolayers (ML)
(Pearsall et nl., 1987; Pearsall et al., 1989). At an intended layer thickness of 1 ML,
there were anomalous spectral features suggesting either lack of continuity or atomic
26 JOHNC. BEAN

TEMPERATURE (C)
850 750 650 550

IOOOJ- q

I I I I I I I I I
8.5 9.5 10.5 11.5 12.5
1000 I TEMPERATURE (K)

FIG. 13. Comparison of growth rates by various growth techniques. The APCVD and UHVCVD data
were extracted from preceding figures. The GSMBE data are from Hirayama el al. (1991). For these CVD-
based techniques, data all fall sharply at lower growth temperatures. The MBE growth rate is independent
of substrate temperature (over the indicated range) and a function only of e-gun evaporation sources. Data
are given for an MBE system such as that of Fig. 1 using 150 cc capacity, 7.5 cm diameter Si charges spaced
approximately 500 cm from substrate.

steps. Raman data also support the conclusion that MBE GeSi layers can be grown
smoothly and continuously down to almost one ML, at which point roughness or steps
limit the lateral continuous dimension of the layer (Araujo Silva et al., 1996a, b).
For RTCVD, minimum layer thickness has been inferred from photoluminescence
(PL) measurements on quantum wells of diminishing thickness (Xiao et al., 1992b).
As well thickness decreases, quantum size effects should push up bound energy states
leading to a blue shift in the PL signal. This was, indeed, observed and it indicated that
wells of well-defined thickness could be grown down to at least 33A.
For UHVCVD, TEM data and electrical results from resonant tunneling devices (Is-
mail et al., 1991) indicate good layer control down to at least 50 A. The real number
is probably considerably lower than this as suggested by APCVD data that examined
 1 GROWTHTECHNIQUES AND PROCEDURES 27

this issue more completely. In that APCVD work, a combination of X-ray diffraction
data and PL quantum size effects suggested that layers could be grown at thicknesses
of 10 A with interfacial roughness < 2 A.
There is a second, more subtle, aspect of GeSi layer thickness control: the observed
tendency of Ge, in GeSi layers, to move into overlaying Si layers. The movement
is not symmetric, ruling out diffusion as the mechanism. Instead, Ge moves upward
towards the growth surface and it is almost certain that this is a surface segregation
phenomenon similar to that observed for many dopant atoms. Early Ge segregation
data came primarily from surface analytical tools found on MBE systems (Zalm et al.,
1989; Grevesteijn et al., 1989; Godbey and Ancona, 1993). Later, more quantitative
profile data have been measured by SIMS on materials grown by various techniques.
SIMS has the advantage of following concentration tails down to trace levels, but it is
not accurate at the top of the profile where ionization probabilities will be affected by
the impurity concentration. In general, SIMS segregation profiles are approximately
exponential and, where possible, these curves have been converted into a characteristic
decay length. For single Ge monolayers grown in Si by MBE at 500"C, a decay length

hydrogen, at pressures of -
of -20 A was measured (Ohta et al., 1994). Addition of either atomic or molecular
5 x torr, cut this length to -5A. In the one pub-
lication comparing techniques (Grutzmacher et al., 1993b); both MBE and APCVD
segregation lengths were approximately independent of growth temperature. An MBE
value of 20 8, was again measured, compared to 8 A for APCVD. UHVCVD values
did vary with growth temperature, falling from -45 A at 700°C to less than 10 8, at
515°C. These results again support the suppression of segregation by hydrogen, in that
APCVD is grown in an H2 ambient and UHVCVD films are known to retain surface H
at the lower growth temperature.
As a trace element in Si, Ge is soluble and produces no direct electrical activity.
The more important question is thus whether segregation hinders growth of thin GeSi
layers by blurring one interface. Extrapolation of the SIMS trace data suggest that at
least in MBE films of 10-20 A, thickness control could, indeed, be degraded. How-
ever, that extrapolation contradicts a large body of MBE data showing well-defined
superlattice growth at 2-10 atomic monolayers (3-15 8,). If one applies the SIMS de-
cay length of 20A, one would conclude that it would be essentially impossible to grow
a Si/GeSi MBE superlattice with 2 ML (3 A) layer thicknesses (i.e., e-3/20 = 0.86).
With even 10 ML silicon spacer layers, in those spacers, alloy composition would fall
by only 50%. This conclusion clearly contradicts electroreflectance, Raman and TEM
data and suggests that the initial Ge fall is significantly more abrupt than measured
in the tail of the SIMS distribution. Strong, high level, segregation is also inconsis-
tent with a variety of MBE superlattice device and bandstructure measurements. It
thus seems most likely that Ge segregation produces only very dilute tails for which
there will be little modulation of bandstructure and hence little or no effect on device
structures.
 JOHN c. BEAN
2. DOPING

Doping presents challenges for all of the foregoing low-temperature growth tech-
niques. Details were given in the foregoing but are summarized here for comparison.
For conventional MBE, using evaporated elemental dopants, extremely sharp profiles
can be grown but maximum doping levels are limited by segregation effects to values in
the mid-10'8/cm3 range. Doping by simultaneous low-energy implantation overcomes

current. For the author's system, at low growth rate, doping of -

segregation and maximum concentrations are then limited by the available implanter
1 x 10'9/cm3 is
possible. Implantation energy blurs dopant profiles at a resolution of about 25 A as
inferred from both theory and measurements of setback effects in modulated doped
structures.
For all of the CVD-based techniques, similar dopant chemistries lead to similar in-
corporation behavior. Boron works extremely well as a P-type dopant producing abrupt
profiles and maximum concentrations are well above lO2'/crn3. The N-type is signif-
icantly more difficult. With phosphine, reports indicate an incorporation limit similar
to the thermal MBE limit of 5 x 10'8/cm3. APCVD data, at least, also describe an
apparent reactor memory effect for P that could limit profile abruptness and minimum
doping levels.

3. MAJORITY
CARRIERTRANSPORT

In the GeSi literature, there has been intense competition to achieve high electron
mobilities with modulation-doped structures. However, these data are measured in
films that are grown well above strained layer limits such that relaxation occurs by for-
mation of misfit dislocation networks. This relaxation is necessary to produce tension
in Si layers that induces the conduction band discontinuity necessary for carrier seg-
regation. In principle, the necessary relaxation could occur without extending defects
into the electrically active layers. However, for reasons to be detailed in what follows,
this does not occur, and all of these N-type modulation-doped layers have high defect
densities of 106-10'2/cm2. These densities are not so much a feature of which growth
technique is used as they are a product of layer thicknesses, compositions, and growth
rates. As such, they should not be used as a basis for comparing techniques but will be
discussed in the section on pseudo-bulk GeSi.
P-type modulation doping does not depend on misfit dislocation formation and
should provide valid comparison of nominally defect-free material. The earliest re-
ports of P-modulation doping cited 10 K values of 3000-4000 cm2N-s for MBE layers
(People et al., 1984; People and Bean, 1987). A subsequent UHVCVD publication,
while claiming "the highest hole mobilities ever reported" had a near identical value
of 3800cm2N-s (Wang et al., 1989). The APCVD and RTCVD papers report values
of 2000 (Grutzmacher et al., 1993c) and 2500 (Venkataraman et al., 1991) cm2N-s,
 1 TECHNIQUES
GROWTH AND PROCEDURES 29

respectively. In these 2D hole gases, mobility depends critically on the exact choice
of both carrier concentration and the very small (-100 A) separation between the gas
and the dopant ions. These values are so close that differences could easily be due to
variation in these parameters.

4. PHOTOLUMINESCENCE

In Si and GeSi, the indirect bandgap precludes efficient electron hole recombination
to produce light. Weak photoluminescence (PL) can be observed, but there is strong
competition from recombination at nonluminescent sites such as metallic impurities.
Those same impurity sites accelerate the recombination of electrically injected minor-
ity carriers in key devices such as HBTs. In the HBT, the reduction in minority carrier
lifetime will reduce current gain and adversely affect leakage characteristics. Because
photoluminescence strengthens as interfering impurities are eliminated, it can be used
to assess material purity. Further, in certain instances, the luminescence features can
be used to identify specific impurities or defects. Unfortunately, for Si materials it is
a difficult technique with few skilled practitioners. Data on PL are briefly reviewed
by Cerdeira in Chapter V. To summarize, some of the most complete results have been
measured by many researchers (Xiao et al., 1992; Mi et al., 1992; Souifi et al., 1992)
for RTCVD materials. In these and related reports, particular importance is attached to
the presence of spectral features such as “no phonon lines”. Qualitatively similar, near-
bandedge, spectra have been reported for MBE (Fukastsu et al., 1992; Usami et al.,
1992) UHVCVD (Terashima et aZ., 1993) and APCVD (Grutzmacher et al., 1993a). In
principle, intensities could yield comparative information but PL data are always re-
ported in “arbitrary units” (presumably because of experimental challenges). As such,
the following electrical measurements of minority canier lifetime yield a more quanti-
tative comparison of minority carrier behavior.
In addition to near-bandedge data, there have been recurring reports of broad, sub-
bandgap emission for MBE layers grown at particularly low temperatures, such as
400°C. These features disappeared in more conventional 600°C layers and are at-
tributed to defects induced by extreme low temperature growth where, in a sense, in-
complete ordering at the growth surface induces formation of point defects, such as Si
interstitials or vacancies (Noel et al., 1990; Terashima et al., 1993). This attribution
is supported by in situ comparisons of material grown with and without the presence
of surface hydrogen, which would be expected to sharply alter surface point defect
generation.

5. MINORITY LIFETIME
CARRIER

More direct, electrical measurement of minority carrier lifetime is still far from
straightforward. The effect of interest, recombination at impurities and defects, can
30 JOHNC. BEAN

be easily masked by intrinsic recombination at layer surfaces. For Si on Si epitaxy,

surface recombination can be eliminated by oxidation at T > lOOO"C, which then also
facilitates determination of bulk lifetime from the inversion behavior of MOS capac-
itors. This is not possible for GeSi layers where 1000°C post-growth processing can
cause catastrophic degradation. Further, the limited thicknesses of GeSi layers means
that there is always a nearby Si/GeSi interface at which recombination may occur in
even hyperpure and perfect material. Thus, a growth technique is best judged by the
Si on Si lifetime, which provides an upper limit on the intrinsic GeSi value. Lifetimes
inferred from GeSi/Si diodes then give a lower, but almost certainly pessimistic, bound
that may be dominated by heterojunction recombination.
For MBE of Si on Si, an upper bound of 75 pS was reported for a system in which
heaters and e-gun sources are carefully configured, as described in the foregoing (Hi-
gashi et d., 1990). For the same system, a lower bound of 5 1 p S was determined
for thin GeSi layers. For RTCVD, an upper bound of 94 pS was reported for Si on
Si (Sturm et al., 1986) and a lower bound of - l p S for GeSi (Schwarz and Sturm,
1990). For UHVCVD, a Si on Si upper bound of 160 pS has been cited (Nguyen et
al., 1986) but newer data on GeSi are bit muddier. In particular, a report on an electron
cyclotron resonance variant of UHVCVD cites GeSi lifetimes values of up to 100 pS
(Hwang et al., 1996). However, not only is it unclear how heterojunction recombina-
tion was avoided for such long-lived carriers, but in fact, layer thicknesses were not
even given in this report. Overall, an upward trend is suggested for Si on Si values,
as one moves from totally metal MBE systems to metal and glass RTCVD systems, to
fully glass UHVCVD tubes. However, differences between the best data are relatively
small and are dwarfed by variations reported within a given technique by different au-
thors. The obvious conclusion is that current results more strongly reflect the care and
sophistication employed in particular experiments rather than the ultimate limitations
of the techniques. These variations can be readily explained by the sensitivities of the
various techniques to impurities, but the persistent variability represents a challenge to
the entire growth community.

V. Nonplanar Growth

GeSi is cited (Swalin 1972) as a prototypical alloy for which phase segregation will
not occur and many properties can be linearly interpolated from Si and Ge end points.
This ideality was thought to persist to atomic dimensions where Si and Ge atoms would
randomly substitute for one another within the tetrahedral crystal structure. On a larger
scale, films did exhibit nonideal tendencies towards roughening and defect formation
but, as detailed here, conditions were found under which these could be largely avoided.
As such, early work mostly ignored or avoided these irregularities and focused on
growth of very thin, uniform, planar films. More recently, however, attention has turned
to films that are either spontaneously or deliberately nonuniform. This section will
 1 GROWTHTECHNIQUES
AND PROCEDURES 31

discuss that work, focusing first on spontaneous mechanisms of atomic ordering and
islanding, and then turning to deliberate growth of limited, selective layers and pseudo-
bulk GeSi.

1. ATOMICORDERING

Atomic ordering has been one of the more intriguing yet frustrating phenomena en-
countered in GeSi. In 1985, Ourmazd and Bean (1985) observed weak superlattice
electron diffraction spots in GeSi layers. These spots indicated a clear, spontaneous,
rearrangement of Si and Ge atoms to form an alternating sequence of atomic planes, as
depicted in Fig. 14. This layering occurred on { 111) planes even though the epi layer,
itself, was deposited on a (100) surface. In the as-grown layers, the diffraction spots
were very weak but could be enhanced by a sequence of annealing and quenching.
Overall, diffraction intensities indicated that a relatively small volume of the epi layer
had assumed the ordered configuration. Nevertheless, the result was exciting because
it suggested a spontaneous means by which the normal cubic symmetry of column IV
semiconductors could be broken. This, in turn, could enable phenomena, such as piezo-
electricity or optical second harmonic generation, that would otherwise be prohibited
by the symmetry of normal Si crystals or in random GeSi alloys.

FIG. 14. Depiction of the spontaneous atomic ordering inferred from electron diffraction data on GeSi
films. Along a [l 113 direction, the atomic stacking sequence is Ge-Ge-Si-Si. This ordering is not a function
of growth which, in fact, occurred on a (100) plane (equivalent to the top horizontal face of the cube).
32 JOHN c. B E A N
Models suggested that ordering occurred as a means of slightly reducing the strain
energy in lattice mismatched films (Littlewood, 1986; Martins and Zunger, 1986).
These could be interpreted in terms of bond stiffness: the stronger, higher melting
point Si had the strongest, stiffest, bond (Si-Si). Ge had the weakest (Ge-Ge). Si-Ge
could be expected to be intermediate in stiffness. A random ordering of the weaker
Si-Ge and Ge-Ge bonds would not facilitate larger scale strain relaxation along atomic
planes. The Si-Si-Ge-Ge ordering would allow this by creating long range, more flexi-
ble Ge-Ge shear planes. These models did not entirely resolve the precise atomic order
for, in addition to the structure shown in Fig. 14, the Si-Si-Ge-Ge stacking sequence
could be offset by one plane, putting the Si-Ge bonds perpendicular to the stacking
direction. Either sequence would account for the observed diffraction data, although
strain relief models favored the original structure.
It became more problematic when researchers at IBM (LeGoues et al., 1989; Kuan
and Iyer, 1991), reported similar but much stronger, ordered diffraction data in thick,
relaxed GeSi on Si films. These films were nominally strain free, removing the appar-
ent driving force for ordering. Further, their analysis suggested the alternate layering
structure already discussed here. These data prompted new models of the ordering pro-
cess based on segregation phenomena occurring at the growing crystal surface. This
work, due largely to Jesson et al. (199 1; 1992; 1993) examined the details of atomic
bonding at single atomic surface steps as they grow across a crystal surface. As the
step moves laterally, it covers atomic sites that alternate in their detailed atomic con-
figuration. These configurations have different energies and, it is suggested, should be
energetically more attractive to either Si or Ge atoms. It is thus argued that, although
deposition may lead to random Si and Ge site selection, at the step edge these energet-
ics will drive the displacement of energetically misplaced atoms (e.g., Ge in GeSi) to
form a surface structure that ultimately lays down a bulk-ordered atomic configuration.
There is still significant controversy as to whether surface segregation or bulk strain-
relief processes drive the aforementioned ordering and about the precise details of the
resultant arrangements (LeGoues et al., 1993a, b). These effects, while weak and elu-
sive, have nevertheless now been observed by many research groups. Further, there
have been experimental observations of both piezoelectric (Xie et al., 1987) and op-
tical second harmonic generation (Baribeau, private communication) that could not
occur in random alloys. These and other effects could be of significant device utility if
ordering processes could be better controlled and strengthened. A clear resolution of
the mechanisms might yield the understanding necessary to drive such improvements.

2. ISLANDS AND WIRES

In the 1980s, work on GeSi was almost entirely directed at defining those condi-
tions that would produce smooth continuous layer growth. When “adverse,” nonplanar
growth conditions were encountered, they were recorded (as in Fig. 3) and avoided.
 1 GROWTH
TECHNIQUES
AND PROCEDURES 33

Starting about 1990, n o ~ p h l a Igrowth

’ was revisited as a possible virtue to be stud-
ied and exploited. This reversal was prompted by the recognition that, as structures
approach the scale of quantum mechanical wavelengths, their physical properties may
be radically altered. These alterations, broadly described as “quantum size effects,”
include changes in the density of states and folding of bandstructure that can be used
to tune the absorption strength and wavelength of semiconductor structures (Sakaki,
1994). Additionally, in these quantum microstructures there is at least the theoreti-
cal possibility that one might finally achieve light emission, the “holy grail” of silicon
materials research (Bean, 1992). In the spirit of this chapter, this section will survey
techniques that have been employed to fabricate such microstructures but will leave
detailed discussion of their properties to other more appropriate chapters of this book.
TO fabricate quantum structures, the natural response is use the lithographic tech-
niques that have made microelectronics so successful. There is, unfortunately, a prob-
lem of scale. Conventional photolithography depends on photons at UV wavelengths
of no smaller than 0.2 p m . Quantum effects are most strongly manifested at much
smaller dimensions, in the 10-100 nm range. Thus one must: 1) Turn to more exotic
but finer scale electron beam lithography; 2) find a means of shrinking conventional
optical lithographic features; or 3) take an entirely different approach.
Electron beam lithography might be used to pattern existing uniform layers, remov-
ing material such that the remaining structure exhibits quantum effects. However, at
very fine scales, etching generally requires “dry” processes employing energetic atoms
that can leave damaged material at the edges of an etched semiconductor layer. As
the edge to volume ratio of a fine quantum dot is particularly high, edge damage might
completely mask or eliminate quantum effects. An alternative is to use lithography only
for definition of a shadow masking layer through which epi will then be deposited. At
comparatively crude millimeter scales, this approach was first applied by Tsang and
Illegems (1977) and Tsang and Cho (1978) for free-standing masks with III-V MBE.
For more conventional surface oxide masks and Si MBE, this was extended to 0.5 p m
dimensions by Bean and Rozgonyi (1982). Finally, as the significance of quantum
dots was fully appreciated, Bruner et al. (1994) used this approach to fabricate micron-
sized GeSi quantum dots for which the photoluminescence signals gave clear evidence
of size effects. Their fabrication scheme is depicted schematically in Fig. 15. They
fabricated dots down to 2 p m diameter but much smaller masks could be defined with
electron beam lithography. For MBE and hydride-based CVD techniques one would
ultimately be limited by deposition on the mask producing a narrowing and eventual
occlusion of fine openings. This should not occur in halogen-based CVD. However,
this author is not aware of work that has combined and fully exploited these elements
to produce shadow masked epi structures at sub 0.1 p m dimensions.
The second alternative is to use a combination of more conventional lithography
and to implement some means of shrinking features. The most common approach,
again first demonstrated with III-V semiconductors, is to first use optical lithogra-
phy to define relatively coarse grooved masks. Anisotropic chemical etches are then
34 JOHN C. BEAN

FIG. 15. Geometry used by Bruner er al. (1994) in early experiments to fabricate arrays of GeSi dots.
Holes were defined by photolithography on a two-layer dielectric mask. Etching solutions were chosen
such that the lower layer over-etched producing an overhang. Materials deposited on this shadow mask then
formed the desired isolated dots on the substrate. Mask (and material deposited on the mask) could then be
chemically “lifted off” for evaluation of the dots.

selected such that the “V” shaped trenches are etched in the substrate. The mask is
then removed and the patterned substrate exposed to reactant fluxes that would nor-
mally produce uniform deposition. However, at the “V” trenches, under conditions of
high adatom of mobility, there is a natural tendency for excessive material to accumu-
late at the bottom of the trench and for the deposit to thin or grow discontinuously at the
sharp upper comers. This produces triangular cross-section “wires” of epi. For GeSi,
this approach was demonstrated by the work of Usami et al.( 1994) using the geometry
at the left of Fig. 16. Wire pairs have also been grown in the parallel corners of flat-
bottomed grooves (Hartman et al., 1995) or on ridged structures. Aside from the use of
more conventional, coarser, optical lithography, these approaches have the advantage
that wire dimensions can be tuned by limiting the thickness of the deposit or by biasing
growth conditions between uniform or more localized growth. Wires are illustrated
but square dots would be similarly produced at the bottoms of square pyramidal de-
pressions. These structures have been successfully employed to explore quantum size
effects at scales smaller than those of the shadow masked dots that have already been
discussed here. Looking forward to possible quantum devices, this technique would
appear to have two principal limitations. The first is that while fine structures can
be produced, they would be separated by the coarser “V” trench dimensions, limiting
packing densities. Further, for the finest structures grown only at the apex of the “V,”
the extreme nonplanxity of the surface might challenge subsequent metallization or
lithographic steps needed to complete a circuit structure.
In the absence of simple ultrafine lithographic techniques, recent work has turned
towards exploitation of spontaneous film islanding. In even strain free films, chemical
dissimilarities between substrate and epi yield high interfacial energies that can drive
 1 GROWTH TECHNIQUES
AND PROCEDURES 35

FIG. 16. Depictions of schemes to produce quantum wires. Substrate with (100) surface is masked by
oxide and stripes opened by photolithography. Exposed substrate is then etched by anisotropic etches (such
as KOH or ethylene-diamine-pyrocatechol)for which etching is ultimately limited by (1 11) planes (Petersen,
1992). Result is a substrate with fine V-shaped grooves or ridges. The etched substrate is overgrown with
GeSi epi under conditions of high adatom mobility (generally, higher temperatures). Epi then tends to round
off comers, producing isolated deposits in bottoms of grooves or on top of ridges. For V-groove at left,
“quantum wire” can be narrowed below the photolithographic dimension of groove by early termination of
GeSi epi.

the formation of discontinuous layers. The simple and familiar analog is the beading
of water on a clean glass surface. Detailed atomistic models predict more complicated
phenomena, such as the Stranski-Krastinov mode in which islanding occurs only after
the initial growth of several smooth layers. Strain, such as that found in commensurate
growth of GeSi on Si provides an additional islanding force. As described in early
models by Luryi and Suhir (1986), islands add lateral free surfaces at which a strained
deposit partially relaxes. This reduces the net system energy and provides a tendency
towards islanding even in the absence of interfacial energy terms. These effects were
understood in the earliest experimental work but, outside of a few detailed studies (Pid-
duck et al., 1992), experimentalists largely sought growth conditions that would avoid
nonplanar growth and thereby facilitate growth of very thin layers and superlattices.
The potential of quantum structures kindled the recent hope that islanding alone
might now be exploited as a fundamental nonlithographic means of making large num-
bers of fine quantum structures. Early data, such as Fig. 3, define the growth conditions
under which islanding will occur but provide no information on island sizes or distri-
butions. Over the last few years a flurry of investigations have attempted to fill in these
details and provide evidence of quantum effects through phenomena such as photo-
luminescence (Apetz et al., 1995; Sunamura et al., 1995; Schittenhelm et al., 1995;
Krishnamurthy et al., 1997; Kim et al., 1997; Chen et al., 1997; Persans, 1997). At
the physics level, these studies have been both interesting and promising. However,
regardless of the occasional use of terms such as “self-organized” or “self-assembled”
in titles, this work has largely documented the random statistical nature of nucleation
36 JOHN C. BEAN

2.5 nm Si,,,Ge,,s/Si(OO1)

FIG. 17. The A F M image of surface of single Ge75Si25 layer with average thickness of 2.5 nm, grown
under conditions in which islands are produced. Note wide range of island sizes and essentially random
distribution.

processes. That is, while there are average island sizes and average separations de-
termined by surface kinetics and energetics, variations are quite large. An example is
given by the AFM data of Fig. 17 (from Physics Today, May 1996). These surfaces do
indeed provide a ready means of producing a large number of very fine semiconductor
dots. However, it is difficult to envision a circuit structure that could make use of such
randomized distribution of sites and sizes.
The preceding data are for single layers of islands. Work by Carlino et al., (1996a,
b) explored multiple roughened GeSi layers embedded in superlattices. In this work
there were indications that in multilayer structures, thickness variations were no longer
entirely random in position. The indication, in a sense negative, was “conical shaped
defects” wherein a thick or Ge-enriched region on an early layer apparently produced
a strain field that led to enhanced concentration of Ge above that point, in overlaying
layers. The overall effect was to produce an expanding, upward facing, cone of Ge en-
riched regions that could grow to the point that the localization of strain would nucleate
crystallographic defects.
These observations were consistent with concurrent calculations by Tersoff et al.
(1996) on the strain interaction between multiple islanded layers within GeSi/Si super-
lattices. The results of these calculations are depicted schematically in Fig. 18. In the
1st Ge (or GeSi) layer on Si, island size and position are approximately random. How-
ever, larger islands do require collection of more material and thus larger islands will
tend to be farther apart. This 1st islanded Ge layer is then overgrown with a Si spacer
layer of some fixed thickness (vertical island sizes are greatly exaggerated in Fig. 18),
and a 2nd Ge island layer grown. Above the 1st layer Ge islands, their larger atoms
 1 GROWTHTECHNIQUES
AND PROCEDURES 37

Ge layer 5

Ge layer 1

FIG. 18. Schematic representation of Tersoff et al. model (1996) taking into account influence of strain
produced by initial layer of GeSi islands on arrangement of islands in subsequent GeSi layers. The GeSi
layers are separated by fixed thickness Si spacer layers. Islands are depicted as pyramids only to show their
relative volume and position (actual islands would be much smaller and have more complex geometries).
Strain of initial GeSi islands tends to dilate Si spacer layer above, enhancing growth of Znd layer islands at
those positions. However, as growth progresses, islands tend towards spacing tbat is entirely independent of
initial island pattern. Ultimate spacing is, instead, a multiple of the Si spacer layer thickness.

induce a local lattice dilation that extends through the overlying Si spacer layer. This
local dilation then provides a particularly attractive (low mismatch) site for the 2nd Ge
island layer and, as found in this simulation, 2nd layer islands tend to nucleate imme-
diately above 1st layer islands. This effect, also evident in von Kanel’s conical defects,
is readily understood. The surprise occurs when the calculation continues, evaluating
strain interactions and energy minimization through the growth of a full island super-
lattice. Islands ultimately shift to a spacing that is, instead, a simple multiple of the
Si spacer layer thickness! In the simulation of Fig. 18, this final spacing is smaller
than that of the 1st island layer. However, a companion simulation, assuming a very
fine 1st layer distribution, converged on the same (then coarser) spacing in the final
layer. As island spacing becomes more regular, so should the size distribution. As
strange as these simulations are, they have been confirmed experimentally (Teichert et
al., 1996) as indicated by our AFh4 data showing the surface of such an island super-
lattice in Fig. 19. Ordering is not perfect but the contrast with the single island layer of
Fig. 17 is dramatic and the progress towards true self-organization significant. Results
do, however, still fall short of the organizational perfection one expects of a circuit.
Work will continue on harnessing these spontaneous mechanisms as device physicists
begin to give serious thought as to how these organized 3D quantum structures might
be incorporated in functional device architectures.
38 JOHN c. BEAN
20 x (2.5 nm Si,,,Ge,,, / 10 nm S i ) on Si(001)

FIG,19. Experimental confirmation of model in Fig. 18. The AFM image of the surface of 2Cperiod
superlattice of nominal 2.5 nm Si.025Ge0.75 layers separated by 10-nm Si spacers. Note strong increase in
island regularity compared to single island layer of Fig. 17.

3 . SELECTIVE
AREAEPITAXY

Selective area epitaxy (SAG) is produced in situations where precursors can be cho-
sen such that deposition will continue on an exposed semiconductor but not on common
masking materials, such as Si02 and Si3N4. Selective area growth has already been al-
luded to and certain advantages described. However, its true significance is appreciated
only when one contemplates the full sequence of steps necessary to fabricate a mod-
em integrated circuit. Normal, planar, nonselective epitaxy must be applied only very
early in that sequence when either the full substrate is still exposed or at least large
areas are revealed. One might think that a “lift off’ process might be applied later in
this sequence, but for crystalline device material it is difficult to define windows and
lift off overgrown material without leaving damaged boundaries (if, indeed, damaged
boundaries do not occur during growth!). If epi is deposited across the wafer, early in
the fabrication sequence, one is limited to rather simple morphologies (planes now and
perhaps organized islands in the future). Further, this layer will be exposed to all of the
subsequent processing steps, many of which involve significant heating. This heating
can yield undesirable diffusion of dopants, interdiffusion of layers or, for metastable
GeSi layers, nucleation of defects. Many attractive alternatives are opened up if one
can come in late in the circuit fabrication sequence and instead deposit small, isolated,
high-quality epi layers in lithographically defined windows. Indeed, through factors
 1 GROWTHTECHNIQUES
AND PROCEDURES 39

such as the reduction of coupling capacitances, this option can make the difference
between satisfactory and unsatisfactory circuit performance.
MBE provides the antithesis of SAG growth: its precursors, atomic Si and Ge, will
condense on any cool surface regardless of its chemistry. The situation is very different
when halogen precursors such as Sic14 are employed. Silicon tetrachloride decom-
+
poses via the reaction Sic14 = Si 2C12. This reaction is reversible in that free Cl2
will etch Si. Under normal growth conditions, this etch rate is obviously rather slow
for crystalline Si (or growth might slow and stop as C12 reaction products accumu-
lated). However, the rate is much higher for amorphous and polycrystalline Si. This
discrepancy means that should a S i c 4 molecule react and deposit Si on a surrounding
mask, noncrystalline Si will be rapidly etched away even as Si continues to grow in an
adjacent open window to the substrate.
Halogen selective area growth is a “classic” effect in CVD epitaxy and it is rele-
vant to this chapter only where it has been extended to selective area growth of GeSi.
The Stanford RTCVD group reported one of the earliest such experiments (Noble et
al., 1990). They employed G e a and dichlorosilane precursors with GeSi growth oc-
curring at 625°C over a Si substrate partially covered by thin Si02 fingers. Auger
spectroscopy gave no evidence of Ge deposition on the oxide mask, despite the fact
that its precursor was not halogenated. It was noted, however, that the GeSi window
deposits did contain arrays of misfit dislocations with typical spacings of 0.5 bm. The
2000 A thick Si8oGe20 layer would have strain exceeding equilibrium limits, but in
uniform layers significant defect nucleation would not be expected. This discrepancy
was thus attributed to enhanced nucleation of defects at the edges of the deposits. A
similar paper by Zhong et al. (1990) confirmed selective growth with the same use of
only a single halogenated precursor but provided no defect data.
Sedgewick’s APCVD group published a series of papers on selective GeSi growth,
culminating in the fabrication of a selectively grown resonant tunneling diode. The
initial work (Agnello et al., 1991) used a simple dichlorosilane and germane precur-
sor mix, identical to the RTCVD work already discussed, and reported on growth of
layers with 1 5 4 4 % Ge. Smooth, unfaceted selective layers were grown but, while it
was noted that in TEM analysis “occasional defects originate at the oxide sidewall,” no
densities or spacings were given. High-resolution x-ray diffraction was also employed
for a 260 ASi56Ge~layer grown at 550°C. Roclung curve widths were interpreted to
give an upper bound of no more than lo5 misfit dislocations/cm2. In follow-up pa-
pers (Segewick et al., 1993; Zaslavsky et al., 1992), HC1 was added to the reaction
environment in what is described as a “more traditional” approach to selective epitaxy.
The implication was that selective growth quality improved and data from a successful
selectively grown resonant tunnel diode were given. However, in the absence of com-
parable TEM or x-ray data, the degree of improvement and thus the importance of the
added HC1 are not clear.
For GSMBE, the NEC group has provided a number of reports on selective GeSi
growth. In contrast to the work already discussed, and most of the CVD work, they
40 JOHN c. B E A N
did not use halogens. Simple disilane and germane precursors were instead employed
at temperatures of 630°C to produce films of 16, 22 and 31% Ge (Hirayama et ul.,
1990a). It was reported that RHEED patterns degraded for x = .3 1, usually an indi-
cator of either surface roughening and/or high defect densities. In conventional CVD,
hydride precursors produce selective epitaxy only for a brief initial growth period, after
which deposits are nucleated and grow rapidly on masking oxides. For low temperature
growth of pure Si, a maximum selective thickness of 500 A was reported before onset
of oxide overgrowth (Murota et al., 1989). In this GSMBE paper, the claim of hydride-
based selectivity is supported only by the apparent absence of the normally rough poly-
crystalline surfaces on the oxide mask and on a comparison of layer thicknesses. These
data support a significant degree of selectivity (i.e. growth rate in window >> growth
rate over oxide). However, the near absolute selectivity seen for halogen precursors is
neither confirmed nor expected. In most applications, it is not absolutely necessary that
no material grow on the mask. However, it can be very damaging if imperfect material
grows at the edge of the window where it can serve as a current leakage path or as the
source for subsequent defect nucleation. A subsequent paper uses the aforementioned
GSMBE recipe to fabricate a selectively grown GeSi heterojunction bipolar transistor
(Hirayama et ul., 1990b). Transistor characteristics confirm the expected heterojunc-
tion suppression of reverse injection from the base. However, detailed and wide range
I-V data are not given and it is thus not possible to exclude the possible existence of
perimeter defects.
The question of possible nonhalogenated selective growth is also addressed in a lone
report of selectivity by hydride UHVCVD. This paper by Racanelli and Greve (1991b)
does not claim absolute selectivity but instead describes an extension of the “incuba-
tion period” over which nucleation and growth on the oxide mask are delayed. The
extension is attributed to the etching of early nuclei by either hydrogen or germane. A
maximum delay of 67 min was reported, during which up to 1070 A of 600°C material
could be deposited within the masking windows, prior to loss of selectivity. This incu-
bation period was used to grow selective P- SissGels layers on N-Si substrates. For-
ward I-V characteristics were comparable to those achieved with nonselective diodes.
However, reverse leakage scaled as the perimeter length of the selective diodes, again
suggesting the possibility of defective edge growth.

4. STRAIN-RELAXED
GESI AND GESI PSEUDO-SUBSTRATES

The preceding discussion focused exclusively on growth of pseudomorphic or strain-

ed layer GeSi: that is, layers for which the lattice mismatch between Si and GeSi was
accommodated purely by compression of the alloy layers. The alternative, misfit dis-
location accommodated growth is depicted at the top right of Fig. 20. In their ide-
alized forms, both modes produce epitaxy in which there are no dislocations within
the epitaxial layers. However, in the misfit mode, at the boundary between layers, the
 1 TECHNIQUES
GROWTH AND PROCEDURES 41
MISFIT

EPITAXIAL LAYER

SUBSTRATE CRYSTAL

STRAIN

FIG.20. Schematic of alternate growth modes when epitaxial layer is grown on substrate with smaller
lattice constant (e.g., GeSi on Si). Top right: misfit dislocation accommodated growth where both layers
retain bulk, cubic, unstrained lattice configuration. In this mode, the difference in lattice constant is mani-
fested by occasional planes ending at the interface, with edges of incompletely bonded atoms. These “perfect
edge dislocations” would occur approximately once every 100/(lattice mismatch in %) planes. Bottom right:
alternate strained-layer growth mode in which thinner epi layers compress laterally to adopt substrate planar
spacing. This mode requires no energetic dislocations and is generally favored as epi growth begins.

net difference in atomic spacing means that periodically a plane must terminate. The
atoms at that termination will not have normal 4-fold tetrahedral bonding. That row of
atoms thus constitutes a “dislocation line” at which anomalies such as carrier trapping
and generation may occur. This would obviously present a problem in thin layers for
which interfaces are nearby. However, for thick layers (e.g., “thick” 2 carrier diffusion
lengths) there might be little electrical disadvantage to using such layers. Further, there
is one strong disadvantage in limiting oneself to strained layer epitaxy: for GeSi/Si
structures in which only GeSi is strained, the difference in bandgap is manifested al-
most exclusively in the valence bandedge discontinuity. This is ideal for NPN HBT’s
but effectively eliminates most other heterojunction device-based ideas that involve
confinement of electrons. In particular it precludes modulation-doped transistors (or
HEMTs) and heterojunction N-MOS alternatives.
Electrons can be confined if Si layers are grown under tension (details of these ef-
fects are discussed by Jaros and Shaw in Chapter 4). This can be achieved if a Si
substrate is overgrown with a very thick GeSi layer. That GeSi layer will then form
misfit dislocations, relaxing its strain to provide what might be considered a “pseudo
42 JOHNC. BEAN

GeSi substrate.” Thin Si layers grown on such a “substrate” would then be subject to
tension, producing a conduction bandedge discontinuity that can trap electrons. These
possibilities have been actively explored, particularly by Kasper and Abstreiter, with
the goal of developing fast electron-based GeSi/Si devices. Unfortunately, at a larger
scale, the misfit configuration of Fig. 20 is almost never achieved. The problem is that
for very thin layers, the alternative strained layer growth mode is almost always ener-
getically favored. It is not until that strained layer grows to a certain thickness that the
energetic expense of dislocations is justified and that dislocations will begin to form.
However, at that point, planes must be added (or deleted) from the crystal surface. That
process is depicted schematically in Fig. 21. As each plane grows downward and then
sideward, both its bottom and side edges will be bounded by lines of incompletely
bonded, dislocated atoms. The extensions of that dislocation line through the layer
are referred to as “threading” dislocation segments. Unlike the ideal, interfacial, misfit
segment, these threading arms penetrate the entire epi thickness, compromising any
device within that volume.
Figure 21 depicts misfit “half-loops’’ of varying length. To fully relax the strain in a
layer, a total interfacial misfit dislocation length is required (as this is equivalent to a
net length of added or deleted atomic plane). There is no requirement on the net thread-
ing dislocation length. Indeed, for a wafer, loops might grow all the way to the wafer
edge, producing strain relief without threading arms. In real life, as the strained layer
critical thickness is passed, strain drives both the lateral extension of an existing loop

FIG. 21. Three-dimensional depiction of “dislocation lines” bounding the deleted planes of Fig. 20, top
right. If plane extends all the way to the limits of the crystal (far left of figure), there is a row of misbonded
atoms only in the interfacial plane. Because planes are deleted only after epi thickness has built up. more
likely configuration is shown at center where there are a number of smaller growing deletions. These are
bounded by dislocation “loops” having an edge of mis-bonded atoms in both the interface and two “threading
arms” through the epi. At right, possible consolidation of two loops to form a larger loop, eliminating two
such threading arms.
 1 GROWTHTECHNIQUES AND PROCEDURES 43
and the nucleation of new loops. A given loop will only grow to the edge of a wafer if it
can do so before strain is completely relieved by nucleation of additional, shorter, half-
loops. Because loop extension and nucleation are both thermally activated, the balance
between a few long loops and many short loops will be a function of temperature. Acti-
vation energies are given by Hull in Chapter 111. Unfortunately, at the low temperatures
commonly required to avoid GeSi roughening and islanding, those energies strongly
favor the nucleation of new loops before existing loops can extend all of the way to
wafer boundaries. The common resulting configuration is the one found in the center
of Fig. 21, in which epi is compromised by threading dislocations. The alternate con-
figuration has been achieved only for very dilute GeSi layers (2% Ge), where islanding
could be avoided in high temperature (lO8O0C),high-growth rate CVD epitaxy (Roz-
gonyi et al., 1987). These layers were almost completely threading dislocation free,
but to avoid roughening, they were limited to Ge fractions so low that they effectively
offered no useful heterojunction characteristics.
Several ideas have been investigated to overcome the aforementioned situation. First,
the energetics mean that while early loops cannot grow to the wafer edge quickly
enough, they might grow to the edge of a more sharply limited mesa of deposit. This al-
ternative, explored by Fitzgerald (1989) using MBE on trenched Si substrates, showed
some promise. However, a more circuit-compatible, planar alternative is presented by
selective area growth in mask windows. This was the motivation for much of the SAG
work discussed here. While that work contains some evidence of dislocation extension
to SAG edges, no group has yet provided a dramatic demonstration of a SAG, strain-
relaxed device. A third approach, explored by Hull et al. (1992), instead used MBE
growth over oxide islands to force threading dislocation arms into known, avoidable
locations. Those islands were staggered such that any growing dislocation loop would
quickly extend laterally to intersect an oxide pad where its extension would cease. The
idea was then that device patterns might be laid out in the known regions between those
pads, effectively avoiding threading dislocation arms. Again, at the level of TEM defect
assessment, this idea looked promising but it has not yet been extended to successful
device fabrication.
Another approach involves possible merging of two dislocation loops into one.
Loops are driven to extension by the strain they relieve as they add (or delete) a plane of
atoms. On the other hand, their extension is inhibited by the energy of the misbonded
atoms on the dislocation loop. As the loop extends, the number of misbonded atoms
increases, effectively producing a line tension. This tension inhibits the growth of an
isolated loop but can drive the consolidation of two loops. As depicted in Fig. 22a,
when two loops meet (or approach), their consolidation relieves the same net strain en-
ergy but, by eliminating the adjacent threading arms, reduces the net dislocation length
and energy. This process results in a net 50% decrease in areal density of threading
arms and might continue until virtually all loops combine into an ideal pure interfa-
cial misfit dislocation array. There was early experimental evidence that this process
could be enhanced within multistrained layer semiconductor superlattices. In such a
44 JOHNC. BEAN

FIG. 22. Cross-sectional depiction of possible consolidation of dislocation loops in misfit accommo-
dated GeSi on Si growth. At left, consolidation of two loops, such as that shown in Fig. 21, right. At right,
more complex sample having many strained GeSi layers, spaced by Si (with or without strain). Loops will
then tend to jog at any strained interface. Multiplicity of jogs may enhance probability of loops merging and
consolidating.

superlattice, there is a tendency for loops to extend not only at the substrate interface
but at each strained layer interface, maximizing the chance of intersection (Fig 22b).
These superlattice “dislocation filters” were proposed as an almost magical solution
to misfit accommodated epitaxy. There was, indeed, evidence that they could be used
to decrease threading dislocation densities from very high levels (10’0-10’2/cm2) to
much lower levels (e.g., 105-106/cm2), but from these lower levels, further progress
could not be made (Hull et al., 1988). Dramatic realtime TEM films (Hull and Bean,
1993) of ongoing relaxation of GeSi strained layers proved that the problem lay in the
3D nature of the dislocation intersection problem. If by pure chance, two dislocation
loops nucleate and grow along the same atomic plane, the process occurs as described
here. However, if loops grow together on parallel but somewhat displaced planes, a
different situation may develop. Consider, for instance, relaxation of 1% mismatched
layer (e.g., Ge25Si75 on Si). In this situation, strain is fully relaxed by the deletion of
planes 100 atomic planes apart. If two loops nucleate and grow together at a separa-
tion of less than 100 planes, their extension and overlap would actually overrelieve the
strain placing the GeSi locally in tension. This increase in energy stops further loop
extension, resulting in a configuration where adjacent threading arms are too far apart
to combine and are frozen in place.
The final and ultimately most heavily utilized means of growing relaxed GeSi re-
lies on a combination of the aforementioned mechanisms. Very thick, compositionally
 1 GROWTHTECHNIQUES
AND PROCEDURES 45

graded GeSi buffer layers are grown at high temperature to maximize the velocity of
loop extension and the probability of ultimate loop-to-loop recombination. As defined
in experiments by Fitzgerald et al. (1991a; 1992), the sharpest defect reduction may
require total thicknesses approaching 10 ,um with growth often conducted at 900°C

at densities down to -
by RTCVD. Threading dislocation counts at the surface of such layers were measured
105/cm2. While far from bulk Si densities of near zero, or
strained-layer GeSi densities more typically in the 10-1 000/cm2 range, these values
are nevertheless low enough that they have facilitated a variety of exploratory device
investigations on electron confinement. However, the final defect density in these “sub-
strates” is judged, even by their developers, to be much too high for application in cir-
cuits (Fitzgerald et al., 1991b). There have been rare attempts at growth of true GeSi
substrates by bulk crystal growth techniques (Losada et al., 1995) but commercially
available substrates are not yet available. Thus commercially oriented work on GeSi
devices is limited to the much more perfect, strained layer GeSi on Si configurations
detailed in this chapter.

VI. Summary

GeSi strained layer materials have now been grown by a variety of techniques, with
control at or approaching atomic dimensions. Contrary to certain claims, the best mate-
rial grown by each technique is generally similar and of a very high quality, as demon-
strated by device results. Distinctions occur primarily in subtleties such as doping or
selectivity, or in issues relating to suitability for manufacturing. On the other hand,
there persist significant gaps in our understanding of these growth processes. Some of
these gaps, such as a detailed understanding of CVD doping, may be esoteric. Others,
such as understanding of roughening and ordering of both atoms and islands, may be
critical in enabling future, radically altered, and improved device technologies.

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 SEMICONDUCTORS AND SEMIMETALS, VOL. 56

CHAPTER2

Fundamental Mechanisms of Film Growth

Donald E. Savage, Feng Liu,Volkmar Zielasek,
and Max G. Lagally
UNIVERSITY OF WISCONSIN
MADISON.WISCONSIN

I. INTRODUCTION. . . . . . . . . . . . . , . . , . , . . , , , . . . . . , . . . . . . . . . . 49
I . Equilibrium Growth Modes . . . . . . . . . . . . , . . . . . . . . , . . . . . . . . . . . 50
2. Kinetic Processes During Vapor Deposition . . . . . . . . . , . . , . , . . . . , . . . . . 52
3. Kinetic Growth Modes . . . . . . . . . . . . . , , , . . . . . . . , ...., . . . . . . 53
11. SILICON . . . . . . . , . . . . . . . . . . . . . , . . .., ., .., . ., ., .. . .. . . 56
1. Crystal Structure . . . . . . . . . . . . . . . . . ..... ... .. . ., ... . . . . . 57
2. Growth of Si on Si(OO1)(Atomistic Mechanisms) . , ...... ... ...... , ... . 62
3. Thermodynamic Properties and Equilibrium Surface Morphology . . .... .. . . . . . 75
111. HETEROEPITAXIAL GROWTH: GE ON SI , . . . . . . . . . , . . . . . . . . . , . . . . . . 79
I . Growth of the Ge Wetting Layer on Si(OO1) . . . . , . . . . . . . . . . , . . . . , . . . . 79
2. Nucleation of Coherent ‘Hut’-Islands . . . . , . . . . , , . . . . , . . . . , . . ..... 86
IV. SIGE ALLOYFILMS. . . . . , , . . . . . . . . . . . . . . . . . , . , . ., ... .. ... 90
I . Roughening and Coherent 3-0 Island Formation in Alloys . . . . . . ., .... , . . . . 92
2. Multilayer Growth . . . . . . . . . . . . . . . . . . . . . . . . .
I ..., .. ..... 93
...........................................
V. SUMMARY 94
REFERENCES . , . . .. . . ...... .... ., . . . . , . . , . . . ... . . ... . . . 96

I. Introduction

In this chapter, we review the fundamental mechanisms involved in the process of

growing epitaxial films. We will begin with a general discussion of thermodynamic
predictions of film morphology and continue with a discussion of equilibrium growth
modes. We will then identify key kinetic processes occurring during growth that may
limit the film’s ability to equilibrate.
Our initial discussion will be applicable to any growth system. We will then focus on
the specific system of silicon on silicon, concentrating on recent work to extract atomic-
scale mechanisms of growth. We will finally describe Ge and SiGe alloy growth on Si,
in which an understanding of both thermodynamics and kinetics is needed to explain
and ultimately to control film structure and morphology.
Copynght @ 1999 b) Academic Press
All nghts of reprduction in any form reperved
ISBN 0-12-7521 61-X
0080-8784199 $30 00
50 DONALD
E. SAVAGE, FENGLIU,VOLKMAR ZIELASEK, AND MAX G. LAGALLY

1. EQUILIBRIUM
GROWTHMODES

A natural starting point for learning about film growth is a discussion of the SO-
called equilibrium growth modes (Bauer, 1958), which represent limiting cases of how
a film can grow on a substrate. While no growth can occur at equilibrium and most
film growth is performed far from equilibrium, it is useful to consider thermodynamic
limits.
Thin crystalline films grown near equilibrium exhibit one of three growth modes,
depicted schematically in Fig. 1, the Frank-van der Menve (layer-by-layer), Stranski-
Krastanov (layer-cluster), and Volmer-Weber (cluster) modes (Bauer, 1958). The mode
in which a particular materials combination will grow depends on the relative bond
strengths of atoms in the deposited layer and between these atoms and the substrate
atoms, as well as the degree of lattice match between the two materials. A film will
initially wet the substrate if the adlayer-substrate bond is sufficiently stronger than the

FIG. 1. A schematic illustration of the three equilibrium growth modes: (a) Frank-van der Merwe
(layer-by-layer): adatoms fill in a layer before nucleating the next; (b) Stranski-Krastanov (layer-cluster):
the growth initially starts layer-by-layer but changes over to cluster growth due to the buildup of strain
energy: and (c) Volmer-Weber (cluster): the 3-D clusters form immediately because the deposited atoms do
not wet the substrate.
 2 FUNDAMENTAL
MECHANISMS OF FILMGROWTH 51

adlayer-adlayer bond to overcome any strain energy generated to grow the adlayer in
registry with the substrate. In this simple description of growth, reaction or interdiffu-
sion is not allowed.
A more formal way to predict growth mode involves the relationship between surface
and interfacial free energies. Surface free energy is defined as the free energy to create a
unit area of surface on an infinite bulk solid. Given specific (per area) surface energies
for the substrate and film as ys, y f , respectively (where these are the values for the
semi-infinite crystals), and an interfacial energy yin, where the subscript i stands for
interface and n stands for the number of monolayers of film deposited, monolayer-by-
monolayer growth occurs only when

for all values of n (Bauer and van der Merwe, 1986). The term y f . differs from y f to
allow for an n-dependent surface strain. The term yin includes the excess free energy
needed to create the initial interface between two different materials yio. plus the ad-
ditional free energy arising from strain due to lattice mismatch between the overlayer
film and the substrate.
In the opposite extreme, one obtains cluster growth when, for all values of n,

AYn = Y f n + Yin - Y,> 0 (2)

In this case the overlayer does not wet the substrate. In the intermediate case, the ad-
layer initially wets the substrate, but because of lattice mismatch, as n increases, strain
energy contributes to yin to the point at which the film no longer wets. Typically, at
this point, misfit dislocations are incorporated to relieve strain and, given sufficient mo-
bility of adatoms, preferential growth will occur in the relaxed region, leading to the
nucleation of 3-D clusters. Alternatively, roughening of the growth front can relieve
strain at the expense of additional surface energy. For example, for pure Ge deposited
on Si(OO1) nondislocated 3-D structures form to relieve strain energy (this will be dis-
cussed in detail in Section 111). The film thickness at which Eq. (1) no longer holds is
one of the definitions of the critical thickness, below which the overlayer film grows
in registry with the substrate. The concept of critical thickness will be discussed in
more detail in Section 111, with specific application to strain relaxation in the absence
of dislocation formation, for which strain is relieved by growth-front roughening or
islanding. The concept of critical thickness, applicable in the limit in which dislocation
formation relieves strain, is covered in detail by Hull in Chapter 3.
In principle, layer-by-layer growth occurs only for a material deposited on itself. In
that special case yf,, = ys and f i n = 0. For species deposited on an unlike substrate
there is generally some lattice mismatch and layer-by-layer growth will occur only up
to some finite thickness. Thus for a system of B deposited on A one expects either the
layer-cluster or the cluster-growth mode. There are exceptions in more complicated
growth systems, such as ternary and quaternary 111-V alloys, in which it is possible
52 DONALD
E. SAVAGE, FENGLIU, VOLKMAR ZIELASEK, A N D M A X G. LAGALLY

to have essentially lattice-matched growth by choosing the appropriate alloy composi-

tion.
Equations (1) and (2) show that it would be quite difficult to grow a coherent strained-
layer superlattice of two unlike materials A and 8.If A wets B, then B will not wet
A. The fact that binary strained-layer superlattices can be grown shows that more is
involved than thermodynamics, that is, kinetics also plays a role. To grow a binary
strained-layer superlattice, one would like ) / A x Y B and zz 0. Interdiffusion, chem-
ical reaction, or surface segregation also can change surface wetting and the growth
mode. We will return to superlattices towards the end of the chapter.
So far, we have discussed thermodynamic predictions only and these in a very sim-
plistic way. While thermodynamics cannot be violated, it is clear that additional terms
can be folded into interfacial energy. For example, where surface segregation of the
more weakly bonded material occurs to reduce surface free energy, the resulting natural
wetting layer, sometimes called a surfactant, can alter growth dramatically. Materials
that form strongly bonded compounds at the interface or strongly interdiffuse will also
change the interfacial energy. All the terms needed to describe fully the thermodynam-
ics of growth are therefore not a priori obvious.

2. KINETICPROCESSESDURINGVAPORDEPOSITION

Film growth cannot occur, by definition, under equilibrium conditions. In most cases
growth occurs under conditions of supersaturation far from equilibrium. Therefore, ki-
netics will play an important role in determining film morphology. One can obtain
a great range of growth morphologies when one considers the kinetics (Zhang and
Lagally, 1997). Kinetic processes can be partly controlled by varying substrate tem-
perature and deposition rate. In an evaporative growth process, such molecular-beam
epitaxy (MBE), in which one can independently control sample temperature and depo-
sition rate, one can influence which of the kinetic processes is rate limiting, allowing
some control over film morphology.
During vapor deposition, a clean substrate in an ultrahigh-vacuum environment is
exposed to the vapor of the growth materials. As adatoms are continuously deposited
onto the substrate, the system is driven into supersaturation, that is, the 2-D vapor pres-
sure is higher than at equilibrium. A condensed phase, either a 2-D island or 3-D clus-
ter, will then form to relax the system back toward equilibrium. Two major processes
form a condensed phase from a 2-D vapor: nucleation and growth (see, for example,
Matthews, 1975; and Lewis and Anderson, 1978). Arriving atoms make a random walk
on the surface and, when meeting each other, form islands. The rate limiting step is
the formation of a critical nucleus, which is defined as an island that is more likely
to grow than decay (Venables, 1973). The nucleated islands grow by further addition
of adatoms, and the lateral accommodation kinetics determine the growth shape of the
islands. Growth continues until deposition is interrupted. Thereafter, coarsening, in
 2 FUNDAMENTAL
MECHANISMS
OF FILMGROWTH 53
deposition deposition
0 re-evaporation 0
step I
incorporation i
tI I
r-CX)- 0
-
1
I

j.,nucleation island coarsening surface

v incorporation migration
interdiffusion

FIG.2. Schematic illustration of major processes occumng during growth from the vapor.

which islands evaporate laterally and the adatoms diffuse to larger islands, controls the
dynamics of further ordering. The driving force is the difference between the local
equilibrium vapor pressures around the large and small islands.
An adatom, in addition to meeting another to form a nucleus, meeting an existing
island (growth), or traveling between existing islands along a concentration gradient
(coarsening), may also meet one of these fates: walking into a special sink site like a
substrate step, diffusing into the bulk of the substrate, or re-evaporating from the sur-
face. Figure 2 schematically illustrates these processes during growth from the vapor.
Not shown in the figure is another possible influence of steps, the presence of repulsive
or attractive potentials that reduce or enhance surface migration in the vicinity of steps.
We will discuss each of the individual kinetic processes in more detail for the specific
case of Si deposited on Si(OO1) in Section 11.2. Before doing so we begin with a quali-
tative discussion of the influence of kinetics on growth in terms of commonly observed
kinetic growth modes.

3 . KINETICGROWTH
MODES

Because film growth can be performed under conditions far from equilibrium, a vari-
ety of growth-front morphologies can be obtained depending on which kinetic process
is rate limiting (Zhang and Lagally, 1997). Several growth regimes have been observed
so frequently they have been given specific names. These should not be confused with
the idealized equilibrium growth modes discussed in Section I. 1. In Fig. 3, examples of
three kinetic growth modes observed in homoepitaxy (the deposition of a material onto
a like substrate) are shown schematically. They are kinetically rough growth, layer-by-
layer growth, and step-flow growth. Kinetically rough growth occurs in the extreme
limit of a high deposition rate and slow lateral diffusion of adatoms, in which atoms
migrate only on the order of a few lattice sites before they incorporate into the growing
film or are buried. Growth under such conditions leads to a rough surface for which
the roughness amplitude increases with increasing film thickness (Yang et al., 1993).
54 E. SAVAGE, FENGLIU,VOLKMAR ZIELASEK, AND MAX G . LAGALLY
DONALD

FIG. 3. A schematic illustration of three commonly observed kinetic growth modes at 1/2 (left column)
and 1 monolayer (right column) coverage. (a) Step-flow growth: deposited atoms incorporate only at steps.
(b) Layer-by-layer growth: there is insufficient mobility for adatoms to reach steps and 2-D islands nucleate,
grow, and coalesce. There will be some second-layer nucleation before the first is completed, causing a
gradual roughening of the surface. (c) Kinetically rough growth: there is no lateral diffusion, that is, an atom
sticks where it lands.

In the extreme case, if the surface diffusion coefficient is zero and all adatoms stay
where they land, the roughness of the growth front will diverge following the Poisson
distribution as the thickness increases.
As the growth rate is reduced or the substrate temperature is raised (increasing
adatom mobility), the regime of layer-by-layer growth can be achieved. In this growth
mode, adatoms have sufficient mobility to find one another, nucleate 2-D islands that
grow, coalesce, and ultimately fill in the initial starting surface at -1 monolayer of de-
position. This mode is characterized by the periodic increase and decrease of surface
steps (boundaries of the 2-D islands). The period corresponds to the deposition of a
monolayer. This mode was initially observed by indirect methods, that is, by reflection
high-energy electron diffraction (RHEED) and low-energy electron diffraction (LEED)
(Larsen and Dobson, 1988) and more recently by direct atomic-scale imaging methods
 2 FUNDAMENTAL OF FILMGROWTH
MECHANISMS 55

such as scanning tunneling microscopy (STM) and low-energy electron microscopy

(LEEM) in which 2-D islands are imaged directly. The layer-by-layer growth mode
usually shows an increase of surface roughness with coverage because the previously
deposited layer is never completely filled in before the next layer nucleates.
A better way to ensure a smooth surface during deposition is to grow in the step-
flow growth-mode. All crystal surfaces will contain some density of monatomic-height
steps, at the least those steps tilting the surface away from a high-index crystallographic
face caused by polishing error. For example, prime Si(OO1) wafers have a typical mis-
cut of - 0.1 to 0.2”, giving a monatomic-height step every 70 nm to 35 nm, respec-
tively. The surface looks like a staircase with atomic-height risers. Step-flow growth
is achieved when deposited atoms have sufficient time to migrate and incorporate into
a step before other atoms deposited on the surface increase the supersaturation suffi-
ciently to force nucleation on the terraces. The staircase structure is preserved as steps
simply migrate across the surface.
Growth in step flow is desirable for keeping the surface smooth. To maintain it, one
either deposits relatively slowly or heats the substrate to a high enough temperature

For example, one needs typically a temperature of -

for adatoms to diffuse far enough to incorporate into steps before nucleating islands.
970 K for a growth rate of
-1 ML/min to achieve step-flow growth during MBE growth of Si on Si(OO1) (Theis
and Tromp, 1996).
Potential-energy barriers for crossing steps can play an important role in stabilizing
or destabilizing a smooth growth morphology. If, for example, there is a kinetic barrier
for diffusion downward over steps, rough growth occurs because 2-D islands will nu-
cleate preferentially on top of existing 2-D islands. In the limit of fast lateral diffusion,
but no diffusion downward over steps, a “layer-cake structure” develops. An example
(Esch, 1996) is shown in Fig. 4. A barrier comparable to or smaller than the adatom
lateral diffusion barrier will allow atoms to diffuse off the top terrace of 2-D islands.
If, in addition, the island edges are good sinks (attachment sites) for growth, there is
a net depletion of adatoms in the vicinity of island edges and a concentration gradient
helping downward diffusion develops. The supersaturation on top of islands is there-
fore lowered, reducing the probability of nucleation, especially near an island edge.
This behavior helps to smooth the growing film by delaying nucleation on existing 2-D
islands.
A barrier to “downward” diffusion over steps helps to stabilize the step-flow growth
mode by making the step spacing more regular. Flux captured by a terrace will be in-
corporated into its uphill step if it cannot diffuse over the downhill step. Thus, initially
wider terraces will capture more adatoms, causing the adjacent “up” terraces to grow
more quickly, thereby reducing the width of the initially wide terrace. Conversely, a
reduction in the bamer to downward diffusion can destabilize the step-flow mode, as
wide terraces advance more quickly than narrow ones, leading to step bunching and
ultimately to 2-D island nucleation on the wide terraces, as the diffusion distance no
longer suffices for adatoms to reach steps.
56 E. SAVAGE,FENGLiu, VOLKMAR
DONALD AND M A XG. LAGALLY
ZIELASEK,

FIG.4. An STM image (lateral scale 4400 A) of 5 monolayers of Pt deposited on Pt(ll1) at 470 K
exhibiting a “layer-cake” morphology indicating high barriers for diffusion downward over steps. The height
distribution of the deposited material can be modeled with a Poisson distribution (reprinted with permission
from Esch, 1996).

11. Silicon

We will introduce concepts of growth kinetics using the model system of the evap-
orative growth of Si on Si(OO1). Thermodynamics predicts smooth growth because
a material will always wet itself. Departures from smooth growth will be caused by
kinetic barriers. By studying these departures quantitatively on the atomic scale, one
can infer the energies of activated processes. One of the main features of Si(OOl), its
 2 FUNDAMENTAL MECHANISMS
OF FILMGROWTH 57

highly anisotropic surface structure, has an important influence on the growth mor-
phology and kinetics. Before we discuss the specifics of growth, we briefly review
the crystal structure of the (001) face of silicon, which is most commonly used as the
growth substrate.

1. STRUCTURE
CRYSTAL

Today, crystal growth techniques render available device-quality Si wafers as large

as 300 mm (12 in) in diameter (Wacker, MEMC), cut from dislocation-free single-
crystal rods. The Si bulk structure is determined by (sp3)-hybridization of the silicon
atoms, leading to four equivalent covalent bonds to nearest neighbors in a tetrahedral
coordination. The bulk lattice is diamond-like, that is, face-centered cubic with a basis
formed of two Si atoms at (0, 0,O) and (1/4, 1/4, 1/4), respectively (see Fig. 5). The
cubic lattice constant is 0.543 nm at room temperature, corresponding to a Si-Si bond
length of 0.235 nm. All low-index surfaces exhibit reconstructions, that is, a reordering
of the surface atoms with respect to their bulk positions. In general, the reordering of
the surface atoms is induced by a partial rebonding of their highly directional dangling
orbitals, lowering the surface free energy significantly.
With few exceptions the subsequent discussion of growth on Si will be restricted
to the (001) surface orientation (Fig. 6). It is technologically the most important and
has been investigated thoroughly. The formation of dimers (Fig. 6b) lowers the sur-

FIG.5 . Perspective view of the silicon bulk lattice. The cubic unit cell and the face-centered positions
are denoted by straight and dashed lines, respectively. The four atoms that are located fully within the unit
cell are shown with their nearest neighbor bonds (dark lines).
58 DONALD
E. SAVAGE, F E N G L I U , VOLKMAR ZIELASEK, A N D MAX G . LAGALLY

FIG.6. Dangling-bond configurations on (100) surfaces of elemental group IV semiconductors. (a) Two
dangling bonds (hybrids with a single electron) on each surface atom in an ideal bulk-terminated surface.
(b) One dangling bond on each atom in a dimer. (c) Charge transfer from downward atom to upward atom
in a buckled dimer.

face energy by about 2 eV per dimer, reducing the number of dangling bonds by one
per surface atom at the expense of introducing an additional anisotropic surface stress.
Proposed by Schlier and Farnsworth (1959) on the basis of low-energy electron diffrac-
tion experiments, the dimerization was first directly “seen” using STM by Tromp et ul.
(1985). The dimers form rows along the { 110) directions perpendicular to the dimer
bonds, leading to pronounced anisotropies in surface properties that are relevant to
growth, such as adatom diffusion and interaction between adatoms and substrate steps.
The surface energy can be lowered by rehybridization of surface bonds, which leads
to the tilting (“buckling”) of the surface dimers. One atom of the dimer adopts a planar
sp’-like configuration and moves down while the other moves up and adopts a p-like
configuration (Fig. 6c). The buckling, like the dimerization, decreases electronic en-
ergy at the expense of increasing strain energy. Its minimization leads to alternate
 2 FUNDAMENTAL
MECHANISMS
OF FILM GROWTH 59

buckling directions along the dimer rows, giving rise to c(4 x 2) and p(2 x 2) re-
constructions (Fig. 7), which have been observed at low temperatures by low-energy
electron diffraction (LEED) (Kevan and Stoffel, 1984; Tabata et al., 1987) and by STM
(Wolkow, 1992). Ab initio calculations (Pandey, 1985; Payne et al., 1989; Roberts and
Needs, 1990; and Ramstad et al., 1995) show that the surface energy of buckled dimers
is indeed lower than that of symmetric dimers, but the energy difference is very small
(about 1.0 eV). Thus, at high temperatures, where most growth processes are carried
out, surface dimers rapidly switch their orientation, leading to an averaged symmetric
appearance in STM and (2 x 1) patterns in LEED. At 120 K the c(4 x 2) reconstruction
is most prevalent. Dimer buckling at high temperatures is often induced by surface
defects and steps (Wolkow, 1992). We refer only to the (2 x 1) reconstruction in the
following discussion.

FIG. 7. Schematic top view of three possible reconstructions on Si(OO1). Top region: (2 x 1); middle:
p(2 x 2); bottom; c(4 x 2). Open and solid circles mark atom positions: their size indicates different layers of
atoms, with the largest circles in the outer layer. In the lower two reconstructions, the two atoms in a dimer
having slightly different heights because of buckling are indicated by solid and open circles. The unit mesh
of each reconstruction is depicted by a dark rectangle. For the c(4 x 2) structure, the primitive unit mesh is
depicted by the rhombus.
60 DONALDE. SAVAGE,FENGLIU,VOLKMAR
ZIELASEK,A N D MAXG. LAGALLY

Because of the symmetry of the diamond structure, the dimer row direction is or-
thogonal on terraces separated by an odd number of monatomic steps, giving rise to
both (2 x 1) and (1 x 2) domains. These domains occur even on nominally perfectly
oriented surfaces, which have few accidental (polishing induced) steps. The surface
stress anisotropy induced by the dimer rows gives rise to long-range step-step interac-
tions and causes the steps on these surfaces to meander significantly.
Two types of monatomic steps exist. Step segments for which the upper-terrace
dimer rows are parallel (perpendicular) to the step are called SA(Sg) (Chadi, 1987). On
vicinal surfaces miscut towards a { 110)direction by a few degrees or less, the two types
of steps alternate. Usually, SA steps are smooth while SB steps are rough, containing
many kinks and segments of SA termination. For simplicity, however, we still call a
step nominally SA ( S g ) if it is oriented in the (110) direction and step segments along
the average edge are SA ( S B ) .We call terraces on the upper side of the rough Sg steps
(2 x I ) and the other orientation (1x 2). Surfaces with miscut toward the [ 1001direction
are composed of steps that run nominally at 45" to the dimers; for such surfaces all the
steps and terraces are indistinguishable and the (2 x l), (1 x 2) nomenclature becomes
arbitrary.
If the surface is miscut by more than -1.5" towards (110), double-atomic-height
steps begin to form and their fraction increases with increasing miscut angle (Schluter,
1988; Griffith and Kochanski, 1990; Wierenga et al., 1987; Griffith et al., 1989). Al-
though there can be two types of double steps ( D A and Dg)(Chadi, 1987), only D B
steps form (Wierenga et al., 1987; Griffith et al., 1989). Combined with stress-induced
step-step interactions (Alerhand et al., 1990) this energetic preference leads to a pre-
dominance of (2 x 1) domains over (1 x 2) domains. The B-type of steps (Sg and
D B ) can have two kinds of edge structures: rebonded and nonrebonded. Experiments
(Wierenga et al., 1987; Griffith et al., 1989; Kitamura et al., 1993) show that the re-
bonded S B and D g step edges appear much more frequently than their nonrebonded
counterparts on natural surfaces, in agreement with total-energy calculations (Chadi,
1987). Figure 8 shows a schematic side view of the atomic structure of single- and
double-atomic-height steps on Si(O01).

FIG. 8. Schematic side view of (a) single- and (b) double-atomic-height steps on Si(OO1). Prefixes n-
and r- denote nonrebonded and rebonded steps. Horizontal bonds are dimers of (1 x 2) terrace; solid circles
denote projections of dimers of (2 x 1) terrace, whose bond directions are normal to the plane of the figure.
 2 FUNDAMENTAL OF FILMGROWTH
MECHANISMS 61

FIG. 9. Top and side views of the dimer-adatom-stacking fault (DAS) model of the Si(l11)-(7 x 7)
reconstruction. The adatom layer (large shaded circles) and two double layers (open and solid circles) are
indicated. The stacking fault is in the left half of the unit cell. (Reprinted with permission from Takayanagi
et al., 1985.) The side view is taken along the long diagonal of the unit cell.

The { 111) surface of Si is of some interest because it has served extensively as a sub-
strate for experiments on surface structure and film growth. Si( 111) exhibits a promi-
nent (7 x 7) reconstruction (Schlier and Farnsworth, 1959) after annealing or when
grown epitaxially. The number of dangling bonds is reduced by adatoms that saturate
three dangling surface bonds by introducing only one new one. The stress induced by
the adatoms is relieved by a complex surface structure, the dimer-adatom-stackingfault
(DAS) model (Takayanagi et al., 1985), shown in Fig. 9. The (7 x 7) unit cell consists
of two triangular subunits. One of them (left half, Fig. 9) contains a stacking fault,
producing wurtzite-type stacking of the outermost two double layers. There are six
adatoms in each subunit, in a ( 2 x 2) arrangement. They are located directly over the
second-layer atoms and each binds to three first-layer atoms. The faulted and unfaulted
subunits are separated by a triangular network of partial dislocations, and dangling
bonds along these dislocations are partially saturated by the formation of dimers (three
dimers at each triangle edge), which are linked by 8-member rings. At the corners
of the unit cell, that is, the crossing points of the dislocations, there are holes (comer
holes) exposing large portions of the second double layer. Around the corner holes,
atoms are connected by 12-member rings.
62 DONALDE. SAVAGE,
FENGLIU, VOLKMAR
Z I E L A S E K , A N D M A X G. LAGALLY

2. GROWTH OF SI ON SI(001) (ATOMISTICMECHANISMS)

a. Adatom Adsorption: The Initiation of Growth

In order to begin growing a film, adatoms exposed to the substrate must initially
stick to the surface. Typically an adatom adsorbs in a metastable site on the surface,
from which it can migrate and ultimately incorporate into the growing film. There is
also the possibility of re-evaporation. If the holding potential, the binding energy to the
initial adsorption site, is high compared to the thermal energy of the substrate (kT), the
adatom will have a high probability of remaining on the surface until it is incorporated.
For Si growth on Si below the temperature at which evaporation becomes significant
(T < 800 "C),the sticking coefficient (the ratio of atoms that remain on the surface
to those impinging on the surface) is, for all practical purposes, 1, a regime called
complete condensation.
For a semiconductor surface, the presence of dangling bonds, the directionality of
bonding, and surface reconstruction produce multiple adatom adsorption sites (Fig. 10)
as well as complex diffusion pathways. The observation of the formation of Si islands
with atomic resolution at the initial stage of MBE growth has become possible with
STM (Hamers etal., 1989 and 1990; Lagally et al., 1989 and 1990; Mo et al., 1989 and
1990a; Hoeven et al., 1989 and 1990), but it has not been possible in general, because
of its rapid motion, to image directly the individual adatom, especially to record its ex-
act location and its motion. At low enough temperature, a single adatom (bound only

0 0 0 0 0 0 oeo o o
0 0 0 0 0 0 0
.
0 0 0
F D-D 0
D-D*
0
0 0 0 0
0
0F-F0
0 0 0 0 0 0 0 B-B 0 0 0
0 .
0 0 0 0 0 0 0 0 0 0

FIG. 10. Potential-energy minima (solid squares) for a Si adatom adsorbed at various sites in the Si(OO1)
(2 x 1) unit cell calculated by ab inifio (a) and Stillinger-Weber (b) potentials. The global minima are at
M and F in (a) and (b), respectively. Arrows mark the proposed diffusion pathways. ( c ) Four possible
high-symmetry ad-dimer configurations.
 2 FUNDAMENTAL
MECHANISMS
OF FILMGROWTH 63

to the atoms in a lower plane) can be observed by STM. Two recent low-temperature
STM experiments (Wolkow, 1995; Wu, 1996) have identified multiple adsorption sites
for an adatom, but the most probable position for an adatom to sit is at the midpoint of
the ends of two adjacent dimers along a dimer row (M site in Fig. 10(a)), in agreement
with the absolute minimum predicted by ah initio theories (Brocks et al., 1991; Q.-M.
Zhang et al., 1995; Smith et al., 1995). These studies indicate that the location of an
adatom can be influenced by substrate-mediated long-range adatom-adatom interac-
tions, making the scenario of Si adatom adsorption more complicated. In addition to
the multiplicity of potential adsorption sites, the dynamics of the adsorption process of
Si on Si(OO1) is expected to be strongly temperature-dependent.
There have been extensive theoretical investigations of Si adatom adsorption and
diffusion on Si(OO1). The potential-energy surface of a Si adatom on Si(OO1) has been
mapped out by both ah initio (Brocks et al., 1991; Q.-M. Zhang et al., 1995; Smith
et al., 1995) and empirical calculations (Smith et al., 1995; Wang and Rockett, 1991;
Z. Y. Zhang, 1991; Lu et al., 1991; Srivastava and Garrison, 1991; Toh, 1992; Roland,
1992a), but the empirical calculations, using either Tersoff (I 989) or Stillinger-Weber
(SW) (1985) potentials, are all in disagreement with ah initio calculations in predicting
the most stable adsorption site. In Fig. 10, local minima in the potential-energy surface
for an adatom sitting at various sites in the (2 x 1) unit cell are marked for two rep-
resentative calculations: one (Brocks et nl., 1991) based on density functional theory
Fig. 10(a), the other (Z. Y. Zhang et al., 1991; Lu et al., 1991) using the SW potential,
Fig. lO(b). Besides the difference in total number of local minima, in Fig. 10(a) the
absolute minimum is at the M site, while in Fig. 10(b) it is at F. Figure lO(c) shows sev-
eral possible ad-dimer attachment sites, where B-B is the site consistent with growth
of the bulk crystal lattice.
In principle, ah initio calculations are capable of giving reliable predictions. At the
present time, however, limited computational resources prevent ab initio calculations
from achieving their full potential. Approximations are often made in model system
size, basis function expansion, and Brillouin zone sampling (integration) (Ramstad
et al., 1995). Empirical calculations are quantitatively less reliable, especially when
they are applied to surfaces, because the empirical potentials are usually developed by
fitting to bulk properties. Also, a short-range cutoff employed in the empirical poten-
tials introduces additional errors in treating a dynamic process like surface adsorption
or diffusion, in which bond-breaking and bond-formation processes are involved. Re-
gardless of these shortcomings, the computational efficiency gives empirical potentials
the advantage that they can be easily implemented into molecular dynamics and Monte
Carlo algorithms to simulate adsorption and diffusion in real time so that more insight-
ful information of growth dynamics can be obtained.
Two such studies, by Z. Y. Zhang et al. (1991) and Srivastava and Garrison (1991),
reveal that as atoms are deposited onto the surface, the most preferable adsorption sites
at the initial stage are not necessarily the energetically most stable sites. Because the
system is far from equilibrium, the population at a given local minimum site is not
64 E. SAVAGE, FENGLIU,V O L K M A R Z I E L A S E K , AND MAX G . LAGALLY
DONALD

determined by its energy relative to other sites but rather determined by the escape
rate of an adatom at this site. The kinetic barriers calculated from empirical potentials
suggest that the Si adatoms are preferentially adsorbed on top of the dimer rows rather
than in more stable places between dimer rows, leading to a so-called “population
inversion” (Z. Y. Zhang et al., 1991; Lu et al., 1991). Kinetic barriers obtained in a
recent ab initio calculation (Q.-M. Zhang et al., 1995) may also produce this inversion.
According to this calculation, if an adatom lands on top of a dimer row, the kinetic
barrier to migrate along the dimer row is 0.55 eV and the barrier to escape from the
dimer row by jumping into the trough between dimer rows is 0.60 eV, so the adatom
spends a long time on top of the dimer row before jumping into the trough (see Fig. 10).
If an adatom lands in the trough between dimer rows, the kinetic barrier to migrate
along the trough is at least 0.75 eV and the barrier to leave the trough is 0.70 eV, so
the adatom stays a short time in the trough before jumping onto the top of a dimer
row. Consequently, more adatoms will end up diffusing on top of the dimer rows at the
initial stage of growth. Such a population inversion may have an impact on nucleation
(see Section 11.3).

b. Direct Measurement of Si Self-Diffusion with STM

Surface diffusion is the most important kinetic process during growth. Technologi-
cally, understanding surface diffusion will lead to better control of the growth param-
eters necessary to achieve atomically smooth interfaces. For layer-by-layer growth
surface migration helps to smooth the growth front, hence a low diffusion coefficient
will result in a rough surface. In the extreme case, if the surface diffusion coefficient
is zero and all adatoms stay where they land, the roughness of the growth front will
diverge following the Poisson distribution as the film thickness increases.
The diffusion of adatoms on a solid material is a fundamental problem in surface
science, one that has attracted attention for many years. In spite of its importance,
however, reliable measurements of surface diffusion coefficients are rare, especially for
semiconductor surfaces. In particular, the diffusion coefficient at zero coverage, that
is, the pure migration of adatoms on the surface, is difficult to determine. Macroscopic
methods based on the observation of the spreading of an initially well-defined distribu-
tion of adatoms (Bonzel, 1972; Mak et al., 1987) or the decay of intensity oscillations
in reflection high-energy electron diffraction with increasing temperature (Neave et al.,
1983) may be ambiguous because of the influence of surface defects such as steps and
because of interactions between adatoms themselves. Field ion microscopy (Ehrlich
and Hudda, 1966) can measure the pure migration of a single adatom in an elegant
manner. However, it is limited in the materials that can be studied because of the high
field necessary for imaging, and has seen little application to semiconductors.
Because STM gives atomic resolution, it would seem to be an ideal method to follow
the diffusing atom to give a direct measurement of the diffusion coefficient. The rapid
motion of Si adatoms at temperatures typical for STM operation has so far prevented
 MECHANISMS
2 FUNDAMENTAL OF FILMGROWTH 65

such measurements. Alternatively one can examine 2-D island densities for a fixed
coverage at different growth temperatures following a quench to room temperature. If
the dose is low enough that a significant number of islands is not lost to coalescence
(growing together), the island density equals the density of critical nuclei, We will use
the growth of Si on Si(OO1) as an example of this method.
Mo et al. performed the seminal work to determine the surface diffusion coefficient
of Si on Si(OO1) in a series of papers in 1991 and 1992. Based on STM analysis of
the number density of islands far from steps and the width of denuded zones at the
steps, the activation energy for diffusion is determined to be Ea = 0.67 f 0.08 eV
-
with a prefactor of DO lop3cm2/s. The diffusion is highly anisotropic: the surface
migration is at least 1000 times faster along the dimer rows than perpendicular to them.
The method has since been widely applied to other systems (Voigtlander et al., 1993;
Stroscio et al., 1993; Brune et al., 1994; Dun et al., 1995; Vasek et al., 1995; Bott
et al., 1996). In this section, we review the major details of the work by Mo et al. (e.g.,
1991 and 1992).

Dependence of island number density on the diffusion coefficient (theory) As

adatoms are deposited on a surface at sufficiently low temperatures, they either form
islands or walk into steps. The competition between island formation and step incor-
poration results in a spatial distribution of stable islands with denuded zones around
those steps that are good sinks for the adatom and a uniform distribution far from the
steps. By establishing the dependence of island number density on the diffusion co-
efficient, it is possible to determine the diffusion coefficient by measuring the island
density without observing the individual adatom.
At the center region of a wide terrace (hence a negligible influence of steps), an ar-
riving adatom will either form a new island with another free adatom (nucleation) or
walk into an existing island (growth). The surface diffusion coefficient determines how
large an area an adatom interrogates in unit time. Therefore, the diffusion coefficient
controls the outcome of the competition between nucleation and growth, and hence
determines the number density of stable islands after deposition to a certain dose at a
given deposition rate. A large diffusion coefficient, for instance, means a high probabil-
ity for an arriving adatom to find an existing island before another adatom is deposited
in its vicinity to provide a chance for nucleation. As a result, a large diffusion coeffi-
cient yields a lower number density of stable islands. Quantitatively, the relationship
between island number density and diffusion coefficient has been established through
a simple dimensional argument (Mo et al., 1991 and 1992; Pimpinelli et al., 1992).
The deposited adatoms make a random walk on the surface. The diffusion coeffi-
cient, D , for a random walk process is
D = J a2 (3)
where J is the number of hops made in unit time and a is the step size, here taken
to be the lattice spacing. The lifetime T A of an adatom is controlled by two different
66 DONALD
E. SAVAGE,
FENGLIU,VOLKMARZIELASEK,
AND MAXG. LAGALLY

collision rates, W A A (adatom-adatom collision) and WAI (adatom-island collision), in

such a way that the “death rate” of adatoms is

n/TA = 2WAA + WAl (4)

where n is the number density of free adatoms deposited at a rate of R , n = R ~ A .
According to the theory of random walks (Montroll, 1964; Barber and Ninham, 1970),
the number of sites visited by the adatoms after J = DrA/a2 hops (for large J’s)
during their lifetime is approximately C ( D t A / a 2 ) d / 2where
, d is the dimension of the
random walk and C is a constant that depends on the dimensionality and the capture
number of the single adatoms or islands. On the average, an area of 1 / n is~associated
with each adatom ( n =~ n ) or island ( n =~ N ) enclosing l/(nBU2)lattice sites. Hence
the probability of an arriving adatom to collide with an existing adatom or island is
Cn B a2( D t A/ a2)d/2.Multiplying this by nsA yields the collision rates W A A and W A J ,

WAB = C?lnBa2-d(DrA)d’2/tA (5)

The nucleation rate or the rate of increase of the island number density is
d N / d t = W A A = Cn2a2-d(DtA)di2/tA (6)
At the very beginning of the deposition, the island density is negligible, so the decay
of adatom density is mainly caused by nucleation, that is, n/rA = 2WAA. For a large
enough diffusion coefficient, the island density catches up rapidly and collision with
islands becomes the dominant factor in limiting the adatom lifetime t ~which, should
be much shorter than the deposition time t (in order for this analysis to hold). Now
n / r A E W A I , so that
C N u ~ - ~ ( D ~=A1 ) ~ / ~ (7)
Substituting Eq. (7) into Eq. (6) yields
N2/d+i d N = ~ - 2 / d ( ~ 2 ~ 2 - I4 D
/d
) dt (8)
By integration, we have
N(2+2id)= C-2/d(2 + 2/d)(RQ/D)a(2-4/d) (9)
where Q = Rt is the total dose deposited up to time t . Thus we have a general form of
the dependence of the island number density on diffusion coefficient as

N - x = 1/(2 +2/d) (10)

For isotropic diffusion, d = 2, x = 113; for highly anisotropic diffusion, d = 1,
x = 114 (Pimpinelli et al., 1992; Mo et al., 1992a). An example applying this analysis
will be shown in Section II.2.b.
Several assumptions and approximations have been made in the aforementioned di-
mensional argument. Therefore the analysis can be applied only under appropriate
 2 FUNDAMENTAL MECHANISMS
OF FILMGROWTH 67

conditions. For Eq. (6) to be valid, the dimer must be the stable nucleus (critical nu-
cleus i = 1 atom). Generally speaking, this assumption appears to be correct for
strongly bonded materials (metals, semiconductors) (Lewis and Campbell, 1967) at
not too high temperatures. For Si/Si(OOl), single dimers are observed to be stable up
to 600 K by STM (Mo et al., 1991). However, a LEEM experiment shows that the
stable-nucleus size increases rapidly with increasing growth temperature, reaching a
size of 650 dimers at 970 K (Theis and Tromp, 1996). The authors extrapolated their
measurements to the temperature range in which STM experiments were performed
and showed that their results were consistent with a single-dimer stable nucleus at the
STM growth conditions.
Recent STM experiments suggest that the picture that the dimer sitting in a minimum-
free-energy site is the stable nucleus from which 2-D islands grow may be overly
simplistic, at least at low temperature. This issue will be explored in more detail in
Section 11.2.c.

Diffusional anisotropy measurement Because Si(OO1) has two-fold symmetry, it is

natural to expect the surface migration to be anisotropic. Mo and Lagally (1991a,b)
showed direct experimental evidence of anisotropy in the surface diffusion of Si and
Ge on Si(OOl), based on STM analysis of the width of denuded zones (areas without is-
lands because adatoms can reach and incorporate into steps before nucleating islands).
All theoretical studies based on total-energy calculations (discussed in Section 11.1)
confirm the experimental determination that surface diffusion is faster along the dimer
rows.
As shown in Fig. 11, on the down terrace of an SB step, dimer rows are parallel
to the step [(l x 2) domain], while on the up terrace of an Sg step, dimer rows are
perpendicular to the step [(2 x 1) domain]. Thus, the mechanisms of diffusion toward
the step on these two neighboring terraces are different: either along or perpendicular
to the dimer rows. Because S g steps are symmetric sinks that absorb adatoms equally
well from up and down terraces (Mo and Lagally, 1991a; Mo, 1991), an anisotropy in
the diffusion rate will result in an asymmetry in the two denuded zones around an Sg
step.

Diffusion coefficient and activation energy In Section II.2.b we showed that the
surface diffusion coefficient of adatoms can be determined by measuring the island
number density after deposition at a given rate and to a certain dose. One such mea-
surement for Si diffusion on Si(OO1) has been made (Mo et d.,1991). The outline of
their experiments is as follows: a sub-ML dose (e.g., 0.07 ML) of Si adatoms is de-
posited onto Si(OO1) held at different temperatures; when the deposition is shut off, the
sample temperature is simultaneously quenched to near room temperature by turning
off the heating power; the sample is then transferred to the STM for scanning; scans
are made near the centers of the large terraces to avoid the interference of steps; many
scans are obtained to achieve good statistics; and the number of islands in each scan is
68 DONALDE. SAVAGE,
FENGLIU, VOLKMAR
ZIELASEK,
A N D MAXG. LAGALLY

FIG. 11. Scanning tunneling micrographs, 5000 A x 5000 A, showing the asymmetry of denuded zones
around Se steps. The Si is deposited at a rate of 1/400 ML/s to 0.1 ML coverage at two growth temperatures:
(a) 563 K; (b) 593 K. The surface steps down from the upper left to the lower right. The white bars correspond
to the directions of the dimer rows on the terrace. (Reprinted from Surface Science, 268, Y.W. Mo, J. Kleiner,
M.B. Webb, and M.G. Lagally, Surface self-diffusion of Si on Si(OOl), pp. 275-295, (1992) with permission
from Elsevier Science.)

counted to obtain an average number density. Equations (9) and (10) are then used to
obtain the diffusion coefficient.
Figure 12 shows STM images of 2-D islands formed after deposition at different
temperatures. From such images, a plot of island density vs inverse temperature can
be constructed. It shows Arrhenius behavior over a range of temperatures. At too low
a temperature the quench rate after deposition is too slow to ensure that all islands are
formed during deposition, a necessary condition of the modeling relating island num-
ber density to the diffusion coefficient. At too high a temperature the island number
density drops dramatically because of coarsening, an additional ordering mechanism
that becomes important at low deposition rates when the supersaturation is small. Us-
ing such data a quantitative determination of the diffusion coefficient is made with the
aid of computer simulations. Simulated island densities have been compared to the
experiments for the same total deposited dose, using a solid-on-solid model (Mo et al.,
1991). Figure 13(a) is a plot of the calculated number density of islands vs the jump
rate, for three models that incorporate different diffusional and sticking anisotropies.
For a sufficiently high jump rate, the island number density is proportional to J-'13
for isotropic diffusion and J-'14 for anisotropic diffusion, in agreement with the di-
mensional argument. For a very small jump rate, the mean time for adatoms to find
an existing island is longer than the total deposition time and most islands are formed
after deposition, resulting in a constant island number density (Mo, 1991).
Figure 13(b) shows Arrhenius plots of the diffusion coefficients obtained by fit-
ting the three models in Fig. 13(a) to the measured island density at several temper-
 2 FUNDAMENTAL OF FILM GROWTH
MECHANISMS 69

FIG. 12. Scanning tunneling micrographs of islands formed after deposition at different substrate tem-
peratures at a rate of 11600 ML/s to 0.07 ML coverage. (a) T = 348 K, 250 A x 250 A; (b) T = 400 K,
300 A x 300 A: (c) T = 443 K, 300 8, x 300 A; (d) T = 500 K, 400 8, x 400 A. The islands formed
at higher deposition temperatures are larger than those at lower temperatures, with lower number densities,
because of the larger diffusion coefficients at higher temperatures. The islands in each image are counted to
obtain an average number density for each temperature. (Reprinted from Surface Science, 268, Y.W. Mo, J.
Kleiner, M.B. Webb, and M.G. Lagally, Surface self-diffusion of Si on Si(OOl), pp. 275-295, (1992) with
permission from Elsevier Science.)

atures. Using the curve that incorporates a 1OOO:l diffusional anisotropy, an activa-
tion energy for surface diffusion of adatoms of 0.67 eV and a pre-exponential factor
of cm2/s are obtained (Mo et al., 1991j (a higher anisotropy gives a virtually
identical activation energy). Assuming the diffusional anisotropy is all ascribed to a

-
difference in activation energy, the activation energy for diffusion across dimer rows
becomes 1 eV. Although essentially all calculations predict the anisotropic diffusion,
the kinetic barriers from ab initio calculations agree quantitatively better with these
experimental values.
The experimentally derived barriers for diffusion should be considered as average
values because only a single adsorption site and two orthogonal diffusional directions
are used in the computer simulations; on a real surface, multiple adsorption sites and
complex diffusion pathways can be involved. From the measured diffusion coefficient,
one would expect that the motion of a monomer will be slow enough to be observable
at -200 K. However, in reality monomers can be observed only at much lower temper-
atures (Wolkow, 1992; Wu, 1996) suggesting that there exists on top of the dimer rows
a fast diffusion pathway with lower barrier than the average, leading to a faster motion
of monomers than what one would have expected. Several different models have been
proposed theoretically: Brocks et al. (1991) proposed a zigzag path connecting two
most stable adsorption sites (Fig. lO(aj); Z. Y. Zhang et aE. (1991) and Srivastava and
70 DONALDE. SAVAGE,
FENGLIU,VOLKMAR ZIELASEK, AND MAX G. LAGALLY

FIG. 13. Determination of diffusion coefficient from island densities. (a) Calculated relationship be-
tween the island number density and the jump rates of adatoms. Three of the curves are from computer
simulations with different diffusional anisotropy assumptions while the fourth curve is from rate equation
calculations. Circles: isotropic sticking and diffusion. Diamonds: rate equation, isotropic sticking and dif-
fusion. Squares: anisotropic sticking and isotropic diffusion. Triangles: anisotropic sticking and diffusion.
The anisotropic diffusion assumes a jump rate along the dimer rows of 1000 times that perpendicular to the
dimer rows. The anisotropic sticking assumes a probability of one for sticking at the ends and zero at the
sides of islands. Simulations are for the same deposition condition as in experiments (Fig. 12). (b) Diffusion
coefficients obtained from comparison of the measured island number density with those from computer
simulations using three different models. Notations are the same as in (a) (Mo et al., 1992b). (Reprinted
from Sutfuce Science, 268, Y.W. Mo, J. Kleiner, M.B. Webb, and M.G. Lagally, Surface self-diffusion of Si
on Wool), pp. 275-295, (1992) with permission from Elsevier Science.)

Garrison (1991) proposed that the diffusion occurs predominantly on top of dimer rows
(Fig. 1 O(b)); Roland and Gilmer (1992a) suggested exchange events between adatoms
and substrate atoms during diffusion.

c. Growth: Adatom-step Interaction

Epitaxial island growth and step flow growth are understood better than the initial
nucleation step. At typical STM experimental deposition rates of -0.001 MWs to
-0.01 MLh, between room temperature and -500 K, the growth proceeds via 2-D
islands (Harners et al., 1989 and 1990; Lagally et al., 1989 and 1990; Mo et al., 1989
and 1990a); above 500 K, the growth proceeds via step flow (Hoeven et al., 1989 and
1990). Annealing experiments (Mo et al., 1989 and 1990a) clearly show that the shape
of the as-grown islands is controlled by kinetics, because it differs from the equilibrium
shape. The as-grown islands consist of a few dimer rows with an aspect ratio as high
as 20: 1 (Hamers et al., 1989 and 1990; Lagally et al., 1989 and 1990; Mo et al., 1989
and 1990a). Analyses show that the highly anisotropic shape is caused by the large
difference of lateral accommodation coefficient in two orthogonal directions rather than
by anisotropic diffusion (Mo et al., 1989 and 1990a). Arriving adatonis stick to the
 2 FUNDAMENTAL OF FILMGROWTH
MECHANISMS 71

ends of dimer rows ( S B steps) at least one order of magnitude better than to the sides of
the rows (SA steps). For the same reason, in the higher-temperature step-flow growth
mode, SB steps advance to catch up with SAsteps, resulting in a single-domain surface
(Hoeven et al., 1989 and 1990). The anisotropic accommodation has also been shown
to play a key role in the 2-D kinetic roughening of the growth front of the step under
step-flow or near-step-flow conditions (Wu et al., 1993). In the following we discuss
experiments (Mo and Lagally, 1991a; Mo, 1991) that allow one to investigate in detail
the nature of the adatom-step interaction.
The interaction between adatoms and surface steps is one of the most important
microscopic aspects of growth kinetics. The nature of this interaction determines the
growth rate and shape of islands, the mode of step-flow growth, and the width and
asymmetry of the denuded zone around steps. The width of a denuded zone is con-
trolled by the adatom sticking coefficient at the step and the energy barrier for adatoms
to cross the step, in addition to surface diffusion and its anisotropy. It is possible to
address each effect individually.
The relative magnitudes of the lateral sticking coefficients of adatoms at the SA
and SB steps can be studied by analyzing denuded zones on any single terrace that
is bounded by the two types of steps. Figure 14 shows an STM image of a large

FIG. 14. The spatial distribution of 2-D islands on a large terrace (-700 & . wide), showing a large
anisotropy in the denuded zones that reflects the anisotropy of the lateral sticking coefficients of adatoms
at Sa and Ss steps. Field of view: 1.0 x 0.9 bm. Approximately 0.1 ML was deposited at 563 K and
at a rate of 1/4000 ML/s. The surface steps down from the lower left to the upper right. (Reprinted from
Surface Science, 248, Y.W. Mo and M.G. Lagally, Anisotropy in surface migration of Si and Ge on Si(001),
pp. 313-320, (1991) with permission from Elsevier Science.)
72 DONALDE. SAVAGE,FENGLIU, VOLKMARZIELASEK,
AND MAX G. LAGALLY

single terrace about 7000 A wide, created by applying a small external stress to the
wafer (Men et al., 1988) (the effect of the external strain on growth kinetics is neg-
ligible) (Webb et aL, 1990 and 1991). The terrace is bounded by an SB step at the
downstairs side (the upper left) and an SA step at the upstairs side (the lower right).
On each side are much smaller minor-domain terraces. The bright strings on the ter-
race are 2-D islands. An obvious asymmetry exists in the spatial distribution of the
islands: the denuded zone near the SB step is much larger than that near the S A step.
Because diffusion towards the two steps must be the same everywhere, this asymme-
try is clear evidence for the anisotropy in the lateral sticking coefficients of adatoms
at the two types of monatomic steps: Sg steps are good sinks for adatoms while
SA steps are not. Quantitative analysis of the highly anisotropic shape of growth is-
lands shows that the ratio of sticking coefficients of a monomer at Sg and S A steps
is at least 1O:l (Mo et al., 1989 and 1990a; Mo, 1991; Wu, 1996). Mo (1991) also
pointed out that for a dimer-wide island to grow preferentially at its ends, a monomer
must have some residence time at the end of the row, waiting for another monomer
to come to form the next dimer. Indeed, monomers trapped at the end of dimer
rows have since been frequently observed (Bedrossian, 1995; Wu, 1996; Swartzen-
truber, 1997).
S B steps are not only good sinks but also symmetric sinks: that is, they adsorb
adatoms coming from either up or down terraces equally well (Mo and Lagally, 1991a).
This conclusion is reached by analyzing the denuded zones around steps in (100) di-
rections, which are at 45" to the dimer rows of both domains. In this configuration,
all the terraces are equivalent and the diffusion toward any step on both the up and the
down terraces is identical. Figure 15 shows STM images of the island distributions
around (100) steps. In Fig. 15(a), the four denuded zones shown have the same widths.
The middle terrace is so narrow that the two denuded zones from the bounding steps
nearly overlap. For the conditions in Fig. 15(b), the denuded zones are wider than the
terrace. Although 45" steps are not pure Sg steps, microscopically the Sg step seg-
ments are adsorbing the adatoms with at least one order of magnitude greater sticking
coefficient (Mo et al., 1989 and 1990a; Wu, 1996). Thus one can conclude that SB
steps are symmetric sinks for adatoms either from up or down terraces.
The existence of a large denuded zone on the up-terrace side of S B steps (Fig. 14)
suggests that, in addition to Sg steps being good sinks, there can be no significant
barrier for adatoms to cross downward over S B steps, because a barrier would act
to keep atoms on the terrace and thus reduce the denuded zone even if the sticking
coefficient at the S B step is large. The absence of a denuded zone on the down-terrace
side of SA steps indicates that SA steps are poor sinks and, at least to a certain degree,
mirrors for arriving adatoms. In Fig. 14, the SA step at the lower right corner is very
close to the next Sg step. If adatoms could easily cross an SA step from the down
(2 x 1) terrace, they would climb over to the up (1 x 2) terrace and get absorbed by
the next SB step or by the kinks in the SA step. This step crossing would result in a
large denuded zone on the down ( 2 x 1) terrace of the SA steps even though SA steps
 2 FUNDAMENTAL MECHANISMS
OF FILMGROWTH 73

FIG. 15. Scanning tunneling micrographs, 5000 A x 5000 8,showing symmetric denuded zones around
(100) steps. Approximately 0.1 ML of Si was deposited at a rate of 11400 ML/s, at (a) 563 K, and (b) 593 K,
respectively. The surface steps down from top to bottom. The underlying dimer rows run 45' to the steps
and form a chevron pattern orthogonal to the directions of the long axes of the deposited islands. (Reprinted
from Surfiuce Science, 248, Y.W. Mo and M.G. Lagally, Anisotropy in surface migration of Si and Ge on
Si(O01), pp. 313-320, (1991) with permission from Elsevier Science.)

themselves are poor sinks. No such denuded zone is observed; hence the S A steps must
have a significant stepcrossing barrier.
The adatom-step interaction has also been studied extensively by theory
(Q.-M. Zhang, 1995; Roland and Gilmer, 1991 and 1992b; Z. Y. Zhang et al., 1992;
Srivastava and Garrison, 1993). The results of an ab initio calculation (Q.-M. Zhang
et al., 1995) are in very good agreement with the experimental conclusions described
above, showing that SA steps are poor sinks for adatoms both because the binding en-
ergy of an adatom at the SA step edge is comparable to that on the terrace and because
the barrier for adatoms that have adsorbed to the SA step from the lower terrace to
escape the S A step is low. These are necessary conditions for SA to act as a mirror,
but a significant stepcrossing barrier is also needed. Rebonded Sg steps (see Fig. 8)
are good sinks for adatoms because the binding energy to the SB step is large and be-
cause adatoms approaching the SB step from the upper terrace encounter only small
barriers to cross the step edge. All empirical calculations (Roland and Gilmer, 1991
and 1992b; Z. Y. Zhang et al., 1992; Srivastava and Garrison, 1993) have reached the
conclusion that Sg steps are much better sinks for adatoms than SA steps, but they
wrongly predict that only nonrebonded SB steps bind adatoms strongly. Experiments
(Kitamura et al., 1993; Wu, 1996) show that most SB steps appearing on the surface are
rebonded and hence for growth to occur they must bind adatoms also. The measure-
ments of Swartzentruber (1997) corroborate this conclusion, showing that monomers
attach preferentially to rebonded S B steps.
74 DONALDE. SAVAGE,FENGLIU,VOLKMAR A N D MAXG. LAGALLY
ZIELASEK,

One of the remaining challenging questions concerning growth of Si on

Si(OO1) is how ad-dimers (stable nuclei) transform into epitaxial dimer-row islands
or even whether they do. Although a single ad-dimer is most frequently observed at the
epitaxial position on top of a dimer row, it does not bind an adatom (Brocks and Kelly,
1996); theory predicts that only in-trough dimers can attract adatoms, but they form
“dilute” ad-dimer rows rather than epitaxial dimer rows (Bedrossian, 1995; Brocks and
Kelly, 1996). A high-resolution STM image of a dilute dimer row is shown in Fig. 16:
the location of the ad-dimers is found to be at D-D* sites, schematically shown in
Fig. IO(c). It has been speculated that the dilute ad-dimer rows are transient structures
mediating the formation of anisotropic epitaxial dimer-wide islands from single ad-
dimer nuclei (Mo et al., 1989 and 1990a; Bedrossian, 1995; Brocks and Kelly, 1996).
Several molecular dynamics (Z. Y. Zhang and Metiu, 1991; Rockett, 1994) and Monte
Carlo simulations (Dijkkamp et al., 1992) have been carried out to explore the mi-
croscopic mechanisms of the formation and growth of epitaxial islands, but none has
observed the dilute ad-dimer row structure. Other mechanisms, for example, substrate
dimer opening due to adatom insertion, have been proposed (Z. Y. Zhang and Metiu,
1991; Rockett, 1994). But these also have not been confirmed experimentally. Thus
there remains a large gap in understanding the very initial stage of island formation
from the stable nucleus.

FIG. 16. A high-resolution STM image of an adsorbed diluted-dimer row island containing 11 atoms,
with a monomer attached at the left end. The ad-dimer bonds are parallel to the dimer bonds in the underlying
rows and centered between the rows (sites D-D* in Fig. 1O(c)). The image is taken at a sample bias of
+0.8 eV. In this example the ad-dirners are Ge deposited on Si(OO1) at room temperature (from Qin et a / . ,
1998). The diluted-dimer row is indistinguishable from a Si diluted-dimer row. The dimer structure is
affected by the presence of the dimer row island.
 2 FUNDAMENTAL OF FILMGROWTH
MECHANISMS 75

d. Growth: Coarsening

If growth is performed under conditions close to equilibrium or if deposition is inter-

rupted, coarsening must be included in an analysis of the growth process. The average
supersaturation of free adatoms on the surface continues to reduce through nucleation
and growth until it is nearly eliminated. At this stage, islands of different sizes exist
in equilibrium with their local vapor pressures. The local equilibrium vapor pressure,
that is, the concentration of free adatoms around an island, is inversely proportional to
the radius of the island (Porter and Easterling, 1981; Mo, 1991). Hence there will be
locally different concentrations of free adatoms on the surface. As a consequence of
Fick’s law of diffusion, net fluxes of adatoms flow from small islands to large ones.
Following nucleation and growth, therefore, the system is further organized by the
coarsening process: large islands grow at the expense of small ones. The driving force
decreases as the islands become more uniform in size, leading to the phenomenon of
Ostwald ripening (Ostwald, 1901) in which a distribution of islands with uniform size
results.
Theis and Tromp (1996) have shown, using LEEM, that Si growth on Si(OO1) at
elevated temperatures occurs very near equilibrium. Under the deposition conditions
of TSubstrate = 970 K and growth rates ranging from 0.1-2 monolayers per min, the
impinging flux increased the adatom concentration by only 1.75% above the equilib-
rium adatom concentration. As most Si films for technological use are deposited at
such “high” temperatures, rather than at the lower temperatures of an STM experi-
ment, coarsening can be an important process in the growth of Si films used for device
applications.
In separate work, Theis, Bartelt, and Tromp (1995) concluded, from a LEEM study,
that the coarsening of 2-D islands on Si(OO1) can be understood in a common frame-
work with step fluctuations. In addition, they demonstrate that coarsening is strongly
influenced by the nearest-neighbor correlations between islands. Thus, coarsening is
more complicated than the simple model of 2-D islands communicating with an aver-
age 2-D gas of adatoms arising from the average 2-D “vapor pressure” of the islands.

PROPERTIES AND EQUILIBRIUM

3. THERMODYNAMIC
MORPHOLOGY
SURFACE

While it is essential to understand growth kinetics to achieve controlled film growth,

manipulating kinetic processes also requires a good understanding of the thermody-
namic properties of the surface. The relative rate of a kinetic process is dependent on
thermodynamic balances among different configurational states. By choosing properly
the initial configuration of states, it is possible to alter the kinetic route for subsequent
growth. For example, the growth of 111-Vsemiconductors on vicinal Si(OO1) templates
is largely controlled by the initial step configurations (Kroemer, 1986; Fukui and Saito,
76 E. SAVAGE, FENGLIU,VOLKMAR ZIELASEK, AND MAX G . LAGALLY
DONALD

1987). In this section, we discuss the thermodynamic properties of equilibrium surface

structures and morphologies on Si(OO1).

a. Equilibrium Shape of Si Islands and Energetics of Steps

It has been shown that the highly anisotropic shape of as-grown Si islands, with an
aspect ratio as large as 15 to 20, is determined by growth kinetics rather than being
an equilibrium property (Mo et al., 1989 and 1990b). Upon annealing at -600 K, the
islands become more rounded, with a much smaller aspect ratio of about 2 to 3 (Mo
et al., 1989 and 1990b). This has also been confirmed by two LEEM experiments in the
same temperature range (Swiech and Bauer, 1991; Theis ef al., 1995). At equilibrium,
the shape of an island is controlled by its boundary free energy. For Si(OOl), S A and Sg
steps comprise the island boundary, and so the difference in the free energies of these
two steps determines the island anisotropy. At low temperature, when the entropy
contribution to the free energy is small, the aspect ratio of the equilibrium island shape
reflects the ratio of S A and SB step energies. The observed aspect ratio of islands of 2
to 3 at 600 K is in accord with the measured step energies (Swartzentruber et al., 1990;
Swartzentruber, 1992), once entropy has been included.
Swartzentruber et al.( 1990) have performed an STM analysis of the equilibrium dis-
tribution of steps and kinks on Si(OO1). For steps bounding wide terraces, the kink ex-
citations at the individual step sites are shown to be statistically independent and each
excitation obeys a simple Boltzmann distribution. From the analysis, Swartzentruber
et al. derived S A and SB step energies of 0.028 eV1atom and 0.09 eVlatom, respectively.
A similar analysis by Zandvliet et al. in 1992, involving a somewhat more complicated
model, gives S A and S B step energies of 0.026 eV1atom and 0.06 eV/atom, respectively.
The S A and SB step energies have also been determined from LEEM measurements of
island shape and step fluctuations (Bartelt et al., 1994; Theis et al., 1995). The results
from STM and LEEM are in very good agreement (Bartelt et al., 1994).
As temperature increases, the entropy component of the free energy becomes domi-
nant and the difference between S A and Sg step free energies becomes smaller, leading
to a more isotropic shape of islands. The LEEM images (Swiech and Bauer, 1991;
Theis et al., 1995) show that the equilibrium aspect ratio of island decreases from
2.6 at 970 K to 1.5 at 1370 K. The higher-temperature ratio is consistent with values
of 1.25 to 1.43 observed for single-atom deep sublimation holes (trenches) by reflec-
tion electron microscopy at 1200-1400 K (Latyshev et al., 1988; Mktois and Wolf,
1993). This agreement is no surprise, as these trenches are also bounded by SA and SB
steps.

b. Equilibrium Step Conjigurations

Nominal surface Step configurations on vicinal Si(OO1) surfaces have been a subject
of intensive study because, in practice, vicinal surfaces are used in device fabrication
 2 FUNDAMENTAL
MECHANISMS
OF FILMGROWTH 77

as the growth template, utilizing the steps to facilitate smooth growth by step flow. On
vicinal Si(OO1) with a small miscut (< 1.5") toward [110], SA and SB steps alternate,
separating 2 x 1 and 1 x 2 domains. If the surface is nominally singular (miscut by less
than a few tenths of a degree), the equilibrium populations of these two domains are
about equal (Men et al., 1988). Men et al. showed that the relative populations of the
two domains can be changed if uniaxial stress is applied to the wafer at a temperature
sufficiently high so that the step mobility is high. The domain that is compressed along
the dimer bond by the applied stress is favored. The experiment is well understood
by a theoretical model developed in 1988 by Alerhand et al. The theory shows that,
in the presence of an anisotropic intrinsic surface stress, a flat surface, for example,
Si(OOl), is unstable to the formation of elastic-stress domains separated by steps. The
discontinuity of stress at the step introduces a force monopole, giving rise to an elastic
step-step interaction that lowers the surface energy with a logarithmic dependence on
step separation ( L ) (Marchenko, 1981; Alerhand et al., 1988), E s = C1 - C2 ln(L/a),
where C1 denotes the step formation energy per unit length, C2 reflects the strength of
the interaction, which is related to the stress anisotropy and elastic constants, and a is
a microscopic cutoff length on the order of a lattice constant. The surface assumes the
lowest-energy configuration with an optimal step separation of LO= n u exp(Cl/C2 +
1). Therefore, a surface with sufficiently low step density could reduce its energy by
introducing extra steps. When a uniaxial external stress is applied to such a surface,
the favored domain type will grow at the expense of the other, as shown by experiment
(Men et al., 1988).
Further LEED and STM experiments have been done to determine quantitatively
the intrinsic surface stress anisotropy of Si(OO1) (Webb et al., 1990 and 1991). A
measurement of the population asymmetry of (2 x 1) and (1 x 2) domains as a function
of the external strain gives a value of 0.07 f 0.01 eV/A for this anisotropy. The stress
anisotropy of Si(OO1) has also been calculated by various theoretical methods (Payne
et al., 1989; Meade and Vanderbilt, 1990; Garcia and Northrup, 1993; Dabrowski et al.,
1994) and good agreement with experiment has finally been reached after several years
of controversy (Garcia and Northrup, 1993; Dabrowslu et al., 1994).
Although the theory of Alerhand et al. (1988) provides a good understanding of
the experimentally observed behavior of steps on Si(OO1) under an external stress, the
spontaneous formation of extra steps to reduce the size of the stress domain predicted
by theory is not observed on nominally singular Si(OO1). Instead, the existing steps be-
come wavy in the low-step-density regions, as observed in 1992 by Tromp and Reuter
in a LEEM experiment. Calculations by Tersoff and Pehlke in 1992 also predict that
at large enough step separations, straight steps are unstable against the formation of
long-wavelength undulations. These undulations lower the surface strain energy by
effectively reducing the size of the stress domains so that the step-step separations be-
come closer to the optimal value of LO. Furthermore, step undulations are kinetically
preferred and are compatible with step flow. Therefore, step undulations preempt the
formation of extra steps.
78 E. SAVAGE, FENGLIU, VOLKMAR
DONALD ZIELASEK, A N D MAX G . LAGALLY

Vicinal surface Step configurations on vicinal surfaces are more complicated and
their behavior is less well understood. As the miscut angle increases, double-atomic-
height steps ( D B ) start to form (Olshanetzky and Shklyaev, 1979; Kaplan, 1980;
Wierenga et al., 1987; Aumann et al., 1988; Griffith et al., 1989; Griffith and Kochan-
ski, 1990). Theoretical calculations (Chadi, 1987) show that the formation energy of
D B steps is lower than the sum of SA and SB step energies. But, as first pointed
out by Vanderbilt et al. in 1989, the elastic step-step interactions must be included
to determine the equilibrium step configurations on a vicinal surface. Using a one-
dimensional elastic model, Alerhand et al. in 1990 showed that the surface with single-
atomic-height steps at a small miscut angle is actually a true equilibrium structure
rather than a kinetically limited structure, as had been thought earlier. The model also

atomic-height-step surface to the double-atomic-height-step surface at 0, -

predicts that, at T = 0, there exists a first-order phase transition from the single-

as the miscut angle (0) increases. At finite temperature, thermal roughening of SB

0.05"

steps shifts the transition to higher angles, for example, giving a value of S,
at T = 500 K. This model was extended (Poon et al., 1990 and 1992) by adding
- 2"

extra elastic interaction terms that result from the force dipoles associated with steps
(Marchenko, 1981). The predicted phase transition was then shifted to -1" at T = 0
and -3" at T = 500 K. Pehlke and Tersoff (1991) searched for the global mini-
mum step configuration of a vicinal Si(OO1) surface in a T = 0 analysis by extend-
ing Poon's calculation, allowing a random mixture of single and double steps and the
variation of all the step positions. They show that, at the small angle at which only
single-atomic-height steps appear, the population of (2 x 1) and (1 x 2) domains
can be asymmetric, and the population of (2 x 1) domains increases gradually with
increasing miscut angle, in good agreement with RHEED (Tong and Bennett, 1991)
and STM experiments (Swartzentruber et al., 1992). As the angle increases, double-
atomic-height steps start to form and their concentration increases with increasing an-
gle. However, they appear in a mixed phase, consisting of a complex sequence of
single and double steps, rather than a pure phase or a coexistence of two spatially sep-
arated phases. Extending the T = 0 analysis to higher temperature, Pehlke and Tersoff
(1991) constructed the phase diagram of the vicinal Si(001) surface. They showed that
there is a critical temperature above which no phase transition exists at all. Below the
critical temperature, the transition takes place through a quasi-continuous sequence of
weak first-order transitions.
Experimentally, however, no indication of a first-order phase transition has been
observed. Instead, the step concentration changes continuously with both miscut angle
(Swartzentruber et al., 1992) and temperature (de Miguel et al., 1991). Experiments
also indicate that at high temperature and large angles, a simple one-dimensional elastic
model becomes unsatisfactory (de Miguel, 1992).
 OF FILMGROWTH
2 FUNDAMENTAL MECHANISMS 79

111. Heteroepitaxial Growth: Ge on Si

Because of the technological potential of Si-Ge and Si-GeSi heterojunctions, for ex-
ample in high-speed heterobipolar transistors and in optoelectronic devices, the growth
of germanium on silicon has been studied intensively for several years. Qualitatively,
Si and Ge are quite similar in their structural and electronic properties. They both
form with the diamond crystal structure. The Ge lattice, however, is expanded by 4.2%
with respect to the Si lattice and the Ge-Ge bond is weaker than the Si-Si bond, lead-
ing to a smaller surface energy. Consequenlly the system Ge/Si is usually discussed
as a classical model for the Stranski-Krastanov growth-mode (see Section 1.1). The
simple picture of a smooth pseudomorphic wetting layer growing up to a certain crit-
ical thickness and being followed by the introduction of dislocations and the growth
of dislocated 3-D clusters, however, provides only one limiting thermodynamic guide-
line. The compressed Ge overlayer shows a variety of morphological instabilities with
respect to the underlying substrate in order to relieve strain (Liu et al., 1997). The in-
stabilities are not necessarily accompanied by misfit dislocation formation, but instead
offer alternative pathways for strain relief.

1. GROWTH
OF THE GE WETTING LAYERON sI(oo1)

a. Submonolayer Growth

The strain induced by the lattice mismatch between the substrate and the growing
species affects both thermodynamics and kinetics (Liu et al., 1997). In the submono-
layer regime the 4.2% lattice mismatch between Ge and Si has only
little effect on the kinetics of growth of Ge on Si(OO1) and it has been shown both
experimentally (Mo and Lagally, 1991a; Lagally, 1993) and theoretically (Srivastava
and Garrison, 1992; Roland and Gilmer, 1993; Milman et al., 1994) that Ge submono-
layer growth on Si(OO1) is essentially the same as Si(OO1) homoepitaxy.
In general, Ge atoms deposited onto a Si(OO1) substrate at room temperature form
2-D epitaxial islands and follow the sequence (Mo and Lagally, 1991a and 1991b;
Mo ef al., 1991; Mo et al., 1992b; Lagally, 1993; Liu and Lagally, 1997a) of adatom
adsorption, adatom diffusion, nucleation of islands, and growth of dimer row islands
just as in silicon homoepitaxy (Section 11.2.b). A first-principles calculation of the
potential-energy surface for a Ge adatom on Si(OO1) (Milman et al., 1994) shows that
the most stable adsorption site for a Ge adatom is at an “M-site,” that is, in the trough
next to a dimer row and midway between two dimers along the row, just as for a Si
adatom (Brocks et al., 1991).
Analogous to the STM measurements of Si diffusion on Si(OO1) (Section 11.2) the
activation energy, the prefactor, and the anisotropy were determined for Ge diffusion on
Si(O01) from the temperature dependence of the island density and the areas of denuded
80 E. SAVAGE,FENGLIU,VOLKMAR
DONALD ZIELASEK,A N D MAX G. LAGALLY

FIG. 17. Ge islands grown on Si(001) at low coverages. The spatial distribution (here for 0.1 ML
Ge deposited within 100 s at 570 K) shows essentially the same anisotropies that are observed for Si(001)
homoepitaxy. The STM scan range is 500 nm x 500 nm. The surface reconstruction alternates between
(2 x 1) (terraces 1 and 3) and (1 x 2) (terrace 2) domains separated by atomic-height steps. The surface steps
down from lower right to upper left. A denuded zone forms near to the SB step on terrace 3. (Reprinted from
Sutface Science, 248, Y.W. Mo and M.G. Lagally, Anisotropy in surface migration of Si and Ge on Si(001),
pp. 31 3-320, (1991) with permission from Elsevier Science.)

zones that appear at steps. Figure 17 shows Ge islands on Si(OO1) grown at 620 K and a
denuded zone near the Sg step. The diffusion coefficients for Ge on clean Si(OO1) and
on Si(OO1) covered by 1 monolayer of Ge are compared to the results for Si diffusion on
Si(OO1) in Fig. 18. On clean Si(OO1) the diffusion of Ge adatoms is highly anisotropic
and single atoms move along the dimer row direction about 1000 times faster than
across the dimer rows, the same result as for Si adatom diffusion on Si(OO1). The
activation barrier for diffusion of Ge on clean Si(OO1) also resembles that of Si, but the
prefactor is an order of magnitude smaller, implying that Ge atoms diffuse more slowly
on Si(OO1) than do Si atoms (Lagally, 1993). The calculated diffusion barriers (Milman
et al., 1994; Brocks et al., 1991) agree well with the experiments. Diffusion of Ge on
Si(OO1) covered by 1 ML of Ge is different: it is nearly isotropic, the activation energy
is lower, 0.48 eV vs 0.67 eV, but the prefactor is also lower, sufficiently so that the
diffusion coefficient is overall lower. The explanation is believed (Lagally, 1993) to be
related to scattering of the diffusing Ge atoms off the dimer vacancy lines discussed in
Section lb.
At room temperature, for growth of Ge, the as-grown 2-D epitaxial islands again
have a highly anisotropic shape, because of the large difference in sticking coefficients
of adatoms to different step edges (Mo and Lagally, 199 1a and 199 1b; Mo et al., 199 1;
Mo et al., 1992b; Lagally, 1993) annealing at higher temperatures (-600 K) changes
 2 FUNDAMENTAL
MECHANISMS
OF FILMGROWTH 81

-si~\ A
Q M X X ) G e on Si(OO1)
ULAAA Si Ge on 1ML Ge o n Si(OO1)
on Si(OO1)

A
0
a, 10

a
10

FIG. 18. Comparison of the monomer diffusion coefficients for Si on Si(OOI), Ge on clean Si(OOl), and
Ge on 1 ML Ge/Si(001) after formation of dimer vacancy lines. The diffusion coefficient is highly anisotropic
for Si and Ge on clean Si(OO1) and nearly isotropic for Ge on 1 ML Ge/Si(OOl). The activation energy for
diffusion changes from 0.67 eV for Si and Ge diffusing on clean Si(OO1) to 0.48 eV for Ge diffusing on 1 ML
GelSi(001).

the islands into a much more rounded shape whose aspect ratio is determined by the
energetics of two types of monatomic-height steps (Mo et al., 1989). The smallest and
the most obvious stable structure on the surface at room temperature is a single Ge
ad-dimer, from which it is deduced that the size of critical nuclei is one atom (Mo and
Lagally, 1991a and 1991b; Mo et al., 1991; Mo et al., 1992b; Lagally, 1993).
It should be noted that an understanding of the atomistic pathway from a
single adatom to islands of ad-dimers is still missing for both Si and Ge on Si(OO1).
Recent STM measurements demonstrate that two Ge adatoms on adjoining "M-sites"
of the Si(OO1) substrate (adsorption sites D-D* in Fig. IO(c)) can form a stable pair
of adatoms that differs from an ad-dimer (Qin and Lagally, 1997). Because chains of
these adatom pairs have been observed, it is suggested that adatom pairs and metastable
structures of various sizes involving adatom pairs represent the missing link between
single monomers and the formation of dimer row islands (Qin et al., 1997). If this
is the case, island formation might not be dominated by the nucleation of single ad-
dimers on top of the substrate dimer rows, and hence the concept of the critical nu-
cleus and the diffusion parameters derived from this concept would have to be reeval-
uated.
82 DONALDE. SAVAGE,FENGLIU, VOLKMAR A N D MAX G. LAGALLY
ZIELASEK,

b. Formation of Dimer Vacancy Lines

Initial strain relaxation of the Ge overlayer is primarily achieved by forming addi-

tional dirner vacancies. Total-energy calculations (Tersoff, 1992; Yu and Oshiyama,
1995; Liu and Lagally, 1996) show that dimer vacancies actually have a negative for-
mation energy on the Ge/Si(OOl) surface with respect to the uniformly strained Ge
overlayer, and hence they are energetically even more favored to form in a Ge layer
on Si(OO1) than on clean Si(OO1). Although the kinetics of vacancy formation are not
known, we should expect that dimer vacancies are also kinetically more favored to
form on Ge/Si(OOl) than on clean Si(OOl), because it is easier to break Si-Ge or Ge-Ge
bonds than to break Si-Si bonds.
A rebonding of second-layer atoms in the dimer vacancies plays an important role
in the mechanisms of vacancy formation and strain relaxation in Ge-covered Si(OO1).
Vacancies can serve as a strain-relief mechanism by simply providing room for the
expansion of the Ge overlayer. Without rebonding, however, vacancy formation would
cost too much chemical energy through the creation of dangling bonds. The rebonding
of second-layer atoms in the vacancies not only eliminates the dangling bonds but
also introduces a large tensile stress, which cancels and actually overcompensates the
large compression along the dimer rows in the Ge overlayer (Tersoff, 1992; Liu and
Lagally, 1996). Thus, vacancy formation is driven both by the reduction in the number
of dangling bonds and by strain relaxation.
As the Ge coverage (ffG,) approaches 1, surface vacancies order into lines forming a
(2 x n ) reconstruction consisting of dimer rows that are interrupted by missing dimers
every n lattice spacings where n is typically 10-12. The reconstruction that has been
observed by both STM (Mo and Lagally, 1991b; Kohler et af., 1992; Iwawaki et al.,
1 9 9 2 ~ and
) LEED (Kohler et al., 1992; Iwawaki et al., 1992a,b). Although dimer
vacancies readily form on clean Si(OOl), a well defined (2 x n ) pattern begins to appear
only beyond 0.8 ML Ge coverage (&,) (Wu et al., 1995; Wu, 1996), suggesting that
the reconstruction (i.e., the ordering of vacancies) is related to relief of misfit-induced
compressive strain in the surface (Tersoff, 1992; Kohler et al., 1992). This conclusion
is supported by an STM observation (Mo and Lagally, 1991b) that at the tops of large
3-D Ge clusters, where the strain is relaxed, flat (001) facets show only a perfect (2 x 1)

Si(OO1) surface with QG, -

reconstruction. Figure 19 shows an STM image of a (2 x n ) structure on a Ge-covered
1.6 ML. The vacancy lines (VLs) are dark because of the
lower altitudes of the dimer-vacancy sites. The (2 x n ) reconstruction is not perfect;
each dimer vacancy (DV) fluctuates around its mean position. The meandering of the
VLs is dictated by the competition between the ordering process, driven by the DV-DV
interaction to minimize elastic energy, and the disordering process, driven by a desire
of the system to maximize its configurational entropy.
There exists a preferred spacing, nag, between two neighboring DVs on the same
dimer row. When they are too far apart, the compressive stress in the overlayer is not
relieved enough; if they are too close, the stress is “over-relieved.” Effectively, this
 2 FUNDAMENTAL
MECHANISMS
OF FILMGROWTH 83

FIG.19. Scanning tunneling micrographs (45 nmx45 nm) of Si(OO1)coveredby -1.6 MLGe, showing
atomically resolved structures on three terraces separated by monatomic steps. The dimer vacancy lines, vis-
ible as dark lines, and the dimer rows that are perpendicular to the vacancy lines form a (2 x n ) superstmcture
on the terraces.

balancing of tensile and compressive stresses amounts to a short-range repulsive, long-

range attractive interaction between DVs on the same dimer row, as shown directly by
total-energy calculations (Tersoff, 1992; Liu and Lagally, 1996).
The thermal fluctuation of DVs causes n to have a distribution function P,(n),
peaked at an optimal value of n (P,(n) is the probability of finding dimer vacancies
on the same dimer row separated by n dimers). Figure 20 shows two such distribution
functions for Bee = 0.8 ML and 1.6 ML, respectively (Wu et al., 1995). They are
determined by counting n in individual dimer rows of many STM images like those
shown in Fig. 19. As the Ge coverage increases, more vacancies are created to relieve
the increasing misfit strain. Consequently, the optimal value of n in Fig. 20 decreases
with increasing Ge coverage, from -1 1 at 0.8 ML to -9 at 1.6 ML, consistent with an
earlier LEED measurement (Kohler et aE., 1992) and a recent theory (Liu and Lagally,
1996).
The formation of dimer vacancy lines drastically changes the kinetics of
growth of Ge after the completion of the first Ge monolayer. It has been shown that the
diffusion of Ge adatoms on a one-monolayer Ge-covered Si(OO1) surface is much less
anisotropic than on clean Si(OO1) and that overall the effective diffusion coefficient is
lower (see Fig. 18) (Lagally, 1993). The lower activation energy evaluated from Fig. 18
would indicate that it is easier for Ge atoms to diffuse over a Ge lattice than a Si lattice.
Because the microscopic diffusion mechanism along unperturbed sections of the dimer
rows is expected to be the same as on the clean Si(OO1) surface, that is, anisotropic and
fast along the dimer rows, it is suggested that the dimer vacancy lines impose an addi-
tional barrier for diffusion along the dimer rows, making the diffusion overall slower
and more isotropic. This view is supported by simulations (Roland and Gilmer, 1993;
Yu and Oshiyama, 1995).
84 E. SAVAGE,
DONALD FENGLIU,VOLKMAR A N D MAXG. LACALLY
ZIELASEK,

Separation n(a,)
FIG.20. Separation probability distributions P, of adjacent dimer vacancies on the same dimer row at
(A) OG, - 0.8 ML and (B) 0Ge - 1.6 ML, respectively. Distributions are determined from images such
as the one shown in Fig. 19. The graph shows that dimer vacancies organize into regular lines at higher Ge
coverage.

c. Intermixing

Using deposition from a Ge source at typical evaporation rates onto a Si(O01) sub-
strate with small miscut at temperatures of 500-700 "C one would expect the layer to
form via step-flow growth, that is, the atoms have enough mobility to reach steps. Un-
der these growth conditions, however, interdiffusion between Si and Ge becomes sig-
nificant. Theory (Liu and Lagally, 1996) shows that, at true equilibrium, there should
be considerable intermixing of Ge into the top few Si layers. The Ge adatoms are not
just incorporated at the steps but over the entire surface by exchanging places with Si
atoms in the surface dimers to form Si-Ge mixed dimers or Ge dimers. The displaced
Si atoms diffuse to and are incorporated at the steps to give the typical signature for step
flow. This picture is inferred from experimental observations (Tromp, 1993; Patthey
et al., 1995). If the Ge adatoms were adsorbed at step edges, forming continuous areas
of Ge-covered Si that expand with increasing coverage, one would expect immediate
formation of a (2 x n ) structure corresponding to 1 ML coverage in those areas, which
would thus form a distinct phase coexisting with the bare-Si areas. Instead, STM stud-
ies (Mo and Lagally, I991b; Mo et al., 1991; Mo et al., 1992b; Kohler et al., 1992;
Iwawaki et al., 1992c; Croke et al., 1991; Butz and Kampers, 1992; Chen er al., 1994;
Wu et al., 1995; Wu, 1996) show that dimer vacancies and then ordered vacancy lines
gradually form uniformly on the entire surface upon Ge deposition. The intermixing
 2 FUNDAMENTAL OF FILMGROWTH
MECHANISMS 85

affects both the value, n , of the vacancy spacing and the shape of its confinement po-
tential. An experiment by Li et al. (unpublished) demonstrates that it is possible to
obtain different n values and distribution functions P,(n) for the same Ge coverage by
using different growth and annealing procedures to induce Si/Ge intermixing. STM
has, however, so far not been able to separate spectroscopically Si and Ge atoms in
close proximity, and thus the atomic-level composition of a mixed Si-Ge layer has as
yet not been determined. Such measurements are nevertheless potentially possible (Qin
and Lagally, 1998 unpublished).

d. Steps and Morphology at Higher Ge Coverage ( 2 ML and above)

The deposition of Ge on vicinal Si(OO1) (that is, a surface that contains steps cre-
ated by miscutting from a singular surface) significantly influences the monolayer step
morphology (Wu et al., 1995; Liu et al., 1997). With increasing coverage, the ini-
tially smooth SA step becomes rougher than the initially rough S g step, which actually
smoothens. This phenomenon can be used to extract the influence of Ge on step en-
ergies. On a strained surface, the step energy contains mainly two contributions. One
is positive and local, resulting from bond distortion along the step. The other is neg-
ative and nonlocal, resulting from strain relaxation associated with the creation of the
step. Both contributions decrease the step energy as the Ge concentration is increased
in the uppermost layers. First, because the strength of a Ge-Ge bond or a Ge-Si bond
is weaker than that of a Si-Si bond, an overall smaller step energy is expected as Si-Si
bonds are replaced by Ge-Ge and Ge-Si bonds. Second, at higher Ge coverage, the
surface is more strongly strained, and the elastic energy released by the creation of a
step is larger because it relaxes more strained bonds. Figure 21 shows the measured
dependence of the step energy of the two types of steps, S A and S B , on the Ge cover-
age. Both step types show a decrease in energy, although the effect differs in magnitude
(Wu et al., 1995; Liu et al., 1997). The measurements of Wu et al. (1995) also show
that the stress anisotropy of the surface reverses with Ge coverage from the anisotropy
exhibited by clean Si(OO1). The crossover point of zero stress anisotropy occurs at a
coverage of about 0.8 ML.
The change in step energies and the change in surface stress magnitude and anisotropy
with increasing Ge coverage both influence the further evolution of the morphology of
the growing Ge film. This evolution is shown for the first three monolayers of Ge in
Fig. 22 (Lagally, 1993). Beyond a coverage of -2 ML of Ge, the surface morphol-
ogy changes to a patchy layered “wedding cake” one. Apparently the increasing stress
can no longer be accommodated by increasing the density of vacancy lines. Increasing
stress anisotropy also contributes to the breakup of the 2-D layers. Steps are created.
These steps relieve stress (Wu, 1996; Liu et al., 1997). This patchy, quasi-2-D mor-
phology represents, at an atomic level, the layer-to-cluster transition predicted by the
Stranski-Krastanov model. Clearly the picture is not as simple as a clean, abrupt transi-
86 DONALD
E. SAVAGE,
FENGLIU, VOLKMAR
ZIELASEK,A N D MAX G. LAGALLY
2.5 1 I I I I I I I

0.5 I I I

0 0.5 1.o 1.5 2.0

FIG.2 1. Dependence of the energies of SA (circles) and SB (diamonds) steps. The energies are in units
of k T and given for a step of length 2a0, where a0 is the distance between true adjacent dimers along a dimer
row. (Reprinted with permission from Liu e t a / . , 1997.)

tion from a continuous 2-D layer to clusters. Clusters will form on this patchy template
with increasing Ge coverage, as described next.

2. NUCLEATIONOF COHERENT ‘HUT’-~SLANDS

For pure Ge deposited on Si(OOl), the strain relaxation mechanisms described so far
extend the thickness of the wetting layers up to 3 ML (Asai et al., 1985; Gossman et al.,
1985; Zinke-Allmang ef al., 1989; Mo eta]., 1990b; LeGoues et al., 1990; Eaglesham
and Cerullo, 1990; Mo, 1991; Mo and Lagally, 1991b; Tersoff, 1991; Lagally, 1993)
even though by the third ML it is not possible to make a complete 2-D layer. The
misfit strain is partially relaxed by the (2 x n ) reconstruction, by the creation and
morphological modulation of steps, and by breakup of large terraces into 2-D islands.
As one grows Ge on Si(OO1) beyond the first -3 monolayers, strain energy that can
not be released in that way will continue to build in the film and the growth mode
changes from 2-D to the formation of epitaxial 3-D structures. At a late stage these
3-D structures relax to the Ge (or SiGe if an alloy is deposited or if intermixing occurs
in the 3-D structures) lattice constant, with interface dislocations between the substrate
and the island. For clarity, we refer to the strained, coherent, epitaxial 3-D structures
as 3-D islands and the relaxed structures as clusters.
In 1990 Eaglesham and Cerullo showed with cross-sectional transmission electron
microscopy (CTEM) that Ge deposited to a thickness beyond 3 monolayers on Si(OO1)
initially formed 3-D islands that were coherent with the substrate, that is, without dislo-
cations. They proposed that the islands relieved strain by relaxing outward while at the
 2 FUNDAMENTAL
MECHANISMS
OF FILMGROWTH 87
Ge/Si(001) 450°C

FIG.22. Scanning tunneling micrographs (300 nmx300 nm) of the morphology of Ge layers on Si(OO1)
for coverages of 1.2, and 3 ML, respectively. The layers were deposited under identical conditions, chosen
so that the first monolayer grows in a step-flow mode. Further annealing does not change the morphology.
The surface becomes increasingly rough as the Ge coverage increases, a consequence of increasing stress
and the concomitant decrease in step creation energy. (Reprinted with permission from Lagally, 1993.)

same time compressing the underlying Si substrate. Also in 1990, Mo et ul. followed
the formation of small, faceted islands of Ge on Si(OO1) for deposits beyond 3 mono-
layers using STM. The 3-D island growth exhibited unusual behavior compared with
the usual Stranski-Krastanov growth mode, in that the island density rather than island
size increased dramatically with increased coverage. In addition, Mo et al. (1990b)
proposed that these islands were coherently strained and grew as an intermediate step
before the formation of large dislocated clusters at much higher coverages.
The 3-D islands have well-defined facets (Mo et al., 1990; Mo, 1991; Eaglesham
and Cerullo, 1990; Lutz et ul., 1994). In particular, STM has identified them as hut-
88 DONALDE. SAVAGE,
FENGLIU, VOLKMAR
ZIELASEK,
AND MAX G. LAGALLY

like with predominantly a prism shape (with canted ends), in some cases a four-sided
pyramid, with perfect { 105) facet planes on all four sides (Mo et al., 1990, Iwawaki
et al., 1991 and 1992b, Tomitori et al., 1994). Their principal axes are strictly aligned
along two orthogonal (100)directions. The [ 105) facets make a shallow (- 11”) angle
with the underlying Si(OO1) plane. An STM image of a Ge hut on Si(OO1) is shown in
Fig. 23.
The four facets in these so-called “hut” islands (Mo et al., 1990) appear always with
perfectly completed layers. This and the observation that the number density of the huts
increases rapidly while their size grows slowly as the Ge coverage is increased indicate
that the formation of huts is driven by the low surface free energy of { 105) facet planes.
Because hut clusters form preferentially at lower growth temperatures (< 500 “C) and
because they transform completely to macroscopic dislocated clusters after annealing at
higher temperatures (Mo et aZ., 1990), they are believed to be a metastable intermediate
phase leading eventually to the formation of these macroscopic dislocated clusters (Mo
et al., 1990; Mo, 1991; Eaglesham and Cerullo, 1990; LeGoues et al., 1990).
The kinetics of hut-island formation are still unclear. The concentration at low
growth temperatures of coherent hut islands is much higher than that of dislocated
macroscopic clusters, indicating that huts are much easier to nucleate, with a lower
formation barrier. Thus, hut islands define the onset of the transition from 2-D to 3-D
growth and provide an easier kinetic path for the ultimate formation of the equilibrium
rough surface consisting of dislocated macroscopic clusters. The small formation bar-
rier for huts can result from the low surface energy of their { 10.5) facets (see discussion
that follows). It is also suggested that (100) steps (running at 45” to the dimer row di-
rection), formed in the initial Ge layers may lower the hut formation barrier by acting
as nucleation sites (Mo et al., 1990b; Chen et al., 1995).
Stress relaxation via the formation of 3-D clusters, although the natural route accord-
ing to the Stranski-Krastanov mechanism, is an unconventional view in the general lit-

Frc. 2 3 . A single coherent “hut” island as “seen” by STM (perspective view). The base dimensions are
40 nrn x 28 nm and the height of the hut is 2.8 n m . (Reprinted with permission from Mo eral., 1990b.)
 2 FUNDAMENTAL OF FILMGROWTH
MECHANISMS 89

erature of heteroepitaxialfilm growth, which mostly discusses dislocation formation in

films grown, at sufficiently low temperature, beyond their critical thickness (discussed
in detail by Hull in Chapter 3). Theories show that under appropriate conditions, coher-
ent islands can be not only energetically more stable than both strained epitaxial films
and dislocated islands (Vanderbilt et al., 1991; Tersoff and Tromp, 1993; Tersoff and
LeGoues, 1994) but also kinetically favored over the nucleation of dislocations (Ter-
soff and LeGoues, 1994). The coherent islands allow the partial relaxation of strain
by elastic deformation at the expense of introducing extra surface area. In general,
the strain-relaxation energy is proportional to the volume of the island ( V ) , while the
increase of surface free energy scales with the surface area ( V213).For a 3-D island
of trapezoidal shape with a small facet angle, the total free energy can be expressed
as
E = aTV213 - bs2V (11)
where a and b are coefficients related to the island facet angle, V is the volume of
the island, E is the misfit, and r is surface free-energy anisotropy between the normal
orientation and the beveled edge (Tersoff and LeGoues, 1994). Clearly, for a suffi-
ciently large island (or an equivalent pit), formation of the island (or pit) is energeti-
cally favored. Kinetically, the thermal activation barrier is proportional to 1‘3/~-4 for
nucleating clusters, but scales as E - ~(LeGoues et al., 1993) for nucleating dislocations
(Tersoff and LeGoues, 1994). Thus, for large misfit (large E ) , formation of coherent
3-D islands is kinetically favored over dislocation formation, while for small misfit,
dislocation formation is favored.
The formation barrier also depends sensitively on surface free energy anisotropy
(r).The smaller the value of r, the lower the barrier. In addition to the 3-D hut is-
lands, larger coherent multifaceted 3-D islands with steeper facet angles (referred to
as “domes”) have been observed (Mo et al., 1990b; Medeiros-Ribeiro et al., 1998),
with a transformation from the huts to the domes with increasing coverage. It is likely
that the difference in surface energies between the strained Ge( 100) and (105) faces
is rather small, making the 3-D hut islands kinetically favorable over the larger mul-
tifaceted islands, which contain other faces with surface energies much higher than
that of the strained Ge(100) face. On the other hand, the larger 3-D dome islands are
energetically more stable than hut islands by incorporating faces with steeper facet an-
gles to allow more strain relaxation (Lutz et al., 1994; Tersoff and LeGoues, 1994).
The energetic argument is consistent with the observation that 3-D hut islands form
preferentially at lower temperature and transform to larger islands after annealing at
high temperature (Mo et al., 1990b). Also at higher temperature, r becomes gener-
ally smaller due to increased entropy; the islands will have multiple facets with less
well-defined overall shape and structure (Mo et al., 1990b). Finally, of course, dis-
location formation at the interface between 3-D dome islands and the substrate and
relaxation of the islands to the Ge or SiGe lattice constants occurs to provide ultimate
stress relief.
90 DONALDE. SAVAGE, FENG L I U , VOLKMAR ZIELASEK, AND MAXG. LAGALLY

In order to grow thicker smooth films, it is possible to delay or suppress 3-D island
formation by decreasing E (e.g., by lowering the concentration of Ge in a SiGe alloy
that is deposited), by decreasing r, for example, by using surfactants (Cope1 et al.,
1989), and/or by growing at low temperature. Surfactants may, however, also change
surface diffusion, a kinetic parameter.
The strain relaxation in 3-D hut islands has been studied by x-ray diffraction
(Steinfort et al., 1996). Profiles through crystal truncation rods show side peaks around
the central rod originating from scattering from the { 105) hut facets. The expansion of
the lattice parameter in the huts produces an asymmetry in the intensity of these side
peaks. By modeling the variation of the lattice constant simply as increasing quadrat-
ically with the height of the hut islands and simulating the diffraction profiles, a good
agreement with the experimental results is obtained assuming full relaxation (to the Ge
lattice constant) at the tops of the huts and a relaxation (from the Si lattice constant)
of 0.5% at their bottom. Knowledge of the cluster size is crucial for this evaluation.
The model, so far, does not consider the strain field in the Si substrate (Eaglesham and
Cerullo, 1990).
Recently, there has developed an intense interest (Shchukin et al., 1995; Tersoff
et al., 1996; Steinfort et al., 1996; Liu and Lagally, 1997b) in the { 105)-faceted hut
islands (Mo et al., 1990b) because of their potential applications as quantum dots (La-
gally, 1998). To obtain uniform electrical and optical properties in such quantum dot
arrays, it is necessary to develop ways to control the size and size distribution of coher-
ent 3-D islands. For example, one can attempt to optimize parameters that influence
the island growth hnetics, such as deposition rate and substrate temperature, in order
to narrow the 3-D island size distribution. We briefly describe approaches for such op-
timization in Section IV.2. Alternatively, one can grow 3-D islands on lithographically
patterned substrates. While such an approach gives a well-ordered array, the density is
then limited to the resolution of the lithography.

IV. SiGe Alloy Films

Silicon and germanium are miscible over the entire binary alloy composition range,
showing a nearly ideal solid solution behavior. Because strain can be tuned by changing
alloy composition, one expects that the growth of Sil-,Ge, alloy on Si can act as
model system to understand the influence of strain on growth. In reality, however,
alloy growth is complicated by the presence of surfaces. For example, germanium is
well known to segregate to the surfaces of Si and Sil-,Ge, alloys because dangling
Ge bonds cost less energy than dangling Si bonds, lowering the surface free energy. In
addition, in the presence of a nonuniform surface strain such as produced by clustering
(roughening), there is a driving force for lateral concentration gradients (Guyer and
Voorhees, 1995). Thus, Ge should preferentially incorporate in regions in which strain
has been relaxed while Si will incorporate preferentially in regions that are still lattice
 2 FUNDAMENTAL OF FILMGROWTH
MECHANISMS 91

matched to the substrate. Alloy concentration gradients were confirmed experimentally

by Walther et al. in 1997. In addition, during the growth of SiGe alloy in nearly equal
concentrations, an ordered phase will form that does not appear in the bulk alloy. The
ordering occurs by phase separation of Ge and Si into alternate bilayer { 111) planes.
This ordering is discussed by Bean in Chapter 1.

In general, phenomenology similar to that found in the growth of pure Ge on Si(OO1)

is observed for the growth of SiGe alloys. During the initial growth of the alloy a (2 x n )
reconstruction forms to relieve the surface stress generated as approximately 1 mono-
layer of Ge segregates to the surface (Butz and Kampers, 1992).’ As the coverage
is increased, monolayer-height steps bunch, relieving additional stress (Teichert et al.,
1996). If the film is grown thick enough, stress relaxation occurs through the formation
of coherent faceted 3-D islands or through the formation of misfit dislocations. Ulti-
mately, dislocation formation is the dominant stress relaxation mechanism. Dislocation
nucleation can be promoted on “rough” surfaces by stress concentration in cusps where
nondislocated 3-D islands initially touch (Jesson et al., 1995).

The stress state and, hence, thermodynamics of the heteroepitaxial system can be
modified by growing SiGe alloys of different compositions. Under given growth con-
ditions (temperature, growth rate, sample orientation and miscut, etc.), the mode of
stress relaxation depends critically on misfit strain, that is, the alloy composition dur-
ing the growth. As discussed in the previous section, the activation barriers for different
modes of strain relaxation (nucleation of a dislocation or a coherent faceted 3-D island)
scale differently with misfit strain ( F ) . The competing paths for stress relaxation have
been confirmed by growth of SiGe alloys on Si(OO1) (Tersoff and LeGoues, 1994). At
low Ge concentration with misfits below 1%,dislocations form before noticeable sur-
face roughening, whereas at high Ge concentration coherent 3-D islands appear before
dislocations form. Growth temperature will also play a role; alloy films at lower tem-
perature will remain smooth until eventual dislocation formation for higher states of
strain (Tersoff and LeGoues, 1994).

Understanding the conditions under which dislocation formation relieves

strain before clustering occurs is crucial in the growth of relaxed SiGe alloy layers
with a low dislocation density at the film surface. The presence of clusters before the
formation of dislocations can alter severely the nucleation mechanism of dislocations,
yielding an unacceptably high dislocation density (Tersoff and LeGoues, 1994; Jesson
et aE., 1995).

‘Surface segregation is suppressed if hydrogen ties up surface dangling bonds. Chemical vapor deposition
from H-containing precursors will leave the surface H terminated at temperatures at which H desorption from
the surface is the rate limiting step.
92 DONALDE. SAVAGE,
FENGLIU,VOLKMAR
ZIELASEK, A N D MAXG. LAGALLY

AND COHERENT 3-D ISLAND FORMATION

1. ROUGHENING IN ALLOYS

The morphologies of Sil-,Ge, alloy films are found to be similar to those observed
for Ge on Si(OO1) for a wide range of Ge concentrations (x L 0.15). They have been
obtained with a variety of deposition techniques including MBE, CVD, gas-source
MBE, and solid-phase epitaxy. While the general features are similar, there are differ-
ences that raise questions about the mechanism of the morphological transformation.
The SiGe films deposited using gas-source MBE by Cullis et al. in 1992 were de-
scribed as having ripples. The ripples were observed to extend along [ 1001 and [OlO]
directions with slopes -11" from the (001) substrate. In cross-sectional TEM images
the waviness appeared somewhat rounded; however, the values of angle and the di-
rections the ripples extend are consistent with those of the (105) faceted coherent 3-D
islands observed in pure-Ge growth. Observations of ripple spacing over a wide alloy
concentration range (Pidduck et al., 1993) were fitted well with continuum elastic-
ity models of thermodynamic strain relief (Asaro and Tiller, 1972; Grinfield, 1986;
Srolovitz, 1989) that predict that strained films are unstable to roughening. In such
models the average ripple amplitude ( t ) and wavelength (A) are related to misfit strain
( E O ) and are described with the inequality

where Y is Young's modulus and y is the surface free energy per unit area (Pidduck
et al., 1993). A plot of t / A 2 as a function x2 where x is the percent Ge concentration
in the alloy, yielded a straight line for x ranging from 0.15 to 0.27, in good agreement
with the model.
Jesson et al. (1995) deposited alloy films at room temperature and subsequently
annealed them at elevated temperatures to allow the film morphology to relax towards
local equilibrium. Ge concentrations of 50% in the alloy film were used. The authors
observed isolated pyramidal 3-D islands with { 1051facets and under certain conditions
pyramid-shaped pits. The authors concluded that their observation of isolated faceted
3-D islands was evidence that they arose through a nucleation process, indicating that
3-D island formation is an activated process.
These two very different views of how similar-looking morphologies arise show the
difficulty in attempting to understand morphology evolution by looking at the final
stage of a process. While the formation of faceted 3-D islands indicates an activated
process, the question remains as to what is controlling the separation of islands or
ripples. For alloys with lower Ge concentrations it is quite possible that kinetic rough-
ening may be enhanced by strain relaxation, building in a preferred separation between
mounds or ripples. At a later stage in the growth these could transform into faceted
islands after a critical slope is reached. In higher-Ge-concentration alloys, it appears
that strain induced in the substrate causes mounds or islands to repel and so nucleate
preferentially away from existing islands.
 2 FUNDAMENTAL
MECHANISMS
OF FILMGROWTH 93

Understanding roughening or islanding in alloy films is additionally complicated by

lateral as well as vertical concentration gradients (Guyer and Voorhees, 1995; Walther
et al., 1997). Any full description of the mechanism must include these effects as well.

2 . MULTILAYER
GROWTH

The ability to grow strained-layer superlattices of {SiGe alloy/Si} on Si without dis-

location formation was demonstrated long ago (Bean et al., 1984). To prevent dislo-
cation formation, the volume strain energy must be kept below a critical value or at
least low enough so that kinetics limit the formation of dislocations. In the first case,
the films are stable and dislocations will not form. In the second case, the films are
metastable with respect to dislocation formation.
From the simple thermodynamic arguments about growth modes presented in Sec-
tion 1.1, one would expect that it would be impossible to grow a strained-layer su-
perlattice. If SiGe alloy initially wets Si, it is expected that Si will not wet the SiGe
alloy film. It must be remembered, however, that the arguments for equilibrium growth
modes are idealized and contain simplifying assumptions. One factor that helps Si to
grow smoothly on a strained alloy substrate is that at least one monolayer of Ge will
segregate, reducing the surface free energy of the Si film and allowing it to wet more
readily. In films deposited by CVD, for which Ge segregation is suppressed, surface
hydrogen reduces the surface energy of the Si film, again helping it to wet the SiGe
alloy layer.

a. Step Bunching in Multilayers

Headrick and Baribeau (1993), using low-angle diffuse x-ray scattering, demon-
strated that interfaces in SiGe/Si superlattices exhibit a 1-dimensional-grating like mor-
phology parallel to the substrate surface that is correlated vertically through the su-
perlattice. The grating-like behavior was attributed to replication of substrate steps.
Detailed x-ray scattering measurements by Phang et al. (1994) varying the alloy com-
position confirmed the presence of the grating-like interfacial morphology; the authors
concluded, however, that the morphology arose from step bunching during growth of
the alloy layers, with the buried interfaces having a “sawtooth”-like morphology. By
determining the substrate vicinality with high-angle x-ray diffraction they showed that
no new steps were created to make the interface “sawtooth,” but instead, steps move
alternately closer together and farther apart, that is, they bunch. For a fixed alloy layer
thickness of 25 A and a Si spacer layer of -100 A, step bunching was not observed
for a 30% Ge alloy concentration, but was observed for alloy concentrations of 50%
and above, suggesting that strain is causing the bunching. Atomic-force microscopy
images of the outer-surface roughness were consistent with the description of the mor-
phology derived from the scattering measurements. A model developed by Tersoff
94 DONALD
E. SAVAGE, F E N G LIU,VOLKMAR ZIELASEK, AND M A XG. LAGALLY

et al. in 1995 explained many of these observations; nevertheless there are still open
questions. The driving force for step bunching in a strained overlayer occurs through
long-range step-step interactions (Tersoff et al., 1995). If silicon is deposited onto a
step-bunched SiGe alloy layer, the steps should become more uniformly spaced with
increasing Si film thickness, that is, steps should debunch, because the driving force
for bunching is removed. Phang et al. (1994) saw little debunching during the growth
of 100 8, Si spacer layers. The mechanism for vertical correlation of step bunches is
also not fully understood. Phang et al. (1994) suggested that long-range strain fields
propagating through the spacer layer caused bunches to line up, but made no calcu-
lation. An alternative possibility is that step bunches have vertical correlation simply
because they grow in step-bunch flow and that the vertical correlation is a geometric
effect dependent only on bilayer thickness and the height of the bunch.

6. Self-organization of 3 - 0 Islands in Multilayers

When alloy films that exhibit coherent 3-D islands are grown in a superlattice with
silicon spacer layers of sufficient thickness to smooth out the roughness introduced by
the islands, experimental observations show a remarkable improvement in the organiza-
tion of the islands in the top layer (Liu and Lagally, 1997b). The islands become more
equiaxed, exhibit a narrower size distribution, and begin to align in an ordered square
array, narrowing as well their separation distribution (Teichert et al., 1996). Figure 24
shows AFM images comparing a single 25 A thick, 75% Ge alloy layer and the top
alloy layer of a superlattice that consists of 40 such layers separated by 39 1008, thick
Si spacer layers. In addition to the increased ordering of the size, shape, and position
of the coherent 3-D islands, the average size has approximately doubled. The AFM
images after the completion of a Si spacer layer do not show a remanent morphology
from the underlying islands. The authors postulated that the organization was caused
by an enhanced nucleation of islands on top of buried islands, which occurs because of
nonuniform strain propagated through the spacer layer. The observation of 3-D-island
correlation from layer to layer in a superlattice has been made in III-V (Xie et al., 1995)
and in SiGe/Si/SiGe structures (Rahmati et al., 1996) with CTEM. Recent CTEM mea-
surements on SiGe/Si superlattices show the correlation and, additionally, give insight
into the mechanism of organization and embedding of the 3-D islands (Mateeva et al.,
1997).

V. Summary

In this chapter we have explored the fundamental mechanisms of the growth, on

the atomic scale, of Si on Si and of Ge on Si. For Si on Si(OO1) quantitative analysis
of STM measurements of morphological features, such as 2-D islands and monatomic
 2 FUNDAMENTAL MECHANISMS
OF FILMGROWTH 95

20 I (2.5 am Si,&e,,, i 10 am Si)an Sl(OO1)

FIG. 24. Three-dimensional A F M images of coherent hut island distributions illustrating the effect of
multilayering on narrowing the size and spacing distribution. (a) Single layer: 3-D view of a 2.5 nm thick
film of Si0.25Ge0.75 deposited on Si(OO1). (b) Twenty bilayers of 2.5 nm Si0.25Ge0.75 and 10 nm Si, grown
on Si(OO1): the islands have become square pyramids, very well arranged and uniform in size, and about
twice as large as in (a). (Reprinted with permission from Teichert er al., 1996.)

steps, makes possible the determination of fundamental properties such as the diffusion
coefficient of adatoms, the incorporation mechanisms of adatoms into steps or islands,
and the energetics of the atomic steps themselves. The growth of Ge on Si(OO1) is com-
plicated by lattice-mismatch-induced strain. Measurements at initial stages of growth
(submonolayer coverage) show phenomena quite similar to those in Si homoepitaxy,
that is, similar diffusion, diffusion anisotropy, and incorporation into steps or islands.
At later stages in the growth, new phenomena take control: the change in the surface
reconstruction to (2 x n) for strain relief, the breaking up of the surface into 2-D patches
at higher Ge coverage and, beyond a critical thickness, the formation of coherent 3-D
islands. In the growth of 3-D SiGe alloy films, additional phenomena such as lat-
eral and vertical ordering of 3-D islands deposited in superlattices occur. While much
is known about the fundamental mechanisms of growth in both SUSi and GeISi, open
questions remain. In particular the transition from nucleation to subsequent growth, the
influence of strain on submonolayer structure and dynamics, the mechanisms by which
coherently strained 3-D islands grow and order, and the morphological transitions that
occur when 3-D islands are buried in a matrix material are not fully understood and are
topics of active research.
96 DONALD E. SAVAGE, FENGLIU,V O L K M A R Z I E L A S E K , AND MAXG . LAGALLY

ACKNOWLEDGMENTS

The preparation of this chapter was in part supported by NSF and by ONR. Work
described herein that was performed by the authors was supported by NSF, ONR, and
AFOSR.

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 SEMICONDUCTORS AND SEMIMETALS.VOL. 56

CHAPTER3

Misfit Strain and Accommodation in SiGe Heterostructures

R . Hull
DEPARTMENT
OF MATERIALS
SCIENCE
AND ENGINEERING
OF VIRGINIA
UNIVERSITY
CHARLOTTESVILLE.
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I . ORIGINOF STRAIN IN HETEROEPITAXY. . . . . . . . . . . . . . . . . . . . . . . . . . . 102

11. ACCOMMODATION OF S T R A I N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
1. Elastic Distortion of Atomic Bonds in the Epitaxial Layer . . . . . . . . . . . . . . . . . 103
2. Roughening of the Epitaxial Layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3. Interdifision across the Epilayer/Substrate Interface . . . . . . . . . . . . . . . . . . . . 105
4 . Plastic Relaxation ofstrain by Misfit Dislocations . . . . . . . . . . . . . . . . . . . . . 107
5. Competition Between Different Strain Relief Mechanisms . . . . . . . . . . . . . . . . . . 108
111. REVIEWOF BASICDISLOCATION THEORY. . . . . . . . . . . . . . . . . . . . . . . . . . 109
1. Definition and Geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
2. Energy of Dislocations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3. Forces on Dislocations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4. GlideandClimb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
5. Geometry of Interfacial Misfit Dislocation Arrays . . . . . . . . . . . . . . . . . . . . . . 113
6. Motion of Dislocations: Kinks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
7. Dislocation Dissociation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
8. Partial versus Total Misfit Dislocations . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
IV. EXCESSS T R E S S , EQUILIBRIUM S T R A I N A N D CRITICAL THICKNESS ............ 120
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
2. Matthews-Blakeslee Framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
3. Accuracy of the MB Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4. Other Critical Thickness Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
5. Extension to Partial Misfit Dislocations . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
6. Models for Critical Thickness in Multilayer Structures . . . . . . . . . . . . . . . . . . . 128
V. METASTABILITY A N D MISFITDISLOCATION KINETICS. . . . . . . . . . . . . . . . . . . 131
1. Basic Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
2. Misfit Dislocation Nucleation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
3. Misfit Dislocation Propagation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
4 . Misfit Dislocation Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5. Kinetic Modeling of Strain Relaxation by Misfit Dislocations . . . . . . . . . . . . . . . . 152

A l l irl.rr .c.O.-.A.”.L.. .. -”., ...?-.--.-

Copynghr @ 1999 by Academic Press
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102 R. HULL

VI. MISFIT A N D THREADING DISLOCATION REDUCTION TECHNIQUES. . . . . . . . . . . . 155

I . Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
2. BufferLayers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
3. Threading Dislocation Filtering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
VII. CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
REFERENCES .......................................... 164

I. Origin of Strain in Heteroepitaxy

The fundamental origins of strain in heteroepitaxy are from two sources: (i) The
difference in lattice parameter between epitaxial layer(s) and substrate. (ii) Differential
thermal expansion coefficients between epitaxial layer(s) and substrate.
Consider a thin epitaxial layer with free lattice parameter a, deposited upon an in-
finite substrate with lattice parameter n,. If the lattice parameter difference between
substrate and epitaxial layer is accommodated entirely elastically, as in Fig. l(a), and
assuming for the moment that the thermal expansion coefficients of the two materials
are equal, then the elastic strain in the epitaxial layer is given by’:

For a, > a,, the strain in the epitaxial layer is compressive and e is positive; for a, < a,
the strain in the epitaxial layer is tensile and E is negative.
The lattice constants of Si and Ge at room temperature are 0.5431 and 0.5658 nm,
respectively; Ge,Sil-, lattice parameters, a@), have been tabulated by Dismukes et
al. (1964). They observed slight deviations from Vegard’s law (Le., slight deviations
+
from the relationship a(x) = a ~ i X ( U G ~- asi)). If this deviation from linearity is

-
defined by A = a(x) - [asi +X(UG, - asi) ] , maximum values of A -0.007 nm were
found at x 0.5. A parabolic fitting to the data of Dismukes et al. at room temperature
-
(Herzog, 1995) yields

a ( x ) = 0.5431 + 0.01992~+ 0 . 0 0 2 7 3 3 ~nm~ (2)

In practice, relatively little error (of order 0.1% error in a(x) and 7% error in ~ ( x )is)
involved if the room temperature value of a(x) is assumed to follow the linear form

a(x)= 0.5431 + 0.0227~nm (3)

‘Note that we are assuming an infinite substrate thickness here, such that all lattice mismatch strain is
accommodated by the epitaxial layer. For substrate thicknesses that are not effectively infinite with respect
to the epitaxial layer, strain will be partitioned between substrate and epitaxial layer. In practice, typical Si
substrate thicknesses are several hundred microns, which is effectively infinite with respect to any reasonable
epilayer thickness.
 3 MISFIT STRAINAND ACCOMMODATION 103

whence, from Eq. (1)

EO(X) = 0.0409~ (4)
The simplified relations of Eqs. (3) and (4) will be used in the remainder of this chapter.
In general, materials have temperature-dependent lattice parameters via thermal ex-
pansion coefficients (which are themselves temperature dependent). The linear thermal
expansion coefficients, a ( x , T ) have been measured as functions of temperature for Si,
Ge and Ge,Sil-, alloys (Wang and Zheng, 1995). The values of a(x,T ) are some-
what nonlinear with Ge fraction and temperature, but for the range 0-800 "C, within
accuracies of order 10%

asi +
= (2.7 0.0026T) x low6
a~~ = (5.9+0.0021T) x
Linear interpolation for intermediate Ge, Si 1 compositions will generally overesti-
mate a ( x , T ) , especially for higher x and T . Nevertheless a linear interpolation of
Eqs. 5(a) and (b) will yield estimates for a @ ,T ) which are accurate to order 30%
a ( x , T ) = [(2.7 + 3 . 2 ~ +) (0.0026 - 0.0005x)TI x (6)
The thermal mismatch stress, E T S , induced as a function of change in temperature,
A T , with respect to a substrate with thermal expansion coefficient, asub(T),is thus

For example, considering a Geo.2Sio.s layer grown upon a Si substrate, at 550 O C

(a typical temperature for molecular beam epitaxy, MBE, growth), we have E T S
2x
-
that is, just a few percent of the lattice mismatch strain EO. Thermal m i s -
match strains are thus relatively small compared to lattice mismatch strains. They can,
however, become important at large epitaxial layer thicknesses where lattice mismatch
strain is largely accommodated by misfit dislocation generation at the crystal growth
temperature, and thermal stresses are induced during cooling to room temperature, as
will be discussed later in this chapter.

11. Accommodation of Strain

In strained layer epitaxy, the lattice parameter difference between a thin epitaxial
layer and an epitaxial substrate can be accommodated by several mechanisms.

1. ELASTICDISTORTION
OF ATOMICBONDS I N THE EPITAXIAL
LAYER

This configuration is shown in Fig. l(a). The in-plane lattice parameter of the epi-
taxial layer uep is distorted to that of the substrate a,. The epilayer lattice parameter
104 R. HULL

a b C

FIG. 1. Schematic illustration of mechanisms for accommodation of lattice mismatch strain: (a) elastic
distortion of epitaxial layer; (b) roughening of epitaxial layer; (c) interdiffusion; (d) plastic relaxation via
misfit dislocations.

perpendicular to the interface, sen, then relaxes along the interface normal, to produce
a tetragonal distortion of the unit cell (recall that in their unconstrained states, Si, Ge
and Ge,Sil-, have diamond cubic lattices). The magnitude of the tetragonal distortion
is given by
aen/aep ‘V + +
1 ~ ( 1 ~)/(l - v) (8 1
Here, E is the epilayer strain (which may have relaxed from 60 if any of the relaxation
mechanisms in Sections 11.2, 3, and 4 have operated), and u is the Poisson ratio of
the epilayer material. For an elastically isotropic cubic crystal, u is derived from the
appropriate elastic constants by the relation u = c12/(c11 ~ 1 2 ) Values
. +of c1 1 and c12
(Landholt-Bornstein, 1982) for Ge and Si then yield u = 0.273 and 0.277 for Ge and
Si, respectively. The generally quoted value for u in Ge,Sil-, in the literature is 0.28,
which we shall use henceforth.
The sense of the tetragonal distortion in Eq. (8) is positive (aefl> aep)for a, > a,,
that is, the epilayer lattice relaxes outwards along the interface normal. For a, < u , ~ ,
the tetragonal distortion is negative (aen < a,), and the epilayer relaxes inwards along
the interface normal.
The tetragonally distorted epitaxial layer stores an enormous elastic strain energy (of
the order 2 x 107Jm-3 for a lattice mismatch strain of 0.01). The stored elastic strain
energy in the epitaxial layer, per unit interfacial area, is given by continuum elasticity
theory as2
E,i = 2 G 4 ( 1 + u)h/(l - u ) (9)
Here h is the epilayer thickness and G is the epilayer shear modulus. As Si and Ge
are relatively anisotropic elastic materials, average shear moduli are generally used
2Equation (9) assumes that all strain accommodation is elastic. If any of the lattice mismatch strain
is relaxed by the mechanisms discussed in Sections II.2., 3., and 4.. then E, should be replaced by F , the
remaining elastic strain.
 3 MISFIT STRAIN AND ACCOMMODATION 105

in strained layer theory, derived by averaging over the appropriate elastic constants,
or elastic compliances, denoted, respectively, by the Voigt and Reuss average moduli
(Hirth and Lothe, 1982). The Voigt and Reuss methods give for G in Si, Ge values of
6533 GPa and 68,56 GPa, respectively. This use of isotropic elasticity theory com-
bined with these average elastic moduli is a significant approximation, compared to a
rigorous application of anisotropic theory. However, the mathematical complexity in
calculating the strain fields of dislocations in anisotropic materials is daunting (Hirth
and Lothe, 1982), so less precise isotropic theory is generally used. This can lead to
errors of the order 20% in subsequent calculations.

2. OF THE EPITAXIAL
ROUGHENING LAYER

As shown schematically in Fig. l(b), roughening of the epitaxial layer surface allows
atomic bonds near the surface to relax towards their equilibrium length and orientation.
The basic energetic competition in this process is between the surface energy of the
epitaxial layer (representing an increase in the system energy as surface roughening
increases the total surface area, and hence surface energy, of the epitaxial layer) and
elastic energy (which is reduced by roughening, therefore representing a decrease in
the system energy). This mechanism will not be treated further in this chapter, as it is
dealt with in detail in the chapter by Savage in this volume.

3. INTERDIFFUSION ACROSS THE EPILAYER/~UBSTRATE

INTERFACE

As the areal strain energy density, given by E q . (9), varies as E:, lowering of the aver-
age strain by interdiffusion will reduce the elastic strain energy stored in a heteroepitax-
ial system. For example, consider the highly simplified configuration where an initially
abrupt interface between a Ge,Sil-, epilayer of thickness h nm and an infinite Si sub-
strate undergoes an interdiffusionalprocess, such that the Ge,Sil -, layer redistributes
+ +
itself into a layer of thickness h h~ nm, and a uniform Ge fraction of x h / ( h h ~ ) .
+
The initial areal energy density will reduce from k'x2h to k'x2h2/(h h ~ )where , k'
is the relevant constant of proportionality from Eq. (9). In the limit that h~ tends to
infinity, the strain energy tends to zero. Of course, the abrupt diffusion profile implied
by this theoretical experiment is highly unphysical, but the principle of strain energy
reduction via interdiffusion will hold for any diffusion profile with a monotonic decay
of Ge fraction.
Interdiffusion at Ge,Sil-,/Si and Ge/Si interfaces has been studied by several au-
thors. Early studies by Fiory et al. (1985) established the presence of significant inter-
diffusion at temperaturesof 800 "C and higher in a 10 nm Si/14 nm Ge0.24Si0.76/Si(1~)
structure via HeC ion channeling and backscattering studies. As this structure is be-
low the critical thickness criterion for relaxation of strain via formation of a misfit
dislocation array, relaxation of strain in this structure was determined to occur via in-
106 R. HULL

FIG. 2. Measurements of interdiffusion at Ge,Sil -,/Si interfaces: Arrhenius plot of the diffusion
coefficient of Ge in strained Si/Ge,Sil-,/Si structures for x = 0.07 (circles), x = 0.16 (squares); x = 0.33
(triangles), derived from diffusion in the tails of the diffusion profile (filled symbols) and at the peak of the
diffusion profile (open symbols). Solid line is an extrapolation of Ge tracer diffusion in bulk Si (McVay
and Ducharme, 1974). Reprinted from Thin Solid Films 183, G.F.A. Van de Walle, L.J. Van Ijzendoorn.
A.A. Van Gorkum, R.A. Van den Heuvel, A.M.L. Theunissed and D.J. Gravestein, “Germanium Diflususion
and Strain Relaxation in Si/Sil-,Ge,/Si Structures,” pgs. 183-190. 1990, with permission from Elsevier
Science, The Boulevard, Langford Lane, Kidlington OX5 IGB, UK.

terdiffusion. A more extensive study by Van de Walle et al. (1990) derived diffusion
coefficients for Ge in Si/GexSil-,/Si structures. A summary of their data is shown
in Fig. 2. The measured diffusion constant appears to be relatively independent of Ge
fraction in the range x = 0.07-0.33. This is in contrast to earlier measurements of the
diffusion coefficient measured for Ge in large-grain polycrystalline Ge, Si 1--x material

up to a maximum at x -
(McVay and DuCharme, 1974), where diffusion was noted to increase rapidly with x
0.8. Van de Walle et al. observed that diffusion in the tails
of the Ge concentration profiles correlated well with measured diffusion coefficients
for Ge diffusion in bulk Si, whereas measured diffusion constants in the peaks of the
Ge concentration were an order of magnitude greater. The measured diffusion con-

-
stants suggest that diffusion lengths of the order of one monolayer at 800°C would
take 1 hr in the Ge tail. Thus strain relaxation by interdiffusion is not expected to be
a significant factor during growth of relatively dilute (i.e., low Ge fraction) and thick
 3 MISFITSTRAIN AND ACCOMMODATION 107

(compared to one monolayer) Ge,Sil-, layers on Si substrates, for techniques such

as MBE and ultrahigh-vacuum chemical vapor deposition (UHV-CVD) where growth
temperatures are typically less than 800 "C.
A configuration where interdiffusion can represent a significant strain relaxation
mechanism, even at typical MBE growth temperatures, are the monolayer-scale Ge-
Si superlattices which at one time were widely fabricated in pursuit of efficient optical
emission (see chapters by Cerdeira, Campbell, and Shaw and Jaros in this volume).
Chang et al. (1990) reported diffusion coefficients in monolayer-scale Ge-Si superlat-
tices that were consistent with the diffusion constants measured for Ge in pure Si, and
by Van de Walle ef al. for tail diffusion. Baribeau (1993) and Lockwood et al. (1992)
studied similar systems and concluded that for atomically abrupt interfaces, diffusion
was indeed of the order of that associated with Ge diffusion in bulk Si, but that existing
intermixing or segregation at the interfaces could dramatically enhance diffusion, due
to strong increase in Ge diffusivity with increasing x in Ge, Sil Under such condi-
tions, substantial diffusion (enough to homogenize a multilayer structure consisting of
alternating layers of 4.5 monolayers of Si and 3.5 monolayers of Ge) was observed for
a 20-s anneal at 700 "C.

4. PLASTIC OF STRAIN B Y MISFITDISLOCATIONS

RELAXATION

As shown schematically in Fig. l(d), another mechanism for strain relief is via gen-
eration of an interfacial dislocation array, known as a misfit dislocation array, which
allows the epitaxial layer to relax towards its bulk lattice parameter. This is a very
prevalent mechanism for strain relief in Ge, Si 1-,-based heterostructures. It is exper-
imentally observed, and theoretically predicted, that the misfit dislocation array forms
only in epitaxial layers thicker than a minimum thickness, known as the critical thick-
ness h,.
The interfacial dislocation array relaxes elastic strain energy by allowing the aver-
age lattice parameter of the epitaxial layer to relax towards its unconstrained value.
However, the dislocations have a self-energy &is, manifested by the stress field they
produce in the surrounding crystal. Thus the energy of a heteroepitaxial system con-
taining a total line length L of interfacial dislocation is (ignoring surface roughening
and interdiffusion)
Etot = Eel(L, h ) +Edis(L, h ) (10)
We know from Eq. (9) that E,) varies linearly with h . As each unit length of dislo-
cation will reduce a finite amount of strain in the epitaxial layer (this will be discussed
more fully in the next section of this chapter), we can also deduce that F decreases
linearly with L . The energy of the dislocation array will increase with L , and at rela-
tively low values of L (specifically such that the average separation of the interfacial
dislocations is less than the epilayer thickness), this increase will be linear as will be
discussed in Section 111 of this chapter. At higher dislocation densities (i.e., greater L ) ,
the increase will no longer be linear, due to the importance of dislocation interactions.
108 R. HULL

Finally, as we shall also see in Section 111, the self-energy of an individual dislocation
varies logarithmically with its distance from a free surface. Thus for low dislocation
densities
Etot= k l h ( ~ o- +
k3L ln(k4h) (11)
In this equation kl through k4 are constants whose magnitudes will be derived in
later sections of this chapter. Comparing Eq. (1 1) to Eq. (9), the change in total energy
as a result of the introduction of the dislocation array is

AE,,, = k3L ln(k4h) + klk?jhL2 - 2 k l k 2 h ~ ~ L (12)

For h > hc, we would of course expect that AEtot < 0, namely, that introduction
of the dislocation array lowers the energy of the system. For h < h,, A EtOt > 0, that
is, the dislocation array is not energetically favored. The critical thickness is found by
finding that value of h for which the change in total energy A Et,,, for introduction of a
single misjit dislocation is zero. Thus we take the limit of Eq. (12) as L --f 0, allowing
solution for h = h,
h, = k3 ln(k4hc)/2klk2~o (13)
For a given epitaxial layer thickness h > h, and residual lattice-mismatch strain E =
(eo - k2L), the minimum energy configuration will correspond to (GEtot/GL)h,s= 0,
allowing solution for the equilibrium value of L from Eq. 12:3

k3 ln(k4h) = 2hklkz[eo - k2L] (14)

Before a more rigorous development of models for the critical thickness and equi-
librium misfit dislocation densities (i.e., evaluation of the constants ki in the foregoing
equations), we will briefly review the relevant aspects of dislocation theory.

5 . COMPETITION
BETWEENDIFFERENT
STRAINRELIEFMECHANISMS

Of the strain relief mechanisms discussed in the preceding four sections, interdiffu-
sion is significant only at growth or annealing temperaturehime cycles of order 800 "C/
1 hr or greater (except for the relatively specialized configuration of monolayer scale
Si:Ge superlattice structures). Thus, interdiffusion is not a significant mechanism at
the growth temperatures typically used during MBE or UHV-CVD growth, although it
could conceivably be significant during high-temperature post-growth processing (e.g.,
implant activation or oxidation processes).
Relaxation via surface roughening can occur for any epitaxial layer thickness (see
chapter by Savage in this volume). Strain relaxation by misfit dislocations occurs only
for layer thicknesses greater than the critical thickness. Both processes are kinetically
3Note that substitution of L = 0 into Eq. (14) reduces this expression to Eq. (13) as expected.
 3 MISFIT S T R A I N AND ACCOMMODATION 109

limited, either by surface diffusion lengths in the case of surface roughening, or by

nucleatiodpropagation barriers in the case of misfit dislocations. These two processes
may be competitive, such that the strain relaxed by surface roughening (which may
occur before a sufficient epilayer has been deposited for misfit dislocations to be ener-
getically favored) reduces or eliminates the driving force for dislocation introduction,
or they may be cooperative, as in the observed reduction of energetic barriers for dislo-
cation nucleation associated with surface morphology (Cullis et al., 1994; Jesson et al.,
1993, 1995), and surface morphology induced by misfit dislocations (Hsu et al., 1994;
Fitzgerald and Samavedam, 1997). Tersoff and LeGoues (1994) modeled the introduc-
tion of misfit dislocations into planar epilayers, and into surface islands or pits. They
demonstrated that if the energy barrier is essentially zero for dislocation introduction
into islands or pits (this should be regarded very much as an approximation, although it
is reasonable that the activation barrier is greatly reduced with respect to a planar sur-
face), a temperature dependent critical strain (of order 0.01) exists above which strain
relief is dominated by dislocation injection into roughened surfaces, and below which
dislocation injection into planar surfaces is favored. This is consistent with general
experimental observations that roughening of Ge,Sil-, epilayers is greater for higher
Ge concentrations and temperatures. The detailed balance between roughening and
dislocation generation, however, is still a topic of active experimental research and
simulation.

111. Review of Basic Dislocation Theory

We now briefly review the salient properties of dislocations pertinent to understand-

ing their role in relieving lattice mismatch. For a full description of dislocation theory,
the reader is referred to the volume by Hirth and Lothe (1982).

1. DEFINITIONAND GEOMETRY

A perfect or total dislocation is a line defect bounding a slipped region of crystal. A

circuit drawn round atoms enclosing this line will have a closure failure as illustrated
in Fig. 3(a); this closure failure is known as the Burgers vector of the dislocation. For a
perfect or total dislocation, the Burgers vector is a lattice translation vector. Although
the line direction of a given dislocation may vary arbitrarily, its Burgers vector is con-
~ t a n t .A~ total dislocation cannot end within the bulk of a crystal-it must terminate
4Apart from a possible difference in its sign, depending upon the convention used. A widely accepted
convention for determining the sign of the Burgers vector is to draw the circuit from start S to finish F in the
direction of a right-handed screw, R H-the so-called F S I R H convention (Bilby et al., 1955). Under this
convention, the opposite sides of a dislocation loop have opposite Burgers vectors’ signs.
110 R. HULL

FIG.3 . (a) Illustration of the Burgers vector of a total dislocation (in this example an edge dislocation,
with the line direction u running perpendicular to the page). The dislocation core is at X. A circuit of
5 atoms square, which would close in perfect material, demonstrates a closure failure, the Burgers vector b.
when drawn around the dislocation core. Reprinted from R. Hull and J.C. Bean, Chapter 1, Semiconductors
and Semimetals Vol. 33, ed. T.P. Pearsall, (Academic Press, Orlando, FL, 1990). (b) Illustration of the
misfit dislocation (AB) I threading dislocation (BC) geometry at a Ge,Sil-,/Si interface. Reprinted with
permission from R. Hull and J.C. Bean, Critical Review in Solid State and Materials Science 17. 507-546
(1992). Copyright CRC Press, Boca Raton, Florida.

at an interface with noncrystal (generally a free surface, but possibly also an interface
with amorphous material), at a node with another defect, or upon itself to form a loop.
The geometrical requirement that a dislocation must terminate at another disloca-
tion, upon itself, or at a free surface means that something has to happen with the ends
of misfit dislocations-they cannot simply terminate within the interface. If the defect
density is relatively low and dislocation interactions thus unlikely, the most obvious
place for the misfit dislocation to terminate is at the nearest free surface, which will
in general be the growth (i.e., epilayer or cap) surface. This requires threading dis-
locations, which traverse the epitaxial layer from interface to surface, as illustrated in
Fig. 3(b), and in general each misfit dislocation will be associated with a threading
defect at each end, unless the length of the misfit dislocation grows sufficiently that it
can terminate at the wafer or feature (e.g., mesa) edge, or at a node with another de-
fect. Propagation of misfit dislocations occurs by lateral propagation of the threading
arms. These threading dislocations are extremely deleterious to practical application of
strained layer epitaxy. For many potential device applications, a high interfacial misfit
 3 MISFIT S T R A I N A N D ACCOMMODATION 111

dislocation density is tolerable if the epilayer quality is sufficiently high at some dis-
-
tance from the interface (say, 1 wm or so). Threading dislocations compromise this
possibility. Techniques for reducing these threading defect densities will be discussed
in Section VI of this chapter.
The character of a dislocation is defined by the relationship between its line direction
u and its Burgers vector, b. If b is parallel or antiparallel to u, the dislocation is said
to be of screw character. If b is perpendicular to u, the dislocation is said to be of
edge character. In intermediate configurations, the dislocation is said to be of mixed
character. As u may vary along a dislocation but b may not, a nonstraight dislocation
will vary in character along its length.

2. OF DISLOCATIONS
ENERGY

A dislocation has a self-energy arising from the distortions it produces in the sur-
rounding medium. This energy may be divided into two contributions, those arising
from inside and those arising from outside the dislocation core. The distortions of
atomic positions inside the core are sufficiently high that linear elasticity theory does
not apply (dangling bonds may also exist, producing electronic contributions to the
energy). The dislocation core energy is not well known, but depends upon both the
material type (predominantly the nature of the interatomic bonding) and the disloca-
tion Burgers vector and character. The dimensions of the core are also uncertain, but
theoretical and experimental estimates of its diameter are of the order of the magni-
tude of the Burgers vector for covalent semiconductors and several Burgers vectors for
metals (Hirth and Lothe, 1982). Outside the core, atomic distortions may be modeled
using linear elasticity theory and exact expressions for this energy can be derived. The
self-energy per unit length of an infinitely long dislocation parallel to a free surface a
distance R away is5

In this equation, 8 is the angle between b and u and a is a factor intended to account for
the dislocation core energy (a is generally estimated to be in the range 1 4 in semicon-
ductors). The dislocation self-energy thus varies as the square of the magnitude of its
Burgers vector. This strongly encourages the Burgers vector of a total dislocation to be
the minimum lattice translation vector in a given class of crystal structure. For the di-
amond cubic (dc) structure of Ge,Sil-,, Si and Ge, this minimum vector is a/2(011).
This is indeed the Burgers vector almost invariably observed for total dislocations in
these structures. The value of R in Eq. (15) pertinent to calculations of interfacial mis-
5Strictly speaking this formula is derived for a dislocation within a cylindrical volume of inside radius b/u
and outside radius R, but application to a planar free surface a distance R from the dislocation is generally a
good approximation. We also continue to use the asumption of isotropic elasticity in this treatment.
112 R.HULL

fit dislocation energies for uncapped strained epilayers is generally the epitaxial film
thickness h . For interfaces with very high defect densities, a cut-off parameter R , cor-
responding to the average distance between defects p (if this is less than the distance
to the epilayer surface), is more appropriate. Thus if we consider the total energy of an
interfacial misfit dislocation array, the energy of the m a y will increase approximately
linearly with dislocation density for p > h , as each dislocation will have essentially the
same self-energy given by Eq. (15) with R = h. For p 5 h , however, the array energy
will increase sublinearly with density, as the energy of each dislocation will be given
by Eq. (15) with R - p ; the energy per dislocation will then decrease approximately
logarithmically as p decreases.

3. FORCESON DISLOCATIONS

The self-energy of a dislocation produces a virtual force pulling it towards an im-

age dislocation on the opposite side of a free surface. The simplest case is for an
infinite straight screw dislocation running parallel to a free surface whose image is a
dislocation of opposite Burgers vector in vacuu, equidistant from the surface. Other
configurations have more complex image constructions. Image effects also exist across
internal interfaces between materials with different shear moduli.
The stress field around a dislocation produces an interaction force, Fij, between two
separate dislocations. The magnitude of this force is again configuration dependent.
For the simplest case of parallel dislocation segments, the interaction force per unit
length is given by
Fj,i = Gkj, (bj . bj)/ R' (16)
where R' is the separation of the two segments and kin is the constant of proportionality
(equal to 1/2 n for parallel screw segments). This force is thus maximally attractive for
antiparallel Burgers vectors, maximally repulsive for parallel Burgers vectors and zero
for orthogonal Burgers vectors. The general expressions for FiJ are more complex, but
are relatively straightforward to derive (Hirth and Lothe, 1982).

4. GLIDEA N D CLIMB

Motion of dislocations occurs most easily within their glide planes, which are the
planes containing their line direction and Burgers vectors. For a screw dislocation,
u is parallel to b and thus any plane is a potential glide plane. For mixed or edge
dislocations, there is only one unique glide plane whose normal is given by b x u. Glide
also occurs by far the most easily on the widest spaced planes in a given system because
the Peierls stress (Peierls, 1940) resisting dislocation motion decreases with increasing
planar separation. For diamond cubic, zinc blende and face-centered cubic crystals
this corresponds to the { 111] sets of planes, and these are the almost ubiquitously
 3 MISFIT S T R A I N AND ACCOMMODATION 113

observed glide planes in these structures. Glide occurs by reconfiguration of bonds at

the dislocation core to effectively move the core one atomic spacing; this process is
further aided by nucleation and motion of atomic-scale kinks, which will be discussed
shortly. No mass transport of point defects is required in the glide process. Motion out
of the glide plane, called climb, however, has to occur by extension or shrinkage of the
half plane terminating at the dislocation core, requiring mass transport of point defects.
Such diffusion processes are generally very much slower than glide processes in most
temperature regimes.

5 . GEOMETRYOF INTERFACIAL MISFITDISLOCATION

ARRAYS

The resolved lattice mismatch stress a, acting on a misfit dislocation with Burgers
vector b is given by the Schmid factor S (Schrnid, 1931)
a, = aos = 0 0 cos h cos fp (17)
where h is the angle between b and that direction in the epilayerhubstrate interface
perpendicular to the misfit dislocation line direction, fp is the angle between the glide
plane and the interface normal, and 00 is the lattice mismatch stress, given by standard
isotropic elasticity theory as
00 = 2C&(l + ~ ) / ( -l U ) (18)
-
In the Ge,Sil-,/Si system, a0 9 . 4 ~GPa, an enormous stress!
The effective strain relieving component of the misfit dislocation is given by

beR = b cos h (19)

Equation (17) shows that only dislocations gliding on planes inclined to the interface
will experience a resolved stress (for fp = 90", cosfp = 0; for fp = 0", h = 90" and
cos h = 0). For the Ge,Sil-,/Si(100) orientation, the four possible inclined { 111)
glide planes intersect the (100) interface along orthogonal in-plane [Oil] and [Ol-I]
directions, with a pair of glide planes intersecting along each direction. The orientation
of one of these glide planes, and the accompanying possible a/2( 110) dislocations are
shown in Fig. 4. The intersectionsof the glide planes with the interface thus produces a
square mesh of interfacial dislocations, as shown experimentally in Fig. 5. In general,
only dislocations with Burgers vectors lying within these { 111) planes will be able to
move by glide. For a given glide plane three such Burgers vectors exist, for example,
for the (-111) plane in Fig. 4, b = a/2[101], a/2[110] or a/2[01-1]. Of these three
Burgers vectors, the last is a screw dislocation and will not experience any resolved lat-
tice mismatch stress as cos h = 0. The first two are of mixed edge and screw character
and are known as 60" dislocations, corresponding to the angle between b and U. From
Eq. (19), only 50% of the magnitude of their Burgers vectors projects onto the inter-
 FIG. 4. Schematic illustration of the geometry of misfit dislocations at a Ge,Sil-,/Si(100) interface.
One inclined (-1 11) glide plane and consequent interfacial [Ol-11 dislocation direction are shown, together
with the possible a/2(110) Burgers vectors orientations, where bl is of edge type and h2 and b3 are of 60"
(glide) type. Reprinted with permission from R. Hull and J.C. Bean, Critical Review in Solid Srare and
Materials Science 17,507-546 (1992). Copyright CRC Press, Boca Raton, Florida.

1Bc3 11:

FIG. 5 . Schematic illustrations of the symmetries of interfacial misfit dislocations at

Ge,Sil-,/Si(lOO), (110) and ( 1 11) interfaces. Solid straight lines show the interfacial misfit dislo-
cations; dashed lines outline intersecting ( 111) glide planes. Also shown are experimental verifications
of these interfacial dislocation geometries from plan view (electron beam perpendicular to Ge, Sil -.r/Si
interface) TEM.

114
 3 MISFITS T R A I N A N D ACCOMMODATION 115

facial plane, thus they are only 50% effective at relieving lattice mismatch. Because
of their ability to propagate rapidly by glide, these are the general total dislocations
associated with strain relief in Ge,Sil -,-based heterostructures. The final possibility
to consider is that of edge dislocations, for example, for the configuration of Fig. 4,
b = a/2[0-1-1]. Such dislocations have their Burgers vectors lying within the interfa-
cial plane and are 100% effective at removing lattice mismatch. The Burgers vectors
do not, however, lie within any glide plane, and thus these defects must move by far
slower climb processes. Such edge dislocations are, however, frequently observed at
high strains (of order 2% or greater) in the Ge,Sil-,/Si (Hull and Bean, 1989a; Kvam
et al., 1990; Narayan and Sharan, 1991) and many other lattice-mismatched heteroepi-
taxial semiconductor systems. It is somewhat mysterious that such dislocations can
be prevalent, because of the requirement for motion by climb. It has been suggested
that they are formed by reaction of 60" dislocations on different glide planes (Kvam et
al., 1990; Narayan and Sharan, 1991); for example, for an interfacial misfit dislocation
line direction u = [0111, an edge dislocation of Burgers vector a/2[01-1] could be
+
formed by the reaction a/2[10-1](1-11) a/2[-110](11-1) (in this reaction the square
brackets refer to the dislocation Burgers vector and the curved brackets to the glide
plane). Because they are prevalent at low and moderate strains, subsequent discussion
will concentrate primarily on 6Ooa/2(101) glide dislocations.
The geometry of misfit dislocations will be different on surfaces other than (100).
If the dislocations glide on inclined { 11l } planes, the interfacial misfit dislocation line
directions will be defined by the intersection of these planes with the relevant interface.
The expected geometries for (loo), (110) and (1 11) interfaces are illustrated schemati-
cally and experimentally in Fig. 5.
At the enormously high lattice mismatch stresses that can exist in strained layer sys-
tems, the presumption of dislocation glide on the widest spaced planes in the structure,
that is, { 111) planes for the diamond cubic (dc), zinc blende (zb) and face-centered

(EO -
cubic (fcc) structures, may be overcome. As was first observed in highly strained
-
0.03; a0 5 GPa) (Al)GaAs/Ino.4Gao.6As/GaAs(lOO) zb structures by Bonar
et al. (1992), secondary slip systems may operate at these enormous stresses. In the
work of Bonar et al., a/2(101) dislocations were observed gliding on { 110) planes,

- -
producing (010)misfit dislocation directions in the (100) interface. The same slip sys-
tem has since been observed in Ge0.86Si0.~4/Si(100)(EO 0.035,ao 8 GPa) struc-
tures by Albrecht et al. (1993). The observations of this secondary slip system at these
enormous lattice-mismatch stresses may be related to a more efficient Schmid factor,
and, therefore, higher a, for a given ao.For the (lOl){lll}slip system, Sill = 0.42.
For the (101){110}system, Silo = 0.50. Therefore the extra resolved stress on the

-
(lOl){llO}system compared to the (101){111}system is cro(S110 - S111)
or
-
0.4 - 0.6 GPa for the structures described by Bonar et al. and Albrecht et al.
0.08~0

This more efficiently resolved applied stress may allow a secondary slip system with
higher Peierls stress to operate. At lower strains (< 0.03), however, the (1lo){11I} slip
system appears to operate ubiquitously.
116 R. HULL

6. MOTION OF DISLOCATIONS:
KINKS

The glide process is facilitated by nucleation of atomic-scale lunks along the prop-
agating dislocation line, with lateral motion of the kink arms transverse to the dislo-
cation line effectively moving the entire dislocation length. In the absence of kinks,
dislocations in semiconductors typically lie along well-defined crystallographic direc-
tions corresponding to minima in the crystal potential (known as Peierls valleys). These
are the (01I ) directions for the dc structure of Ge, Sil -,
. Formation of a kink requires
motion of a small length of dislocation line across the potential, or Peierls, barrier be-
tween valleys. Subsequent lateral motion of the kink arms also involves motion over a
secondary Peierls barrier. This process is illustrated in Fig. 6. In metals the energy re-
quired to form and move these kinks is relatively low-typically less than of the order
0.1 eV-because of the low Peierls barriers resulting from the relatively weak metallic
bonding. This low kink energy in metals means that the dislocations are not strongly
constrained to lying within Peierls valleys, and thus are not very straight. Dislocation
motion and configurations in semiconductors, however, are typically dominated by the
Peierls barriers. In materials that are purely covalently bonded such as Ge and Si, the
glide activation energies are particularly high, for example, 1.6 eV in Ge and 2.2 eV
in Si for stresses in the tens to hundreds of MPa regime (Alexander and Haasen, 1968;
Patel and Chaudhuri, 1966; Imai and Sumino, 1983; George and Rabier, 1987). These
glide activation energies arise from the Peierls barriers that have to be overcome in

I
J c
I

FIG. 6. Motion of dislocations by kink pairs in a semiconductor crystal. A small length s of a straight
dislocation line jumps an interatomic distance q transverse to the line, to from a kink pair. The kinks then
run parallel to the dislocation line by successive jumps of interatomic distance a, thereby effectively moving
the entire dislocation line a distance q to the right.
 3 MISFITSTRAIN AND ACCOMMODATION 117

forming and moving kinks. The details of the kink nucleation and propagation process
have been derived in some detail by Hirth and Lothe (1982) and corresponding disloca-
tion velocities u as functions of temperature and applied stress calculated. These lead
to an expression of the form

u = UOD," exp[-E,(a)/kT]

where uo is a prefactor containing an attempt frequency (commonly taken to be of the

order of the Debye frequency), kink jump distances and an inverse dependence upon
temperature and E , (a)is the glide activation energy. Based upon the double kink the-
ory (Hirth and Lothe, 1982), the prefactor uo and the activation energy &(a) depend
upon the propagating dislocation length. (This essentially depends upon whether kinks
collide with each other before reaching the end of the propagating dislocation segment.
It is generally assumed that they do in bulk samples, whereas for very short propagat-
ing dislocation lengths, as may occur in thin epilayers, kinks may reach the end of the
propagating segment before colliding with each other.) The activation energy is also
predicted to exhibit a stress dependence at applied stresses that are a significant fraction
of the Peierl's stress. Consistent with the double kink theory (Hirth and Lothe, 1982),
the pre-exponential power m is found experimentally to be of the oriler 1.0 at stresses
of the order tens of MPa in very pure Si (Imai and Sumino, 1983).
The kink model for dislocation motion is widely accepted, and experimental results
are generally well described by Eq. (20). There is some variation in the measured
magnitude of m , which is found to vary in the range 1.0-2.0 (Alexander and Haasen,
1968); this variation may arise partly from difficulties in separating pre-exponential
and exponential stress dependence of the measured velocities. Also, the prefactors
derived from measurements on bulk semiconductors typically are 2-3 orders of magni-
tude lower than the Hirth-Lothe theoretical predictions (Imai and Sumino, 1983). This
may be due to obstacles to dislocation motion (Moller, 1978; Nititenko et al., 1988,
Kolar et al., 1996) such as point defects, impurities, inhomogeneities in the dislocation
core structure etc., or to entropic effects in kink formation or migration (Marklund,
1985), or to charge states associated with dangling bonds at kinks (this latter model
is supported by observations of a doping dependence of dislocation velocity [Hirsch,
19811).

7. DISSOCIATION
DISLOCATION

A final major consideration is that total dislocations may be dissociated into partial
dislocations. A partial dislocation is a dislocation whose Burgers vector is not a lattice
vector. In fcc, zb and dc materials a very common partial dislocation corresponds to a
stacking fault in the cubic ABC stacking sequence of atoms along (111) directions. The
partial dislocations bounding these stacking faults have Burgers vectors of a / 6 ( 112) or
118 R. HULL

a / 3 ( 111) and are called Shockley and Frank partials, respectively. Only the Shockley
partial can glide within (11I} planes. Total dislocations can dissociate if they can lower
their energy according to the requirement that C b 2 is less after the dissociation than
before (recall from Eq. (15) that the self-energy of a dislocation is proportional to b2).
For example, the reaction

+
~ / 2 [ 1 1 0 ]= ~/6[121] ~/6[21-1] (21)

is energetically favorable. The resulting partial dislocations mutually repel each other
and glide apart on the (-1 1-1) plane. This produces a ribbon of stacking fault between
them, and at some point the extra cost in energy from the stacking fault balances the
interaction energy of the two partials. Typical dissociation widths in unstressed Si
and Ge are of the order of a few nm, implying stacking fault energies y of the order
50-80 mJ mP2 (Gomez et al., 1975; Cockayne and Hons, 1979; Bourret and Desseaux,
1979). Similar stacking fault energies have been measured in epitaxial Ge,Sil --I layers
(Steinkamp and Jager, 1992; Hull et al., 1993). A high-resolution electron microscope
lattice image of the dissociation reaction of Eq. (21) at a Geo,7sSio,25/Si(100) interface
is shown in Fig. 7.
The existence of partial dislocations, and the possibility of dissociation, can signifi-
cantly affect the energetics of dislocation motion. For example, the partials may have
different core structures and charge states from each other and from the undissociated
dislocation. The Peierls barriers for motion of partial dislocations may be different than
for motion of a total dislocation, particularly if kink formation and motion on the two

FIG.7. Cross-sectional (electron beam parallel to a Geo,7sSi0,25/Si( 100) interface) TEM lattice image
of dissociation of a 60°b = a/2(101) dislocation into h = a/6(21I ) Shockley partials, separated by a region
of stacking fault.
 3 MISFITS T R A I N A N D ACCOMMODATION 119

partials are correlated (Heggie and Jones, 1987). The existence of partial and dissoci-
ated dislocations may also be of significance in dislocation nucleation and motion, as
will be discussed in Section V.

8. PARTIAL VERSUS TOTALMISFITDISLOCATIONS

The dissociation reaction described by Eq. (21) also has significant implications for
the microstructure of misfit dislocations. We characterize the different partials in this
equation according to the angle 8 between their line directions u and Burgers vectors b.
For dissociation from the 8 = 6Ooa/2(101) total dislocation, the two a/6(211) partials
have 8 = 30" and 8 = 90", respectively. The resolved lattice mismatch stress, from
Eq. (17), on these two partials is very different. In general, the Schmid factors for the
three types of dislocations are ordered

The order in which the partials move as the dissociated a / 2 (101) defect propagates
is determined by a geometrical construction known as the Thompson tetrahedron con-
struction (Thompson, 1953). This construction is based upon the requirement that the
stacking fault bounded by the two partials produces only second-nearest stacking vio-
lation in the cubic lattice, that is, faults of the type ABCABCBCABCA, which is a rel-
atively lowcmergy planar fault (-- 50-80 mJ mW2in Si, Ge and Ge,Sil-,, as described
in Section 111.7), as opposed to nearest neighbor stacking violation,
ABCABCKABCAB, which is a much higher energy planar fault.
For compressively strained layers grown on a (100) surface, such as Ge,Sil-,/
Si( loo), the Thompson tetrahedron construction shows that for creation of an intrinsic
stacking fault the 30" partial leads and the 90" partial trails as the dissociated a / 2 ( 101)
dislocation propagates through the lattice. From Eq. (22), the trailing partial then ex-
periences a greater lattice mismatch stress than the leading partial. The two partials
are therefore compressed more closely than their zero-stress equilibrium separation.
(In the limit of very high applied stresses, it may not be energetically favorable for the
a / 2 ( 101) dislocation to dissociate at all in this configuration.) In this condition, the
narrowly dissociated defect can be accurately approximated by a single 60"a/2( 101)
dislocation.
For other interfacial configurations, for example, tensile strain layers on (100) in-
terfaces (Ge,Sil-,/Ge(100)), or compressively strained layers on (110) or (I 11) in-
terfaces (GexSil-x/Si(l 10) and Ge,Sil-,/Si(ll 1)), the 90" partial leads. In these
configurations, therefore, the leading partial experiences a greater resolved lattice mis-
match stress than the trailing partial. This will increase the equilibrium separation, and
if the net stress on the leading 90" partial is sufficiently greater than on the trailing 30"
partial, the restoring stress due to the stacking fault energy between the partials can be
120 R . HULL

FIG. 8. Cross-sectional TEM image ([220] bright field near the [I-101 pole) of a 41 nm
Ge0,33Si0,67/Si(lIO)structure, showing stacking faults produced by passage of a/6(211) partial misfit dis-
locations. Reprinted with permission from R. Hull er ul. Appl. Phys. Left. 59, 964, Figure 3(a). Copyright
1991 American Institute of Physics.

overcome, and the dissociation width becomes infinite. The 90°a/6(21 1) partial will
then effectively propagate as an isolated partial misfit dislocation, leaving a stacking
fault in the lattice as it propagates (Fig. 8). In Section IV we will analyze the condi-
tions under which this can occur, and find solutions in ( h ,x) space for which the partial
dislocation is favored.

IV. Excess Stress, Equilibrium Strain and Critical Thickness

1 . INTRODUCTION

We will now analyze more rigorously the conditions that define whether strain in
a lattice-mismatched heterostructure is accommodated elastically or by misfit disloca-
tions (in the limits where there is no interdiffusion across the epilayer/substrate inter-
face, and where the epilayer surface is planar, that is, we ignore the relaxation mech-
anisms discussed in Sections 11.2 and 11.3). In particular, we will derive quantitative
expressions for the critical thickness for the onset of misfit dislocation relaxation, the
equilibrium amount of relaxation for 12 > h,, and the net or effective driving stress
acting on a misfit dislocation.

2. MATTHEWS-BLAKESLEE
FRAMEWORK

Perhaps the most intuitive and general framework for analyzing these quantities is
that originally developed by Matthews and Blakeslee (MB) (Matthews and Blakeslee,
1974, 1975, 1976; Matthews, 1975), and illustrated in Fig. 9. The original MB treat-
 3 M I S F I T S T R A I N AND ACCOMMODATION 121

FIG.9. Schematic illustration of the Matthews-Blakeslee model of critical thickness

ment analyzed the net force on a threading dislocation. We will derive an equivalent
analysis in terms of stresses, which enables extension to more general results.
The primary stresses acting on the dislocation are shown in Fig. 9. The resolved
lattice mismatch stress a, drives the growth of misfit dislocations by lateral propagation
of the threading arm. This is because growth of misfit dislocations (up to an equilibrium
density) relaxes elastic strain by allowing the epitaxial layer to relax towards its free
lattice parameter. The magnitude of a, has already been given in Eqs. (17) and (18).
We also know from Section I11 that misfit dislocations have a self-energy, arising from
their strain fields in the surrounding crystal. This produces a restoring stress ar (MB
referred to the corresponding force as the “line tension” of the dislocation), which acts
so as to inhibit growth of the misfit dislocation. The magnitude of this stress is easily
derived from the equation for the self-energy per unit length of dislocation, Eq. (1 5).
In addition, for partial misfit dislocations, there is a restoring force due to the energy
of the stacking fault created by passage of the defect vsf. The net stress (or following
the nomenclature of Dodson and Tsao (1987) the “excess stress” ue,) is thus given by

Here, E is the residual elastic strain in the system following partial plastic dislocation
relaxation, defined by E = EO - [(bcosh)/p]. Other parameters in Eq. (23) have
been previously defined in the text. Note that the generally quoted form of the MB
model includes only the forces corresponding to a, and O T . Also, in the original MB
framework, the quantity a was generally taken to be of magnitude e , such that they
rewrite ln(ah/b) as [ln(h/b) I]. +
Figure lO(a) shows the dependence of a,, upon epilayer thickness h, using standard
values (which we will assume in calculations henceforth, unless otherwise quoted) for
(100) epitaxy of u = 0.28, cos8 = 0.5, cosh = 0.5, b = 3.9 nm, G = 64 GPa,
E =0.41~ (where x is the Ge fraction in Ge,Sil-,), and a = 2. At very low values of
122 R. HULL

FIG. 10. Variation of (a) a,, and (b) eey with epilayer thickness h for a Ge0,25Si0,75/Si(IOO)structure.
Reprinted with permission from R. Hull and J.C. Bean, Critical Review in Solid Stare andMateriais Science,
17, 507-546 (1992). Copyright CRC Press, Boca Raton, Florida

h , vexis large and negative. This corresponds to the regime where introduction of misfit
dislocations increases the energy of the system. With increasing h, ae, becomes less
negative, until at h = h, it becomes equal to zero. This defines the critical thickness of
the system. For increasing h > h,, a,, becomes increasingly positive (in the absence
of plastic relaxation), up to an asymptotic limit of a, - O , ~ Jindicating
, that the misfit
dislocation array is increasingly energetically favored in the structure. The equilibrium
configuration of the system for any h > h , is that aeX= 0.
The magnitude of the critical thickness is found by solving Eq. (23) for a,, = 0 and
h = h,. For total dislocations (i.e. b = a / 2 ( 101)) where y = 0, this yields6

h , = b( 1 - u cos2 0) 1n(ahC/b)/[8n(1 + u)s cos h] (24)

At increasing h > h,, increasingly larger densities of interfacial misfit dislocations are
favored, and correspondingly smaller amounts of residual elastic strain E . For h > 12, ,
the equilibrium residual elastic strain seq is found by solving Eq. (23) for a,, = 0 and
E = E , ~ . The variation of E , ~with h is plotted in Fig. lO(b).

'Equation (24) thus effectively yields the values of kl , k z . k i , and k4 in Eq. ( I 3)

 3 MISFITS T R A I N AND ACCOMMODATION 123

FIG. 11. Predictions of the MB theory for the critical thickness h, in Ge,Sil-,/Si(100) structures
for different values of the core energy parameter a. Also shown are experimental measurements of h , for
different growthhnealing temperatures from the work of (a) Bean et al. (1984), (b) Kasper et al. (1973,
(c) Green et al. (1991), and (d) Houghton etul. (1990).

Equation (24) does not have analytical solutions, but is simple to solve numerically.
Solutions to this equation for the Ge,Sil-,/Si( 100) system are shown in Fig. 11. It is
seen that the equilibrium critical thickness decreases rapidly with increasing Ge con-
centration, as the volumetric strain energy density increases as e2.
Also shown in Fig. 11 are experimental measurements of critical layer thickness in
the Ge,Sil-,/Si( 100) system from different groups, at several different growth tem-
peratures. In the limit of high-growth temperatures (relative to the melting points of the
materials, T, = 1412 "C for Si and 940 "C for Ge, with close to linear interpolation
for melting temperatures of intermediate alloys [Stohr and Klemm, 1939]), experiment
and equilibrium prediction agree well. At lower growth temperatures, experiment and
theory are seen to diverge increasingly, in that increasingly larger critical thicknesses
are measured experimentally as the growth temperature decreases. We shall discuss in
Section V of this chapter that this divergence is due to the thermally activated kinetics
of generation of the misfit dislocation array. In brief, as the equilibrium critical thick-
ness is exceeded, plastic relaxation by generation of interfacial misfit dislocations is
favored, but activation barriers exist to the nucleation and propagation of misfit dislo-
cations. With decreasing temperature, the nucleation and propagation rates decrease,
and plastic relaxation by misfit dislocations lags increasingly behind the equilibrium
limit. The "experimental" critical thickness at a given growth temperature then be-
comes that epilayer thickness at which strain relaxation, or dislocation generation, is
first experimentally detected (Fritz, 1987). Dodson and Tsao (1987) first demonstrated
convincingly how kinetic modeling of this minimum detectable dislocation density pro-
cess could accurately predict a "temperature-dependent'' critical thickness.
124 R. HULL

3. ACCURACYOF THE MB MODEL

How accurate are the predictions of Eq. (24), in light of the perspective that there
have been many refinements or recalculations of the critical thickness since MB orig-
inally developed their model? First, there are several approximations in the original
formulation of this equation by MB. It assumes isotropic elasticity theory, whereas as
we have already discussed, Si and Ge are relatively elastically anisotropic. The treat-
ment of the dislocation core energy, where linear elasticity theory can no longer be
applied, is very oversimplified. This core energy is approximated by assuming that we
can apply standard elasticity theory outside of a “core radius” r, = ba, and accounting
for the core energy inside a cylinder of radius r, by simply adding on a fixed energy
per unit length of dislocation, Ecore:
E,,, = [Gb2(1 - u COS* 0)/471( 1 - v ) ]ln(a) (25)
We can only ascribe a if we know EcOre. Accurate estimates of this quantity re-
quire sophisticated a b initio calculations of the core structure (Nandekhar and Narayan,
1990; Jones et al., 1993). In addition, E,,,,, and therefore a , are invariant with h only
for h >> b, and will vary with the character of the dislocation, that is, the value of
8 . Estimates of cy in the literature vary from - 0.5 - 4 (Nandekhar and Narayan,
1990; Hirth and Lothe, 1982; Perovic and Houghton, 1992; Beltz and Freund, 1994;

suggesting a -
Ichimura and Narayan, 1995), with the more recent total energy calculations generally
1. We assume a value a = 2 in subsequent calculations. This varia-
tion in a affects the critical thickness calculation most significantly at higher E (higher

for EO -
x in Ge,Sil-,/Si), and lower h,. For example, if h = 1 nm (corresponding to h,
0.04), In(ah,/b) varies between 0.9 and 2.3 as a varies between I and 4, a
variation of 160%. However, if h = 10 nm (corresponding to h, for 60 - O.Ol), the
corresponding variation of ln(ah,/b) is between 3.2 and 4.6, or a potential error of
40%.
In summary, the MB model in the form of Eqs. (23) and (24) should be regarded as
approximate, to an accuracy perhaps 20-50% for critical thicknesses greater than a few
nanometers. This makes it a very useful model.

MODELS
4. OTHERCRITICALTHICKNESS

Our initial discussion of strain relaxation by misfit dislocations in Section 11.4 in-
troduced the concepts of misfit dislocations and critical thickness qualitatively using
energetic arguments. This was the basis of the earliest models of critical thickness de-
veloped by Frank and van der Merwe (1949a,b,c), who used a one-dimensional Fourier
series to represent interactions between atoms in the epilayer and substrate, and demon-
strated the concept of critical thickness. Subsequent development by Van der Merwe
and co-workers (Van der Merwe, 1963; Van der Merwe and Ball, 1975; Van der Merwe
 3 MISFITS T R A I N AND ACCOMMODATION 125

and Jesser, 1988) developed the theme of calculation of the energy of a misfit disloca-
tion array, including dislocation interaction energies, and comparison to strain energy
relaxed within the epitaxial layer. Many of these models were mathematically com-
plex, and had analytical solutions only in the limits of very thin and very thick epitaxial
layers. Nevertheless, the energy balance approach derived in these papers set the foun-
dations for subsequent development in this field, and enjoyed considerable success in
predicting the critical thickness in body-centered cubic metal systems.
Formally, the evaluation of critical thickness should be equivalent using either en-
ergetic or mechanical constructions, providing equivalent approximations are made in
the two approaches (Willis et al., 1990).
We now summarize the salient features of some other critical thickness models
which have been developed as refinements of, or alternatives to, the MB framework:

(a) The model of People and Bean (1985, 1986), which attempted to reconcile theory
with the early MBE measurements of h, in the Ge,Sil-,/Si(100) system (Kasper
et al., 1975; Bean et al., 1984). This model assumed the self-energy of the disloca-
tion to be localized within a certain region (of order five times the Burgers vector
magnitude) centered on the dislocation core. This is in contrast to the usual elastic-
ity treatment of dislocation self energy, and to subsequent verification that the MB
theory describes the Ge,Sil-,/Si(100) system well in the limits of highly sensitive
experimental techniques or very high temperatures (Houghton et al., 1990; Green
et al., 1991).
(b) The model of Cammarata and Sieradzki (1989), who incorporated the concept of
surface stress into the MB framework. For the Ge,Sil-,/Si system they argued
that surface stress will be inward along the surface normal, and thus reduce the
tetragonal distortion of the Ge,Sil-, epilayer and increase h,. These effects are
significant only in the range of high Ge concentration where h, becomes relatively
small.
(c) The work of Willis et al. (1990), who derived a more precise expression for the
energy of an array of misfit dislocations than the original Van der Merwe formu-
lations. Subsequent development of this work using both energy minimization and
force balance analyses (Gosling et al., 1992) has enabled refinement of both the
Matthews-Blakeslee and Van der Merwe models.
(d) The work of Chidambarro et al. (1990) who considered the effect of the orientation
of the threading arm within the glide plane, and also analyzed a quasi-static Peierls
force on the misfit dislocation. Certain orientations (e.g., screw) of the threading
arm were determined to enhance the predicted critical thickness significantly.
(e) Fox and Jesser (1990) have invoked a static Peierls stress as an additional restoring
stress upon a misfitkhreading dislocation, thereby increasing the critical thickness.
It seems to the present author, however, that the effect of the Peierl’s barrier enters
126 R. HULL

into dislocation kinetics, as discussed in a later section, rather than for the static
case of the equilibrium critical thickness.
(f) Shintani and Fujita (1994) have performed a calculation for critical thickness based
upon anisotropic elasticity theory.

Of the forementioned treatments, models (c), (d) and ( f ) represent refinements/

improvements of the original MB formulation, but do not radically alter the predicted
magnitudes of critical thickness or excess stress. Models (b) and (e) represent addi-
tional terms to be considered in the MB analysis; of these models, (b) is significant
only at relatively small critical thicknesses (of order a few nanometers or less), and (e)
does not appear appropriate to the static critical thickness configuration. Model (a) is
radically different from the MB model, but does not have the physical plausibility of
the MB framework. In summary, the MB model remains an extremely useful general
framework for predicting equilibrium relaxation by misfit dislocations in strained layer
heterostructures.

5 . EXTENSION
TO PARTIAL MISFITDISLOCATIONS

So far, our discussion of critical thickness has been restricted to total (b = a / 2 ( 101))
misfit dislocations, which represent the appropriate misfit dislocation microstructure
for interfacial configurations where the 30"a/6(21 1) partial leads in the dissociated
total dislocation. This corresponds to the Ge,Sil-,v/Si(lOO), Ge,Sil-,/Ge( 110) and
Ge,Sil-,/Ge( 1 11) configurations among low index planes. For the interfacial con-
figurations where the 90" partial leads, that is, Ge,Sil-,/Ge(100), Ge,Sil-,/Si( 110)
and Ge,Si~-,/Si(lll), we should analyze the excess stress and critical thickness ap-
propriate to the 90°a/6(21 1) misfit dislocation, and compare to the 60°a/2(101) misfit
dislocation configuration.
To simplify the calculations, we shall consider the 60"a/2(101) misfit dislocation
in its undissociated state. (Consideration of the dissociated 60"a/2( 101) configuration
with the 30" partial leading will generally lead to lower energies than for the undissoci-
ated configuration. Our simplified analysis, therefore, will tend to overestimate slightly
the regimes in which the 90" partial is preferred over the 60" total dislocation.) The
relevant descriptions of excess stress and critical thickness for the undissociated 60"
total dislocation have already been given in Eqs. (23) and (24). For the 90" partial, we
apply Eq. (23) with the relevant value of y , and modify Eq. (24) according to

h , = Gb2cos@(1-ucos2B)ln(ah,/b)/[(8rrbG(1+ W ) E C O S ~ C O S @ ) - ( ~ ~ ~ ~ ( ~ - U ) ) ]
(26)
By comparison of Eqs. (23), (24), and (26), we can then determine which is the fa-
vored dislocation type, 60" total, or 90" partial. The magnitudes of the critical thickness
and the excess stress for the 90" partial dislocation are very sensitive to the stacking
 3 MISFITSTRAIN AND ACCOMMODATION 127

fault energy. Here we use the value of y = 65 mJ m-’ that we have previously deter-
mined for Ge,Sil-, alloys (Hull et al., 1993). A comparison of critical thicknesses for
90”a/6(211) and 6O0a/2(101) dislocations in the Ge,Sil-,/Si(IlO) system is shown
in Fig. 12(a). It is observed that the 90” partial dislocation has a lower critical thickness
at higher Ge concentrations, but the 60” total dislocation has the lower critical thick-
ness at lower Ge concentrations. This transition is essentially due to the stacking fault
energy associated with the partial dislocation: at zero stacking fault energy the 90”
partial dislocation would always have the lower critical thickness, but with increasing

n
E
0

J
Ob!o 0.1 0.2 0.3 0.4
X

’ 0 3 1
n
E
0,
+-.
K 60
v)
0)

2
v
c

O’
I

‘ Oll
NONE
I

0.2
1
0.3
w I

0.4
I

FIG. 12. (a) Comparison of critical thicknesses for 90°a/6(21 1) and 60°a/2(101) dislocations in the
Ge,SiI-,/Si(llO) system, assuming CY = 2 and y = 65 m J m-’. (b) Predicted dislocation microstructure
in the Ge,Sil~,/Si(llO) system as functions of epilayer thickness h and Ge concentration x assuming
CY = 2 and y = 65 mJ m-2. Regions labeled “NONE,” “60” and “90,” respectively, refer to regions where
no dislocations are expected, regions where 60”a/2(101) dislocations are most favored, and regions where
90°a/6(21 1) defects are most favored.
128 R. HULL

stacking fault energy the critical thickness for the partial dislocation increases. The ef-
fect of the stacking fault energy is increasingly significant in thicker layers (because the
total energy of the stacking fault per unit interfacial misfit dislocation length increases).
Thus at lower Ge concentrations, where the critical thickness is higher, the effect of the
stacking fault energy upon h,(90) is maximized, and the 60" partial dislocation has the
lower critical thickness. Thus below a critical Ge concentration, x, hc(60) < h,(90),
whereas for x > x, hc(60) > hc(90).
These trends are also evident in analysis of the energetically favored dislocation type
as functions of epilayer thickness h and Ge concentration x. This is defined by which
dislocation has the greater excess stress acting upon it as a function of ( h ,x). The
results of this analysis for the Ge,Sil-,/Si(lIO) system are shown in Fig. 12(b). For
x < x, the 60" total dislocation is favored for all h. The curve AB corresponds to
the plot of hc(60) in this composition range. For x > x,, the 90" partial dislocation
is favored for lower epilayer thicknesses (and the curve BC corresponds to the plot of
h,(90) in this composition range), but as h increases, the stacking fault energy associ-
ated with the partial dislocation increases and at a thickness h,, (x) defined by the curve
BD, the 60" total dislocation again becomes energetically favored. The locus of BD is
extremely sensitive to the value of y , and we have used the sensitivity of this transition
to experimentally determine y (Hull et al., 1993). Thus, there exists a defined area of
( h ,x) space where the 90" partial dislocation is energetically favored.
The trends of increasing tendency for 90"a/6(21 1) partial dislocations with increas-
ing Ge concentration x and decreasing epilayer thickness have been experimentally
verified in Ge,Sil-,/Si(llO) heterostructures (Hull et al., 1993).

6. MODELSFOR CRITICAL THICKNESS

IN MULTILAYER
STRUCTURES

A very common configuration for strained Ge,Sil-, layers is to be confined between

a Si substrate and a Si cap. For this geometry, the misfit dislocation configuration may
involve interfacial segments either at both interfaces or just the bottom interface, as
indicated schematically in Fig. 13. The double interface configuration is more general,
and is demonstrated experimentally in Fig. 14. The segment of the dislocation loop
at the lower Ge,Sil-,/Si interface allows the lattice parameter of the Ge,Si]-, to be
relaxed toward its equilibrium value by increasing the average lattice parameter of the
material above this dislocation segment. However, in the absence of the misfit disloca-
tion segment at the upper Ge,Sil-,/Si interface, the Si cap would also have its average
lattice parameter increased, thus straining it away from its equilibrium value. The up-
per misfit dislocation segment thus adjusts the lattice parameter in the Si cap back to
its original, unstrained value. The extra interfacial segment increases the dislocation
self-energy, but only in relatively thin Si capping layers is this energy contribution
greater than the strain energy which would otherwise exist in the Si cap. The ranges
of Ge concentrations, epilayer thicknesses and cap thicknesses h,,, which define the
 3 MISFITS T R A I N A N D ACCOMMODATION 129

CAP

EPI

SUB

FIG. 13. Schematic illustration of misfit dislocation configurations at capped Si/Ge,Sil-,/Si struc-
tures: (a) single interfacial dislocation; (b) double interfacial dislocation.

two configurations of Fig. 13, have been studied by several groups (Tsao and Dodson,
1988; Twigg, 1990; Gosling et al., 1993). For the double misfit segment configuration,
the extra interfacial segment modifies the dislocation self-energy and critical thickness
expressions, Eqs. (15) and (24). The self-energy per unit interfacial length of the dislo-
cation dipole is given by the separate energies of the top and bottom dislocations minus
the interaction energy between them. For a capping layer thickness hcap and a strained

FIG. 14. Plan-view TEM image of a 300-nm Si/100 nm Geo.2SiO.S/Si(lOO) structure. Closely
spaced interfacial dislocation pairs correspond to segments of the same dislocation loop at top and bottom
Ge,Sil-,/Si interfaces as illustrated schematically in Fig. 13(b). Reprinted with permission from R. Hull
and J.C. Bean ,Appl. Phys. Lett. 54,92, Figure 2. Copyright 1989 American Institute of Physics.
 R. HULL

layer thickness h , this yields

The last pair of logarithmic terms in this equation is the interaction energy between
the two interfacial dislocations (Hirth and Lothe, 1982). For the limit heap >> h , the
-
entire logarithmic expression simplifies to 2 In(ah/b), or simply twice the energy of
the single interfacial dislocation at an uncapped epilayer. The restoring stress for the
buried layer q - b is then a factor of two higher than for the single layer (as given by
Eq. (23)), and the critical thickness for h, >> b is also approximately a factor of two
higher. In fact this approximation is reasonably accurate for all hcap > h if h >> b.
This factor of approximately two in critical thickness from capping of strained layers
is of great benefit in post-growth processing of practical strained layer devices.
Extension of critical thickness concepts to superlattice structures i s complex due
to the larger number of degrees of freedom involved (individual layer strains and di-
mensions, total number of layers, total multilayer thickness, etc.). Experimentally,
it is generally observed that providing each of the individual strained layers within
the multilayer structure is thinner than the critical thickness for that particular layer
grown directly onto the substrate, then the great majority of the strain relaxation oc-
curs via a misfit dislocation network at the interface between the substrate and the first
strained multilayer constituent (Hull et al., 1986). If individual strained layers within
the multilayer do exceed the relevant single-layer critical thickness, then substantial
misfit dislocation densities will generally be observed at intermediate interfaces within
the multilayer. Thus, for the configuration where individual layers do not exceed the
relevant single-layer critical thickness, the relaxation may be regarded as occurring
primarily between the substrate and the multilayer structure taken as a unit.
A simple energetic model has been developed (Hull et al., 1986),based upon reduc-
tion of the multilayer to an equivalent single strained layer. In this model, a multilayer
structure is considered consisting of n periods of bilayers A and B , of thickness dA and
d B , compound elastic constants k A and k ~ and , lattice mismatch strains with respect
to the substrate of E A and E B , respectively. The amount of strain energy which may be
relaxed by a misfit dislocation array at the substratehperlattice interface is found to
be:

The form of this relaxable energy is equivalent to the average strain energy in the

system, if we assume k A -
superlattice, weighted over the appropriate elastic constants and layer thicknesses. For
the Ge,Sil-,/Si k B and that Vegard’s Law applies (i.e.,
that the strain of Ge,Sil-, with respect to Si varies linearly with x), then the relaxable
strain energy simplifies to that in an equivalent uniform layer of the same total thickness
 3 MISFIT STRAIN AND ACCOMMODATION 131

+
as the superlattice = n(dGeSi dsi), and the average superlattice composition x, =
x&esi/(&esi +
&i).
The preceding analysis provides an equilibrium framework for analysis of critical
dimensions for the onset of misfit dislocation generation in GeSi/Si superlattice struc-
tures. In practice, kinetic effects and dislocation interactions are likely to be very sig-
nificant in these more complex structures (Hauenstein et al., 1989). It has been found,
however, that relaxation kinetics of equivalent single layers at MBE growth tempera-
tures of 550 "Cprovide an approximate guide to kinetic relaxation rates in superlattice
structures (Hull et al., 1986).

V. Metastability and Misfit Dislocation Kinetics

1. BASICCONCEPTS

a. Introduction

To date, we have considered only equilibrium descriptions of the misfit dislocation

array. However, it is clear from the comparison of experimental data with equilib-
rium modeling of critical thickness in the GexSi~-,/Si(1O0) system, as illustrated in
Fig. 11, that there are significant kinetic effects associated with generation of misfit dis-
location arrays. These arise primarily from the substantial energetic barriers generally
associated with dislocation nucleation and propagation, which have to be overcome by
thermal activation, and with interactions between different dislocations in the array. In
this section, we will consider each of these processes in turn.
The primary effect of kinetic barriers in the development of the interfacial dislocation
array is that the magnitude of plastic relaxation will lag behind the equilibrium condi-
tion. This gives rise to nzetastably strained structures. The definition of a metastably
strained structure is that the excess stress on the operative dislocation type aeXis greater
than zero. Increasing excess stress corresponds to increasing metastability of the struc-
ture. The definition of equilibrium is that aeX= 0. Experimentally, we describe the
degree of metastability by a slight modification of Eq. (23)

~ c x 2GS[&o- (bcosh/p)](l
= +
~ ) / ( l- U )
- [Gbcos@(l - ucos28)/4nh(l - u)]ln(ah/b) - y/b (29)
Here, as discussed in Section IV, we have transformed E in Eq. (23) to [ ~ - ( cos
b Alp)],
-
where EO is the initial lattice mismatch strain (a, - a,)/a,, and (bcos A l p ) is the
amount of strain relaxed by the misfit dislocation array. The maximum degree of
metastability in a given structure corresponds to an infinite spacing of the misfit dislo-
cations. As development of the misfit dislocation array proceeds, p and a,, decrease
132 R. HULL

until equilibrium is reached at a,, = 0 and p = pmjn.The value of pmill is found by

solving Eq. (29) for oeex = 0.
Kinetic effects are very substantial in GeSi-based heterostructures, as the covalent
bonds of Ge and Si lattices are relatively strong. Thus, as described in Section 111, the
activation energies for dislocation motion in bulk Ge and bulk Si are of order 1.6 eV
and 2.2 eV, respectively. These values are very much greater than kT at any reasonable
crystal growth temperature. Dislocation nucleation is also generally associated with
significant activation barriers. Thus, particularly at moderate growth temperatures, the
actual development of the misfit dislocation array may lag orders of magnitude be-
hind the equilibrium configuration, and substantial excess stresses (up to 1.0 GPa) may
develop. This is the essential reason for the ability to grow low misfit dislocation den-
sities far beyond the equilibrium critical thickness at lower growth temperatures, as
illustrated in Fig. 11.

6. An Idea of the Numbers Involved in Relaxation by MisJit Dislocations

What kinds of numbers of total misfit dislocation length, interfacial spacings, and
numbers of individual dislocation loops are we considering in strained layer relaxation?
Consider a 10 cm diameter Si(100) substrate. Let a Ge,Sil-, epilayer be grown
upon it with a lattice mismatch of 1% with respect to the substrate. Let the resid-
ual strain in the structure be close to zero (this will be true for a sufficiently thick
epilayer grown at a sufficiently high temperaturc). Let the interfacial misfit disloca-
tions be of the 60" a/2(110) type, such that the Burgers vector magnitude is 0.39 nm.
The required interfacial misfit dislocation spacing will be given by the relation EO =
b cos A l p , as previously discussed. This yields an interfacial misfit dislocation spacing
- 20 nm. The equilibrium misfit dislocation density is thus very high for epitaxial layer
thicknesses that are significantly greater than the critical layer thickness. This means
that dislocation interactions become very important as the structure relaxes plastically
towards equilibrium.
An average dislocation spacing of 20 nm across a 10 cm wafer requires a total length
of the orthogonal interfacial misfit dislocation grid of the order lo6 m (recall that two
separate, orthogonal, dislocation arrays have to be created). Thus f o r complete re-
laxation enormous line lengths of dislocation have to be created (in this example, of
order 1000 km over a 10 cm wafer!). To create this line length in a finite time interval
propagation and nucleation rates will need to be relatively rapid.
So how many misfit dislocations are needed to create this array? Even if each dislo-
-
cation makes a chord from edge to edge of the wafer, lo7 separate dislocations will
be required, or of the order lo5 cm-2 of substrate area. Thus high densities of misfit
dislocation nucleation sources are required. However, this estimate should be regarded
as an absolute minimum required source density. Let us now consider the implications
of finite dislocation propagation velocities (in general, there will not be sufficient time
at temperature for the dislocation to grow to be sufficiently long to traverse the entire
 3 MISFITSTRAIN AND ACCOMMODATION 133

wafer-unless the growth temperature is very high, for example, the growth by CVD
of Ge,Sl-,/Si(lOO) with x 5 0.05 at 1120 "C [Rozgonyi et al., 19871). As will be
discussed later in this section, typical misfit dislocation velocities in GeSi-based het-
erostructures at strains of order 1% are of the order 0.1 - l p m s-l at 550 "C. At a
typical MBE growth rate of 0.lnm s-l, it takes 1000 s to grow a 100-nm epilayer, by
which time an initial strain of EO - 0.01 is typically > 10% relaxed. Based upon the

-
foregoing analysis, a 10% relaxation of the original strain requires a total interfacial dis-
location length lo5 m. The maximum length of individual dislocations, based upon
their propagation velocity, is 0.1-1 mm (the average will obviously be significantly
less than this). Thus a minimum total number of 108-109 dislocation nucleation events

-
are required, corresponding to an areal density 106-107 cmP2, and a nucleation rate
103-104 cmP2 sP1. (These numbers again represent a lower limit to the required
source density as not all dislocations will nucleate at the start of the relaxation process,
propagation velocities will be substantially lower than the number quoted above until
the critical thickness is significantly exceeded, and misfit dislocation interactions may
also slow propagation.) Identification of plausible mechanisms for generating such dis-
location source densities is a critical question in our current understanding of strained
layer relaxation.

2. MISFITDISLOCATION
NUCLEATION

a. Introduction

The precise mechanisms of nucleation of misfit dislocations in strained heteroepi-

taxial systems remain somewhat elusive and controversial. There are many papers on
this topic in the literature, and in this section we will summarize this literature with
respect to nucleation in GeSi-based systems.
The generic candidates for misfit dislocation nucleation sources are:
(a) Heterogeneous nucleation at specific local strain concentrations, due for example to
growth artifacts or pre-existing substrate defects.
(b) Homogeneous or spontaneous nucleation of dislocation loops or half-loops.
(c) Multiplication mechanisms arising from dislocation pinning and/or interaction pro-
cesses. These are generally extensions of classic mechanisms such as the Frank-
Read source in bulk crystals (Frank and Read, 1950).
We will now consider each of these generic mechanisms in more detail.

b. Heterogeneous Nucleation Sources

By heterogeneous nucleation, we mean nucleation of dislocations from sources that

are not native to or inherent in the structure.
134 R. HULL

The original formulations of Matthews and Blakeslee generally assumed that the
required density of defect sources were generated by existing dislocations in the sub-
strate (although they did consider other potential nucleation mechanisms). This may
have been a plausible mechanism for the GaAs substrates of the 1970s that they were
considering, but contemporary commercial Si substrates typically have defect densities
in the range 1-lo2 cm-2. Clearly, these substrates themselves cannot provide sufficient
densities of defect sources, based upon the required source densities discussed in Sec-
tion V. 1.
Other heterogeneous features that may develop during epitaxial growth, or which
arise from incomplete cleaning of the substrate surface prior to growth, can act as
misfit dislocation nucleation sources if there are high local stresses and strains asso-
ciated with them. Examples include residual surface oxide or carbide after substrate
cleaning, particulates on the substrate surface or included during growth, source “spit-
ting,” contaminants, transition metal precipitation, etc. For example, in our experience
of Ge,Sil-, growth upon Si substrates by molecular beam epitaxy (MBE), the most
generic heterogeneous source we observe are polycrystalline Si inclusions, of order
a few hundred nanometers in size, and present at densities of the order lo3 cmP2, as
illustrated in Fig. 15. We believe that these sources are associated with flaking of poly-
crystalline Si from deposits built up on the walls of the growth chamber.
Other heterogeneous sources that have been documented in GeSi/Si heteroepitaxy
include surface nucleation mechanisms associated with trace impurities (-- l O I 4 cmP3)
of Cu (Higgs el al., 1991), and heterogeneous distributions of 1/6(114) diamond-
shaped stacking faults (Eaglesham et al., 1989) that have dimensions of order 100 nm

FIG. 15. Example of a heterogeneous dislocation source (an inclusion of polycrystalline Si that arises
from flaking from the walls of the MBE growth chamber) in a 200-nm Geo.1 5 S i o . ~ ~ / S100)
i ( heterostructure.
Photo courtesy of F. M. Russ.
 3 MISFITSTRAIN AND ACCOMMODATION 135

and act as sources for 60°a/2(110) misfit dislocations. (Defects with similar geome-
tries have been correlated with precipitation of metallic impurities, for example, Fe in
Si [DeCoteau et al., 19921).
Each of the features listed here certainly can provide sufficient source densities if
the growth quality is poor enough (i.e., feature density and, therefore, source den-
sity is high enough), but each should be controllable in high-quality crystal growth
to - lo3 cm-2, or better. Of course, a single source may emit more than one misfit
dislocation, but each source will only be able to relax strain in the heterostructure over
dimensions comparable to the source size (which for isotropic source dimensions must
be no greater than the epitaxial growth thickness). In summary, it is difficult to imagine
that any of these heterogeneous nucleation mechanisms can generate the high densities
of dislocations consistent with the observed relaxation of moderately or highly strained
structures.

c. Homogeneous Nucleation Sources

By homogeneous nucleation, we mean nucleation of dislocations from sources that

are inherent in the structure.
The most obvious homogeneous nucleation source in lattice-mismatched heteroepi-
taxy is the elastic strain, which if sufficiently high can lead to spontaneous (i.e., zero
or negative activation energy) nucleation of dislocation loops or surface half-loops. At
lower strains, homogeneous dislocation nucleation is associated with an energy barrier.
This situation has been modeled by several authors, for example, Cherns and Stowell
(1975, 1976); Matthews et al. (1976); Fitzgerald et al. (1989); Eaglesham et al. (1989);
Hull and Bean (1989a); Kamat and Hirth (1990); Dregia and Hirth (1991); Perovic
and Houghton (1992); and Jain et al. (1995). The general principle underlying these
models is that a growing dislocation loop of appropriate Burgers vector relaxes strain
energy within the epilayer Est, but balancing this is the self-energy of the dislocation
loop itself El (this is closely analogous to the Matthews-Blakeslee critical thickness
criterion for growth of interfacial misfit dislocations). Other energy terms that need to
be considered are the energies of steps created or removed in the nucleation process
ESP(a 60" a/2(101) dislocation, for example, has a Burgers vector component normal
to the surface and must thus always be associated with step creation or removal), and
the energy of any stacking fault created E,f either as a result of dislocation dissociation,
or as a result of separate nucleation of partial dislocations. This produces a total energy
of the form
Er = El - Est i= E,, f Esf (30)
Note that E,f may either increase or decrease the total energy: a stacking fault clearly
increases the system energy, but a 30" partial dislocation, for example, could nucleate
along the path of an existing 90" partial dislocation to remove the existing stacking
fault and generate a total misfit dislocation. The total system energy will in general pass
136 R . HULL

through a maximum value A E (which represents an activation barrier for homogeneous

dislocation nucleation), at a critical loop radius R,.
The magnitude of A E as a function of strain depends sensitively upon the Burgers
vector of the dislocation, the magnitude of the dislocation core energy assumed, and
whether or not ESt and E,f are included in the calculation. Variations between these
different terms cause a range of predicted activation barriers at a given strain in cal-
culations by different authors, but consensus exists that activation barriers approach a
physically attainable limit (of order a few electron volts or less) for strains of the order
2 4 % (corresponding to x 2 0.5 in Ge,Sil-,) , and are unphysically high (100 eV or
greater) at strains below about 1% (corresponding to x 5 0.25 in Ge,Sil-,).
A common expression used for the loop self-energy (Bacon and Crocker, 1965) for
a complete loop of radius R is

El = [Gb2R/2(1 - u)][b:/b2 + (1 - u/2)(1 - b:/b2)][ln(2nRa/b) - 1.7581 (31)

Here b, is the component of the dislocation Burgers vector normal to the loop. The
original Bacon and Crocker expression also contained an extra term due to surface trac-
tions; the magnitude of this extra expression is relatively low and is generally omitted
by most authors.
The strain energy relaxed by the loop is given by

Est = [2nR2G( 1 + u ) E / ( ~- ~ ) ] ( bcos, q5 cos A + b, cos2 q5) (32)

Here b, and be are the glide and climb components, respectively, of the dislocation
Burgers vector. Considering the energy terms in Eqs. (31j and (32) only, the critical
radius is found by setting 6Et/6R = 0, yielding

R, =
{b2tb;/b2 + (1 - u/2)(1 - b;/b2)l[ln(2nRca/b) - 1.758 + 2na/b]} (33)
Sn(l+ u)E(6~COSq5COSh+b,cos~~)

Assuming the most common configuration of 6Ooa/2(101) dislocations moving on

(11 1) glide planes with a (100) interface, we have b, = be = 0, b, = b = 0.39 nm,
cos h = 0.5, cos q5 = m, simplifying Eq. (33) to

&b(l - u/2)[1n(2naRc/b) - 1.758 - 2na/b]

R, = (34)
4&(1 + VIE
This expression may be solved numerically for R, as a function of E and the value
substituted back into Eq. (30) to yield A E
For a dislocation half-loop nucleating at the epilayer free surface, ESt is halved rela-
tive to a full loop, El is approximately halved (this is actually an involved calculation if
done rigorously because of the complexity of the image interaction calculation; these
 3 MISFITSTRAIN AND ACCOMMODATION 137

complexities are generally ignored in the literature, and a factor of a half used), R,
is approximately unchanged, El is approximately halved and A E is approximately
halved. This indicates why surface half-loop nucleation is generally assumed to be
greatly favored over full-loop nucleation within the epitaxial layer. The value of R,
for the surface half-loop is closely analogous to the Matthews-Blakeslee critical thick-
ness for an uncapped epilayer. The small quantitative differences between R, and h,
arise because the dislocation configuration is somewhat different in the two cases, thus
modifying the expression for dislocation self-energy, and because R, is measured in
an inclined { 111) plane, while h, is measured along the interface normal.
Evaluation of the activation barrier A E (for either half- or full-loops) shows that it
increases approximately as the magnitude of the Burgers vector cubed (this strongly re-
duces the activation barrier for partial vs total dislocations [Wegscheider et al., 1990]),
increases strongly with the magnitude of the core energy parameter a and is approxi-
mately inversely proportional to the strain. In Fig. 16 we show the variation of A E with
x for surface half-loop nucleation in the Ge,Si~-,/Si(IOO) system for 60°a/2(110)
dislocations with removal and creation of surface steps as they nucleate; EStis approx-
imated from the relation
ESt= 2Rbx sin3!, (35)
where j3 is the angle between the dislocation Burgers vector and the free surface, and
x is the areal epilayer surface energy, which, following Cherns and Stowell (19759, we
approximate by x
to the value of a.
-
Gb/8. Note the great sensitivity of the results for A E in Fig. 16

The foregoing calculations suggest physically accessible activation barriers (of order
5 eV)7 for strains of order 3 4 % or greater. However, quasi-homogeneous processes
can provide substantial densities of sites at the epilayer surface, which significantly
reduce the homogeneous nucleation barrier. By quasi-homogeneous, we mean fea-
tures in the crystal that, although arising from inherent physical processes in the crystal
growth, represent perturbations in the average crystal structure. For example, we have
demonstrated that statistical fluctuations in the Ge concentration of a Ge,Sil-, alloy
can produce significant densities of local volumes where the Ge concentration is sig-
nificantly higher than the average matrix composition (Hull and Bean, 1989a). Local
Ge-rich regions have also been implicated by Perovic and Houghton (1992) in disloca-
tion nucleation.
Another quasi-homogeneous process that can locally reduce activation barriers for
dislocation nucleation is roughening of the epilayer growth surface. We have already
considered in the analysis of Eqs. (30)-(35) how removal of monolayer surface steps

7Consider the number of surface atomic sites, IOl5 cm-2, available for nucleation, and a nucleation
attempt frequency, which we will approximate by the Debye frequency,
- - s-’ in Si. We thus have a
-
nucleation prefactor of
5 eV activation energy, the Boltzmann factor
yields a significant nucleation rate.
-
lo2* ~ r n - ~ s - ’ .For a crystal temperature of 1000 K, kT 0.086 eV, and for a
lo-”, which when multiplied by the prefactor
138 R. HULL

%
U

w
Q

FIG. 16. Homogeneous activation barriers A E for nucleation of 60°n/2(101) half-loops at

Ge,Sil-,/Si( 100) surfaces, for different values of the dislocation core energy parameter a with removal
of surface steps (RS) or creation of steps (CS).

can reduce activation energies. Local stresses associated with surface steps and facets
(particularly if they are several monolayers, or more, high) can also significantly en-
hance nucleation locally. For example, theoretical (Sorolovitz, 1989; Grinfeld and
Sorolovitz, 1995) and experimental (Jesson et al., 1993, 1995) studies have postulated
and demonstrated the formation of surface cusps during strained epilayer evolution.
These cusps are associated with substantial local stress concentrations, and reduced
barriers for dislocation nucleation. Similar observations of dislocation injection as-
sociated with troughs in surface roughness in the InGaAs/GaAs system have been
described by Cullis et al. (1995).
In general, the boundary between “homogeneous” and “heterogeneous” source mech-
anisms can become indistinct, and to some extent no nucleation event will be truly
homogeneous within the strained layer: loop nucleation will always be energetically
favored at some nonperiodic event, such as a surface step, cusp, or locally enhanced Ge
concentration. This may produce a “hierarchy” of misfit dislocation nucleation sources,
with the lowest activation energy processes exhausted first, and subsequent activation
of increasingly higher activation energy events.

d. Dislocation Multiplication

The most intuitively appealing generic candidate for a source mechanism producing
high densities of misfit dislocations is a multiplication mechanism, by analogy to de-
formation experiments in bulk semiconductors. The idea of a regenerative dislocation
source goes as far back as the Frank-Read source (Frank and Read, 1950). Probably the
first application of this concept to semiconductor strained layer epitaxy was reported
by Hagen and Strunk (1978) for the growth of Ge on GaAs. Their proposed mecha-
 3 MISFITS T R A I N AND ACCOMMODATION 139

FIG. 17. Schematic illustration of the Hagen-Strunk mechanism of dislocation multiplication, (a)-(d).
(e) shows the expected configuration of intersecting dislocations without the Hagen-Strunk mechanism oper-
ating; ( f )shows the expected configuration after operation of the Hagen-Strunk mechanism. Reprinted with
permission from R. Hull and J.C. Bean, Critical Reviews in Solid State and Materials Science 17, 507-546
(1992). Copyright CRC Press, Boca Raton, Florida.

nism, illustrated in Fig. 17, relies upon intersection of dislocations with equal Burgers
vectors along orthogonal interfacial (011) directions within a (100) interface. The very
high energy configuration associated with the intersection is lowered by formation of
two interfacial segments with localized climb producing rounding near the original in-
tersection, as shown in Fig. 17(b). This reduces the very high radius of curvature at the
original intersection, and lowers the dislocation configurational energy. Local stresses
near the dislocation intersection now modify the local energy balance for the disloca-
tion, causing one of the rounded segments of dislocation to move toward the surface, as
shown in Fig. 17(c). When the tip intersects the surface, Fig. 17(d), a new dislocation
segment is formed, which can act as a new misfit dislocation. This process may repeat
many times, producing a regenerative dislocation source.
Several authors have since invoked this mechanism as a dislocation source in
Ge,Sil-,/Si strained layer epitaxy (e.g., Rajan and Denhoff, 1987; Kvam el aE., 1988).
However, the experimental evidence for the Hagen-Stmnk source is often based upon
dislocation configurations as shown schematically in Fig. 17(e), where dislocation seg-
ments align along (011) directions across the original intersection event. The true
“footprint” of the Hagen-Strunk source is as shown in Fig. 17(f) where alignment
across the intersection does not occur. The configuration of Fig. 17(e) is simply that of
Fig. 17(b) where many orthogonal dislocation intersection events have occurred (Dixon
and Goodhew, 1990).
140 R. HULL

Direct evidence for different multiplication mechanisms has been reported by sev-
eral other authors. Tuppen et al. (1989, 1990) used Nomarski microscopy of chem-
ically etched Ge,Sil-,/Si(100) (x 5 0.15, epilayer thickness 0.9pm) structures
to demonstrate greatly enhanced dislocation nucleation activity associated with dis-
location intersections. Two distinct Frank-Read type and cross-slip mechanisms for
the multiplication process were proposed. An important requirement for these spe-
cific mechanisms, and for most other multiplication mechanisms, is the existence of
two pinning points along that segment of dislocation line that acts as the regenera-
tive source. The segment then grows by bowing between the pinning points, and may
eventually configure into re-entrant and re-generative geometries, similar to the Frank-
Read source. In the models described by Tuppen et al. (1989, 1990), dislocation in-
tersections act as these pinning points. Capano (1992) described several multiplicative
configurations, not involving dislocation intersections, for a single isolated threading
dislocation. These mechanisms generally involved dislocation cross-slip following pin-
ning of segments of the dislocation by inherent defects in the dislocation or host crys-
tal (e.g., constrictions in the partial dissociation along the dislocation line). Capano
measured a minimum “multiplication thickness” for these processes of 0.67 p m for
Ge0,13Si0,87/Si(100) structures. This is very consistent with the experiments of Tup-
pen et al. (1989, 1990), who studied 0.5 pm, 0.7 p m and 0.9 p m thick epilayers with
Ge concentration x = 0.13, and first observed evidence of multiplication processes
in the 0.7 p m layer. Capano also modeled the minimum epilayer thickness required
to accommodate the intermediate cross-slip configurations in the multiplication pro-
cesses he described, and derived minimum epilayer thicknesses an order of magnitude
lower than he experimentally observed. The discrepancy was attributed to the density
of available pinning points along the dislocation line.
A very complete description of a Frank-Read type source in Ge,Sil-,/Si epitaxy
has been provided by LeGoues et al. (1991,1992). This mechanism involves disloca-
tion interactions at the interface to provide the required pinning points, and was most
generally observed in graded composition layers. Similar mechanisms have also been
reported by Lefebvre et al. (1991) for the strained InGaAs/GaAs system.
Beanland (1995) described additional multiplication sources in InGaAs/GaAs struc-
tures, involving operation of spiral sources operating either from dislocation interac-
tions, or from the tips of pre-existing edge dislocations.
Albrecht et al. (1995) demonstrated that dislocation multiplication could be asso-
ciated with surface roughening (see discussion in Section V.2.c). They used finite
element modeling to model stress concentrations at ripple troughs in relatively low
Ge concentration (x = 0.03) Ge,Sil-,/Si( 100) heterostructures, which were demon-
strated to lead to dislocation injection into the substrate and subsequent Frank-Read
type multiplication sources.
In summary, it appears that dislocation multiplication mechanisms do occur in
strained GeSi layers. However, a significant density of dislocation pinning points is
required for these mechanisms to operate efficiently. These pinning points can either
 3 MISFITSTRAIN AND ACCOMMODATION 141

occur from dislocation intersections (which requires a significant source dislocation

density), or from inherent features of the dislocation or host crystal (constrictions,point
defects, etc.) It also appears that minimum epilayer thicknesses are required for mul-
tiplication, as intermediate cross-slip or loop configurations have to be accommodated
during the regeneration process. Tuppen et al. (1989, 1990) and Capano (1992) mea-
sured minimum epilayer thicknesses > 0.5 p m for Ge concentrations of x = 0.13,
but LeGoues et al. (1991, 1992) did observe multiplication in graded structures with
thicknesses as small as 200-300 nm.

e. Experimental Measurements of Dislocation Nucleation Rates

A powerful insight can be provided into the epilayer thickness and composition
( h ,x) regimes in which different dislocation mechanisms dominate by experimental
study of dislocation nucleation rates and activation energies. Unfortunately, relatively
little experimental data have been reported for the Ge,Sil-,, or any other strained
layer system. The most extensive experimental work to date has been by Houghton
(1991), who used direct counting of dislocation source densities via optical microscopy
of etched (Si)/Ge,Sil-,/Si(lOO) structures following post-growth annealing. Only
the early stages of strain relaxation were studied (due to the resolution limits inherent
to conventional optical microscopy), where less than about 0.1% of the initial lattice
mismatch strain was relaxed. The number of observed dislocations followed the trend

In this equation B is a constant of the order loi8 s-’. The activation energy for
dislocation nucleation, En is of the order 2.5 eV for 0.0 < x < 0.3, and epilayer
thicknesses in the range 100-3500 nm. Measured nucleation rates were in the range
10-’-105 cm-*s-l. In the Houghton formulation, NO is an adjustable parameter (de-
termined by experimental inspection) for each structure and represents the number of
pre-existing heterogeneous nucleation sites before the anneal is started. Measured val-
ues for NO reported by Houghton were in the range 103-105 cm-* and generally in-
crease for higher x.
Equation (36) implies that, at least in the early stages of relaxation, a12 misfit dis-
locations are nucleated from heterogeneous sources. As discussed in Section V. 1 of
this chapter, this appears implausible during later stages of dislocation-mediated strain
relief. Also note that Perovic and Houghton (1992) later reinterpreted Eq. (36) in terms
of “barrierless” nucleation of dislocations, where it was assumed that the activation
energy of 2.5 eV measured for dislocation nucleation was essentially the 2.2-2.3 eV
activation energy associated with dislocation growth by glide (see Section V.3 of this
chapter), that is, the activation energy of Eq. (36) corresponded to the rate at which
dislocations grew to be significantly large to be detected by optical microscopy.
142 R . HULL

Some other data for dislocation nucleation rates in GeSi/Si heterostructures have
been reported by Hull et al. (1989a) using in situ TEM measurements (these exper-
iments correspond to much later stages of the relaxation process than those reported
by Houghton, as TEM imaging covers a much smaller field of view than optical mi-
croscopy). Nucleation activation energies of the order 0.3 eV were reported for a 35 nm
Geo.25Si0.7s/Si(100)structure, with a prefactor of 2.2 x lo6 cm-2.y-l. The observed
dislocation densities were relatively high (-- 107-108 cm-’), therefore strongly sug-
gesting quasi-homogeneous nucleation in these experiments. Although this activation
energy is very different to that reported by Houghton, overall nucleation rates at compa-
rable excess stress are of the same order of magnitude (e.g., at a temperature of 650 “C
-
in a 100 nm x = 0.23 structure, Houghton reports a nucleation rate 3 x lo4 cm-’s-l,

-
whereas for the 35 nm, x = 0.25 structure, Hull et al. (1989a) reported a nucleation rate
5 x lo4 cm-2s-’). In capped Si/Ge,Sil-,/Si(100) structures (0.10 < x < 0.30)
-
we have measured activation energies in the range 0.5-1.0 eV (Hull et al., 1997).
Nucleation data from the work of Houghton and of Hull et al. is shown in Fig. 18.
Other quantifications of misfit dislocation nucleation in the Ge,Sil-,/Si system
are the work of LeGoues et al. (1993), relating to the Frank-Read-like multiplication
mechanism proposed by that group, and Wickenhauser et al. (1 997), relating to hetero-

energy for the former mechanism of

of 6 x 10’ ~ m - ~ s -from
l
-
geneous nucleation in Geo.16Sio.84layers. LeGoues et al. (1993) inferred an activation
5 eV, and a total dislocation nucleation rate
the amount of crystallographic tilt of the epilayer produced
by differential dislocation densities on different glide planes in Ge,Sil-, layers grown
on misoriented Si( 100) substrates. Wickenhauser er al. (1997) determined a heteroge-
neous source (the physical nature of the source was not identified) activation energy of
2.8 eV.

Summary of Misfit Dislocation Nucleation

From the discussion of the preceding few subsections it is clear that there is not a
universal model for dislocation nucleation in GeSi-based heterostructures, and, further,
that we should not expect such a universal model.
The very high dislocation nucleation rates associated with strain relaxation in higher-
strained systems are consistent with homogeneous, or quasi-homogeneous processes
(such as alloy clustering, or epilayer roughening) in this strain regime. Although
calculations of true homogeneous nucleation predict that strains of order 3 4 % or
higher are required for appreciable nucleation rates, local stresses associated with
quasi-homogeneous processes appear to lower this strain threshold down to 2% or
even 1%. At strains below this level, it appears that a combination of heterogeneous
nucleation and multiplication dominates. The initial heterogeneous stage is severely
source limited, thus the metastable growth regime at low strain and low temperature is
very large, as indicated in Fig. 11. As the network of dislocations from heterogeneous
 3 MISFITSTRAIN AND ACCOMMODATION 143

a 10' .
-
nn 10'.
"
u- 10'
t-
4
*
U
102
0
I-
$ lo'

d
2 100

10'9

06 I 1 I .6
INVERSE TEMPERATURE, looo/T K - I

A
J
i
I
lo2 1
m
A
RHx=OZS,h=35nm
R H x=O 30, h=30 nm
DCH xdJ.23, h=l OOnm

L
1 OI6
7 8 9
A10
l/kT (J-lxlO19)

FIG. 18. (a) Measured misfit dislocation nucleation rates during annealing of (Si)/Ge,Si*-,/Si( 100)
heterostructures; A = 20 period superlattice of 32 nm .%/lo nm G ~ o . ~ o S ~ D
O .=~ 500
O ; nm Geo.035Sio.965;
E = 3000 nm Ge0.035Si0.965; F = 190 nm Ge0.17Si0.83; G = 100 nm Ge0.23Si0.77. Reprinted with
permission from D.C. Houghton, Appl. Phys. Lett. 55, 2124, Figure 2. Copyright 1990 American Institute
of Physics. (h) Comparison of nucleation rates measured by Houghton (1991) (DCH) and Hull etal. (1989a,
1997) (RH) for Ge,Sii-,/Si(100) -
structures with similar composition (x 0.2-0.3) and excess stress.

sources eventually develops, the required dislocation intersection events generally as-
sumed to be required to fuel multiplication processes can occur.
We can thus tentatively map out three broad nucleation regimes: in high strain sys-
tems (> 1-2%), relaxation is by homogeneous and quasi-homogeneous nucleation
processes. In low strain systems (- 1% or less), heterogeneous sources provide the
initial background dislocation density in the low epilayer thickness regime of the order
of a few hundred nanometers or less. Multiplication mechanisms then become domi-
nant in the low strain, high thickness regime.
144 R. HULL

Experimental mapping of dislocation nucleation rates and activation barriers have so

far provided little additional insight into delineating these different nucleation regimes.
The only extensive existing data set from Houghton is apparently consistent with het-
erogeneous sources in the low strain regime.

3. MISFITDISLOCATION
PROPAGATION

Experimental descriptions of dislocation motion are relatively well developed, and

in general follow straightforwardly from treatments of dislocation glide in bulk Si and
Ge crystals, as reviewed in Section 111and described by Eq. (20)

u = ugmm exp[-E,,(a)/kT]

For misfit dislocations in Ge,Sil-, heterostructures, we shall also use this equation
to describe dislocation velocity, using the excess stress for CJ in the prefactor.
- -
In the low stress (10-100 MPa) regime for intrinsic, pure crystals, EL, I .6 eV
in Ge and 2.2 eV in Si. The prefactors are very similar for the two materials ( u g

faster in Ge than Si (by a factor -

3 x 10-'m2Kg-'s) (Alexander and Haasen, 1968) and thus dislocations glide a lot
5000 at 550 "C). Thus we should expect that for
Ge,Sil-, alloys the glide activation energy will decrease, and the glide velocity will
increase, with increasing x. Unfortunately, the dependence of E , ( x ) from bulk crys-
tals is not known (apart from recent measurements very near x = 1.0 (Yonenaga and
Sumino, 1996), which scaled well from measurements on bulk Ge), and in general we
are restricted to linear interpolation of the values for bulk Si and Ge. The composition
dependence of E,(x) in Ge,Sil-, alloys is further complicated by the relationship be-
tween x and o:it is predicted that kink nucleation energies (and hence glide activation
energies) are reduced at sufficiently high applied stresses (Seeger and Schiller, 1962;
Hirth and Lothe, 1982), such as are typically encountered in Ge,Sil-,/Si heteroepi-
taxy for all but the most dilute Ge concentrations. The stress dependence of the disloca-
tion velocity is still somewhat uncertain in bulk Si and Ge crystals, let alone Ge,Sil-,
alloys; undoubtedly part of this uncertainty depends upon how the stress dependence
is apportioned between the prefactor and the exponential in Eq. (20). However, there is
strong evidence from bulk measurements in Si that the activation energy E , is stress-
dependent for (T of the order of a few hundred MPa or more (Kusters and Alexander,
1983). In general, these stress effects will also need to be deconvoluted in glide ac-
tivation energy measurements at the enormous stresses (of order 1 GPa), which can
be present in Ge,Sil-, heterostructures. An extensive set of measurements by Imai
and Sumino (1983) has yielded a linear stress dependence, nz = 1 .O in Eq. (20), at
stresses of the order tens of MPa in Si, and this is also the dependence predicted by the
generally accepted microscopic model of dislocation motion, the Hirth-Lothe diffusive
double kink model (Hirth and Lothe, 1982).
 3 MISFITS T R A I N A N D ACCOMMODATION 145

Misfit dislocation propagation velocities in (Si)/Ge, Sil --x /Si( 100) heterostructures
have been studied by several groups, using either in situ TEM observations (Hull et
al., 1989a, 1991a; Nix et al., 1990) or chemical etching and optical microscopy (Tup-
pen and Gibbings, 1990; Houghton 1991; Yamashita et al., 1993). In Fig. 19, we plot
measured dislocation propagation velocities vs excess stress a,, from these different
groups for a temperature of 550 "C (interpolated where necessary from measurements
at other temperatures). The data between different groups and different techniques
agree relatively well. Note that even the relatively limited vertical scatter of data in this
plot is not necessarily due to experimental error, as there are factors other than just ex-
cess stress (primarily Ge concentration in the Ge,Sil-, alloy, as discussed previously)
which determine dislocation velocity.
In our own work we have made hundreds of measurements of misfit dislocation
velocities from a wide range of (Si)/Ge,Sil -,/Si( 100) heterostructures (see, for ex-
ample, Hull et al., 1991a; Hull and Bean, 1993). The data from different structures
can be effectively normalized to each other by plotting the logarithm of the quantity v*
inverse temperature, where:
[0.6x(eV)/kT]
u* = [v,e- 1/sex (37)

In this expression, v, is the measured dislocation velocity and the quantity

e-[0.6x(eV)lkT1 accounts for the 0.6 eV glide activation energy difference between Ge
and Si, such that we are assuming E , ( x ) = 2.2 - 0 . 6 ~eV in Ge,Sil-,. Equation (37)
therefore effectively normalizes the measured dislocation velocity to an equivalent ve-
locity at an excess stress of 1 Pa in pure Si. In Fig. 20, we plot our measurements of
misfit dislocation velocities from a wide range of (Si)/Ge,Sil -x/Si( 100) heterostruc-
tures (Hull et al., 1991a; Hull and Bean, 1993), normalized according to Eq. (37).

1 )4

FIG. 19. Measured dislocation Propagation velocities in (Si)/Ge,SlI -, /Si(lOO) heterostructures vs

excess stress oex at 550 "C from Houghton (1990), Hull et al. (1991a, 1993), Tuppen and Gibbings (1990),
Nix et al. (1990), and Yamashita et al. (1993).
146 R. HULL

-
h
-33 \4 1

-
M
- -35 ~

Y -31
f
v
3 -39-
B
-
L -41
-43
~

- "*=

-45 '
7 8 9 10 1
l/kT (J-1x1019)

FIG. 20. Normalized dislocation velocities for uncapped and capped (300 nm Si)Ge, Sil -,/Si(lOO)
structures. Faint dashed lines either side of the main regression lines correspond to 0.7 confidence bounds.

Note that there is a systematic difference in normalized velocity for capped vs un-
capped Ge,Sil --x layers. We have ascribed this difference to different microscopic
kink mechanisms for dislocation propagation motion in these two geometries.
The regression line fits to the data in Fig. 20 are given for uncapped structures (a)
and capped structures (b) by
u* = ,-(7.8+l.4),-(2.03+0.10 eV)/kTm2S~g-I
(a)
*= ,- ,-1.93+0.10 eV)/kT m 2 s ~ g - I
( 10.4fl.4) (
(b) (38)

To calculate the misfit dislocation velocity at a given temperature in a given (Si)/

Ge,Sil -x/Si( 100) heterostnicture, therefore, one simply multiplies the relevant u* by
a
,
, ,iO.WeV)lkTI
Note that Eqs. 38(a) and (b) are still largely empirical, as they ignore further mi-
croscopic details of the diffusive double kink model such as the dependence in some
regimes of the velocity upon the length of the propagating dislocation line (see Sec-
tion 111.6) and single vs double kink dynamics (Hirth and Lothe, 1982; Hull et al.,
1991a; Hull and Bean, 1993). A stress-independent activation energy is also implied
by the form of Eqs. 38(a) and (b), although note that the regression calculations give ac-
tivation energies 1.9-2.0 eV, which is less than the 2.2 eV activation energy that would
be expected from the normalization to equivalent velocities in Si. (The lower value
of 1.9-2.0 eV corresponds to an average 0.2-0.3 eV reduction in activation energy
due to the stress dependence.) However, from the regression coefficients of Eqs. 38(a)
and (b) ( R = 0.93 and 0.96, respectively), it is apparent that the equations offer good
semiempirical descriptions of misfit dislocation velocities.
There have been other attempts to fit measured dislocation propagation velocities
systematically to an empirical model. Houghton (1991) modeled his measurements
 3 MISFIT S T R A I N A N D ACCOMMODATION 147

of misfit dislocation velocities using a slightly modified version of Eq. (20): u =

uo(oex/G)me(-EL,/kT) with m = 2, uo = (4 i 2) x 10" ms-', and a constant ac-
tivation energy of E , = 2.25 f 0.05 eV for 0.0 < x < 0.3 in (Si)/GeXSil-,/Si(100)
structures. The higher pre-exponential factor, m, may be accounted for by the assump-
tion of the constant activation energy: the higher Ge concentration structures (which
in general will correspond to the structures with higher excess stresses) will have en-
hanced velocities due to the lower dislocation glide activation energy in Ge than in
Si. Assumption of a constant value for E , will therefore tend to overestimate the
pre-exponential stress dependence of dislocation velocities in higher Ge concentration
films, producing an artificially high value of rn.
Tuppen and Gibbings (1990) studied misfit dislocation velocities in
(Si)/GexSil-,/Si(lOO) structures with relatively low Ge concentrations (typically x i
0.15). They observed a linear pre-exponential dependence of velocity upon excess
stress, m = 1 in Eq. (20), and a prefactor consistent with bulk Si and Ge measure-
ments (UO = 2.81 x m2Kg-'s). The measured glide activation energy was
E , ( x ) = 2.156 - 0 . 7 ~
eV, which is somewhat lower than predicted from bulk values
(perhaps due to the theoretically predicted stress dependence of the activation energy).

-
They also observed in certain structures a dependence of the dislocation velocity upon
the threading dislocation length L f i h (this relationship arises from the orientation
of the threading arms within the inclined { 111) glide planes), where h is the Ge,Sil-,
epilayer thickness, consistent with the predictions of the double kink model (Hirth and
Lothe, 1982) for dislocation lengths, L << X, with X the average distance between
kinks. (Note that the double kink model also predicts an increase in activation energy
in this regime, compared to the bulk regime where L >> X.This was not observed by
Tuppen and Gibbings, however.) A similar length dependence has been reported by
Yamashita et al. (1993).
In Fig. 21 we show data from misfit dislocation velocities in GeXSil-,/Ge(100)
structures (Hull et al., 1994). These structures are in the low strain (x > 0.8) regime,
such that the preferred dislocation type is b = a/2(101) (total dislocation), rather
than the b = a/6(211) (partial dislocation) configuration, which would be expected

Ge,Sil-, layers ( E -
at higher strains (see Section 111.8). Figure 21(a) shows that for comparably strained
0.008) grown on Ge(100) and Si(100) substrates, dislocation
velocities are much higher for the Ge-rich alloy grown on the Ge substrate than for the
Si-rich alloy grown on the Si substrate, as expected from the lower activation energy
for dislocation glide in Ge than Si. In Fig. 21 (b) we show how these measurements of
dislocation velocities in Ge,Sil-,/Ge( 100) structures follow the same scaling laws as
the structures grown on Si substrates, as defined by Eq. 38(a).
Studies of misfit dislocation velocities in GexSi~-,/Si(ll0) structures (Hull and
Bean, 1993) have enabled comparison of the velocities of b = a/6(211) and b =
a/2(101) Burgers vector misfit dislocations. As illustrated in Fig. 22, the partial dis-
locations actually have lower velocities than the total dislocations. This is somewhat
surprising, as we would expect the motion of the total a/2(101) dislocation to be con-
148 R. HULL

13 1 i
1

.-... -.
1
-t 685A x=O 18, Si(100)
750A x=0.80, Ge(100)
I
-1 ____ _ _ _ _
_J
i
A

8 9 10 11 12
l/kT (J-lxlO19)

-34~ . I

FIG. 2 1. (a) Comparison of measured dislocation velocities in Ge,Sil-, layers with comparable atrain
and excess stress grown on Si(100) and Ge(100) substrates. (b) Normalized dislocation velocities in
Ge,Sil-, layers grown on Si(100) and Ge(100) substrates. Reprinted with permission from R. Hull er
a/. Appl. Phys. Leu. 65, 327, Figures I and 3. Copyright 1994 American Institute of Physics.

-34 G
-36 -
-3 8
-40 -
-42 -
-44-

-46; 9 10
l/kT (J-1x1019)

FrG. 22. Experimental measurements of dislocation velocities for 60"a/2( 101) and 9Oou/6(211) misfit
dislocations in Ge, Sil-, /Si( 110) heterostructures. Velocities are normalized according to Eq. (37).
 3 MISFITS T R A I N A N D ACCOMMOI)I\TION 149

trolled by the slower of the two (i/6(211) partials into which it is dissociated, that is,
the maximum velocity of the total dislocation would be limited to that of the slower
of the two partials. Hull and Bean (1993) suggested that this apparent dichotomy can
be resolved by consideration of details of the kink nucleation process (essentially the
effect of stacking fault energies within the critical kink configurations).
The data o n dislocation glide in bulk Si and Ge also reveals strong dependence upon
dopant and other impurities (Hirsch 1981; Imai and Sumino, 1983; George and Rabier,
1987). Some measurements of dopant and impurity effects upon dislocation glide in
Ge,Sil-, heterostructures have also been made. Gibbings et rtl. (1992) studied the ef-
fect of both p-type (€3) and n-type (As) doping upon dislocation velocities in strained
Ge,Sil .-, layers grown upon Si( 100) substrates. Consistent with studies of doping
effects upon dislocation velocities in bulk Si, it was found that high n-type doping
(1 l o i 7 cm-j) could enhance dislocation motion in the Ge,Sil-., layer, while p-type
doping had relatively little effect. The effects of very high (- 10'9-102"~ m - oxygen
~ )
concentrations upon dislocation glide velocities in strained Ge,Sil -.r layer have also
been studied (Nix et al., 1990; Noble et al., 1991; Hull et al., 1991b). These studies
concluded that misfit dislocation velocities were reduced and critical thicknesses for
dislocation introduction increased, presumably by locking effects of the oxygen upon
dislocation motion. Finally, Pethukov (1995) has considered the effects of composi-
tional fluctuations within the GeSi alloy upon dislocation propagation.

4. MIsm DISLOCATION IKTERACTIONS

Interaction between misfit dislocations is a critical process in the later stages of plas-
tic relaxation. The primary interaction mechanism arises from the force between two
dislocation segments, which results from the interaction of the strain fields around
them. As described by Eq. (16), this force is generally inversely proportional to the
segment separation, and proportional to the dot product of the two dislocations Burg-
ers vectors. Calculation of the exact magnitude, components and spatial variation of
this force is complex for the general configuration, but relatively straightforward for
simplified configurations (e.g., for parallel screw dislocations, the force per unit length,
F / L = Gh2/2n).
The most dramatic effect of misfit dislocation interactions is that they can pin motion
of propagating dislocations, effectively leading to effects that are analogous to work-
hardening in metals (Dodson 1988, Hull and Bean, 1989b; Freund, 1990. Gosling etal.,
1994; Fischer and Richter, 1994; Gillard and Nix, 1995; Schwarz. 1997), as illustrated
experimentally in Fig. 23. To understand this, consider the case of a total dislocation
propagating along an (011 ) direction in a (100) interface. and about to intersect a pre-
150 R. HULL

FIG. 23. Experimental demonstration of misfit dislocation blocking events in a 300 nm S1/59 nm
Ge0,18Si0,82/Si(100) heterostructure.

existing orthogonal interfacial dislocation, as illustrated schematically in Fig. 24. The

excess stress driving dislocation motion is o,, = a, - 07. If the Burgers vectors
of the two dislocations are parallel, there will be a repulsive interdislocation stress
between them, which will act against the excess stress, and whose magnitude will
depend upon the longitudinal coordinate along the threading arm (it will be highest at
the points of closest approach near the interface, and lowest near the epilayer surface).
As the two dislocations come closer, this repulsive stress will exceed the excess stress
along greater fractions of the propagating threading dislocation, pinning motion of
those segments of the threading arm. If enough of the threading arm is pinned, it will
be unable to move past the orthogonal dislocation. This is clearly more likely to occur
(because of the l / r dependence of the inter-dislocation force) in thinner epitaxial layers
than thicker epitaxial layers. (Note that although the preceding discussion assumes a
repulsive interaction, that is, parallel components of Burgers vectors, the discussion is

FIG. 24. Schematic illustration of the forces acting on a propagating threading dislocation ( B C ) when
cr, and oy are the Matthews-Blakeslee lattice
it encounters a pre-existing orthogonal misfit dislocation (D);
mismatch and line tension stresses, respectively; OD is the horizontal component of the inter dislocation
stress between D and B C .
 3 MISFITS T R A I N A N D ACCOMMODATION 151

quantitatively the same for attractive interactions, that is, anti-parallel components of
Burgers vectors, as the net stress is then reduced as the propagating dislocation attempts
to pull away from the intersection event. For simplicity, we will assume repulsive
dislocation interactions in subsequent discussion, but the concepts will be the same for
attractive interactions.)
Thus, dislocation pinning events are most likely in thinner layers. Substantial dis-
location densities in thin layers occur more readily in structures that are initially more
highly strained (because the critical thickness is lower and dislocation nucleation and
propagation kinetics are more rapid than lower strained structures). Thus these pinning
events tend to be more critical in growth of higher strain, lower thickness structures.
This is one reason why, for a given amount of relaxation, higher strain systems have
higher threading dislocation densities than lower strain systems (Hull and Bean, 1989b;
Kvam 1990).
The pinning process has been modeled in detail by Freund (1 990), Gosling et al.
(1994) and Schwarz (1997). These authors evaluated the elastic integrals for this con-
figuration, and modeled the regimes of epilayer thickness and strain ( h ,E ) where this
blocking occurs. Results from the work of Freund are shown in Fig. 25. The formula-

0 case A
A case B
-E
C

J
W

FIG.25. Plot of minimum strain required for passage of a 60°a/2(101) misfit dislocation past a pre-
existing orthogonal 60"a/2(101) misfit dislocation at a Ge,Si~-,/Si(100) interface vs epitaxial layer thick-
ness. The solid line marked A corresponds to the case where the misfit dislocations Burgers vectors are
inclined at 90' to each other and the solid line marked B corresponds to the case where the misfit disloca-
tions Burgers vectors are parallel to each other. The dashed line corresponds to the minimum strain analog
to the critical thickness for misfit dislocation introduction. Reprinted with permission from L.B. Freund,
J. Appl. Phys. 68, 2073, Figure 11. Copyright 1990 American Institute of Physics.
152 R . HULL

tion of Gosling et al. (1995) is relatively amenable to analytical approximations, and

to evaluation of a more general calculation, the mean position-dependent stress field
om(I-) experienced by a propagating dislocation.
Inspection of Fig. 25 shows that there is a region of ( h ,6) space for which dislo-
cation blocking is possible. The lower bound of this region is defined by the critical
thickness h , ( ~ ) below
, which dislocation motion is not energetically favored (inde-
pendent of any interaction processes). The upper bound is defined by the curve hb(&)
(note that the locus of this curve depends upon the angle between the Burgers vectors
of the intersecting dislocations). For intermediate thicknesses hc(&) < h < h b ( & ) ,
pinning of propagating dislocations will occur. For thicknesses h > hb(&),blocking
will not occur, but the propagating dislocation will be slowed during approach to the
intersection event (for a repulsive interaction stress), as the local net stress is reduced
by the interaction stress. Conversely, as the propagating dislocation moves away from
the interaction event, the net stress is increased by the repulsive interaction.
Dislocation interactions also inhibit complete strain relaxation in any thickness of
strained epilayer (this will have significant ramifications for the reduction of threading
dislocation densities, as will be discussed in Section VI of this chapter). This is be-
cause as the residual elastic strain tends to zero, the blocking thickness hb(&)tends to
infinity. Thus, in the latest stages of strain relaxation, dislocations will find it difficult
to propagate past each other in any epitaxial layer thickness, leaving residual threading
dislocation densities.

5 . KINETICMODELING OF STRAIN RELAXATION B Y MISFITDISLOCATIONS

The processes of dislocation nucleation, propagation, and interaction define the ki-
netics of relaxation by misfit dislocations. There have been several attempts to com-
bine these processes into predictive models of strain relaxation. Dodson and Tsao
(1987) published the first comprehensive kinetic description of relaxation by misfit
dislocations in Ge,Sil -n /Si heterostructures. They combined the concepts of excess
stress, bulk parameters for dislocation propagation, and dislocation multiplication aris-
ing from a pre-existing dislocation source density, into a theory of plastic flow, thereby
producing a predictive equation for strain (and hence dislocation density) for finite time
at temperature
+
d [ A ~ ( t ) ] / d=r CG2(so- A & ( t )- Ecq)2(Ae(r) E,) (39)
Here, A s ( t ) is the amount of strain relieved by misfit dislocations, EO is the initial
lattice mismatch strain, E, arises from an initial “source” density of dislocations from
which multiplication proceeds, eeq is the equilibrium strain in the structure, predicted
by solution for E of Eq. (23) with oeX= 0, and C is a constant (C and E, were found
to be 30.1 and lop4, respectively, from fitting to available data). Using this model,
Dodson and Tsao were able to predict a wide range of experimental measurements of
strain relaxation in GeSi heterostructures. In particular, they were the first to demon-
 3 MISFITS T R A I N AND ACCOMMODATION 153

K I N E T I C MODEL
( 5 5 0 0I~ x . BEAN E r AL
550'C
0
\
0 - KASPER ET AL
s
v
3
lo - 750°C

K I N E T I C MODEL
( 7 5 0 ~ ~

0 0.01 0.02 0.03

LATTICE MISMATCH

FIG. 26. Predictions of temperature-dependent "critical thickness" (as defined by the Ge,Sil --x layer
thickness at which misfit dislocations are first experimentally detected) from the Dodson-Tsao model and
corresponding experimental data in the Ge,Sil -x/Si(lOO) system from Bean et al. (1984), Tg = 550 "C;
and Kasper et al. (1975), Tg = 750OC. Reprinted with permission from B.W. Dodson and J.Y. Tsao, Appl.
Phys. Lett. 51, 1325, Figure 3. Copyright 1987 American Institute of Physics.

strate convincingly that kinetic modeling of the minimum detectable strain relaxation
(or equivalently, minimum misfit dislocation density) accurately predicted temperature-
dependent critical thicknesses, as illustrated in Fig. 26. In subsequent work, Tsao et
al. (1988) constructed a framework for describing relaxation kinetics by misfit disloca-
tions in Ge,Sil -,/Ge( 100) heterostructures in terms of deformation mechanism maps
(Frost and Ashby, 1982). Experimentally, it was found that temperature and excess
stress were the critical parameters in determining plastic relaxation rates, consistent
with thermal activation of dislocation nucleation and motion, as discussed previously
in this section. For example, it was determined that the onset of detectable strain reiax-
ation (using Rutherford backscattering spectroscopy, with a detectable strain relaxation
of - 1 part in lo3) occurred at excess stresses of 0.024 G and 0.0085 G at 494 "C and
568 "C, respectively. This is consistent with much more rapid relaxation kinetics at
the higher temperature. Dodson and Tsao (1988) subsequently developed scaling re-
lations for relaxation by misfit dislocations in GeSi heterostructures as functions of
temperature and excess stress

As(gex1, Ti)/A&(oe,o, To) = (a,-xi/a,,o)2elE(g,exo)/kTo - E ( O ~ I ) / ~ T I(40)

I

where A&(ce,1, T I )represents the degree of plastic relaxation for a structure with ex-
cess stress u , , ~at a temperature Ti during a growth or annealing cycle, and As(cr,,o, To)
represents a relaxation standard for a structure with excess stress ae,0 and temperature
154 R. HULL

To. The effective activation energy E(o,,J was determined to be given by (Dodson and
Tsao, 1988)

where T, is an effective alloy melting temperature obtained by a linear weighting of

the melting temperatures of the pure components.
Hull et al. (1989b) attempted to model the strain relaxation process in GeSi het-
erostructures by direct measurement of the fundamental parameters defining misfit
dislocation kinetics, and subsequent incorporation into a kinetic model. The relevant
measurements were made by direct in situ TEM observations and quantification of
misfit dislocation nucleation, propagation and interaction processes, followed by in-
corporation into the equation'

where A&(t), L ( t ) , N ( t ) and u ( t ) are the degree of strain relaxation by misfit dislo-
cations, total interfacial misfit dislocation length per unit area of interface, number of
growing dislocations per unit area of interface and average dislocation velocity at time
t , respectively. The integral is evaluated over all time for which a,, > 0, for either
growth or post-growth annealing. Experimental descriptions are used for N ( t ) and
v(r). The effects of misfit dislocation interactions are incorporated by reducing N ( t )
by the number of dislocations pinned according to the previous discussion in this sec-
tion, and by incorporating an empirical velocity-stress-temperature relation in a regime
where dislocation interactions strongly affect propagation rates (Hull et al., 1989a,b).
Comparisons of this model with experiment are shown in Fig. 27.
Subsequent models have modified and developed the concepts embodied in Eq. (42);
Houghton (1991) applied a version of Eq. (42) to the initial stages of relaxation. In this
regime, where misfit dislocation densities are low, dislocation interactions are relatively
unimportant, and the integral in Eq. (42) simplifies to the product of the expressions for
dislocation nucleation and propagation, which were directly measured by Houghton,
and represented by the e q ~ a t i o n : ~

where NO is the initial source density of misfit dislocations at time t = 0. Typical

measured values of NO were in the range 103-105 cm-*. Gosling et al. (1994) further

*The exact relationship between A s and L ( t ) depends upon the shape of the substrate, and Eq. (42) is
strictly true only for a square or rectangular substrate. For a circular substrate, a constant of proportionality
4/71 should be included in the middle expression in Eq. (42).
'Note that the equation's presentation here is identical to its presentation in work by Houghton (1991).
The reason that it does not appear to be dimensionally correct is that various constants (e.g., a factor G-"')
are combined into the perfactor term of I .9 x lo4.
 3 MISFITSTRAIN A N D ACCOMMODATION 155

-
FIG.27. Comparison of the predictive strain relaxation model of Hull et al. (1989b) with experimental
data for a 35 nm Ge0.2sSi0.75 layer annealed for 4 min at successively higher temperatures: (a) average
distance between misfit dislocations p ; (b) areal density of threading dislocations N ; and (c) average misfit
dislocation length 1. Reprinted with permission from R. Hull et al., J. Appl. Phys. 66, 5837, Figure 6.
Copyright 1989 American Institute of Physics.

developed the concepts of Eq. (42), using more complete descriptions of misfit dislo-
cation interactions, and a fittable form for dislocation nucleation. They were able to
successfully reproduce the experimental data of Fig. 27.
In summary, although the different models developed to date for predicting relax-
ation rates by misfit dislocations in Ge,Sil-, heterostructures may at first sight appear
to have different forms, they generally attempt to combine the concepts of misfit dislo-
cation nucleation, propagation, and interaction to construct a framework for predicting
relaxation kinetics. In general, the framework of Eq. (42) has been adopted for this ki-
netic modeling. Quantitative implementation of this framework, however, will depend
upon the strain and relaxation regimes under consideration. In general, a universal
model for misfit dislocation relaxation kinetics is unlikely to have a simple analytical
form due to existence of different mechanistic regimes, and due to the complexity of
some of the constituent processes (e.g., interactions, multiplication).

VI. Misfit and Threading Dislocation Reduction Techniques

1. INTRODUCTION

Silicon substrate wafers can now be routinely grown with fewer than 10 disloca-
tions per cm’, representing a remarkable degree of structural perfection. Homoepitax-
156 R. HULL

ial growth of Si can compete with this level of structural quality. If Ge,Sil-,-based
strained layer epitaxy is to compete with existing device technologies, either it must
offer unique and overwhelming advantages over bulk or homoepitaxial structures, or
it must be of sufficient structural perfection to be compatible with existing processing
technologies. In this section, we will discuss prospects and techniques for attaining
Ge, Sil-, layers (especially supercritical structures) of the required structural quality.
The magnitude of defect densities tolerable in device and circuit manufacture is a
somewhat subjective (and controversial) topic, but maximum permissible densities of
order lO5cmP2 in majority carrier devices, lo3 cmP2 in discrete minority carrier de-
vices, and I0 cmP2 for Si integrated circuit technology are the ranges of numbers typ-
ically quoted.
The only reliable way to avoid misfit and threading dislocations in strained layer
epitaxy is to remain below the equilibrium critical thickness, and many technologi-
cal applications of Ge,Si 1 -,are evolving towards subcritical layers. This, however,
places extremely severe limitations on layer thicknesses, as demonstrated by Fig. 1 1,
which will have ramifications for device growth, processing, and doping. An exam-
ple where such layer dimensions are compatible with these constraints, however, is the
Si/Ge,Sil-,/Si heterojunction bipolar transistor (Harame et al., 1995a,b), where a for-
tuitous combination of strain-induced bandgap lowering and a high valence band offset
have allowed useful bandgap variation at relatively low x , thus enabling Ge,Sil -, base
layers which can be of practical use, while remaining below the critical thickness.
Tolerably low defect levels may also in principle be achieved by growth in the
metastable regime, that is, at layer thicknesses greater than the Matthews-Blakeslee
equilibrium critical thickness, if the structure is grown at sufficiently low tempera-
tures, strains, and excess stresses that the misfit defect density is still relatively low.
Post-growth thermal exposure during device processing will cause further nucleation
and propagation of dislocations, however. To prevent further significant degradation,
therefore, each time-temperature cycle during processing would typically be restricted
to less than that of the original growth cycle. This may be an impractical restraint.
In addition, device fabrication processes may enhance plastic relaxation. For exam-
ple, Hull et al. (1990) have shown that contact implantation and thermal activation
in a Si/Ge,Sil-, /Si heterostructure significantly enhances misfit dislocation genera-
tion rates compared to unimplanted structures, via formation of high densities of misfit
dislocation sources from condensation of point defects into dislocation loops during
implant activation.

2. BUFFERLAYERS

An important technique for attempting to separate device quality material regions

spatially from dislocated interfaces is incorporation of sacrificial buffer layers (e.g.
Kasper and Schaffler, 1991). In this concept, a thick (of order 1 ,urn) Ge,Sil-, layer is
 3 MISFITS T R A I N A N D ACCOMMODATION 157

grown upon the Si substrate, such that almost complete relaxation of lattice mismatch
strain occurs via misfit dislocation generation. This produces a fully developed interfa-
cial misfit dislocation array, with a residual density of threading dislocations traversing
the buffer layer to the growth surface. The device-quality material is then grown upon
the buffer layer (and generally, closely lattice-matched to it). In this configuration, the
density of threading dislocations extending through to the device will be the important
metric for structural quality. Several techniques have been developed for filtering these
threading dislocations, to reduce their density to acceptable levels.

3. THREADING
DISLOCATION
FILTERING

a. Introduction

One mechanism for filtering of threading dislocations is for the misfit segments to
grow sufficiently long that they terminate at the edges of the wafer. The ideal relaxed
epilayer configuration would then correspond to two orthogonal sets of parallel, equally
spaced (011) dislocations running across the entire (100) wafer. This would result
in no threading dislocations propagating through the buffer layer. In practice, finite
dislocation propagation rates and blocking via dislocation interactions prevent this (see
Section V of this chapter). Dislocation propagation can be enhanced either by growing
at higher temperatures, or by post-growth annealing (the latter may be preferred due to
likely surface morphology problems in strained layer growth at higher temperatures).
Lateral motion to the edges of a standard Si wafer (i.e., diameter 10-20 cm), however,
is still highly improbable because as relaxation by dislocations proceeds towards its
equilibrium limit, the excess stress becomes increasingly low causing (i) dislocation
blocking to become increasingly prevalent and (ii) propagation velocities to become
increasingly low.
Dislocation interactions, however, can be exploited to advantage if dislocation anni-
hilation processes can be encouraged. As illustrated in Fig. 28, threading dislocations
of opposite Burgers vectors can attract each other and annihilate, transforming two dis-
location loops into one, and removing two threading dislocations from the structure.
Both thermal annealing (either during growth or post-growth), and growing the buffer
layer to greater thicknesses will enhance the total annihilation probability. These pro-
cesses can be extremely effective at high threading dislocation densities, where such
interaction events are statistically likely, but as the density decreases, so does the prob-
ability of further dislocation interactions and further defect reduction. This renders the
annihilation process virtually ineffective at lower threading defect densities. Typical

the substrate are of order 107-109 cm-2 after growth of -

threading defect densities in uniform buffer layers grown with an abrupt interface to
1 p m for strains > 1%
(Kasper and Schaffler, 1991). Lower strain systems may allow perhaps one order of
magnitude reduction in this density because of reduced dislocation pinning events.
158 R. HULL

FIG. 28. Schematic illustrationa of possible mechanisms for dislocation threading arm interac-
tiodannthilation events in a strained layer superlattice. Reprinted from R. Hull and J.C. Bean, Chapter 1 ,
Semiconductors und Semimetals, Vol. 33, ed. T.P. Pearsall, (Academic Press, Orlando, Florida, 1990).

Note that differential thermal expansion coefficients are significant in this geometry,
as they may cause substantial defect generation in structures that are fully relaxed at the
growth temperature. Thus in the Ge,Sil-,/Si( 100) system, complete relaxation of the
compressive lattice mismatch stress at the growth temperature will result in a tensile
strain during cooldown due to the higher thermal expansion coefficient of Ge, Sil --x
than Si. This can generate new misfit dislocations or cause extended splitting of the
a/6(211) partial dislocations, which constitute a dissociated a/2( 101)total dislocation,
as discussed in Section 111.7, leaving a 90" a/6(112) partial at the (100) interface.

b. Graded Layers

A promising technique for minimizing dislocation blocking processes in buffer lay-

ers is continuous grading of strain in the buffer layer. Compositional grading of buffer
layers in the Ge,Sil-,/Si system (e.g. Fitzgerald et ~ l . 1991;
, Tuppen et nl., 1991)
has yielded threading defect densities in the range 105-106 cm-* for lattice mismatch
strains as high as 3% and buffer layer thicknesses in the range 1-10 pm. The main
benefit of such compositional grading is that instead of the misfit dislocations being
confined to a single Ge,Sil-,/Si interface, there will be a distribution through the epi-
layer to compensate for the continuously varying strain field. This provides an extra
degree of freedom for misfit dislocations to propagate past each other (as they may be
at different heights in the structure) and thus minimize pinning events. The vertical dis-
tribution of misfit dislocations can also vary during specimen cooldown after growth,
minimizing the effects of differential thermal expansion coefficients. There has been
considerable work on modeling and measurement of strain relaxation in such compo-
sitionally graded layers (Tersoff, 1993; Shiryaev, 1993; Tongyi, 1995; Mooney et al.,
1995; Li et al., 1995). In particular, it is observed experimentally (and predicted theo-
retically) that dislocation pileups within the graded layers can cause significant surface
 3 MISFITSTRAIN AND ACCOMMODATION 159

morphology (Shiryaev et al., 1994; Samavedam and Fitzgerald, 1997), with significant
ramifications for technological applications of these structures. Such effects can be
ameliorated by growing on off-axis substrates (Fitzgerald and Samavedam, 1997) and
by intermediate chemical-mechanical polishing stages (Currie et al., 1998).

c. Strained Layer Superlattices

The probability of threading dislocation annihilation processes can be substantially

enhanced by providing specific directions for threading dislocation motion. This is
the underlying concept of strained layer superlatrice filtering, originally proposed by
Matthews and Blakeslee (1974, 1975, 1976). This technique consists of growth of a
stack of strained layers, generally on top of the relaxed buffer layer. The thickness
and strain of each individual layer within the stack is designed to be insufficient to
allow significant nucleation of additional dislocations, but sufficient to deflect threading
dislocations into being misfit dislocations at the superlattice interfaces (this translates
effectively into the criterion that the MB critical thickness be exceeded, but not by
too much!). For a (100) interface the interfacial misfit dislocations are constrained
to move along the interfacial (011) directions, thereby increasing the probability of
their meeting, interacting, and annihilating (compared to random motion of threading
dislocations within their slip planes in the absence of the superlattice). Many groups
have since claimed successful application of this technique, in a range of different
strained layer semiconductor systems e.g. (Olsen el al., 1975; Dupuis et al., 1986;
Liliental-Weber et al., 1987). Typically, threading dislocation density reductions from
the range 108-109 cm-2 down to 106-107 cm-2 were claimed. However, again as the
threading dislocation densities decrease, the probability of interaction and annihilation
also decreases. Quantitative analysis of these probabilities (Hull et al., 1989c) suggests
that defect densities much below lo6 cm-= are unlikely to be achieved.

d. Limited Area Growth

A very promising approach to reducing threading dislocation densities is limited area

epitaxy, that is, growth on mesas or in windows, typically with dimensions in the range
10-100 pm. One potential advantage of the limited area is that the number of heteroge-
neous dislocation nucleation sites within this reduced growth area may be vanishingly
small, thus inhibiting generation of misfit dislocations altogether (at sufficiently high
strains, however, quasihomogeneous nucleation at the mesa edges is likely to oper-
ate). The most important advantage, however, is in reduction of threading dislocation
densities, as the dislocation now only has to propagate a far more limited distance to
reach the mesa edge than it would have to reach the wafer edge. The classic original
demonstration of the potential of this potential of this technique is that by Fitzgerald et
al. (1988, 1989) in the In,Ga~-,As/GaAs(100) system, as illustrated in Fig. 29, and
160 R. HULL
3000 1 I

0 100 200 300 400 500

Circle Diometer (microns)

3000

b
.-.
f 2500 -
>
-
0

.
-D
2000

2
1500 -

L
0
v

I O[110]
-g
1000

.t
_I
500

0
0 I00 200 300 400 500
circle Diameter (misrona)

FIG. 29. Illustration of the benefits of reduced area growth: linear density of interfacial misfit dis-
locations vs mesa diameter for 350 nm Ino.osGag.9sAs layers grown onto GaAs substrates with (a)
1.5 x lo5 cm-' and (b) lo4 cmP2 preexisting dislocations in the substrate. Reprinted with permission
from E.A. Fitzgerald et al., J. Appl. Phys. 65, 2220, Figures 4(a) and 4(b). Copyright 1989 American
Institute of Physics.

subsequently developed by several other groups in a range of strained semiconductor

systems (Matyi et al., 1988; Lee et al., 1988; Guha et al., 1990; Noble et al., 1990;
Knall et al., 1994).
The primary disadvantages of the limited growth area technique are the reduced di-
mensions for device processing, and in configurations such as mesa growth, a highly
nonplanar geometry, which may be incompatible with some processing steps. One at-
 3 MISFITS T R A I N AND ACCOMMODATION 161

tempt to address these shortcomings was described by Hull et al. (1991~)who devised
a substrate patterning technique involving a two-dimensional array of oxide dots, in
which neighboring dots were slightly offset from each other with respect to the inter-
facial (011) directions. Thus any misfit dislocation traveling along an interfacial (011)
direction must intercept a dot within a path length, A given by simple geometrical anal-
ysis as A = L 2 / s , where L is the interdot spacing and s is the offset of neighboring
dots along the interfacial (011) directions. The misfit dislocation can then terminate at
the crystal/amorphous interface at the dot, thereby annihilating the threading disloca-
tion. Thus the advantages of the limited growth area approach (finite misfit dislocation
propagation lengths for threading dislocation annihilation) are retained in this dot ar-
ray, while allowing connectivity of the structure across the entire wafer, and planar

thickness). Residual threading defect densities -

geometries (if the epitaxial layer thickness is approximately equal to the oxide dot
lo5 cm-* were reported for MBE-
grown Ge,Sil-, layers 200-800 nm thick with x = 0.15-0.20 on the patterned wafers,
whereas growth on unpatterned wafers typically yielded threading dislocation densities
one to two orders of magnitude higher. Post-growth annealing of the patterned struc-
tures to temperatures as high as 900 “Ccaused the structure to relax almost completely
to equilibrium, dramatically enhancing interfacial misfit dislocation densities, but with
threading dislocation densities typically remaining < lo6 cmP2.

VII. Conclusions

The following are summaries of the salient points of each preceding section:
The lattice constants of Ge,Sil-, may be estimated with reasonable accuracy by
linear interpolation of the lattice parameters of Ge and Si. The strain in a Ge,Sil-,-
based heterostructure arises primarily from lattice parameter differences. Differen-
tial thermal expansion coefficients produce a second-order effect.
There are four primary mechanisms for lattice-mismatch strain accommodation: (a)
elastic distortion of the epilayer; (b) roughening of the epilayer; (c) interdiffusion;
and (d) plastic relaxation by misfit dislocations. Of these mechanisms, (c) is only
significant at very high-growth temperatures, or for ultrathin layers. Mechanism (d)
requires a minimum layer thickness (the “critical thickness”) to operate. Mech-
anism (b) is prevalent, especially at higher temperatures and strains. Strain not
accommodated by mechanisms (b)-(d) is accommodated by mechanism (a).
There are extensive and rigorous elastic descriptions of dislocation structure and
properties. Atomistic details at the dislocation core are not so well understood.
Depending on the predictions of the Thompson tetrahedron construction, we need
to consider the possibility of b = a/6(211) partial misfit dislocations, as well as
conventional b = a/2( 101) total misfit dislocations in the diamond cubic Ge,Sil-,
lattice.
 162 R . HULL

(IV) The Matthews-Blakeslee model provides an excellent framework for the critical
thickness for relaxation by misfit dislocations. Other models generally either fall
into the category of a broadly equivalent energetic approach, or into the category of
developments/refinements of the MB theory. Accuracies within a factor two (bet-
ter at lower strains) should be expected for application of the basic MB model.
For configurations where the Thompson tetrahedron construction predicts that the
lattice-mismatch stress acts so as to increase dissociation of a / 2 ( 101) total dislo-
cations into a/6(211) partials, the partial misfit dislocation configuration will be
favored at higher strains and lower epilayer thicknesses.

(V) Finite misfit dislocation nucleation and propagation rates prevent strain relaxation
from keeping pace with the equilibrium condition for typical growth temperatures
and times. This produces metastable (defined as a,, > 0) regimes of growth
in Ge,Si 1 heterostructurep, which become increasingly broad with decreasing
growth temperature. Consequently, relaxation by misfit dislocations is often ex-
perimentally detected only in Ge,Sil -, layers substantially thicker than predicted
by the MB equilibrium theory, the discrepancy increasing with decreasing strain
and temperature. Analysis of observed relaxation processes shows that enormous
lengths of misfit dislocation need to be generated, and very high source densities
are required.
Considerable uncertainty remains about the dominant misfit dislocation nucle-
ation mechanisms in different regimes of strain, epilayer thicknesses and tempera-
ture in the Ge,Sil-,/Si system. The generic mechanisms for dislocation sources
are homogeneous, heterogeneous, and multiplication. True homogeneous nucle-
ation requires high lattice mismatch strains of order 3 4 % , or greater. “Quasihomo-
geneous” nucleation, that is, nucleation aided by inherent physical properties of the
structure, such as random concentrational clustering or surface roughening during
-
growth, can lower this minimum strain threshold down to 1%. Below this thresh-
old, heterogeneous or multiplication mechanisms operate. Heterogeneous sources
are necessarily limited in high quality epitaxial growth, and plastic relaxation that
relies solely upon heterogeneous nucleation will be very sluggish. Multiplication
mechanisms can act as efficient dislocation sources, apparently in any strain regime,
but generally require minimum layer dimensions (of order hundreds of nanometers)
to operate, and typically require precursor heterogeneous sources. In general, re-
laxation at low strains is nucleation-limited. Experimentally, there is a paucity of
nucleation rate data in the Ge,Sil-. system.
Good experimental descriptions of 60”a/2( 101) misfit dislocation propagation
velocities exist for the (Si)/Ge,Sil -,/Si( 100) system. Observed velocities follow
broadly the same trends as those determined from bulk deformation experiments
of Ge and Si. Dislocation velocities depend upon strain, epilayer thickness, and
Ge concentration, and monotonically increase with these parameters. Again, the
propagation component of relaxation by dislocations is much more rapid in the high
 3 MISFIT S T R A I N AND ACCOMMODATION 163

strain regime. Observations in the Ge,Sil-,/Si( 1 10) system allow propagation

velocities of a/2(101) and a/6(211) dislocations to be separately determined.
Dislocation interactions are very important in plastic relaxation, particularly in
thinner films and in the terminal stages of strain relief, where orthogonal interfacial
dislocations can pin each other’s motion. Such pinning processes can stabilize high
threading dislocation densities in the structure.
Kinetic models of strain relaxation rates, incorporating the concepts of disloca-
tion nucleation, propagation, and interaction rates have been developed, and show
reasonable predictive capability. These models are generally based upon the con-
cepts of excess stress, thermal activation of dislocation nucleation and propagation,
and interaction blocking events.
VI) Many techniques have been developed to reduce threading dislocation densities in
Ge,Sil -,/Si structures. These techniques rely on removing threading dislocations
by annihilation either with other defects or by propagation to the edge of the epi-
taxial growth area. Strained layer superlattice filtering relies on threading defects
annihilating through interaction, but this interaction probability decreases as the
threading defect population decreases, running out of steam for areal densities less
than about lo6 cmP2. Thick, compositionally graded layers appear to be promising
in producing low threading dislocation densities, probably because the threading
dislocations are less subject to interaction pinning events as their accompanying
misfit segments are distributed vertically through the graded structure. Substantial
surface morphology can develop from dislocation pileups, however. Reduced area
(e.g., mesa) growth schemes result in lower threading dislocation densities both be-
cause of reduced probability of dislocation nucleation within the reduced area, and
because threading dislocations have to propagate much smaller distances to termi-
nate at the edge of the growth area.

ACKNOWLEDGMENTS

The author would like to thank a large number of colleagues, past and present, for
collaborations and contributions to my understanding of this field. These include: J.
Bean, D. Bahnck, J. Bonar, D. Eaglesham, G. Fitzgerald, L. Feldman, M. Green, M.
Gibson, G. Higashi, Y. Fen Hsieh, T. Pearsall, R. People, L. Peticolas, F. Ross, K. Short,
B. Weir, A. White, Y. Hong Xie (with all of whom I collaborated during my tenure at
Bell Laboratories); E. Kvam (Purdue University); B. Dodson and J. Tsao (Sandia); J.
Hirth (Washington State University); M. Albrecht and H. Strunk (University of Erlan-
gen, Germany); D. Perovic (University of Toronto); D. Houghton (National Research
Council of Canada); C. Tuppen (British Telecomm); D. Noble (Stanford University);
B. Freund (Brown University); F. LeGoues, B. Meyerson, K. Schonenberg, D. Harame,
R. Tromp and M. Reuter (IBM); P. Pirouz (Case Western); and W. Jesser, E. Stach, J.
Demerast and Y. Quan (University of Virginia).
164 R.HULL

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 SEMICONDUCTORS AND SEMIMETALS, VOL 56

CHAPTER 4

Fundamental Physics of Strained Layer GeSi: Quo Vadis?

M. J. Shaw and M. Juros
DEPARTMENT
OF PHYSICS

THEU N I V E R S I T Y O F NEWCASTLE UPON TYNE

NEWCASTLE
UPON TYNE. UNITE0 KINGDOM.

I. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . 169
11. PERFECTSUPERLATTICE SYSTEMS. . . . . . . . . . , . . . . , . . , . . ......... 174
1. Basic Concepts of Superlattice Bandstructures . . . . . . . . . . . . . . , . . . . . . . , 174
2. GeSi Bandstructures from Empirical Pseudopotential
Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ....... 182
111. ELECTRONIC STRUCTURE OF IMPERFECT A N D FINITESYSTEMS . , . . . .. . . ...., 189
1. Bandstructure of Ordered and Disordered Systems . . . . . . . . . . . . . . . .. .... 189
2. Oprical Transitions in a Finite Superlattice . . . . . . . . . . . . . . . . .. .. ..... 193
IV. LUMINESCENCE AND INTERFACE LOCALIZATION . . .. ... ...... . . ..... .. 195
1. Experimental Optical Spectra of SiGe Systems . . . . . . . . . . . , . . .. . . . . . . . 195
2. Impurities at Interface Islands . . . . . . . . . . . . . . . . . . . , . . .. . . . . . . . 197
V. MICROSCOPIC SIGNATURE OF GESIINTERFACES . . . , . . . . . . . . . .. . . . . . . . 199
1. First-Principles Calculations of Si/Ge Superlattices . . . . . . . . . . , .. ....... 200
2. Inte$ace-lnduced Localization at Donor Impurities . . . . . . . . . . . .. ..... .. 203
3. Defect Perturbations to Conduction States . . . . . . . . . . . . . . . . .. . .. .... 207
4. Localization at Ge Impurities in Si Layers . . , . . , . . . . . . . . . . . . .. .... . 21 1
VI. MICROSCOPIC ELECTRONIC STRUCTURE EFFECTS I N OPTICAL SPECTRA .. . . . . . . . 212
VII. CONCLUSION. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ...... . 219
REFERENCES. . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . , . .. ..... 22 1

I. Introduction

The GeSi system has two key applications: in electronic switching (e.g., fast transis-
tors) and in optical devices integrable with Si and SiGe circuitry. Whereas electronic
switching applications are well established in the market place, the viability of optical
applications is still doubtful. The optical response is weak, unstable at higher tem-
peratures and together with other merit parameters (dark current, spectral shape, etc.)
uncomfortably sensitive to material preparation. However, both application domains

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170 M. J. SHAWA N D M. JAROS

rest on the common basic physics, that is, on the possibility of making a heterojunc-
tion potential barrier at the Si/GeSi interface which has a number of well-controlled
tunable properties (e.g., barrier height, transition strengths). In other words, as far as
basic microscopic physics is concerned the success or failure of any GeSi technology
depends on our understanding of the interaction between excited carriers and the in-
terface. In transport devices this interaction determines the mobilities, channel widths,
and lifetimes. In optical devices it also determines the quantum efficiency of absorp-
tion and emission, the dark current, and the operational wavelengths. A long list of
other parameters could, of course, follow. Furthermore, there is a strong link between
optical and electronic processes in that one can serve as a diagnostic tool for applica-
tions involving the other. Whereas electrical measurements tend to inform about sums
of many different contributions, the optical spectra are often highly selective to specific
scattering and excitation processes and it is therefore the latter that figure prominently
on the theorist’s agenda.
In this chapter we aim, first, to outline briefly the key ingredients and tools required
in developing quantitative models of microscopic interactions at interfaces. Second,
we set out to identify a research agenda where microscopic physics is an indispensable
tool in promoting this class of technologies. We argue there that the latest experimental
evidence (particularly optical spectra) points to a radically different class of interactions
that may significantly affect the carrier dynamics in this heterostructure system. It
would appear that the key features of this behavior do not arise from the particle-in-
a-box confinement and related interface interference or scattering normally considered
in the literature, but instead must be sought in the intrafacial parameter space of the
interface-related bonds.
One of the most general features of GeSi heterostructures is the strain that arises
through the difference in the equilibrium lattice constants of bulk silicon and germa-
nium. While the most commonly studied heterostructure systems, AIGaAs-GaAs, are
almost perfectly lattice matched (with mismatch of order 0.1%), silicon and germanium
have a lattice mismatch of over 4%. Despite the large lattice mismatch, it is possible to
grow high-quality pseudomorphic strained layers, provided suitable growth conditions
prevail (Bean et al., 1984; Bean, 1985), and provided the layers are sufficiently thin.
In addition to making pseudomorphic growth of layers more difficult, and leading to
restrictions on layer dimensions that can be grown, one of the consequences of strain is
to rule out one of the simplest and most intuitive of the bandstructure models available
for the study of lattice matched systems. The effective mass approximation (EMA)
method, detailed in a review by Ando et al. (1982), neglects the microscopic crystal
potential variations in the two materials, and represents the heterostructure by assum-
ing a steplike electrostatic potential barrier at each interface. This leads to the simple
“particle-in-a-box’’ picture, which provides a good description of the states in lattice-
matched systems such as AlGaAs-GaAs. However, as described in Jaros (1990), the
model breaks down for systems with significant strain, such as the GeSi layers of inter-
est here. Clearly, in a strained layer the atoms occupy sites significantly shifted from
 4 FUNDAMENTAL
PHYSICS 171

the bulk-like lattice, and the neglect of the microscopic potential variations becomes
invalid. It is therefore necessary to use a microscopic formalism, in which the detailed
atomic positions and potentials may be taken into account.
One such approach is the empirical pseudopotential (EPP) method, described in the
literature for bulk semiconductors by Cohen and Bergstresser (1966) and Chelikowsky
and Cohen (1976), and extended to superlattice structures by Wong et al. (1986) and
Gel1 et al. (1986). In this microscopic formalism, the bulk constituents are described by
a pseudopotential chosen such that a number of empirically known bandstructure prop-
erties (e.g., bandgaps, effective masses) are reproduced. The case of the superlattice
or microstructure may then be treated as a perturbation to one of the bulk constituents,
its wavefunction being expanded over a complete set of the bulk eigenfunctions. The
superlattice perturbation potential is simply the difference between the host potential
and that of the other bulk constituent. As this potential is constructed for each atom in
the unit cell of the superlattice, the correct strained positions of the individual atoms
(determined from elasticity theory) can be incorporated. As a result the EPP scheme
enables us to obtain a good description of the bandstructure of periodic microstructures
even where there is a large strain. Because the microscopic variations in potential be-
tween the layers are taken into account, the bulk momentum mixing resulting from the
scattering of electrons encountering the misplaced atoms is fully described. The EPP
scheme still includes an abrupt step in the potential at the interface, the valence band
offset. This is found to play an important role in the EPP calculation, and is a parameter
of continued experimental and theoretical debate (see review by Franciosi and Van de
Walle, 1996). The role of the band offset is discussed in more detail in Section 11. Also,
this step-like treatment of the interfaces represents a limitation on the scope of the EPP
description. Any physical processes that are governed by the microscopic properties of
the interface region itself will not be included.
Empirical pseudopotential calculations have been shown to correctly predict many
of the observed properties of GeSi layers, and have led to a physical understanding
of many optical and transport phenomena. Much of the theoretical work published
on GeSi heterostructures assumes ideal, perfectly ordered crystals. The EPP approach
can be extended to the case of imperfect systems through the study of larger super-
cells in which pseudorandom or reconstructed interfaces can be represented. Further
approximations are required in this process as the empirical potentials, fitted with re-
gard to the bulk constituents, must be applied to the individual atoms in the disordered
layers. Similarly, the prediction of atomic positions using bulk elastic properties be-
comes less reliable. However, the EPP does enable a microscopic description of the
imperfections to be formulated, and for the effect of these to be determined. Where
the deviations from the bulk-like structure are too great, for example, in the presence
of an impurity atom about which large lattice relaxation takes place, the EPP approach
may become unsuitable. In such cases, as in situations where the microscopic interface
features are to be studied, it is necessary to consider a more sophisticated microscopic
model.
172 M. J. SHAWAND M. JAROS

The local density approximation (LDA) of density functional theory (Hohenberg and
Kohn, 1964; Kohn and Sham, 1965) and ab initio pseudopotentials provide a micro-
scopic description that does not make reference to the bulk crystal properties. These
nonlocal norm-conserving pseudopotentials, derived to describe the electronic struc-
ture of the free atoms themselves (Bachelet et a!., 1982), are fully transferable, de-
scribing the properties of a particular atomic species regardless of its local environment.
Application of such a scheme is therefore ideally suited to the study of disordered lay-
ers and defects, where no reference need be made to bulk-like characteristics, and for
studies in which short-range effects are important. A variety of LDA calculations have
been used to provide detailed analyses of the electronic structure of short period Si-Ge
superlattices (e.g., Froyen et al., 1988; Satpathy et at., 1988; Schmid et a!., 1991).
These computationally intensive schemes provide a very accurate description of the
valence bands through minimization of the ground-state total energy, and are particu-
larly effective in describing structural properties of the system such as the position of
atoms. In addition, the formalism does not require any additional empirical data such
as the valence band offset. The microscopic potential variation in the interface region
is fully included in the calculation, as compared with the steplike interface represented
in the EPP approach. Such LDA calculations are therefore clearly superior to the EPP
method for studies of the microscopic properties associated with the interface region
of the microstructures.
There are many competing factors governing the choice of model to suit a particular
problem. The ability of the LDA to predict the structural relaxations of a system ac-
curately, and describe short-range features such as the microscopic interface potential
provide it with a clear advantage over the empirical approach. However, such advan-
tages must be balanced against the increased computational effort required. While the
EPP can readily be used to study structures with unit cells containing many thousands
of atoms, the increased complexity of the LDA calculations restricts the unit cells that
may be studied to a few hundred atoms on comparable computers. This represents a
very real limitation to the LDA approach, particularly where the dimensions of the unit
cell are large in all three dimensions. On a physical note, while the LDA provides a
particularly accurate representation of the ground state of the system, and hence gives
a very good account of the occupied valence states, the excited states of the system are
not so well described. One well-known consequence of this is the tendency for the
LDA to underestimate vastly the magnitude of the bandgap (an error of order 50%).
As the empirical pseudopotentials are specifically chosen to describe the states at and
around the conduction and valence bandedges such a problem does not exist for the
EPP method. Both methods therefore have a role to play in developing a full under-
standing of the physics of GeSi layers. The most appropriate method to use depends
in each case upon the nature of the particular system being considered and the specific
properties or effects being studied.
In this chapter we apply the theoretical models described in the preceding text to a
study of some of the essential physical properties of GeSi strained-layer heterostruc-
 4 FUNDAMENTAL
PHYSICS 173

tures. The study focuses on the microscopic features of the structures that determine
their key electronic and optical properties, and leads in particular to a detailed exami-
nation of the properties associated with the heterointerfaces themselves. We choose to
concentrate on examples relating to optoelectronic device applications, where the pa-
rameter of greatest interest is the optical strength of the direct transition. For effective
device design it is essential that the nominal growth parameters of the heterostructure
(i.e., its layer widths and alloy compositions) can be related to the bandgap and the
strength of the no-phonon transition. In order that this is possible, microscopically, we
must identify the origin of this transition, and the degradation which might be expected
as a result of structural imperfections, such as disordered layers and impurity defects.
A similar understanding is important for the other parameters that determine the per-
formance of the device, such as the carrier masses and mobilities. In addition, while
the foregoing discussion has been restricted to the case of the linear interband optical
response, there is considerable technological importance attached to the intersub-band
response and nonlinear processes such as harmonic generation. As we shall show,
while many of the GeSi superlattice properties thus predicted are in good agreement
with the observations of experiment, there are also significant discrepancies. In partic-
ular, experimental observations of photoluminescence spectra suggest that the origin
of the no-phonon transition is different to that predicted by most theoretical models.
Clearly, this origin must be identified if the strength of the transition is to be controlled.
These issues are addressed in the following sections.
Section I1 provides an introduction to some of the basic concepts in superlattice
bandstructure physics, such as zone-folding and the band offset. Empirical pseudopo-
tential calculations of perfect Ge/Si superlattices are used to illustrate these concepts,
and to demonstrate the link between parameters such as the layer widths and composi-
tions and key physical properties.
The effect of interface disorder and reconstruction on the strength of the direct op-
tical transition is studied in Section 111. The case of randomly disordered interfaces
is investigated, using the EPP methods. Calculations are also presented for interfaces
modeled according to the chemically driven reconstructions that have been observed
in these structures. In practice, a finite number of superlattice periods must be grown.
Calculations are presented that address the issues raised by this limit to the overall
length of GeSi superlattices.
Optical experiments on GeSi microstructures have indicated that EPP calculations,
even with the inclusion of disorder and imperfections as described in the preceding sec-
tions, are not able to predict the response of superlattices satisfactorily. It is apparent
that there is an additional physical effect that is playing a key role in the optical behav-
ior. In Section IV the experimental observation of luminescence from SiGe structures
is discussed, and the difficulty in providing a satisfactory theoretical explanation of the
experimental findings is described. An argument is put forward for the proposal that lo-
calization at the interfaces is responsible. Real GeSi superlattice structures are known
to exhibit islanding at the interfaces. Such islands modify the behavior of impurities in
174 M. J. SHAW AND M. JAROS

the structures-EPP calculations are presented to provide a qualitative illustration of

this process.
Section V examines the role that the microscopic properties of the interfaces them-
selves might play in the anomalous localization of charge at the interfaces, and how
this might explain experimental luminescence measurements. The LDA calculations
are presented for a number of impurities situated adjacent to the Si-Ge interfaces to
study the effect on the impurity levels. These calculations provide a full description of
the potential variations within the interface bond region, and the interaction between
this and a variety of defects is investigated.
In Section VI we focus on how a number of features in the microscopic electronic
structure of Si/GeSi superlattices may affect the optical spectra produced. We demon-
strate how external electric fields modify the optical response of the structures. We
briefly examine some of the microscopic bandstructure features that must be consid-
ered in the design of optical detectors, through the calculation of absorption spectra.
Finally, we show how manipulation of the higher-lying superlattice minibands may be
used to enhance second-order nonlinearities in the optical response of GeSi superlat-
tices.
Section VII presents a brief summary of the microscopic physical processes that have
been identified in the response of the heterostructures, and the principal conclusions are
outlined.

11. Perfect Superlattice Systems

1. BASICCONCEPTS OF SUPERLATTICE BANDSTRUCTURES

The natural starting point for any theoretical study of GeSi microstructures is a dis-
cussion of the physical properties of the bulk silicon and germanium themselves, and
of strained and unstrained Ge,Sil-, alloys.
The effects associated with the formation of ordered layers of these materials may
then be addressed with reference to their bulk properties. As a result of their wide
technological application, both silicon and germanium have been extensively charac-
terized (e.g. Hellwege, 1982). Further, the theoretical description of their electronic
bandstructure through the use of empirical pseudopotentials is well-established. There
are two features of bulk silicon and germanium that are particularly relevant to the
physics of their microstructures, namely, the indirect bandgaps and the difference in
lattice constants.
Both silicon and germanium are indirect-gap semiconductors, with conduction band
minima lying away from the Brillouin zone center. The separation in k-space of the va-
lence band maxima (which occurs at the zone center r) and the conduction band min-
ima prevents optical transitions across the gap from occurring without the assistance of
phonons. The bandstructure of bulk silicon, calculated using the empirical pseudopo-
 4 FUNDAMENTAL
PHYSICS 175

L r X
FIG. 1 . Bandstructure of bulk Si plotted along the symmetry lines L - r - X , where I- is the Brillouin zone
center and L and X are the wavevectors 2 n / a ( 1 / 2 , 1/2, 1/2) and 2n/a(1,0,0),respectively.

tential approach, and with the particular pseudopotentials of Friedel et al. (1988), is
plotted in Fig. 1 between the zone center r, and the edge of the Brillouin zone along
the [ 1001 direction X , and along the [ 1111 direction. The conduction band minimum
is seen to have wavevector 2n/a(0.8,0,0). The silicon Brillouin zone has six of
these minima (the A valleys) lying along the coordinate axes. Note that the effects of
spin-orbit coupling are not included in the pseudopotentials of Friedel et al. While this
makes a very small change to the Si bandstructure, the effect on the bandstructure of
Ge is more significant. The spin-orbit interaction breaks the 6-fold degeneracy at the
valence bandedge, raising the energy of the highest state (for a full discussion of the
role of the spin-orbit potential, see, e.g., Kittel, 1987). While this has some effect on
the absolute magnitude of the bandgap, to a degree which depends on the particular
material in question, the electronic structure of the conduction bands is virtually un-
changed. Certainly, our discussions concerning the nature of the gap are not affected
by the inclusion of spin-orbit coupling. For germanium, whose calculated bandstruc-
ture is plotted in Fig. 2, the lowest conduction valleys are the L-valleys, where L labels
the wavevectors 2n/a(f1/2, f 1 / 2 , &1/2). Design of superlattices suitable for optical
devices therefore focuses on ways to engineer a direct bandgap.
In many practical situations the design of suitable structures involves the specifica-
tion of layers of Ge,Sil-, alloy. The empirical pseudopotential formalism is based
upon the concept of a periodically repeating system. While this is appropriate in the
case of pure bulk materials, the random distribution of the different species in an alloy
176 M. J . SHAWA N D M. JAROS

L r X
FIG.2. Bandstructure of bulk Ge plotted along the symmetry lines L - r - X , where r is the Brillouin
zone center and L and X are the wavevectors 2n/a(1/2. 112, 112) and 2 x / a ( l ,O,O), respectively.

clearly breaks the translational symmetry of the crystal. In theory, then, one cannot
define a unit cell for an alloy system. Of course, it is possible to obtain a good de-
scription of an alloy by defining a very large unit cell in which the alloy atoms are
randomly assigned. However, such a description of alloys, particularly in the treatment
of alloy layers in heterostructures, proves costly in terms of computational effort. An
alternative approach that is able to provide a good description of many alloy systems,
including the Ge,Sil-, alloy of interest in this paper, is available, namely, the virtual
crystal approximation (VCA) (Jaros, 1985). The VCA assumes that the physical prop-
erties of an alloy, such as its lattice constant, potential, and so on, may be interpolated
between the individual constituents. The alloy is then treated as a perfect “virtual crys-
tal” having these interpolated properties. This restores the translational symmetry of
the system enabling the empirical pseudopotential technique to be used. The band-
structure obtained for a Geo.sSi0.5 alloy using the VCA with a linear interpolation is
shown in Fig. 3. The variation of the indirect-gap with alloy composition is shown in
Fig. 4, in relatively good agreement with the findings of Braunstein et al. (1958). Here
we have explicitly included the reduction in bandgap associated with the spin-orbit
interaction, an effect which increases with the germanium content. While the linear
VCA unsurprisingly fails to reproduce the bowing observed experimentally, the essen-
tial qualitative features are well represented. In particular, the crossover of the Si A
minimum and Ge L minima is clearly seen at x 85% Ge content. For the calculations
presented here the VCA is used for alloy layers except where we are particularly inter-
 4 FUNDAMENTAL PHYSlCS 177

L r X
FIG.3. Bandstructure of unstrained Si0.5Geo.s alloy plotted along the symmetry lines L-T-X, where r
is the Brillouin zone center and L and X are the wavevectors 2 x / a ( 1/2, 1/2, 1/2) and 2n/a( 1,0,0), respec-
tively.

Ge fraction, x
FIG.4. The variation in the indirect gaps of Sil_,Ge, alloy with germanium concentration x , as cal-
culated using empirical pseudopotentials and the virtual crystal approximation. The variation of the L- and
A-valleys are shown individually (A lies in the crystallographic [ 1001 direction).
178 M. J. SHAW
AND M. JAROS

ested in the effects of random disorder (Section III.l), where large supercells are used
to simulate the true random alloy.
When grown as epilayers on Si substrates, the GeSi layers incorporate a large biaxial
strain. The effect of the strain on the alloy is to result in a reduction of the fundamental
gap, which remains indirect in nature (Lang et al., 1985; People, 1986). Figure 5 shows
schematically the relative alignment of the bandedges in Si and in the particular case of
strained Geo.sSio.5alloy. An intuitive description of the strain-induced bandgap reduc-
tion may be obtained by the method of People (1985), where the splittings of the band
extrema are described in terms of the strain tensor and the appropriate deformation
potentials. The strained bandgaps are then obtained by a superposition of these strain-
induced splittings upon the unstrained alloy gaps of Braunstein et al. (1958). Although
this does provide an estimate of the principal strain effects, and leads to the correct
prediction concerning the reduction of the bandgap, such a model does not represent
a complete description of the real physical processes involved. The importance of the
bandgap reduction arising through strain in alloy layers is apparent when the alloy
bandedges are compared to the energy levels in Si/Ge microstructures, as in Fig. 5. In
a Si/Ge superlattice the alignment between the bands in the different layers is governed
by the valence band offset parameter (to be discussed in detail in this chapter). As may
be seen from Fig. 5 the offset does itself result in a reduction in fundamental gap. The
precise energy of the superlattice states is governed by a multiplicity of factors that are
discussed in the following paragraphs. However, the essential point to note is that the
range of energies spanned by the indirect gaps of the strained alloys corresponds to the

Si (strained) Si 4 Ge 4 superlattice

FIG. 5 . Schematic diagram showing the relative bandedge positions in unstrained Si and strained
Si0.5Ge0.5 alloy. Also shown is the band alignment of a SiqGeq superlattice. The transition energies be-
tween superlattice states are shown to span the same energies as the strained alloy.
 4 FUNDAMENTAL
PHYSICS 179

range of superlattice gaps. The gaps of strained alloys and superlattices span the same
energy subspace. This highlights one of the principal challenges facing semiconductor
theory, that is, how to distinguish and characterize the interface-related effects. In other
words, to identify the features that are unambiguously derived from the presence of the
superlattice order, and which cannot arise simply through the presence of random GeSi
alloy. Section V invokes first-principles microscopic theory to address this issue.
First, we must examine in more detail the basic properties of GeSi microstructures.
A direct-gap may be achieved in a superlattice through the increased periodicity of the
structure. This process may best be understood by the concept of zone-folding (People
and Jackson, 1987). As a result of the periodic potential arising from the superlattice
layers, the wavevectors of the superlattice minibands are restricted to a volume of k -
space reduced in the direction of the superlattice period (the small Brillouin zone). The
superlattice states may then be viewed as being constructed from the bands of the bulk
constituents folded into this small Brillouin zone. Such a picture completely neglects
the interactions between the bulk bands, and is therefore not a suitable starting point for
quantitative analysis (however, it provides a useful intuitive description of the role of
the period in determining the superlattice miniband structure). In particular, the zone-
folding picture illustrates how the creation of a superlattice can result in a direct-gap
structure. By choosing a suitable length of period, and hence a suitable small Brillouin
zone, the indirect conduction minima may be folded onto the small Brillouin zone
center. For the silicon minima with wavevectors lying on the r - X axes this folding
may be achieved by a [001]-oriented superlattice. This approach is used in the work
presented in this chapter to engineer direct gap Si-Ge structures.
Of course, it is not sufficient merely to obtain a structure with a direct gap. For the
structure to be useful one requires also that the optical transition strength associated
with the direct interband transitions is reasonable. In the simple zone-folding picture
already described here, the symmetry of the zone-folded state remains essentially X -
like. Consequently, in the absence of band mixing, the direct transition formed by the
folded state will be forbidden. In order that the transition should have a finite oscillator
strength it is necessary to achieve a mixing of the bulk states involved. Such mixing
processes occur when the interactions between bulk bands are included. However, for
many systems (e.g., GaAs-AIGaAs) the degree of band mixing is small, and the folded
states remain optically inactive. For strained epitaxial layers, such as those in GeSi
structures, the displacement of atoms from the unstrained lattice positions presents a
large scattering potential to an electron at an interface. This scattering mechanism
ensures that there is a substantial degree of mixing of states of different bulk character.
The strength of the direct transition to zone-folded states is enhanced by the strain in
the system.
The relatively large difference in the equilibrium bulk lattice constants of silicon and
germanium also plays a key role in the physics of Si, Ge and GeSi layered structures.
Silicon has a lattice constant of 5.43 8, in comparison to the 5.65 A of germanium, a
mismatch of 4.1%.Such a large mismatch results in highly strained layers, giving rise
180 M. J . SHAWA N D M. JAROS

to a number of physical effects. The precise nature of the strain in the layers depends
on the composition of the substrate on which the heterostructure is grown. While for
practical reasons the actual substrate used is usually chosen to be pure Si, the strain in
the microstructure can be adjusted by creating a “virtual substrate” in which an alloy
buffer layer is grown between the substrate and the superlattice (Kasper ef al., 1987).
Asymmetrically strained systems may be grown on, for example, a pure Si substrate.
In this case, assuming a pseudomorphic growth, the lattice constant parallel to the in-
terfaces in all layers will be that of silicon. The silicon layers are thus unsti dried, while
the germanium has a very large biaxial strain. Such systems are restricted to relatively
short layers, the critical thickness, beyond which pseudomorphic growth breaks down
(People and Bean, 1986; Hull et aZ., 1986). The asymmetric strain field also places
a restriction on the total number of periods that may be grown. The symmetrically
strained structure, grown on a Sio.sGeo.5 alloy buffer, has both the Si and Ge layers un-
der strain. However, the strain in each layer is reduced, increasing the critical thickness
and the number of periods that may be grown before the dislocation density becomes
too great. The preceding discussion has focused on the growth of very narrow layers
of pure Ge and Si. Structures of larger dimension may be grown involving GeSi alloy
layers, where the degree of strain depends upon the concentrations in the alloy.
In addition to the effect on the growth characteristics of the layers, the strain has a
dramatic influence on the electronic properties, splitting the otherwise degenerate A
valleys into two equivalent A 1 minima, and four equivalent All minima. The order-
ing of the split minima in each material is determined by the nature of the strain in
the lcver, that is, whether the parallel lattice constant is smaller or larger than the bulk
value. The precise amount of the splitting in each material is critical in determining the
nature of the lowest state in the conduction band, and can alter the particular material
in which it is localized. This may be illustrated by considering as an example the case
of the symmetrically strained system described earlier, where the layers are grown on
a Sio sGeo.5 alloy buffer layer. For such a system the parallel lattice constant of the
substrate, and hence for pseudomorphic growth, the layers, is larger than that of bulk
silicon. The silicon layers have therefore been strained to this larger lattice constant,
resulting in the A 1 minima being lowered in energy relative to the All minima. Con-
versely, the germanium layers are strained to the smaller lattice constant splitting the
degenerate A valleys such that the A 1 minima are highest. These conduction minima
splittings are illustrated schematically in Fig. 6 (where the relative alignment of the
bands in the two layers is fixed by the valence band offset, discussed in what follows).
The numerical values are those obtained from empirical pseudopotential calculations.
As the magnitude of the splitting of the A valleys is comparable to the conduction band
quantum well depths, the strain determines which material acts as a barrier for electrons
in these valleys. For the strain configuration discussed, the parallel and perpendicular
valleys act to confine the electrons in the germanium and silicon layers, respectively,
though the All offset is extremely small. Which of these valleys will give rise to the
lowest conduction state in the superlattice? This depends on the other parameters of
 4 FUNDAMENTAL
PHYSICS 181

Si Ge Si Ge

.k \\ u284meV

(Strained to Sio.sGe0.5)
FIG. 6. The alignment of the strained bulk handedges in a SUGe superlattice strained to a Si0.5Ge0.5
alloy substrate. The splitting of the bulk A minima parallel and perpendicular to the interfaces is indicated,
with numerical data obtained from empirical pseudopotential calculations.

the superlattice, such as the well and barrier widths, as well as the strain. For, while
the AJ- bandedge is clearly the lowest in energy, it is not necessarily the case that the
zone-folded state from this well will lie below the nonfolded states originating in the
parallel valleys. The energy due to quantum confinement in the conduction well of the
A 1 derived zone-center state may be sufficient to lift this state above the nonfolded
minima.
Although the effective mass approximation, leading to the particle-in-a-box picture,
is not sufficient to make quantitative predictions for strained-layer systems, it remains
very useful for an intuitive understanding of the effect of quantum confinement and
its dependency on the structural parameters. The role of the layer widths and compo-
sitions can be deduced from simple particle-in-a-box considerations, provided care is
taken to include strain in the relative line-ups of the bands in the two materials. Having
obtained well profiles from the strained bandedges the qualitative behavior of the mini-
band energies can be determined using the familiar effective mass model. One obtains
the usual increase in electron and hole confinement energies as the layer widths are re-
duced and barrier heights increased. Changes in barrier heights correspond to changes
in the alloy composition of the layers, as well as the lattice constant of the substrate. Of
182 M. J. SHAW
A N D M. JAROS

course, the alignment of bands in the effective mass model is dominated by the valence
band offset parameter.
Much of the physics of heterostructures is determined by the band alignment, usually
described by the valence band offset. The value of the offset determines the relative
energies of the states in the two constituent materials, and as such controls the quan-
tum well depths, degree of wavefunction confinement, and the very nature of the het-
erostructure (i.e., type-I, with holes and electrons confined to the same layer, or type-I1
with confinement in different layers). However, despite considerable effort over many
years, summarized by Franciosi and Van de Walle (1996) and Capasso and Margari-
tondo ( 1987), the theoretical prediction and experimental determination of band offsets
remains a topical issue.
One of the principal questions that must be addressed in theoretical studies of off-
sets is that of whether the offset is intrinsic, that is, solely dependent on bulk reference
levels, or whether it is determined by the particular properties of the interface con-
cerned. Only first-principles methods are able to self-consistently account for charge
transfer at the interfaces to enable the relative alignments to be determined (e.g., Mas-
sidda er al., 1987; Christensen, 1988). The ab initio pseudopotential calculations of
Van de Walle and Martin (1986) enabled the band offset to be deduced from the aver-
age self-consistent potential in a Si/Ge superlattice. The potential was seen to become
“bulk-like’’ a short distance from the interfaces, allowing the average bulk potentials to
be aligned on a common energy scale. Band calculations for the bulk materials pro-
vided the relative positions of the individual bandedges, and thus the actual valence
offsets. The effects of spin-orbit coupling and strain splittings, which will clearly af-
fect the valence bandedge alignment, were included from simple deformation potential
theory (Pollak and Cardona, 1968). The “model solid” theory of Van de Walle (1989)
again worked upon the alignment of the average potentials in the bulk materials, this
time using a simplified model for the bulk charge densities. This method was found
to be successful for a wide variety of materials at nonpolar interfaces. Jaros (1990)
showed that a simple intuitive model, based upon empirical values of the bulk optical
dielectric constant, yielded values for the offset in good agreement with these more
complex methods. The success of this simple model reflects the fact that the principal
conclusion of the first-principles calculations is that the offsets are essentially intrinsic.
However, it should be noted that the intrinsic nature of nonpolar interfaces is not carried
over to polar interfaces, where the microscopic interface properties become critical.

2. GESI BANDSTRUCTURES
FROM EMPIRICAL
PSEUDOPOTENTIAL
CALCULATIONS

To obtain a quantitative description of ideal (i.e., defect-free) (001)-GeSi strained-

layer superlattices, and to study how their key properties are affected by the structural
parameters, we employ an empirical pseudopotential scheme. The extension of the
 4 FUNDAMENTAL
PHYSICS 183

well-established EPP method for the calculation of bandstructures of bulk semicon-

ductors to periodic superlattice systems is performed using a perturbative approach.
The superlattice wavefunctions are expanded in a complete set of eigenfunctions of
a suitable bulk (“host”) crystal

where @ ( a ,k) are solutions to the bulk Hamiltonian

Ho@(n,k) = E ( n , k)@(n,k) (2)

+
The superlattice Hamiltonian H may be written H = Ho V, where V represents the
perturbation arising from the replacement of atoms of the host by atoms of the other
superlattice layers. The perturbing potential is constructed as the difference between
the potential of the atoms in the superlattice unit cell and that of the host atoms. Such
a potential possesses the periodicity of the superlattice, determining the wavevectors
k that appear in the expansion of the superlattice wavefunction (those being the bulk
vectors displaced from the superlattice wavevector by a whole number of superlattice
reciprocal lattice vectors), and the extent of the reduced Brillouin zone of the superlat-
tice. This is the origin of the zone-folding effect discussed previously. The Schrodinger
equation for the superlattice may then be solved by constructing the Hamiltonian ma-
trix and direct diagonalization.
For the expansion over bulk wavefunctions to provide a rapidly converging set of
basis functions it is necessary that they may be matched to the total length of the su-
perlattice; in other words, that the dimensions of the superlattice unit cell are multiples
of the bulk cell dimensions. Of course, as the superlattice consists of strained layers of
two different materials this will not be the case if unstrained bulk is used to generate the
basis functions. This problem is overcome by calculating the basis functions using a
strained bulk cell, with lattice constant in the plane of the interfaces set to the substrate
lattice constant, and lattice constant in the growth direction chosen so that the overall
length of the superlattice unit cell (determined using simple elasticity theory as in Van
de Walle, 1989) is an integral number of bulk (growth direction) lattice constants. In
order to construct the perturbing potential, the positions of the atoms in the strained
superlattice are determined from the empirical elastic constants of the two materials.
As the substitution of the superlattice constituents for the host involves a change in the
position of the atoms, the perturbing potential is relatively large (e.g., compared to that
which would arise in a lattice-matched superlattice like GaAs-AlGaAs). Consequently,
a large number of host bands must be included in the basis to obtain convergence.
The computational implementation of the scheme outlined in the foregoing provides
us with the eigenvalues corresponding to the miniband energies of the superlattice,
and the coefficients A ( n , k) describing the superlattice wavefunctions. The A ( n , k)
coefficients describe the contributions to the superlattice states arising from bulk states
184 M. J. SHAWA N D M. JAROS

of momentum k and bulk band index n. This matrix therefore provides us with a
valuable tool for analysis of the superlattice electronic structure, indicating the bulk
origin of the states. The mixing of states of different bulk momenta or different bulk
character will show up in the magnitude and distribution of the A ( n , k) coefficients for
a given superlattice state.
Having obtained solutions for the superlattice states using the foregoing method, it is
also possible to evaluate the transition probability lMjj l2 for optical transitions between
states i and j
IMij12 = I ( + ~ I P I + ~ ) I ~ (3)
We may therefore use this approach to study the strength of the direct transition across
the gap as the superlattice parameters are varied.
A full description of the application of the empirical pseudopotential method to
strained-layer superlattices is available elsewhere in the literature (e.g., Morrison ef
al., 1987; Wong et al., 1988). For the empirical pseudopotential calculations presented
in this chapter we have used the particular pseudopotentials developed by Friedel et
al. (1988). The band offset incorporated into these potentials is itself derived from the
theoretical prediction of Van de Walle and Martin (1986).
Before we present the results of a systematic study of the superlattice parameters
determining the strength of the direct transition, it will be instructive to consider an
example structure in detail. For this we shall choose the symmetrically strained (i.e.,
grown on a Sio.sGeo.5 substrate) superlattice consisting of four atomic layers of silicon
and four of germanium. While this structure does not in the event prove to be the
most attractive system, it presents a useful demonstration of empirical pseudopotential
calculation, and illuminates some of the basic features of superlattice bandstructures.
The parallel lattice constant all of the superlattice will, for pseudomorphic growth,
be equal to 5.55 A, the lattice constant of a Sio.5Geo.5 alloy. Here we have assumed
a virtual crystal approximation for the alloy, where it is assumed that the lattice con-
stant of the alloy may be linearly interpolated between that of silicon and germanium.
Applying the method of Van de Walle to determine the lattice constant in the growth
direction for the strained layers of Si and Ge we obtain perpendicular lattice constants
as( = 5.35 A, and a y e = 5.74 A. Calculations of the strained bulk Si and Ge band-
structures were performed to determine the relative energies of the bulk bandedges.
These were shown schematically in Fig. 6, where the key numerical values are indi-
cated. In particular, the valence band offset of 284 meV is shown, its value being fixed
for this strain by the Friedel et al. pseudopotentials. For the particular structure de-
scribed here, the lowest electron states in the superlattice will be confined in the folded
A 1 valleys of the Si layers, while the holes are confined in the Ge layers.
The calculated bandstructure of the superlattice is shown along some of the key
symmetry lines in the reduced Brillouin zone in Fig. 7. It is interesting to note that
the minimum of the lowest conduction miniband does not occur at the zone center, but
rather lies some way toward the edge of the reduced zone in the growth direction. The
 4 FUNDAMENTAL
PHYSICS 185

FIG.7. The bandstructure of the SiAGe4 superlattice strained to a Si0.5Ge0.5 alloy substrate is plotted
along the P-r-XII symmetry lines; P is the point lying at the edge of the superlattice Brillouin zone on the
growth axis.

period of two lattice constants of this superlattice results in a reciprocal lattice vector
whose length does not exactly map the Si A 1 minima onto the zone center. For this
reason we would not expect this structure to present a strong direct optical transition.
An additional feature of the particular structure studied here is that the symmetry of the
conduction and valence minibands at r is such that transitions to the lowest conduction
state across the gap are forbidden. This is a consequence of the point group symmetry
of the crystal and the particular period of the superlattice. A full discussion of the point
group symmetries of SiGe structures is given by Satpathy et al. (1988). The ordering
of the two lowest conduction states changes as the length of the superlattice is varied,
with the symmetry-forbidden state lowest in the Si4Ge4 structure. In the systematic
study of the Si,Ge, superlattices presented in what follows, it is the transition to the
lowest optically active state that is considered (this only affects the n = 4 structure).
To investigate fully the parameters affecting the nature of the gap in these structures
we have calculated the transition energies and strengths in a series of Si,Ge, superlat-
tices, grown on a variety of substrates. In addition to the question of how the substrate
and period affect the diredindirect nature and oscillator strength of the structures, we
have also considered the restrictions associated with the critical thickness and the prob-
lem of indirect transitions to the substrate band extrema.
Let us consider first the choice of substrate used. In addition to the strain effects de-
scribed in the previous section, which are critical in determining the nature of the gap
in the superlattice itself (in an “infinite” superlattice), one must also take into account
186 M. J. SHAWA N D M. JAROS

the possibility of transitions to the substrate when a finite number of layers is grown.
For example, if we consider the case of a structure grown on pure silicon, the band-
edges of the silicon layers will align exactly with those of the substrate. However, the
presence of the germanium barriers results in a confinement energy for the superlattice
conduction electrons, shifting the lowest superlattice conduction state above the sub-
strate A valleys. Regardless of the nature of the superlattice-confined electron states,
the system is indirect through transitions to the substrate. Similarly, the choice of a
pure germanium substrate will result in the valence band maximum of the substrate
lying above the maximum in the germanium superlattice layers. In this case, while
the valence maximum remains at wavevector r, the transition is indirect in real space,
with lowest energy transitions from the substrate valence states. Such considerations
indicate that for direct transitions it is necessary to use an alloy substrate. This has the
added attraction that the critical thickness that may be grown is increased, and that the
quality of the epilayers is consequently improved.
The substrate alloy concentration required to obtain both the valence and conduction
extrema from within the superlattice depends on the layer widths, through the con-
finement energies of the conduction and valence quantum wells. Figure 8 represents
the restrictions on the substrate/layer-width choice that result from consideration of
the substrate, including the critical thickness and the role of the nonfolded minima.
Only structures in the unshaded region of the diagram are expected to be suitable for
engineering a direct gap.

Ge

indirect t o Lie substrate

aJ
+

{n sio.5%J.5 duction minima [owest

3
v)

SI
2 4 6 8 10 12 14 16
no. monolayer, n

FIG.8. The unshaded area indicates the combination of substrate and period for which Si,Ge, systems
have both valence and zone-folded conduction extrema within the superlattice. [Reprinted from Marerials
Science and Engineering B7,Turron, R. J., Jaros, M., “Optimization of Growth Parameters for Direct Band
Gap Si-Ge Superlattices,” 37-42, 1990, with kind permission from Elsevier Science S. A,, P. 0. Box 564,
1001 Lausanne, Switzerland.]
 4 FUNDAMENTAL
PHYSICS 187

It is now interesting to examine how the variation of the layer widths and sub-
strate composition affect the oscillator strengths of the direct transitions. To com-
pare the strengths for different substrate compositions we have considered the case of
the Sio.sGeo.5 substrate and the extreme case of the pure germanium. Although the
structures with pure Ge substrates will suffer from the problem of indirect transitions
involving the substrate valence bandedge, these will not affect our calculations of the
transition strengths within the superlattice. These values will serve to illustrate the ef-
fect of the alloy concentration, even though real devices would in fact be indirect. In
Fig. 9 the oscillator strengths are compared for the two different substrate composi-
tions, for a number of different layer widths. The variation with layer widths is studied
in more detail in Fig. 10 for the case of the alloy substrate.
There are two principle features to note from Figs. 9 and 10. First, changing the sub-
strate composition appears to have a generally small effect on the oscillator strengths.
Second, the oscillator strength shows a general decrease with period. These trends may
easily be explained by considering the factors that contribute to the oscillator strengths.
The folding of the A valley on to the zone center to obtain a direct gap is not in itself
sufficient to result in a strong transition; the states remain essentially X-like, and are
forbidden unless there is some r-state character mixed in. The mixing of states of dif-
ferent bulk momenta into the superlattice states arises as a result of scattering of the
bulk-like electrons on encountering the “substituted’ atoms in the barriers. The magni-
tude of this scattering is strongly affected by the strain in the layers that results in atoms
being disturbed from their bulk-like lattice sites. In general, increased strain leads to

.
1.00

3M
8
f:
h
3 0.10
.*
c
c
(
(
.
v

. v

0.01
i $ 4 5 6
no. monolayers, n

FIG. 9. Variation of oscillator strength of lowest direct transition for Si,Ge, superlattices grown on
Ge (triangles) and Si0.sGq.s alloy (circles) substrates. [Reprinted from Materials Science and Engineering
B7,Turton, R. J., Jaros, M., “Optimization of Growth Parameters for Direct Band Gap Si-Ge Superlattices,”
37-42, 1990, with kind permission from Elsevier Science S . A,, P. 0.Box 564, 1001 Lausanne, Switzerland.]
188 M. J. SHAWAND M. JAROS

f!
M
1.000 7
1

*
f?
s
m
0.100-

#
* **
&-i
cr
0
(d
4
* * *
I
.
3
0 0.010-
0

0.001 I 12 18

no. monolayers, n

FIG. 10. Variation of the oscillator strength with period for Sin&, superlattices grown on Sio.sGe0.s
alloy substrates. [Reprinted from Muteriuls Science andEngineering B7,Turton, R. J., Jaros, M., “Optimiza-
tion of Growth Parameters for Direct Band Gap Si-Ge Superlattices,” 37-42, 1990, with kind permission from
Elsevier Science S. A., P. 0. Box 564, 1001 Lausanne, Switzerland.]

an increase in the scattering, and hence in the mixing that occurs. Thus, although the
strain distribution is affected by the substrate composition, the overall magnitude of
the strain does not change, and we find that the oscillator strengths are relatively un-
changed with substrate. Were we to use alloy layers rather than the pure silicon and
germanium, the magnitude of strain would be reduced, and consequently the direct
transitions weakened.
The strength of the scattering also depends on the difference in the potentials associ-
ated with the Si and Ge atoms themselves. The relative effect of these potential differ-
ences is diminished as the layer widths increases. Increasing the widths of the layers
also results in increasingly well-confined states, reducing the overlap in real space be-
tween the conduction and valence states (because the type-I1 superlattice confines the
holes and electrons in different layers). These effects controlling the dependence of
the oscillator strengths on period are largely independent of the choice of substrate,
explaining the fact that the oscillator strengths for the two substrates in Fig. 9 follow
broadly the same pattern.
There are two particular structures for which the direct transition strength in Fig. 10
is seen to be significantly large, namely, the Siz-Gez and Sis-Ges structures. The layer
widths involved in the former are simply too short to be grown accurately with existing
technology (and indeed it is unlikely that such growth could ever be achieved due
to interface reconstructions, see Section 111.1). The Sis-Ges structure is a far better
prospect, though again it demands an extremely accurate growth. The origin of its
 4 FUNDAMENTAL
PHYSICS 189

enhanced transition strength is in the fact that the zone-folding associated with that
particular period results in the conduction minima folded almost exactly onto the zone
center.

111. Electronic Structure of Imperfect and Finite Systems

1. BANDSTRUCTURE
OF ORDERED SYSTEMS
AND DISORDERED

In the previous section results were presented for a series of SiGe superlattices.
These structures were all assumed to be perfect, with no foreign species present in
the layers and with abrupt monolayer interfaces. Of course this does not represent the
situation in real superlattices. There are numerous imperfections that could cause a de-
viation from this idealistic model, including the presence of dislocations,the presence
of impurity atoms, and an imperfect arrangement of the silicon and germanium atoms
themselves. In this section we focus on the latter case, investigating how the presence
of such atomic fluctuations might affect the physical properties of the structures.
We restrict our attention to structures in which the deviations to the perfect superlat-
tice configuration occurs only in the atomic planes immediately adjacent to the inter-
face. In other words we look at structures in which the interfaces are no longer perfect
and abrupt. It is to be expected that the interface region is where the most significant
imperfections would occur. At first sight one might expect that the imperfect interface
layers should be described as a random disorder of the Si and Ge atoms. However,
experimental studies of the interfaces in SiGe structures using scanning transmission
electron microscopy (Jesson et al., 1991) indicate that the breakdown of the perfect
interfaces does not in fact result in a random alloy in the interface planes. Rather, a
number of chemically driven ordered reconstructions of the interfaces have been ob-
served. After these reconstructions a translational symmetry parallel to the interfaces
remains, despite the diffusion of atoms across the interfaces. In this section we compare
both the case of a random distribution of atoms in the atomic layers at the interfaces
and one of the ordered interface arrangements described by Jesson et al. (1991), with
the perfect superlattice. In particular, we examine the effect on the optical transitions
as a result of these interface structures.
In all of the superlattices described in the previous paragraph the translational sym-
metry parallel to the interfaces has been reduced. Even where the ordered reconstruc-
tion takes place, the repeating period parallel to the interface has been dramatically in-
creased. For computational studies of these structures this symmetry breaking presents
a considerable practical problem. While the study of perfect structures may proceed
with only a single atomic spiral, exploiting the full bulk-like symmetry in the plane, the
inclusion of displaced atoms requires the use of a large unit cell in all three dimensions.
For the reconstructed interfaces the unit cell must be large enough to represent the full
190 M . J. SHAWAND M. JAROS

period of the reconstruction, while for the random alloy a unit cell must be used that is
sufficiently large to allow the random nature of the disorder to be described.
The extension of the empirical pseudopotential method for perfect superlattices to
the case of imperfect superlattices with extended unit cells in three dimensions is
straightforward. The change in periodicity parallel to the interfaces simply results in an
increase in the number of the bulk wavevectors that appear in the expansion of the su-
perlattice wavefunction. However, while the conceptual change this represents is very
small, it has a dramatic effect on the practical solution of the problem computation-
ally. The number of bulk wavevectors required for a perfect superlattice is proportional
to the length of the superlattice period. For the three-dimensional cell the number of
terms in the expansion is proportional to the product of the period in the three direc-
tions. As a result the number of bulk wavefunctions that can appear in the superlattice
wavefunction rises dramatically as the unit cell is increased. Because the dimension
of the potential matrix depends on the number of functions in the expansion, the prob-
lem rapidly becomes too large to compute, placing a limit on the size of cell we can
consider. A complete description of the mathematical formalism and computational
considerations required for the results presented below is given by Turton and Jaros
(1993).
To allow the effects of disorder to be analyzed quantitatively it is necessary to define
a measure of the disorder present in a given structure. In this context “disorder” refers
to deviations from the perfect superlattice structure, both random and reconstructed. A
disorder parameter D may be defined as
nmis
D = ~ x - . (4)
ntot
Here, n,is is the number of misplaced atoms and ntOtis the total number of atoms
in the unit cell. Misplaced atoms are defined as those atoms whose species differs in
comparison with the idealized perfect superlattice. The factor of 2 ensures that the
disorder parameter varies between 0 for the perfect structure, to 1 for a completely
random distribution of atoms throughout the whole unit cell, that is, for a random
Sio.5Geo.s alloy.
The effect of random disorder at SiGe interfaces is illustrated in what follows for the
SisGes superlattice grown on Ge substrate. A series of structures was modeled using
unit cells containing 8000 atoms, extending 10 lattice constants in directions parallel
to the interfaces and consisting of 4 superlattice periods. Within these unit cells, the
interface disorder was introduced by randomly assigning the atoms in the interface
layers to represent the perfect configuration, encroachment of Si into the Ge layer or
of Ge into the Si layer. The disorder parameter is chosen by weighting the number of
perfect configurations occurring.
The perfect Si5Ges superlattice grown on Ge is direct-gap, with the lowest con-
duction state derived from the zone-folded minimum. In contrast to the Si4Ge4 case,
where transitions to the lowest energy conduction state were symmetry-forbidden, the
Si5Ges states are reversed and transitions to the lowest conduction state, derived from
 4 FUNDAMENTAL
PHYSICS 191

the folded A 1 minima, are allowed. No-phonon transitions to the higher-lying non-
folded All minima are forbidden in the ideal superlattice, where there is no reduction
of the in-plane translational symmetry. However, for structures with randomly dis-
ordered interfaces the perturbing potential in the plane of the interfaces reduces this
symmetry, and the no-phonon transitions to the Ail minima become allowed. Figure
I1 shows the variation of strengths of the optical transitions to the A 1 and All states as
the degree of disorder is increased.
Two effects are clearly identified from this figure. First, the transition to the non-
folded minima, forbidden in the perfect system (calculated to be 12 orders of magnitude
smaller than the allowed transition-the “computer zero”), is dramatically increased in
strength as the degree of disorder increases. Meanwhile, the direct transition to the
folded A 1 minima is weakened by the disorder at the interface. For an equal number
of the three interface configurations considered, corresponding to a disorder parameter
of 0.267, the strengths of the two transitions become comparable. It is the presence
of the in-plane symmetry-breaking potential introduced by the disorder that results in
a number of newly allowed transitions, and consequently a reduction in the strengths
of the existing transitions. We can see that the existence of a high degree of disorder
in very short period superlattices can result in changes to the optical transition mech-
anisms available. However, it is worth noting that the degree of disorder required for
the All transitions to become comparable in strength to the “perfect” transitions is very
high. For the very short periods involved the interface layers constitute a significant
fraction of the period, and a high degree of disorder can result even where only single-

I
-?

-7 I i___ - -&-A
0 01 02 03
disorder

FIG.1 1 . Squared optical matrix elements (in arbitary units, plotted on a loglo scale) with x polarization
at r as a function of random interface disorder for a SisGes superlattice strained to a Si substrate. The lowest
energy transitions to the All minima (circles) and A 1 minima (triangles) are represented. Where appropriate,
the error bars indicate the variation over a number of different random supercells. The “forbidden” no-
phonon transition to the All minima is calculated to be 12 orders of magnitude smaller than that to the AL
minima and is not plotted. [Reprinted with permission from the Institute of Physics, Turton, R. J., and Jaros,
M. (1993). Sernicond. Sci. Technol. 8,2003.1
192 M. J . SHAW
AND M . JAROS

monolayer fluctuations of the interface are allowed. For a smaller degree of disorder,
such as that indicated on Fig. 11 where D = 0.04, the original transitions to the zone-
folded A 1 minima remain dominant.
How does the reconstruction at Si-Ge interfaces observed by Jesson et al. (1 991)
affect the optical transitions? To illustrate this difference we compare the case of a
perfect Si4Ge7 superlattice with one of the structures identified by Jesson. The recon-
structed interface structure we considered was one consisting of alternating phases A
and C, where A and C refer to the particular interface reconstructions as labeled by
Jesson et al. The disorder parameter for this reconstructed system is calculated to be
0.24. For comparison we also modeled a Si4Ge7 superlattice with randomly disordered
interfaces corresponding to a disorder parameter of 0.24. The results of these calcu-
lations are summarized in Fig. 12, where the strengths of the transitions to the folded
and nonfolded minima are compared for the three systems. Interface reconstruction
can be seen to have reduced the effect of the disorder on the transition strengths. The
reconstructed superlattice shows a stronger transition to the folded minima, while the
enhancement of the transition to nonfolded states is not so great.
The optical characteristics of GeSi structures are therefore seen to be strongly af-
fected by the accuracy with which the layers are grown. Random disorder, even re-
stricted to atoms lying in the planes adjacent to the interfaces themselves, can reduce
the strength of the direct transition to the zone-folded minima by two orders of magni-
tude. The presence of such disordered layers also led to the breaking of the selection
rules governing transitions to the nonfolded minima. Where the disorder in these inter-
face planes is sufficiently high, and for structures of sufficiently short period, the two
transition mechanisms may become comparable. The degradation of the transition to
the zone-folded minima is reduced by the chemically driven reconstructions that have
been observed experimentally.

FIG. 12. Squared optical matrix elements (in arbitary units, plotted on a loglo scale) with z polarization
at r for the three systems considered in the text. Column A corresponds to the perfect SiqGe7 superlattice,
column B to the reconstructed interface, and column C to a randomly disordered system. [Reprinted with
permission from the Institute of Physics, Turton, R. J., and Jaros, M. (1993). Semicond. Sci. Techno]. 8.
2003.1
 4 FUNDAMENTAL
PHYSICS 193

IN A FINITE
2. OPTICAL TRANSITIONS SUPERLATTICE

The calculations in the preceding section implicitly assumed that the superlattice is
a periodic structure of infinite extent. The substrate has been considered independently
of the superlattice itself, as a possible source of indirect transitions, and in fixing the
parallel lattice constant of the superlattice. So far, however, we have not taken into
account the fact that any real superlattice is finite in extent. Indeed, for practical con-
siderations, the actual number of periods that are usually grown is relatively few. In
particular, for asymmetrically strained structures the number of periods is restricted to a
critical length, providing an absolute limit on the length of structure that may be grown
pseudomorphically. While the assumption of a truly periodic system allows for a sig-
nificant simplification of the computational problem, it also introduces a discrepancy
between the model and experiment. In this section the effect on the optical transitions
of the finite nature of real superlattices is examined.
A system for which experimental optical data are available, and which stimulated
considerable interest in ultrashort period superlattices, is the five-period SbGe4 super-
lattice grown on a pure Si substrate. This was studied by Pearsall et al. (1987) who
observed a series of strong optical transitions below the energy of the lowest direct
transitions in GeSi random alloys. The transitions were initially attributed to superlat-
tice order, but there was considerable speculation as to the microscopic origin of these
spectral lines (e.g., Pearsall et aE., 1989; Wong et nl., 1988). Electronic structure calcu-
lations on infinite Si4Ge4 superlattices, using models such as that outlined in Section
11.2, were not able to account for the strength and energies of the observed transitions.
In particular, the energy of the first direct transition is predicted by such calculations
to occur at around 1.2-1.3 eV, not the 0.76 eV of experiment. Only the indirect tran-
sitions to the nonfolded Si A 11 minima could occur at around this energy and these are
forbidden in a perfect structure by symmetry.
A more realistic model of the structure of Pearsall el al. can be achieved by construct-
ing a unit cell containing the five-period superlattice and a thick Si buffer layer (Wong
and Jaros, 1988). While this unit cell is clearly much larger than the eight monolayer
cell required for the infinite structure, the approach allows the computational advan-
tages associated with periodic boundary conditions to be retained. Provided the length
of the Si buffer layers is sufficiently large the calculation ought to describe fairly well
the case of an isolated 5-period system grown on Si and with a Si cap layer (i.e., the
experimental system).
Of course, such a model imposes a periodicity that is absent from the real system and
care must be taken to account for this discrepancy. In the real system the Si substrate
and cap layers behave essentially as unstrained bulk Si, and give rise to 6-fold degen-
erate A minima. In contrast, due to the periodic boundary conditions, the Si buffer
layers in the model behave as wide Si quantum wells, giving rise to a series of states
confined in the buffer layers. The energy of these states is raised by the confinement
energy associated with the finite width of the buffer quantum wells. Correcting our
194 M . J. SHAWAND M. JAROS

computed energies to account for this, the lowest conduction states lie 0.76 eV above
the valence bandedge. Although the energy of these states compares directly with the
lowest observed transition, as mentioned previously, such indirect transitions are for-
bidden by the symmetry of the system, and would not be expected to be observed.
In fact, comparison of the results of the calculations for infinite and five-period struc-
tures shows that the energies and transition strengths are virtually unchanged (Wong
and Jaros, 1988). The finite nature of the structure does not, therefore, contribute an
explanation of the experimentally observed transitions.
However, it is clear from the charge densities of the superlattice states shown in
Fig. 13 that the detailed form of the electronic wavefunctions is significantly altered by
the finite length of the superlattice. In particular, the lowest conduction state confined
to the superlattice itself (i.e., not the buffer layer states) is localized at the center of
the 5-period system. Clearly, no such localization can be represented in the infinite
model. The valence states appear to behave as though they are confined states of a
GeSi quantum well sandwiched between the Si buffer layers. The states have the form
of the typical envelope functions of a simple square well, again a behavior that cannot
be obtained in the infinite structure.

f A >

>A
-40 -30 -20 -10 0 10 20 30 40

FIG. 13. A plot of the charge densities along the growth direction of the five-period superlattice. The
broken lines indicate the positions of the interfaces. At the bottom of the figure the dark blocks indicate the
Ge superlattice layers.
 4 FUNDAMENTAL
PHYSICS 195

To summarize, the fact that in practice only a limited number of superlattice peri-
ods can be grown does not greatly affect the energies and momentum matrix elements.
Although the precise nature of the localizations in the system is significantly affected
by the finite length, the prediction of optical properties due to superlattice states using
infinite systems remains valid. The origin of the observed transitions in the 5-period
Si4Ge4 structures remains to be conclusively identified, although it is now generally ac-
cepted that the transitions are indirect and result from phonon-scattering or lattice im-
perfection (e.g. People and Jackson, 1987; Froyen et al., 1987; Hybertsen and Schluter,
1987).

IV. Luminescence and Interface Localization

1. EXPERIMENTAL
OPTICAL SPECTRA OF SIGE SYSTEMS

In recent years numerous experimental studies of optical phenomena in SiGe het-

erostructures have been reported. Much attention has focused on the photo- and elec-
troluminescence from very short period superlattices (Pearsall et aL, 1987; Zachia et
al., 1990; Presting et al., 1992). The rationale behind the design of such structures was
that the zone-folding effect, related to the long-range superlattice periodicity, could re-
sult in allowed direct transitions. However, the available experimental data does not
support the theory that this mechanism is responsible for the luminescence observed.
Just as the observed transitions of Pearsall et al. (1987) could not be reconciled with
theoretical predictions (as discussed in Section 111.2), so the experimental results of
Zachia et al. were at odds with the theory of zone-folded quasi-direct superlattice tran-
sitions (Schmid et al., 1990). The dependence of the luminescence on temperature
and external fields is, rather, suggestive of an alloy-scattering origin (Ting and Chang,
1986), showing similarity to the behavior of SiGe alloy (Noel et al., 1990; Robbins et
al., 1991) and alloy quantum well systems (Sturm et al., 1991; Northrop et al., 1992).
It has been shown in Section I11 that random disorder, and the interface reconstruc-
tions observed, are capable of introducing an alloy-scattering process comparable to
the theoretical zone-folded transition mechanism. This was demonstrated even for sys-
tems in which interface imperfections were restricted to a single atomic plane on either
side. The evidence at present therefore suggests that in very short-period superlattices
the observed luminescence arises primarily through alloy effects, rather than from the
zone-folding mechanism.
Effects arising through the formation of alloys at the GeSi interfaces can be reduced
by choosing systems with wider layers. The extent of the disorder in the vicinity of the
interfaces that would be required to result in a dominant alloy-scattering luminescence
process in these larger systems is far greater than that which is present in high-quality
MBE samples. Such reasoning led to the proposal by Jaros of double-well structures,
studied experimentally by Gail et al. (1995) and Engvall et al. (1993, and illustrated
196 M. J. SHAWAND M. JAROS

F I G . 14. Schematic diagram of a typical double-well SiGe structure proposed for room-temperature
emission.

schematically in Fig. 14. These structures are designed to result in the lowest conduc-
tion state being confined in the central Si well. Full-scale pseudopotential calculations
for these structures (Turton and Jaros, 1996) give energy gaps in good agreement with
the experimental luminescence energies reported. The calculations predict confined
A 1 and All states, giving rise to strongly allowed and forbidden transitions, respec-
tively, at similar energies. The luminescence observed from these structures is stable at
room temperature as might be expected from the large potentials that are confining the
conduction wavefunctions. In the absence of experimental data one would expect that
it is the zone-folded AL state that would luminesce. However, further experimental
studies of the pressure dependence of the optical spectra conclusively show that it is
the All states that are the source of the photoluminescence (Gail et al., 1996).
As we have shown, the breakdown of the selection rule forbidding transitions from
the nonfolded minima cannot reasonably be assigned to the alloy effects of interface
disorder. For such an effect to allow comparable transitions the quality of the sam-
ples would have to be considerably poorer than is believed to be the case. It is also
reasonable to ask whether the luminescence may originate from the alloy-cladding
layers, though this could only explain the low-temperature behavior. In any case
the computed wavefunctions are found to penetrate only a very short distance into
the cladding layers. It is clear then that there must be some other mechanism enabling
the room-temperature luminescence. One possible mechanism is that of localization
at the interfaces of the heterostructure. In the following sections we study in detail
the role interface localization may play in the luminescence spectra, and the possible
sources of such localized features. First, we use an empirical technique to study im-
purity atoms situated in interface islands. Then we study in detail the effect of the
microscopic interface potential, the microscopic signature of the interface, in the pres-
ence of substitutional defects using ab initio pseudopotential methods.
 4 FUNDAMENTAL PHYSICS 197

2 . IMPURITIES AT INTERFACE ISLANDS

In the preceding section we have argued that the room-temperature luminescence

cannot be ascribed to the alloy-scattering mechanism commonly used to explain low
temperature luminescence in SiGe systems. Rather, we suggested that anomalous lo-
calization at the interfaces of the Si and Ge layers could be the source of the lumines-
cence. In general, luminescence features are found to be insensitive to the microscopic
details of the interfaces, except for ultrathin layers. The confinement of electrons and
holes in the quantum wells results in wavefunctions peaking at the center of the wells,
with only a small fraction of charge sampling the interface regions. Interface effects
would only be expected to dominate optical spectra if there were a mechanism for
localization of the wavefunctions in the interface region. Here we investigate the pos-
sibility of localization occurring at these interfaces using the empirical pseudopotential
method. Despite the limitations of the EPP method in describing microscopic inter-
face effects, principally due to the inclusion of a step-like valence band offset, it is still
possible to extract qualitative information concerning the physical processes involved
from such calculations.
The role of disorder has been shown to be significant only when that disorder com-
prises a large fraction of the crystal. For typical, high-quality MBE interfaces this is
only true of ultrathin layers. Another type of interface imperfection that is thought
to occur in SiGe layers is that of interface islands, by which we mean an incursion
of one material across the interface into the other layer, extending over many atoms
in the plane of the interface. Could such interface islands result in a localization at
the interfaces that is capable of driving the observed luminescence? As in the case of
the random disorder, we shall restrict ourselves to consideration of islands that extend
only one monolayer across the interface. Further, we limit the size of the islands so
that they do not represent changes in the effective layer widths. However, calcula-
tions for a number of material systems and for a variety of island geometries and sizes
have shown that for islands only one monolayer deep, no localized states were formed.
The formation of interface islands is not in itself sufficient to explain the origin of the
luminescence.
However, there remains the possibility that the existence of interface islands could
affect the behavior of an impurity atom situated at the interface. An intuitive view of
the binding energy of impurity atoms in quantum wells holds that the binding energy
will be greatest for impurities situated in the center of the well; essentially this results
from the localization of the ground state electron and hole wavefunctions at the center
of the well. Consequently, the electron-hole recombination processes in quantum wells
are governed by impurities near the center of the-wells. However, it is possible that the
interface island potential could increase the binding energy of the impurity level for an
atom located in the interface island such that it drops below the central site level. Under
such circumstances one could explain the observed luminescence in terms of recom-
bination processes localized at the interfaces of the heterostructures. The calculations
198 M. J. SHAWAND M. JAROS

described below set out to determine whether such a mechanism is plausible, and the
approximate size of interface island necessary to sufficiently lower the impurity level.
Calculations were performed to determine the change in a typical shallow donor
level as the spatial extent of the interface islands was varied. This was compared to
the binding energy at the center of the well. The details of the calculation are reported
elsewhere (Jaros and Beavis, 1993), but essentially involve the inclusion of a model
potential representing the impurity atom. The potential was adjusted to reproduce the
correct behavior in bulk, before being included in empirical pseudopotential calcula-
tions of the quantum well systems. The calculated binding energies are determined at
the center of the quantum well and at the center of the interface islands, and their ratio
computed.
The results for a number of different island configurations are shown in Fig. 15.
Ten different rectangular island geometries were studied and are labeled in order of
increasing area. The actual island dimensions are listed in Table I. Figure 15 shows the
variation with island size of the ratio of the binding energy of a donor at the interface to
one at the center of the quantum well. Results are shown for the SiGe system of interest
here, and for comparison the results for GaAs-AIGaAs and ZnCdSe-ZnSe systems are
also shown. In all cases it can be seen that as the cluster size increases, the binding
energy at the interface increases relative to the well-center value. For the SiGe system

O 6 t :
0 4
0
:
1
f

2
~,, ~, ;
3 b 5 6 7
f

8 9 10
[Luster reference numbers

FIG. 15. For the interface islands listed in Table I, the ratio of the binding energy of a substitutional
donor positioned at the interface to that in the center of the quantum wells is shown. The binding energy at
the interface is calculated with the donor in the middle of the island, and results are shown for Si0.8Ge0.2-Si.
GaAs-Gao~A103As, and Zn0,7&&.24Se-ZnSe quantum-well systems. [Reprinted with permission from
Jaros, M., and Beavis, A. W. (1993), Appl. Phys. Left. 63, 669. Copyright 1993 American Institute of
Physics.]
 4 FUNDAMENTAL
PHYSICS 199

TABLE1. Lateral Island Dimensions

Dimension Area
Island Index (a0 1 (a;,
1 1 x 1 1
2 1 x 3 3
3 1 x 5 5
4 1 x 7 7
5 3 x 3 9
6 3 x 5 15
7 3 x 7 21
8 5 x 5 25
9 5 x 7 35
10 7 x 7 49

the ratio becomes greater than unity when the island increases to 3 x 3; this is the
smallest island size for which the impurity levels are lower at the interface site.
The preceding results demonstrate that it is indeed possible for sufficiently large is-
lands of Si, penetrating just a single monolayer into the Ge layers, to cause localization
sufficient for the recombination properties of SiGe quantum wells to be dominated by
impurity atoms situated at the interfaces rather than at the well center. As a result the
breaking of translational symmetry parallel to the interfaces is sampled strongly by the
carriers, and the breakdown of the selection rules governing the All minima becomes
significant. This supports the hypothesis that the origin of the room-temperature lu-
minescence may lie in the presence of such interface localization sources. However, it
should be noted that quantitative data obtained from the present empirical pseudopo-
tential scheme are not expected to be reliable.

V. Microscopic Signature of GeSi Interfaces

In Section IV we have demonstrated the importance of the Si-Ge interfaces in deter-

mining the optical properties of the GeSi heterostructures. In particular, the difficulty
of interpreting the experimentally observed optical spectra in terms of conventional
bandstructure theory has been discussed. However, the calculations presented so far
have all been based upon a semiclassical model of the interface. That is, the micro-
scopic variation in the potential across the region of the interface bonds has been re-
placed by an abrupt steplike change in potential. While such a picture of the interface
is sufficient to allow a relatively good description of the quantum-confined states in the
superlattice wells, it is essentially a first-order approximation, and is unable to describe
higher-order interface effects. Thus, although the EPP calculations are able to show
the importance the interfaces may have on the optical spectra, in order to obtain the
200 M. J. SHAWA N D M. JAROS

microscopic signature of the interfaces it is necessary to go beyond the semiclassical

picture. To this end we present a study of Si-Ge interfaces in the presence of impurity
atoms using ab initio pseudopotential calculations (Shaw et al., 1996). These provide
a complete description of the short-range potential variations within the region of the
interface bonds themselves (what might be termed the “intraface” properties). This
presents a whole new framework within which to describe the heterostructure systems;
the intrafacial properties provide a fresh basis for our understanding of the physical
behavior, for example, the optical spectra, of the system. The development of such a
microscopic signature of the interfaces opens the way for an unambiguous interpreta-
tion of the observed spectra.
The mechanism that we are proposing to explain the origin of the luminescence in
SiGe heterostructures is closely analogous to the bandstructure enhancement effect in-
voked to explain the luminescence observed in the familiar case of GaP:N, reviewed,
for example, by Jaros (1982). The isovalent nitrogen substitutional defect is character-
ized by a strong short-range impurity potential; although this potential is not sufficient
to introduce deeply localized levels in the forbidden gap, it does alter the nodal charac-
ter of the exciton wavefunction near the impurity site. This breaks the selection rule for
indirect GaP and greatly enhances the oscillator strengths of excitonic recombination
at nitrogen. The coupling between the impurities and the lattice provide an explanation
for the wealth of experimental luminescence and absorption data available (e.g., Mertz
et al., 1972). In the case of antimony in SiIGe heterostructures, however, it is known
that antimony defects themselves are not able to achieve such an effect in bulk Si, and
we propose that it is the interaction between the defects and the interfaces that gives
rise to the luminescence.

1. FIRST-PRINCIPLES
CALCULATIONS OF SI/GE SUPERLATTICES

The first-principles calculations presented here are founded on the well-established

methods of density functional theory described extensively in the literature (e.g., Drei-
zler and Gross, 1990). Using the local density approximation and the ab initio pseu-
dopotentials of Bachelet et al. (1982) we determine self-consistent charge densities for
the superlattice supercells. In addition, the nuclear coordinates of all of the atoms are
fully relaxed to minimize the total energy. Our calculations involve expansion of the
wavefunctions over a basis set of Gaussian orbitals, with s- and p-like character im-
parted through multiplication by appropriate spherical harmonics. The basis included
16 of these functions centered on each atom and 8 centered on the middle of each bond.
The particular formalism used is described in further detail in Jones ( I 988) and Brid-
don (1991). The successful application of this particular implementation of the LDA
to heterostructure systems, and specifically to the study of the microscopic properties
of heterointerfaces, has been verified for a series of perfect AISb/InAs superlattices by
Shaw et al. (1995).
 4 FUNDAMENTAL
PHYSICS 201

FIG. 16. A schematic diagram of the @-atom unit cell of the Si-Ge superlattices. The positions of the
atomic planes are indicated, and the site of the substitutional donor is highlighted. The planes used for the
contour plots are shown: plane A parallel to the interfaces and plane B perpendicular to the interfaces, each
passing through the defect atom.

The calculations were performed on 64-atom unit cells, as illustrated schematically

in Fig. 16. The cells consist of an 8-atom period of the superlattice, with the primitive
unit cell repeated 8 times in the interface plane to form a near cubic unit cell. The sys-
tems studied were Si4Ge4 grown on Sio.sGeo.5(virtual) substrate, and bulk Si strained
to the same substrate. The dimensions of the unit cell in the plane parallel to the inter-
faces were held fixed to a size determined by the lattice constant of the alloy substrate.
This substrate constant was determined using a virtual crystal approximation with the
calculated bulk equilibrium lattice constants. The overall lengths of the superlattice and
strained bulk unit cells in the growth direction were determined by calculation through
minimization of the total energy. The substitutional defects were introduced by replac-
ing one of the atoms in the layer of Si forming one side of the superlattice interface at
the center of the unit cell (see Fig. 16), and at an equivalent point in the strained bulk
Si cell. For each calculation the position of ail of the atoms in the unit cell was fully
optimized.
The charge density in the 64 atom cells was represented by the contribution fromjust
the single zone-center wavevector. This was found to provide a close approximation
to the calculation using the complete set of special k-points, given by Ren and Dow
(1988), which are equivalent to the set of 10 points frequently used to describe the
primitive diamond unit cell (Chadi and Cohen, 1973).
To assist in the interpretation of the results of the full-scale calculations for structures
containing substitutional defects, it is helpful to develop a simple qualitative picture of
202 M. J. SHAWAND M.JAROS

Perfect Crystal Crystal with Defect

AlB Free Defect

Vacancy States Atom

FIG. 17. Schematic diagram representing the simple defect molecule model for a substitutional defect
in a bulk crystal. [Reprinted with permission from the American Physical Society, Shaw, M. J., Briddon,
P. R., and Jaros, M. (1996). Phys. Rev. B54, 16781.1

the states induced by a substitutional donor. The defect molecule model (Jaros, 1982)
provides us with just such a description, and is illustrated schematically in Fig. 17.
Consider first the case of a substitutional defect in a bulk crystal. First, an atom is
removed from the perfect crystal creating a vacancy, and with it a series of vacancy
states. The vacancy has four unbonded sp3 orbitals associated with it, and these will
symmetrize to form a singlet A1 state and triplet T2 states. Next, consider the free-
defect atom, with its s (A1) and p (T2) orbitals being placed at the vacancy site. The
free-atom and vacancy states of the same symmetry interact to give bonding and an-
tibonding resonances: A1 bonding (AlB) and antibonding (AIA) near the bottom of
the valence and conduction bands, respectively, and T2 bonding (T2B) and antibond-
ing (T2A) deep inside the valence and conduction bands. The model applies also to
the case of superlattices, although the symmetry labels ought to reflect the lower point
group symmetry of the superlattice crystal. For the purposes of the present work such a
distinction is not important, and we shall retain the bulk labeling for simplicity. It must
be stressed, however, that the defect-molecule model is an extremely basic model that
takes no account of the interaction between the defect and the lattice, and as such makes
no quantitative prediction concerning the energies of the resonances. It does, however,
provide us with a useful framework and language for the interpretation of the results of
the ab initio calculations.
The defect-related states in which our primary interest lies are the localized reso-
nances, whose features reflect the microscopic interaction of the defect with the lattice.
We do not concern ourselves with the extended shallow donor state, bound by the
Coulomb potential of the ionized donor. The restricted size of the unit cell that can be
 4 PHYSICS
FUNDAMENTAL 203

studied using ab initio techniques makes them unsuitable for studies of extended fea-
tures, which can, in any case, be well-accounted for by simple models. The interesting
physics underlying the behavior of the defects is contained in the localized resonances.
The projection of such effects onto the extended shallow donor and excitonic wave-
functions would provide a direct link to experimental spectra, but is beyond the scope
of the present article.

2. INTERFACE-INDUCED AT DONORIMPURITIES
LOCALIZATION

One of the most interesting impurities in SiGe heterostructures is that of substitu-

tional antimony. The inclusion of Sb layers as a surfactant in the MBE growth process
is found to improve greatly the quality of the heterostructures. However, the use of Sb
in this way inevitably leads to the presence of Sb defects, particularly in the Si layers,
where the tensile strain favors the accommodation of the larger Sb atoms. We therefore
concentrate initially on the behavior of substitutional Sbsi defects at the interfaces of
SiGe superlattices. The ab initio calculations described above were applied to a Si4Ge4
superlattice (grown on a Sio.sGe0.5alloy substrate), in the presence of the antimony de-
fects. In order to identify the effect of the interface potential on the defect-relatedstates
in the superlattice we also compare with calculation of substitutionalSb in bulk Si, with
the Si strained to the same alloy substrate as the superlattice.
Figure 18 shows the computed charge density associated with the A1A resonance
(lying close to the conduction bandedge) for the Sbsi defect in the superlattice. The
charge density in Fig. 18a, b is plotted in the planes A and B, respectively, where A and
B are the planes indicated in Fig. 16. Plane A lies parallel to the interface and passes
through the defect atom, while plane B is perpendicular to the interface, again passing
through the defect atom. The positions of the atoms that were situated in the plotting
planes prior to relaxation, and which moved only a small distance from the plane on
relaxation, have been projected onto the plotting planes.
For comparison,Fig. 19a, b show the charge density of the A l A resonance in bulk Si,
again through planes A and B, respectively. These plots demonstrate the near-spherical
distribution of the localized AIA resonance associated with the Sb defect in strained
bulk Si. Both planes show a highly symmetrical charge density around the defect atom.
This contrasts sharply with the case of the superlatticeillustrated in Fig. 18. In the plane
parallel to the interface, the defect resonance has been strongly perturbed, taking on an
axial shape. Similarly, in the plane perpendicular to the interface, the symmetry of the
charge distribution has been lowered. The changes in the chxgeaensity distributions
between Figs. 18 and 19 indicate a strong coupling between the Sbsi defects and the
Si-Ge interfaces. The introduction of the interfaces has dramatically affected the nature
of the localized A1A resonance. The detailed form of the interface-relatedresonance
in the superlattice is illustrated in Fig. 20, where the charge density is plotted on a
series of slices through the superlattice parallel to the interfaces. One can see that the
204 M. J. SHAWAND M. JAROS

~ - -
b) Plane B 0
I
1
High

FIG. 18. The charge density (arbitrary units) of the AIA resonance of a substitutional antimony defect
in the Si4Ge4 superlattice, plotted in (a) plane A, parallel to the interface, and (b) plane B, perpendicular to
the interface. The circles represent projections of the Si (solid) and Ge (open) atoms that lay in the plotting
plane prior to relaxation, and the open box shows the position of the antimony atom.

interface-induced charge localization occurs most strongly on the Si side of the defect
ion. From Fig. 20 it is apparent just how strongly the defect-interface interaction alters
the spatial charge distribution of the A1A resonance.
At this point it is worth recalling the expectations of the defect-molecule picture.
This simple model predicts the formation of bonding resonances (A1B and T2B, see
Fig. 17) in addition to the A l A resonance observed so far. Are these predictions verified
by our full-scale calculations? Figure 2123 shows the charge density of the lowest-
energy occupied level in our calculation, lying below the bottom of the valence band
in the unperturbed superlattice. This highly localized state is clearly of A1 symmetry,
and corresponds to the A1B resonance. Figure 21b shows the charge density of one of
the T2B resonances lying around the middle of our valence band, the p-like symmetry
apparent. Our ab initio calculations therefore support the qualitative picture provided
by the intuitive defect-molecule model. These lower-energy resonances describe the
 4 FUNDAMENTAL
PHYSICS 205
a) Plane A

High
I
I
I
S l
5m
g
e
€3
0
0
LOW

b) Plane B

High
I
I

0
0
0
Low

FIG.19. The charge density (arbitrary units) of the AIA resonance of a substitutional antimony defect
in bulk Si strained to a Sio.5Geo.5 alloy substrate, plotted in (a) plane A, parallel to the substrate, and (b)
plane B, perpendicular to the substrate. The circles represent projections of the Si atoms that lay in the
plotting plane prior to relaxation, and the open box shows the position of the antimony atom.

modification to the charge associated with the bonding between the defect atom and its
neighbors in the region of the interface. That is, they reflect the changes to the interface
bonds themselves.
It is now interesting to contrast the behavior of the antimony defect with that of
substitutional arsenic (Assi). We return to the study of the A1A resonance close to the
conduction bandedge. The calculated charge density of the Assi AIA resonance is plot-
ted parallel and perpendicular to the interfaces of the SkGe4 superlatticein Fig 22a, b.
The Assi defect is seen to result in a near-spherical localized AlA charge density,
qualitatively very similar to that of Sbsi in bulk Si. In other words, in contrast to the
strong coupling between the antimony and the interfacial potential, the arsenic defect
is largely unaffected by the presence of the interfaces.
From the foregoing discussion it is apparent that there is a significant difference
between the behavior of the antimony and arsenic defects. Specifically, the defect-
206 M. J . SHAWA N D M. JAROS

Hieh SbSi,

FIG.20. The charge density (arbitrary units) of the A l A resonance o f a substitutional antimony defect
in the Si4Ge4 superlattice, plotted on a number of planes parallel to the superlattice interface. The planes
shown lay in the immediate vicinity of the interface at which the defect is placed, from the plane of Ge atoms
forming one side of the interface, through Plane A containing the Sb defect, to the next plane of Si atoms.
The solid circles represent projections of the atoms laying in the planes prior to relaxation, for the three
planes that coincide with atomic planes. The text at the right-hand side of the diagram indicates the atoms
present in the unit cell at each of these layers.

interface coupling has been found to be far greater in the case of the antimony compared
to that of the arsenic. What is the origin of this difference? It is not clear from the fore-
mentioned discussion whether the contrasting behavior originates primarily through a
size effect, that is, where the difference arises mainly through the differing degrees of
lattice relaxation for the two defects, or whether the difference is essentially a chemi-
cal effect, determined by the microscopic nature of the atomic species. Certainly, the
larger Sb atom induces a relaxation in the lattice of around two times that caused by
the As defect, and it could reasonably be expected that this could account for the dif-
ference in behavior. The theoretical method we have employed allows us to isolate
these effects by “freezing” the atoms at nonequilibrium positions. In particular, we can
place, for example, the Assi defect in a unit cell whose positions have been relaxed for
an Sbs; defect, and then calculate the self-consistent charge density. The charge den-
sity of the A1A resonance for just this situation (Assi in a cell with Sbs; positions) is
shown in Fig. 23. The resonance is clearly very similar to the relaxed Ass; resonance
in Fig. 22a suggesting that the different degree of relaxation in the lattice is not the
primary cause of the difference between the antimony and arsenic defect resonances.
The strong defect-interface coupling, which occurs for the antimony defect, is thus
seen to arise through its microscopic “chemical” properties, and not due to the large
 4 FUNDAMENTAL
PHYSICS 207

High 1

FIG.2 1. Charge densities (arbitrary units) in plane A of (a) A1B and (b) T2B resonances of a substitu-
tional antimony defect in the Si4Geq superlattice. The circles represent projections of the Si atoms that lay
in the plotting plane prior to relaxation, and the open box shows the position of the antimony atom.

perturbation to the lattice that it induces. This is verified by calculations of the reverse
case, where the Sbsi defect is placed in the lattice relaxed for Assi. In this case the
resonance remains strongly coupled to the interface, although its energy relative to the
conduction bandedge changes.

3. DEFECTPERTURBATIONS T O CONDUCTION STATES

The introduction of a substitutional defect such as Sbsi or Assi has been shown to
introduce localized resonances that in the case of Sbsi interact strongly with the Si-Ge
interfaces. In addition, however, the presence of these defects, and the localization
of charge associated with them, will perturb the conduction band states of the perfect
208 M. J. SHAWAND M. JAROS

b) Plane B , -,
0 0

i-J
LOW

FIG. 22. The charge density (arbitrary units) of the A1A resonance of a substitutional arsenic defect in
the Si4Ge4 superlattice, plotted in (a) plane A, parallel to the interface, and (b) plane B, perpendicular to
the interface. The circles represent projections of the Si (solid) and Ge (open) atoms that lay in the plotting
plane prior to relaxation, and the open box shows the position of the arsenic atom.

superlattice. In this section we shall study the effect on the conduction states due to the
presence of the Sbsi and Ass; defects.
First, let us examine the lowest two conduction states in the perfect superlattice.
The charge density of these states, integrated in the plane parallel to the interfaces,
is plotted as a function of position in Fig. 24. Inset is a schematic diagram showing
the selection rules for the transitions across the fundamental gap. Note that for the
particular superlattice structure studied here, all transitions between the upper valence
bands and the lowest conduction band are symmetry-forbidden. The lowest energy
allowed transitions across the gap are to the second conduction state.
In Fig. 25 the integrated charge densities are plotted for the lowest conduction band
in the structures with Sbs; and Assi defects. These are compared to the charge density
of the unperturbed superlattice. It is clear from this figure that the symmetry of the
conduction state has changed. This is reflected in the selection rules of the perturbed
 4 FUNDAMENTAL
PHYSICS 209

FIG.23. The charge density (arbitrary units) of the AIA resonance of a substitutional arsenic defect in
the SiqGeq superlattice where the atomic positions are frozen at those of the antimony defect. The charge
density is plotted in plane A and the circles represent projections of the Si atoms that lay in the plotting plane
prior to relaxation, and the open box shows the position of the arsenic atom.

systems illustrated in the inset to Fig. 25. The presence of the defects lowers the wave-
function symmetry and results in allowed transitions to the lowest conduction band. It
is also clear that the strong coupling of the Sbsi defect, which played such a large role
in determining the form of the resonances, also results in an increased perturbation to

I' 0
0

Growth Direction

FIG.24. The charge density of the lowest two conduction states in a perfect SiqGe4 superlattice, inte-
grated in the plane parallel to the interfaces, are plotted along the growth direction. The solid and open circles
at the bottom indicate the positions of the planes of silicon and germanium atoms, respectively. The inset
shows the selection rules for optical transitions across the gap. The symbols 11 and Iindicate the polarization
of the incident light.
210 M. J. SHAWAND M . JAROS

FIG. 2 5 . A comparison )f the charge densities, integrated in the plane parallel to the interfaces, of
the Si4Ge4 superlattice with Sb and As defects. Also shown is the charge density of the perfect stmcture.
The positions of the atomic planes are indicated at the bottom of the diagram (solid-Si planes, open-
Ge planes), and the plane in which the defect occurs is shown. The inset shows the selection rules in the
perturbed systems, with the symbols (1 and Iindicating the polarization of the excitation. [Reprinted with
permission from the American Physical Society, Shaw, M. J., Briddon, P. R., and Jaros, M. (1996). Phys.
Rev. B54,16781.1

the conduction-band wavefunctions. Figure 25 shows that the conduction states are
perturbed to a far greater extent by the Sbs, defect than by ASS,.
The modification of the selection rules suggests that the alteration to the electronic
structure associated with the presence of the defects in the superlattice provides a mech-
anism for changes to the optical response of the systems. Of course, it should be re-
membered that experimental studies of the optical spectra of such structures will be
dominated by the extended features of the system, such as the shallow donor and exci-
tonic states. The microscopic approach, which has been applied here, is not appropriate
for the study of such extended features. However, we have demonstrated that the mi-
croscopic interactions between the defects and the Si-Ge interfaces result in changes
to the electronic wavefunctions that can affect the optical properties of the superlat-
tice. Further, these interactions are shown to distinguish the chemical nature of the
defect. The large perturbation to the form of the conduction states that results from the
defect-interface coupling will clearly also modify the transport properties of the sys-
tem. Again, a full evaluation of the effect on the mobilities and carrier lifetimes, and so
on, does not lie within the scope of this article. It is, however, clear that the localized
interface features identified will play an important role in determining both the optical
and transport characteristics of SiGe structures.
 4 FUNDAMENTAL
PHYSICS 211

4. AT GE IMPURITIES IN SI LAYERS
LOCALIZATION

In most practical applications of SiGe-strained layer systems the formation of layers

containing mixtures of Si and Ge occurs. This may be intentional, where one attempts
to grow an alloy layer or substrate buffer, or may occur naturally through disorder
or reconstruction at interfaces. It is therefore essential to understand how Ge atoms
behave in Si layers, namely, is it appropriate to consider the system as that of a simple
alloy? In most cases it is assumed that layers containing Si and Ge atoms can be very
well described as a simple alloy. Indeed, the use of the virtual crystal approximation
in theoretical studies of SiGe is widespread. However, the model used to describe the
behavior of substitutional donors in the foregoing text can also be used to examine the
effect of a substitutional Gesi defect, effectively the situation in a GeSi alloy.
As expected, the effect of the isovalent defect is generally far smaller than that of the
group-V donors considered so far. The wavefunctions obtained from our calculations
show that the lowest conduction band is only very slightly perturbed from the perfect
superlattice case, supporting the assumption that the alloy description is reliable. How-
ever, the second conduction state, whose charge density is plotted in Fig. 26, shows a
rather surprising feature. There is a considerable degree of localization around the Ge
atom, a feature that is contrary to the predictions of a simple alloy model. This result
suggests that when the full microscopic properties of the interfaces are taken into ac-
count, the Ge atom exhibits a behavior that is not entirely consistent with simple alloy
models. While this is clearly a secondary effect, and while the alloy model does pro-

High

FIG.26. The charge density (arbitrary units) of the second conduction state of a germanium defect in
the SiqGeq superlattice, plotted in the plane parallel to the interfaces. The solid circles represent projections
of the Si atoms that lay in the plotting plane prior to relaxation, and the open box shows the position of the
defect atom. [Reprinted with permission from the American Physical Society, Shaw, M. J., Briddon, P. R.,
and Jaros, M. (1996). Phys. Rev. B54, 16781.1
212 M. J. SHAWAND M. JAROS

vide a good description of most of the properties of GeSi, our predictions do indicate
that the applicability of the alloy model is limited.

VI. Microscopic Electronic Structure Effects in Optical Spectra

In the previous sections we have shown how the microscopic features associated
with the Si-Ge interfaces themselves are reflected in the luminescence spectra observed
from interband transitions in GeSi-strained layer heterostructures. The microscopic
models described in this chapter are also able to predict effects on a number of other
optical phenomena, including absorption and nonlinear optical spectra. Use of these
models can provide a physical understanding of the microscopic processes underlying
the behavior, and to enable the design of optimum structures for particular applications.
In the present section we shall briefly review the essential physics behind some of these
effects.
One of the applications of SiGe structures which has generated great interest in re-
cent years has been the possibility of infrared detector development (Wang and
Karunasiri, 1993; Robbins et al., 1995). To achieve an absorption at infrared wave-
lengths in the 3-5 p m and 10-15 prn ranges, p-doped Si-Si,GeI-, superlattices are
used. Absorption from occupied to unoccupied valence minibands results in an in-
travalence band contribution to the absorption that may be resonantly enhanced at the
photon energies of interest. The infrared photon energies are not sufficient to allow
intertiand absorption to take place. The empirical pseudopotential method enables the
origin of the dominant intravalence band transitions to be identified. It is then possible
to identify key design parameters such as alloy and doping concentrations, layer widths,
and so on, which determine the strength and angular properties of the absorption, and
allow the response to be tuned throughout the infrared spectrum. Such parameters are
necessary for the design of efficient infrared detector devices.
Many calculations of absorption spectra for p-type SiGe infrared detectors are de-
scribed in detail in the literature (e.g., Corbin et al., 1994a, 1994b). Here we shall
provide a brief overview of some of the principal physical insights obtained from the
microscopic theory. In the design of suitable structures one of the most important
factors to consider is the angular dependence of the absorption response. For many
detector applications a large response to light incident normal to the interfaces is most
favorable. However, such a response is made possible only through mixing of the va-
lence minibands, and consequently cannot be described without invoking a microscopic
theory such as that applied by Corbin et al.. In addition, the empirical pseudopotential
approach enables the minibands involved in the dominant absorption processes to be
identified. For the case of a typical p-doped Si-Si,Gei-, quantum well (20-monolayer
well with 15% germanium), the normal incidence response is found to originate from
transitions between the ground heavy-hole state (HH 1) and the ground split-off state
(Sol). A larger parallel incidence response can be identified with the HHl to first
 4 FUNDAMENTAL
PHYSICS 213

->, 200- + 15% Ge

9-
--
309. Ge
. r sepaotion for
......
15% Ge

W
E
C
0
150-
0)
0
Q
Y
o
W
a 100-

1
I I I I I I
20 25 30 35 40 45 50 55
Well width (monolayers)
FIG.27. The variation of the energy (meV) of maximum parallel incidence absorption with well width
(monolayers) for p-doped Si0.85Ge0.15 and Sio.7Geo.3 quantum wells. Also shown is the zone-center (r)
separation of the ground and first excited heavy-hole minibands, transitions between which dominate the
parallel incidence absorption response. [Reprinted with permission from the American Physical Society,
Corbin, E. A,, Wong, K. B., and Jaros, M. (1994). Phys. Rev. B50.2339.1

excited heavy-hole (HH2) transitions. Variation of the well width and/or alloy concen-
tration results in a change in the energy of the maximum absorption response, as shown
for parallel incidence absorption in Fig. 27. Judicious choice of these growth parame-
ters enables the principal response wavelength to be selected. However, the absorption
spectrum includes contributions from throughout the volume of the Brillouin zone that
is occupied by the hole carriers. As a result the energy at which the maximum response
occurs does not correspond to the zone-center energy separation of the minibands in-
volved. Rather, the precise energy of maximum absorption depends on the microscopic
properties of the minibands throughout wavevector space. The discrepancy between the
zone-center miniband separations and the energy of the absorption peak is illustrated
in Fig. 27. A further property that plays an important role in device application is that
of the lineshape, and it is important to consider some of the factors that determine the
shape, and particularly the width, of the absorption peak. For example, the absorption
spectrum is plotted for a number of different doping concentrations, distinguished by
the Fermi level, in Fig. 28. The lineshape of the absorption is found to depend on
the properties of the minibands throughout wavevector space, and is determined by a
number of design parameters including the doping level. Clearly, the task of tuning
214 M. J. SHAWAND M. JAROS

2.5 3.0 3.5 4.0 4.5 5.0 5.5

Wavelength (m)

FIG.28. The imaginary part of the first-order susceptibility (arbitrq units), representing the linear ab-
sorption, is plotted against photon wavelength (m) for several different Fermi energies in p-doped Si0.7Geo 3
quantum wells. The Fermi levels studied, given relative to the energy of the valence bandedge, describe sys-
tems of different doping concentrations. [Reprinted with permission from the American Physical Society,
Corbin, E. A,, Wong, K. B. and Jaros, M. (1994). Phys. Rev. B50,2339.]

the absorption energy, and of optimising structures for particular applications, must be
addressed using a full-bandstructure description of the heterostructures, accounting for
the dispersions of the key minibands.
The microscopic description of the electronic structure provided by the empirical
pseudopotential calculations also enables us to develop an understanding of a wide va-
riety of physical processes that limit the performance of infrared detectors and other
optoelectronic devices. For example, while the absorption process itself is clearly es-
sential to the performance of an infrared detector device, the dynamic properties of the
photoexcited carriers are critical in determining its performance. The carrier lifetime
is one such property, and in many devices it is limited by nonradiative, Auger recom-
bination (Landsberg, 1991). A typical Auger process is shown in Fig. 29, where the
photoexcited carrier in the SO1 band recombines nonradiatively with an electron in
the ground lighthole band (LHl), the excess energy exciting a second lighthole elec-
tron into the HH1 level. Clearly, such a process removes the photoexcited carrier from
the SO1 band from which it would be collected, resulting in a degradation in detector
efficiency. However, it is possible to design the heterostructure such that the energy
separations of the minibands prevents the forementioned process from taking place.
That is, by setting the HH1-LH1 separation greater than that of LH1-Sol, so that the
 4 FUNDAMENTAL
PHYSICS 215

Intersubhand Absorption

Auger Recombination

Electron 2 does not have

FIG.29. Schematic diagram of a typical Auger recombination process by which a photoexcited carrier
in the split-off miniband recombines with an electron in the light-hole miniband. Also shown is the condition
for which this process becomes forbidden. [Reprinted with permission from the American Physical Society,
Corbin, E. A,, Cusack, M., Wong, K. B., and Jaros, M. (1994). SuperlatticesandMicrostructures 16,349.1

energy released by the recombination is not sufficient to allow excitation from LH1 to
HH1, the process is energetically forbidden (see Fig. 29). If such a condition may be
satisfied throughout a substantial fraction of the active region of the Brillouin zone then
an increased lifetime may be achieved. In practice, the elimination of the process over
a sufficiently large volume of the zone has proven difficult to achieve. Furthermore,
this process is just one of a number of similar Auger recombination mechanisms that
can degrade the device performance, the elimination of which requires a considerable
design effort (see Corbin et al., 1996) based upon the microscopic bandstructure of the
heterostructures.
For many applications an important consideration is the behavior of the heterostruc-
ture in the presence of externally applied electric fields, which arise, for example,
through the operating bias of the device. The perturbations to the electronic structure
induced by such fields can significantly modify the response that would occur with no
such field present. Including the electric field as a perturbation to the zero-field super-
lattice potential allows the field-induced properties to be calculated from the results of
empirical pseudopotential calculations (Jaros et al., 1995). Consider, for example, the
case of Si-Ge double-well emitters, which have received considerable attention in the
literature (Engvall et al., 1995; Gail et al., 1995, 1996). The bandedge diagram for
one such structure is shown in Fig. 14, where the central Si layer confines the lowest
conduction level and the valence bandedge states are localized in the narrow Ge layers.
Both Ge layers are 4 monolayers wide, and are separated by 20 monolayers of Si. The
calculated charge densities for the levels close to the bandedges are plotted in Fig. 30
for external electric fields of 0, 1 and 4 x lo5 V/cm-'. With no external applied field
the conduction and valence bandedge states are localized as predicted in the foregoing.
216 M. J. SHAW AND M. JAROS

Charge Densities: alloy substrate with doping of 5 x ; 1 cm3

c2

CI

v1 VI

v2 v2

v3

v4
u v3
v4

FIG.30. The charge densities associated with the confined levels at the conduction and valence band-
edges of the double-well structure shown in Fig. 14. Results are presented for zero field, and for external
electric fields of 1x lo5 V/cm-‘ and 4x LO5 V/cm-’. [Reprinted from Journal of Crystal Growth 157, Jaros,
M., Elfardag, G., Hagon, J. P., Turton, R. J., and Wong, K. B., “Optimisation and stability of optical spectra
of novel Si-Ge quantum well structures in an external electric field,” 1 1-14,1995,with kind permission from
Elsevier Science-NL, Sara Burgerhartstraat 25, 1055KV Amsterdam, The Netherlands.]

With an applied field it can be seen that the conduction state remains well-localized
to the Si layer, despite being confined only by the narrow Ge layers. In addition, the
ground-hole states remain strongly localized in the Ge, though their symmetry has
been modified to result in localization in a single well. Calculations of the transition
probabilities for cross-gap emission processes show that up to fields typically present
in experimental conditions (up to x 1 x lo5 Vkm-’), there is no significant degra-
dation in the emission strength. The design of this structure was performed with such
stability in mind, and experimental studies of such structures show that the emission
does indeed remain stable in the presence of external fields.
So far, we have examined some of the physical properties of superlattices that af-
fect the electronic structure of SiGe superlattices, and how these in turn can affect the
linear optical response (i.e., absorption). There is also great interest in the nonlinear
optical response of semiconductor heterostructures under excitation by intense laser
excitation. Noniinearities in the response of a crystal can give rise to effects such as
harmonic generation, difference frequency generation and an intensity-dependent re-
fractive index, with huge potential for application as optical modulators and optical
signal processing components (e.g., Shen, 1994). Calculations of the nonlinear optical
susceptibilities can be achieved by evaluation of microscopic expressions derived from
density matrix theory, using empirical pseudopotential bandstructures. Such calcula-
tions are described in considerable detail in the literature (e.g., Shaw et al., 1984). As
 4 FUNDAMENTAL
PHYSICS 217

FIG. 3 I . Schematic diagram of the virtual excitation processes that can be resonantly enhanced in
microstructures to achieve large second harmonic generation.

in the case of the linear absorption calculations, the microscopic origin of the contri-
butions to the spectral response can be identified, opening the way for optimization of
the nonlinearity.
Just as p-type SiGe superlattices have been used to exhibit an absorption in the
10-15 p m infrared region of the spectrum, so similar structures can be designed to ex-
hibit an enhanced second-order nonlinear response at these frequencies. By choosing
structures in which there are three equally spaced levels it is possible to resonantly en-
hance the second harmonic generation processes indicated in Fig. 3 1. Such processes,
consisting of three virtual transitions, occur on ultrashort timescales and lead to the
creation of second harmonic radiation. Of course, as the overall response will consist
of contributions from across the populated region of the Brillouin zone, exact achieve-
ment of this enhancement is not possible. A third layer is inserted into the quantum
wells to lower the symmetry of the states. For the symmetric well structures designed
for the study of absorption, all of the components of the second-order susceptibility
tensor are zero. The asymmetric stepped well structures have a lower symmetry and as
a result exhibit five independent nonzero components.
The second-order susceptibility describing the second harmonic generation process,
written x g B ( - 2 w ; w , w ) (where a and j3 are the polarizations of the incident photons
of frequency w and p is the frequency of the second harmonic, 2w response), was calcu-
lated for the p-type (001) 18Sio.gsGeo.15/2Si0.925Ge0.075/40Si superlattice (where 40Si
refers to 40 monolayers, 10 lattice constants of Si). The frequency dependence of the
five nonzero components is plotted in Fig. 32, where the doping concentration is such
that the Fermi level lies 26 meV below the valence bandedge. The full microscopic ex-
pression for the susceptibility, and further details of the calculations, are described in
Shaw et al. (1993). By evaluating specific terms in the expression for the susceptibility
218 M. J. SHAWAND M. JAROS

x10’
1 .o

Component

__ u x

0.09 0.095 0.1 0.105 0.11 0.115 0.12 0.125 0.13

Photon Energy (eV)

FIG. 32. The magnitude of the five independent components of x:dp(-2w; w , w ) in esu, plotted
against the photon energy in electronvolts, for the p-type (001) 18Si0,85Ge0.1~ /2Si0,925Ge0,07~/40Sisu-
perlattice at 0 K. [Reprinted with permission from the American Physical Society, Shaw, M. J . , Wong, K. B.,
and Jaros, M. ( 1993). Phys. Rev. B48,200 I .I

it is possible to identify the particular excitation sequences that dominate the response.
For the principal peak of xzzz (2) at around 100 meV in Fig. 32, the dominant processes
are found to be C+SO+HHl+C and SO+HHl-+C+SO (where HH1 refers to the
ground heavy-hole state, SO refers to the spin split-off state and C refers to states ly-
ing in the continuum). These processes correspond to those illustrated schematically
in Fig. 3 1, which can be resonantly enhanced if the miniband separations are approx-
imately equal. We note that, as in the case of the linear absorption, the maximum of
the second-harmonic response did not in fact correspond to the zone center separation
of the minibands involved. For example, while the HHl-SO1 separation is 107 meV at
the zone center, the peak in absorption occurs some distance from this. This is a result
of the contribution from wavevectors away from the zone center, and the dispersion
of the superlattice minibands. The energy shifts are more prominent for the peaks of
components x:zi and x
!: for which the strength of the key transitions depends upon
the momentum mixing of the minibands. As the momentum mixing is only strong at
wavevectors lying away from the zone center, these components are dominated by such
contributions, and the peak energy is not determined by the zone-center separations.
 4 FUNDAMENTAL.PHYSICS 219

It is clear then that the frequency and angular dependences of the nonlinear response
are governed by the properties (e.g. dispersions, mixing) of the minibands throughout
the Brillouin zone. The design of suitable structures therefore involves a consideration
of the bandstructure properties throughout k-space, and not simply at the zone center.
In particular, the angular dependence of the second-harmonic response is important in
the design process, as this determines the geometry of any device. Specifically, it is
desirable to have a device that operates with normal-incident light, a geometry more
easily realized in practice. This corresponds to light polarized in the x - y plane, and
to, for example, the xzxx( 2 ) component.

These examples demonstrate the essential role played by the microscopic bandstruc-
ture features in the optical spectra of SiGe heterostructures. The principal features in
the linear and nonlinear spectra can be understood in terms of the microscopic transi-
tion processes, and in turn through the properties of the minibands themselves.

VII. Conclusion

The properties of strained layer GeSi heterostructures cannot be well described us-
ing a simple effective mass approximation. While such a model is adequate for under-
standing many of the features of unstrained structures (e.g., AlGaAdGaAs), its neglect
of the microscopic potential variations is no longer reasonable for strained systems,
where the atoms are displaced from the regular lattice positions. It is necessary to use
more sophisticated techniques to capture the microscopic physics that underlies these
structures. One such method is the empirical pseudopotential method in which a micro-
scopic pseudopotential, fitted to reproduce particular empirical data, is included. This
approach provides a good description of most of the properties of ideal systems, and
can be extended to include a perturbative description of features such as disorder and so
on. The computationally intensive density functional theory approach using ab initio
pseudopotentials provides a complete microscopic description, and allows a detailed
study of short-range features of the system unable to be described by the empirical
pseudopotentials. Such a model enables the microscopic signature of the Si-Ge inter-
faces to be studied, opening the way for definitive distinction between microstructure
and strained alloy systems. These two theoretical techniques together provide a means
to obtain a complete description of the GeSi structures.
The bandstructures of perfect GeSi heterostructures, for example, superlattices, are
dominated by the effects of strain and of zone-folding due to the superlattice long-range
order. The precise choice of substrate and layer widths determines the very nature of the
structure, that is, direct or indirect, and as such the suitability for optical applications.
Of course, it is not possible to grow “perfect” structures, and as one might expect the
properties of the structures depend on the quality of the growth process. A study of
random disorder at interfaces and an ordered reconstruction of the interfaces (such as
is observed experimentally) shows that in both cases the strength of the direct transition
220 M. J . SHAW
AND M . JAROS

is reduced, while the indirect transition to the in-plane minima is enhanced relative to
the perfect structure. The effect is sufficiently strong in the randomly disordered case
that the direct and indirect transitions become comparable.
The optical properties of “real” structures are therefore seen to differ from those of
an idealized system. Although the empirical pseudopotential calculations used have
been shown to agree well with many of the experimentally observed phenomena, there
remains a discrepancy with regard to some optical spectra. Experimental observations
of luminescence spectra indicate that the in-plane minima dominate the spectra. The
extent of random disorder required to produce sufficiently strong in-plane transitions
is incompatible with what is known about the samples concerned. A mechanism that
provides a possible explanation involves the role of interface islands. Calculations
indicate that in the presence of sufficiently large islands the optical recombination
will be dominated by impurity atoms at the interfaces, and the breaking of the in-
plane symmetry at the interface could enhance the indirect transitions to the observed
level.
It is clear then that the interfaces play a key role in determining the optical response
of the structures. In many calculations, the interfaces are represented by an abrupt
semiclassical step-like potential, neglecting the microscopic variations of the potential
in the region of the interface bonds themselves. The ab initia pseudopotential cal-
culations presented here include a complete microscopic description of the interface
region, the “intrafacial” properties. These intrafacial parameters govern the behavior
of certain impurities in the vicinity of the interfaces, modifying the optical and trans-
port properties of the structure. In particular, interface-induced localization occurs at
substitutional antimony defects situated adjacent to the Si-Ge interfaces. This localiza-
tion is primarily dependent on the chemical nature of the impurity (rather than, say, its
size) and is the result of the microscopic defect-interface interaction. Such interface
localization effects provide a possible foundation for an understanding of the observed
luminescence spectra.
While the interband transition spectra are governed by transitions weak or forbidden
in the perfect case, and hence require an additional description of disorder and impurity
effects, the intraband optical processes of doped GeSi structures are well described by
the “perfect” calculations. These processes are technologically important in optical
device applications, and show linear and nonlinear optical responses governed by the
details of the superlattice bandstructure. The microscopic origin of the optical response
can be identified, enabling the specific features of the superlattice to be tuned to give
optimum performance.
For GeSi heterostructures to fulfill their enormous potential it is essential to gain an
understanding of the microscopic physical processes underlying their behavior. While
these materials have many inherent advantages with regard to applications, there are
several challenges that must be overcome if their use is to become widespread. Primar-
ily, for optoelectronic applications, upon which we have chosen to focus in this chapter,
one must address the issue of the indirect nature of the materials. Bandstructure en-
 4 FUNDAMENTAL
PHYSICS 221

gineering techniques can be applied to obtain direct-gap heterostructures in which the

optical response is improved. However, there remains the difficulty of growing high-
quality layers in the presence of such high strain. As the calculations of this chapter
show, the optical properties suffer a severe degradation through the existence of dis-
order and reconstruction, common at the interfaces of these strained systems. Perhaps
most significantly, however, it is necessary to be able to characterize and distinguish be-
tween microstructure and alloy-related features. To achieve this we have demonstrated
that a full microscopic description of the heterointerfaces themselves, the “intrafacial”
parameters, provides us with a microscopic signature of the interfaces. Indeed, our
theory indicates, in agreement with experimental data, that some of the key optical and
transport properties of SiGe systems are dominated by the microscopic properties of
the interfaces.
The future development of strained-layer GeSi devices depends, both in the case
of switching applications (e.g., through carrier lifetime) and optical applications (e.g.,
through transition strength), on our understanding of the physics associated with the
heterointerfaces themselves. As we have shown in this chapter, this problem cannot be
addressed using the conventional physical models usually applied to heterostructures.
Rather, a microscopic treatment of the intrafacial parameter space is required. This
defines a clear role for fundamental physics that must be fulfilled to enable continued
advances in strained layer GeSi device technology.

ACKNOWLEDGMENTS

We would like to thank the U. K. Engineering and Physical Science Research Coun-
cil, D.E.R.A. (Malvern), and the Office of Naval Research (USA.) for financial support.
Work on GeSi has been carried out at the University of Newcastle upon Tyne for a num-
ber of years, and we would like to thank those involved, in particular, R. J. Turton, P. R.
Briddon, K. B. Wong, J. P. Hagon, and E. A. Corbin for many helpful discussions.

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 SEMICONDUCTORS AND SEMIMETALS, VOL. 56

CHAPTER 5

Optical Properties
Fernando Cerdeira
INSTITUTO
DE F ~ S I C A

UNlVERSlDADE ESTADUALDE CAMPINAS,

UNICAMP
SAo PAULO,BRAZIL

I . INTRODUCTION . . . . . . . . . . . . . . . . . . . . .......... ... ...... . 226

11. FORMSOF DIFFERENTIAL S P E C T R O S C O P Y BASEDO N
REFLECTIONO R ABSORPTION O F LIGHT. . . . . . . ......... ..... ...... 226
1. General Considerations . . . . . . . . . . . . . . . .. ........ ..... .. ... 226
2. On Pseudo-direct Optical Transitions . . . . . . . . ...... .. ... ., ... ., .. 23 1
3. Other Optical Transitions in Si/Ge,Sil --x and
-,
Ge/Gex Si 1 Microstructures .... . ..... .. ... 236
4. Other Optical Transitions in Ge,Sim Quantum Wells
and Superlattices . . . . . . . . . . . . . . . . . . . 243
111. RAMANSCATTERING ............ ......... ................ 253
1. General Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
2. Raman Scattering in Bulk GexSil-, Random Alloys . . . . ........ .. ..... . 256
3. Raman Scattering by Optic Modes in Ge,Sim QWS and SLs ........ 258
4. Raman Scattering by Acoustical Phonons in Si/Ge
Microstructures ... ... . . .... .. . . ... 260
5. Resonant Raman Scattering . . . . . . . . . . . . . . . . . .. . . . .... ... .... 265
6. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . .... 216
Iv. PHOTOLUMINESCENCE .... . , .., .. ... , . . . . , . . . . . , . . . . . . . . . . 277
I . Introduction. . . . . . . . . . . . . . . . .. . ... . . . . . . . . ..., . . , . , . . 277
2. PL from Bulk Ge,Sil-, Alloys . . . . . . . . . . . . .. .... .. .... . .. .... 218
3. P L from Si/Ge,Sil_, Microstructures . . . . . . . . . . . . . . . . . . . . .. . . ... 280
4. PL from Ultrathin Ge,Si, QWs and SLs . . . . . . . . . . . . . . . . . . . ... .. .. 286
V. CONCLUDING REMARKS . . . . . . . . . . . .. .. . .. . ... . . . . . . . .. . .. . 288
REFERENCES. . . . . . . . . . . . . . . . . . .. ... ... ... . . .... .. . .... 289

Copyright @ 1999 by Academic Press

All nghtP of reproductionin any form reserved.
ISBN 0-12-752164-X
0080-8784/99 $30.00
226 FERNANDO
CERDEIRA

I. Introduction

The optical properties of semiconductors have provided rich information on such

diverse aspects of their physical properties as their electronic and vibrational states and
the existence and nature of defects and impurities. In the particular case of seniicon-
ductor heterostructures, some optical techniques have provided information about their
structure (super-periodicities, layer thicknesses, etc.) and that of their interfaces.
Light incident on a semiconductor surface is partly reflected and partly transmitted.
The reflected light carries information about the electronic states of the material. Part
of the light that enters the semiconductor is absorbed or scattered while the remainder
is transmitted if the sample is thin enough. The energy from the absorbed radiation
can be dissipated (absorption) or re-emitted as photons of different frequencies (pho-
toluminiscence). Photons can also be inelastically scattered by creating or annihilating
elementary excitations within the semiconductor (Brillouin or Raman scattering). By
now, so much information has accumulated about these forms of interaction of elec-
tromagnetic radiation with semiconductors and other materials that good accounts of
the basic physics and experimental details involved in this interactions can be found
in many textbooks and review articles (Yu and Cardona, 1995; Haug and Koch, 1990;
Cohen and Chelinkowsky, 1989; Bassani, 1975). We shall not attempt to duplicate this
work. Rather, we shall give brief introductory descriptions of the optical techniques
that have contributed most to the understanding of the properties of Si/Ge heterostruc-
tures.
These brief descriptions will be provided in any of the sections of this chapter that
contain a discussion of the results obtained by a given technique. Thus, Section I1 is
dedicated to discussing techniques based on reflectivity or absorption of light; Section
111 describes the results of inelastic light scattering; Section IV is devoted to photolu-
minescence. Finally, in Section V we attempt to summarize the main points developed
in the previous sections. Because several techniques have sometimes contributed to an
understanding of a given issue, this division into sections is not ironclad and the results
from several techniques must be discussed together. In doing so, the results from tech-
niques that have not yet been introduced are summarized, postponing more detailed
discussions to the appropriate subsection.

11. Forms of Differential Spectroscopy Based on

Reflection or Absorption of Light

1. CONSIDERATIONS
GENERAL

The quantities experimentally determined by these techniques are related to the real
[EI( w ) ] and imaginary [ ~ 2 ( w )parts
] of the dielectric constant. The latter is sensitive to
processes in which a photon is absorbed, lifting an electron from the valence into the
 5 OPTICALPROPERTIES 227

conduction band. In these processes the total crystal momentum is conserved. Since
the wave vector of the light is very small, compared to electronic wavevectors inside
the Brillouin Zone (BZ), such transitions are essentially vertical and connect conduc-
tion and valence band states of virtually the same k-vector. Peaks and shoulders ap-
pear in ~ ( wwhen) the joint density of states of the bands involved in the transitions
have singularities. These peaks and shoulders can be correlated to similar structures
appearing in the reflectivity R ( w ) or the absorption coefficient a ( w ) of the material.
The photon-energy at which these structures appear give precise values for the energy
difference between valence and conduction band states at important symmetry points
(or along symmetry axes) of the BZ, at which the joint density of states is singular
(van Hove singularities) (Yu and Cardona, 1995; Haug and Koch, 1990; Cohen and
Chelinkowsky, 1989; Bassani, 1975; Cardona, 1969). As an example we show in
Fig. 1 the bandstructure of bulk Ge. In this figure the various electronic transitions
responsible for structure in the optical properties are indicated. The most prominent
structures in the optical coefficients are given names such as Eo (direct transitions at
the BZ center), El (direct transitions along the (111) axis in the BZ), etc. Table I lists
their transition energies for bulk Si and Ge (Yu and Cardona, 1995). Notice that in
both these materials the fundamental gap is indirect, so that optical transitions across
this gap must be assisted by large-wavevector phonons in order to conserve crystal
momentum. Hence, these transitions provide only weak contributions to the optical
constants. These show clear structures only for direct transitions (Fig. 2). In the up-
per curve of Fig. 2 we display the reflectivity of this material. As we can see, not all

FIG. 1. The bandstructure of bulk Ge showing the various direct transitions responsible for the structure
in the optical spectra of Fig. 2. Adapted from Yu and Cardona (1995) with permission. To produce this figure,
the authors of this textbook used data from Cardona and Poll& (1966).
228 FERNANDO
CERDEIRA

TABLEI. Measured energies (eV) of prominent structures in the

optical spectra of bulk Si and Ge.
Transition Si, hw(eV) Ge, hw(eV)
EO 4.185 0.898
Eo + A0 4.229 1.184
El 3.45 2.222
El +A1 - 2.41
Eb 3.378 3.206
+
E;, A;, - 3.39
E2 4.330 4.49
E’1 5.50 5.65
All data refer to low temperature measurements, except for the Eo
transition of Si, which has been taken at room temperature, com-
piled from data listed in Yu and Cardona’s book Fundumenruls of
Semiconduclors ( 1995).

the vertical transitions indicated in Fig. 1 show up clearly in the reflectivity spectrum
of Fig. 2(a). During the sixties, several techniques were developed for modulating
either some sample parameter or the incoming or outgoing beams. These modula-
tions produce spectra that are related to some derivative of the dielectric function. The
process of differentiation suppresses uninteresting backgrounds and produces sharp
structures in the photon-nergy region of the optical singularities. This point is il-
lustrated in Fig. 2(b), where the electroreflectivity spectrum of bulk Ge is shown.
In this technique an ac electric field modulates the optical properties of the material
and the resulting spectrum is related to the third derivative of the dielectric function
(Aspnes, 1973; Aspnes, 1980). Bumps and shoulders in R ( w ) (upper curve) are high-
lighted in the modulated reflectivity spectrum (lower curve). The latter gives good
resolution of critical points, which are almost invisible in the plain reflectivity spec-
trum. Because of this advantage, modulation spectroscopy had a decisive influence
in understanding the bandstructure of bulk semiconductors. Most of the work in this
area was performed in the 1960s and early 1970s and has been extensively reviewed
(Cardona, 1969; Aspnes, 1980). With the advent of semiconductor microstructures,
there was a revival of interest in these techniques. Their applications to semiconduc-
tor superlattices and quantum wells have been recently reviewed by several authors
(Pollak, 1989; Pollak 1991; Pollak and Shen, 1993; Cerdeira, 1993). Of particular
importance have been the techniques of photo- and electromodulated reflectivity, in
which an electric field is modulated within the sample by either depositing a semi-
transparent metal layer on the sample surface and applying an ac voltage between the
front and the back of the sample or by photoinjecting carriers by a modulated sec-
ondary beam. The measured quantity is the ratio between the modulated ( A R ) and
the dc parts of the reflectivity ( R ) . This is related to the third derivative of the dielec-
 5 OPTICAL PROPERTIES 229

Photon Energy ( eV )

a8 I II L\lll* 1 bulk Ge

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

Photon Energy ( eV )

FIG. 2. (a) Reflectivity (adapted from Yu and Cardona (1985)with permission). To produce this figure,
the authors of this textbook used data from Philipp and Ehrenreich (1967). (b) Electroreflectance (adapted
from Pearsall er al. 1989a with permission) of bulk Ge. Peaks in the latter are identified according to the
optical transitions of Fig. 1.

tric constant and is well represented by a, now, standard lineshape function (Aspnes,
1980):

where each term in the sum corresponds to a critical point of energy (lifetime broaden-
ing) E j ( r j ) ;C , and 4, are amplitude and phase factors, respectively, of the transition.
The exponent n depends on the type of critical point. Choosing a value of this param-
eter for SLs and QWs has been the subject of much debate (Cerdeira, 1993). However,
the value obtained for the critical energies by fitting the experimental data with Eq. (1)
230 FERNANDO
CERDEIRA

is remarkably independent of this choice. The usefulness of this technique depends

greatly on this feature of ER and PR lineshapes.
An oblique angle of incidence technique that has been very useful in the last decade
or so is that of spectroscopic ellipsometry. Its name refers the fact that when linearly
polarized light, which is neither polarized parallel nor perpendicularly to the plane of
incidence, is reflected obliquely from the semiconductor surface it emerges elliptically
polarized. By determining the orientation and the ratio of the polarization ellipse axes,
the real and imaginary parts of the dielectric constant can be obtained. Because of
present-day accuracy in these measurements, numerical differentiation of E ( W ) can be
performed that produces similar results to those of modulation spectroscopy (Yu and
Cardona, 1995; Aspnes, 1980). This is illustrated in Fig. 3, where the third derivative of
E ~ ( w )taken
, from ellipsometric data is compared with electroreflectance results (Asp-
nes, 1983). Ellipsometric measurements have provided excellent values of dielectric
constant and refractive indices of a large variety of bulk semiconductors (Aspnes and
Studna, 1983).
The accurate information about critical point energies obtained by the methods de-
scribed in the foregoing paragraphs have had a symbiotic relationship with bandstruc-
ture calculations in the physics of semiconductors. In the following subsections we
discuss the application of differential optical techniques to the determination of critical
points in the electronic transitions of Si/Ge microstructures. When interpreting experi-

-
Photon Energy ( eV )

FIG. 3. (a) Real and imaginary parts of the dielectric constant for bulk Ge, (b) E - 2 d ' / d E 3 [ E 2 ~ l ,
from numerical differentiation of the curve in (a), and ( c ) A s from ER measurements. Adapted from Aspnes
(1980) with permission.
 5 OPTICALPROPERTIES 231

mental data we shall use simple concepts such as those of zone-folding or confinement
of electronic states that can be derived from those of the bulk components. This method
gives a good intuitive understanding of some results but is not applicable to all cases,
so the reader is advised to read Chapter 4 of this volume, where the electronic structure
of these materials is described in great detail.

2. ON PSEUDO-DIRECT OPTICAL TRANSITIONS

It is expected that superlattices (SL) alternating n-monolayers of Ge with m-mono-

layers of Si (Ge,Si,), should produce, through zone-folding, a direct bandgap material
with appropriate choices of n , m and the amount of strain in each type of layer. The
strain can be controlled by the choice of substrate (Si or Ge) and buffer layer on which
the superlattice is grown (see the chapter by Bean). In these superlattices the con-
duction band edge is formed from bulk-Si A states, while the top of the valence band
originates in bulk-Ge r-point states. The A-conduction band of bulk Si forms a degen-
erate sextuplet, one for each (100) equivalent direction. In the SL the multiplet splits
into a doublet ( A J and a quadruplet (All), for the valleys perpendicular and parallel
to the plane of the layers, respectively. Choosing the SL period appropriately, the A 1
can be folded into the Brillouin zone center. This results in a direct gap material if the
2-fold A 1 minima are lower in energy than the 4-fold A 11 ones. This could be achieved
by subjecting the Si layers to a tensile strain. Hence, we should not expect to find di-
rect gaps in SL-grown lattice matched on Si. Paradoxically, it was a report of a strong
optical transition at very low photon energies in such a material that produced a flurry
of activity on the subject.

-
Room-temperature electroreflectance measurements in a Ge4Si4 5-period SL exhib-
ited a very strong line at 0.76 eV, which was tentatively identified as a direct tran-
sition between the valence band and the Al-folded conduction band (Pearsall et al.,
1987). The spectrum, shown in Fig. 4(a), exhibits several other lines that can be at-
tributed to direct transitions and in which zone-folding plays no role. The fact that the
,.,
line at 0.76 eV (labeled “1” in Fig 4(a)) has an intensity that is comparable to those of
these other lines was interpreted as a signature of a quasi-direct transition (i.e., a tran-
sition made direct through zone-folding). Although a tight binding band calculation
by Brey and Tejedor (1987) gave support to this interpretation, the majority of calcu-
lations predicted an indirect gap (ie., they predicted that the lowest conduction-bands
minima were produced by All states) (Wong et al., 1988; Hybertsen et al., 1988). Even
for a pseudo-direct transition, the calculated oscillator strength is much smaller than
the observed one. Subsequent measurements of photocurrent and electroreflectancein

-
the same sample, interpreted with a first-principles band calculation, established the
existence of two indirect absorption edges, at 0.78 and 0.90 eV, respectively, but not
of a direct one (Hybertsen et al., 1988). The photocurrent measurements are shown
in Fig. 4(b). The anomalous oscillator strength of these indirect transitions remained
232 FERNANDO
CERDEIRA

Photon Energy (ev)

I " " " ' " " I

0.2 0.4 06 0.8 1.0 1.2 1.4 16

Photon Energy (ev)

FIG. 4. (a) ER spectrum of a GeqSi4 SL with fitted critical point energies indicated by arrows. (b)
Photocurrent signal for the same sample; the dashed lines show a fit with two indirect absorption edges and
background. Adapted from Hybertsen ef al. (1988) with permission.

unexplained, although Hybertsen et al. (1988) mention end effects (their SL is only 5
periods long) and interface roughness as probable causes. The other lines in the ER
spectrum of Fig. 4(a) were discussed in more detail in a later paper by the same group
(Pearsall et al., 1989a) and their interpretation includes other transitions from the va-
lence band to folded conduction band states whose intensity exceeds greatly that of the
predictions of band calculations. These results will be discussed in Section 11.4, in the
context of higher-energy direct transitions in Ge, Si, SLs.
Next, electroreflectance measurements performed on two Ge,Si, ( n m = 10) +
SLs grown commensurately on Ge substrates are reported by Pearsall et al. (1989b).
These SLs should have pseudo-direct bandgaps, produced by the folding of the A 1
conduction band edge, because they satisfy both the periodicity and strain conditions
previously explained. Their spectra show a rich pattern of strong structures at photon
 5 OPTICALPROPERTIES 233

energiesjust above that of the direct Eo peak of bulk Ge, which they attribute to pseudo-
direct transitions. First-principles band calculations show that such pseudo-direct gaps
exist in this photon energy region, although the transitions associated with them should
have negligible oscillator strength (Schmidt et al., 1991). Hence, the existence of a
pseudo-direct gap does not necessarily explain the structure observed in the spectra of
Pearsall et al. (1989b). This assignment is even less firm when we take into account
the actual structure of the samples used in the experiments. In addition to the thick Ge
buffer layer, each sample contains 20 repetitions of the basic 5-period Ge,(SimSL sep-
arated from one another by 25-nm-thick Ge layers. These thicker Ge layers contribute
to the total spectrum with their own Eo transition and a strong pattern of Franz-Keldysh
oscillations induced by the applied electric field (Aspnes, 1980; Cerdeira, 1993). These
contributions fall into the same photon energy range as that of the pseudo-direct tran-
sitions from the Ge,Si, parts of the sample. In order to overcome the problem of the
Franz-Keldysh oscillations, Yin et aE. (1991) performed a piezoreflectance study on a
series of Ge,Si, SLs, including those previously studied by Pearsall et al. (1989b).
Their piezoreflectance results show that the spectral features that had been identified as
due to pseudo-direct transitions from the SL parts of the samples are, instead, quantum-
confined Eo transitions originating in the 25 nm Ge spacer layers. However, the search
for pseudo-direct transitions continues. Pearsall et al. also reported measurements of
differential transmission on these samples that seem to support the idea of anomalously
strong optical absorption at the pseudo-direct bandedge (Pearsall, 1992; Pearsall et al.,
1995).
While the controversial results of the modulated reflectivity work were being actively
discussed, new evidence from photoluminiscence (PL) work performed on Ge, Si, SLs
was added to the debate. Zachai et al. (1990) reported photoluminiscence experiments
performed on a series of Ge,Si, SLs with different periods and states of strain. The
strain variations were achieved by using either Si or Ge substrates and buffers of par-

-
tially relaxed Si-Ge alloys. In all cases their SLs have many periods (total SL thick-
nesses of 200 nm), so end-effects cannot be invoked here. On the other hand, both
the density of misfit dislocations and interface roughness should be larger here than in
the shorter SLs used in the electroreflectance work (see the chapter by Bean). Figure 5
summarizes the results of Zachai et al. (1990). A very broad and inhomogeneously
broadened peak at -0.84 eV appears in a strain-symmetrized sample with n + rn = 10.
This sample has the right period and strain to have a pseudo-direct gap. This peak is
either absent or very weak in samples that do not meet these criteria (i.e., samples with
indirect gaps). Hence, these authors identified the PL line as a direct recombination,
at the BZ-center, from the bottom of the folded A 1 conduction band to the top of the
Ge-like valence band. This interpretation was hotly disputed by Schmidt et al. on the
basis of their comparison of the photon-energy position of the PL peak and the value
of the pseudo-direct gap obtained in their ab initio calculation for the SL used in the
PL experiment (Schmidt et al., 1990). Also, the calculated oscillator strength for this
pseudo-direct recombination is orders of magnitude smaller than that which would be
234 FERNANDO
CERDEIRA

1 1 1 1 1 1 1 ~ 1 1 1
Si I Ge T = 5 K hL=457.9 nm

Si, Ge2 ( alloy ) IW/ cm2

Si ,*Ge8 IW/crn2

7 - -

Xo.1
- I00W/ cm2
,
urc

A
, . l , l , l , l ,
0.7 0.8 0.9 1.0 1.1
Photon Energy (eV)
FIG. 5 . The PL spectra of several strain-symmetrized Ge,Si,, SLs with n rn = 5 , 10, and 20. All +
have a common thickness ratio rn/n = 1.5 and biaxial strain €11 E I .4% (€11 2 2.7%) in the Si (Ge) layers.
The Ge2Si3 structure has a more alloy-like behavior. Adapted from Zachai et al. (1990) with permission.

required to observe this strong emission. They suggest that the emission line is asso-
ciated with defects (the samples in question are known to have dislocation densities of
between los and 1010cm-2) and point out that remarkably similar emission lines were
observed by other authors in samples where the active region was composed of a ho-
mogeneously strained layer of Ge,Sil-, alloy (Noel et al., 1990). In these samples the
gap is definitely indirect and no zone-folding can be invoked. To counter this criticism,
Meczingar et al. (1993) studied the absorption (via photocurrent) and PL spectra of two
+
Ge,Si, superlattices with n m = 10. These samples were grown in conditions that
guaranteed a very low dislocation density. Figure 6 reproduces their PL and absorption
spectra for a Ge4Si6 SL (upper curves) and a Geo.4Sio.6 alloy grown under the same

-
conditions. The onset of the SL absorption is shifted towards lower photon-energies,
by 100 MeV, in relation to that of the alloy. Comparison between the absorption and
the PL features in the former sample supports the interpretation that the latter origi-
nates in a no-phonon recombination across the gap that produces the absorption edge
(see Section IV).
 5 OPTICAL
PROPERTIES 235

10K - 102
h

v)
c

.-
C
5K =l

- step graded I
-.I m
n 0.031xM.4
I -E
1%..f 0.4
i

10’

5K
I I I I
0.7 0.8 0.9 1.0 1.1
Photon Energy (ev)

FIG. 6. PL and absorption spectra of a GeqSi6 SL and a Ge0.4Si0.6 alloy. Adapted from Meczingar et
~ l (1993)
. with permission.

Combining both results we conclude that the PL of the SL sample is due to a no-
phonon recombination that takes place in the part of the sample containing the Ge4Si4
SL and not in the alloy buffer layer. This seems to support the interpretation of Zachai
et al. (1990). However, this interpretation is not unique. First we notice that the similar
PL features observed by Noel et al. (1990) in Ge,Sil-, quantum wells are also due
to a no-phonon recombination process across the alloy indirect energy gap, that is, to
explain this line no direct gap is necessary. Second, the buffer layer is not the only place
in the sample that contains alloy layers. The results from Raman scattering experiments
in Ge,Si, SLs show that alloy layers form spontaneously at the Ge/Si interface (see
Section III.5.C). Thus these superlattices contain a certain amount of Si-Ge alloy even
when it has not been intentionally included in the sample. Hence, the PL peak could
be equally well interpreted as due to recombination in the alloy regions of the sample
located around the Si/Ge interfaces of the Ge4Si6 SL.
The preceding discussion shows that, although zone-folding does result in pseudo-
direct gaps for samples of appropriate periods and strain, no clear evidence exists that
236 FERNANDO
CERDEIRA

the strong optical structures observed in reflectivity, absorption or PL spectra of some

Ge,Si, superlattices are associated with transitions across this gap. This is made espe-
cially plain by the fact that these strong spectral features also appear in samples where
the gap is clearly indirect. Thus, zone-folding does not appear to be the main reason
behind these strong features in the optical spectra, but rather other components of the
sample, which appear unintentionally during growth, might be responsible for them.
This view is supported by recent theoretical calculations showing that if a disordered
layer exists, extending only f l monolayer (ML) at the Si/Ge interfaces of a 10-ML
period superlattice, alloy scattering becomes the dominant mechanism for recombina-
tion (Turton and Jaros, 1996). This point is thoroughly discussed in the chapter by
Shaw and Jaros, so we need not elaborate any further here. One additional remark
is in order about the interpretation of the results from the type of optical experiments
discussed so far. Most of the uncertainties when interpreting spectra arise from the fail-
ure to answer the following question: Which part of the sample is responsible for the
observed spectral feature? The optical spectra results from the response of the whole
sample, which, aside from the actual Ge,Si, SL, includes buffer and spacer layers as
well as thin layers of disordered material at the interfaces. In some cases the technique
of resonant Raman scattering is able to give an experimental answer to this question
(see the discussion in Section 111.5). However, it is not always possible to perform such
experiments. In these cases theoretical studies must be used to answer this question
(for more information see Chapter 4).

3. OTHER OPTICAL TRANSITIONS

I N SI/GE,SII-, AND
GE/GE,SI~-, MICROSTRUCTURES

The early optical work in Si/Ge microstructures was conducted on quantum wells
(QWs) and superlattices obtained by alternating relatively thick (2.5-25 nm) layers
of Si and Ge,Sil-, alloys grown lattice matched on Si (001) substrates (Bean et al.,
1984). In these structures the quantum wells are composed of a disordered, strained
material. In order to describe the electronic states of the SLs it is necessary first to
understand those of the strained alloy. Experience shows that these can be described
fairly well in the spirit of the virtual crystal approximation (Therodorou et al., 1994).
Within this framework we can attribute to the alloy a bandstructure, which is a weighted
average of those of Si and Ge and that responds to strain similarly to those of the
constituent materials (Abstreiter et al., 1985; Zeller and Abstreiter, 1986; People, 1985;
Lang et al., 1985). Figure 7 shows a schematic representation of a biaxially compressed
Geo.5Sio.5 alloy derived using the approximations just described (Pearsall et al., 1989a).
A comparison between Figs. 1 and 7 shows the similarities between the bandstructures
of the alloy and those of the constituent materials. Figure 7 also shows the optical
transitions responsible for the main features in the modulated reflectivity spectrum.
These transitions are clearly seen in the ER-spectra of bulk, unstrained alloys. The
 5 PROPERTIES
OPTICAL 237

WAVE VECTOR

FIG.7. Schematic bandstructure of a Ge0.5Si0.5alloy subjected to uniaxial tension along the (001) axis.
The two nonequivalent (100) directions are shown. Adapted from Pearsall ef al. (1Y8Ya) with permission.

evolution of the transition energies as alloy composition changes is illustrated in Fig. 8

(Kline et al., 1968). This figure shows that the optical transitions in the Ge,Sil-, alloy
evolve continuously, and indeed linearly in most cases, from those of Si into those of
Ge as x varies from 0 to 1. Disorder seems to affect optical spectra only by introducing
extra broadening in the observed lines. This could be interpreted, within the virtual
crystal approximation, as a disorder-induced relaxation of the conservation of crystal
momentum in the optical transitions. Hence it is possible to think of the states of the
quantum well as resulting from confined alloy bulk states, in the same manner as if the
material of the QW were pure Si or Ge (Therodorou et al., 1994).
These ideas, however, needed to be put to the experimental test. To the best of our
knowledge, the first observation of optical transitions attributable to confined states
in Si/Ge,Sil-, SLs were the resonant Raman scattering measurements of Cerdeira et
al. (1985). The Raman spectrum of these materials is discussed in detail in Section 111.
Here we merely remark that the intensity of a given Raman peak is enhanced when
the incoming or scattered beams have a photon-energy that coincides with that of a
direct electronic transition involving states confined within the same layer as that in
which the vibration originating the peak is confined. Hence, plotting the intensity of a
given Raman line as a function of the photon-energy of the incoming laser ( l i w ~one )
obtains a curve that has peaks whenever l i w ~coincides with such a transition. Cerdeira
et al. (1985) report a resonant enhancement in the cross section of an alloy phonon,
which can be attributed to vibrations of the Si-Ge bond (see Section 111.2), at photon
238 FERNANDO
CERDEIRA

"I
4 1
-*.+-*-*-*-
E2
*-*-*-*-+-

0.4
1.0 0.8 0.6 0.4 0.2 ( 3
Ge X Si

FIG. 8. Evolution of the critical point energies for the main optical transitions in Ge,Sil-, alloys: from
the ER-spectra of Kline et a/. (1968) with permission.

-
energies in the range no, 2.0-2.6 eV , in a series of Si/Ge,Sil-, SLs with a variety
of QW-widths d and alloy compositions x (see Fig. 9). This signals the presence of
an optical transition (or a family of closely spaced optical transitions) between states
confined within the alloy QW. These transitions were tentatively identified as the strain-
split Eo doublet of the alloy layers, modified by stress and confinement (see Fig. 7).
Encouraging as this first indication of quantum confinement in this type of materi-
als was, the resonant Raman experiments did not provide accurate transition energies
for the optical transitions involved. Indeed, even their identification as Eo-like transi-
tions is not unequivocal, because of the proximity of El transitions of the alloy layers.
More detailed information about optical transitions in these materials was later reported
by Pearsall et al. (1986). These authors reported electroreflectance measurements in
Si/Ge,Sil-, SLs in a wide photon-energy range (2.0-4.0 eV). A typical ER-spectrum
is shown in Fig. 10, where the arrows indicate assignments of spectral features to tran-
sitions between electronic states in the SL derived from bulk-alloy electronic states
modified by strain and confinement. These assignments are complicated by the fact
that two multiplets overlap in energy: the Eo(1) and Eo(2) strain-split doublet and the
 5 OPTICALPROPERTIES 239
I
I I I I
G e , Si,,/Si
T = 300 K

- o X=075(d=25i)
0 X=0.65(d=33i)

A X=0,40(d=75A)

I 1 I I i
2.2 2.4 2.6
hOL ( e V )

FIG.9. Raman cross section of the Si-Ge peak vs h o ~ for Si/Ge,Sil-, SLs with different QW-widths
and molar compositions; from Cerdeira et al. (1985) with permission.

PHOTON ENERGY ( eV)

4.00 3.50 3.25 3.00 2.75 2.50 2.25 2.00
I I I I I I
E,+
,
A ’ E, (b)

FIG. 10. ER spectrum (77 K) of a 7.5 nm SiIGe0.45Si0.55 QW, from Pearsall et al. (1986) with perrnis-
sion.
240 FERNANDO
CERDEIRA

El +
and El A1 of the bulk alloy (see Fig. 7). Also, the spectral lines for this strained
and disordered QW-material are rather broad, as can be seen in Fig. 10. Even so, the
assignments in these figures for the Eo doublet are in good agreement with calculations
made on the basis of the well-known behaviors of these gaps with strain, alloy com-
position, and a simple Kronig-Penney-type model, with constant effective masses, to
account for the effects of quantum confinement (Bastard, 1981). The quantum wells
were constructed using band alignments at the Si/Ge interface proposed by Van de
Walle and Martin (1986), which involve very shallow wells for holes and deep QWs
for electrons (as much as 1.8 eV for some of the samples from Pearsall et al., (1986).
These deep QWs should produce a multiplet of transitions associated with each of the
strain-split Eo gaps. The width of the ER lines in the spectrum of Fig. 10 does not allow
resolving the members of these multiplets produced by quantum confinement. As the
El -multiplet confinement cannot be included in a straightforward way, it was ignored
by Pearsall et al. (1 986). Even so, fairly good agreement is found between predictions
made on this basis and optical structures in their ER spectra.
The pioneering work already described here proved that optical spectra in these
structures could be interpreted successfully on the basis of direct optical transitions
in the bulk-QW material, modified by the effects of strain and confinement. These ef-
fects were reasonably well-described for zone-center transitions by elastic theory and
very simple Kronig-Penney-type models, respectively. In order to obtain more accurate
information for comparison with theoretical models, it would be necessary to produce
materials in which the EO and El multiplets were not overlapping. A better-quality
QW-material also would produce sharper spectral lines. This was accomplished by
growing the structures commensurately on Ge substrates and alternating alloy with Ge
layers, that is: Ge/Ge, Si 1--x quantum wells and superlattices. In these structures the
QW-material is pure, unstrained Ge while the strain and disorder appears only in the
barrier (alloy) material. An additional advantage is that in bulk Ge the Eo and El transi-
tions are well separated in energy (-- 1.4 eV, as can be seen in Table I), so the multiple
transitions associated with the Eo optical gaps in the QWs do not overlap in energy
with the structures associated with the bulk El gaps. Optical multiplets associated with
the Eo transitions of bulk-Ge were first observed by piezoreflectance in the thick (29-
143 MLs) Ge QWs formed in the Ge-spacer layers separating thin Ge,Si, short-period
SLs (Yin et al., 1991). These results were already discussed in the previous subsection.
The observed multiplets were described qualitatively by a Kronig-Penney-type
model using constant effective masses. However, predictions differ from actual peak
positions by as much as 110 MeV in some cases. These predictions can be made more
accurate by including the effects of nonparabolicities in the conduction band. These
effects are not negligible in cases such as these, where the confinement energy can be
comparable to, or even larger than, the Eo gap in the bulk material. The matter was
later taken up by Rodrigues et al. (1992), who reported photoreflectance (PR) mea-
surements on two GelGeo.7 Sio.3 SLs with relatively thick( - 10 nm), unstrained, Ge
quantum wells. A typical spectrum from one of these samples is shown in the upper
 5 OPTICALPROPERTIES 241

1'
ER T = 7 7 K

c
Ge-bulk
I
+ 1 1 1 , , 1 1
d
/
1 .o 1.5 2.5
Photon Energy (eV)

FIG. 1 1. PR spectrum of a Ge/Ge0,3Si0,7 SL (upper curve) and ER spectrum of bulk-Ge (lower curve).

curve of Fig. 11. For comparison, the PR spectrum of bulk Ge is shown in the lower
curve of this figure. The multiplet associated with the bulk Ge Eo transitions is clearly
seen in the spectrum of the Ge-QW of Fig. 11. The lines associated with bulk-Ge
El transitions are also clearly seen, but they appear at much higher photon energies.
We discuss first the SL spectral features associated with the Eo gap, which are shown
in greater detail in Fig. 12. Eight lines (labeled A through H, in order of increasing
photon energy) are clearly identified in this multiplet. These lines were interpreted in
terms of the predictions of a simple Kronig-Penney-type model, using the offset of the
average valence bands ( A E u , a uas) an adjustable parameter. The results of these calcu-
lations are shown in this figure as solid (dashed) curves for parity-allowed transitions
at the minizone center (edge), while experimental transition energies are represented
by horizontal dotted lines. The figure on the left-hand side of the spectrum was cal-
culated with constant effective masses, while that on the right-hand side was produced
by energy-dependent masses calculated with the Kane model (Rodrigues et al., 1992;
Kane, 1966). For constant masses the agreement is poor for all but the lowest photon-
energy lines, regardless of the choice of band offset. In contrast, excellent agreement
is obtained when nonparabolicities are included (Fig. 12(c)) for a value of the band
offset of AE,,+ 2: 0.14 f 0.03, which agrees with that proposed by Van de Walle and
Martin (1986). Table I1 compares experimental and calculated values for the transition
energies. In these assignments not only the lines associated with heavy ( h )or light hole
(I) transitions are identified, but also the effects of miniband dispersion are brought into
focus as the structures produced by singular points at the minizone center (r)and edge
(n)become progressively resolved when the transition index (n) increases.
242 FERNANDO
CERDEIRA

Parabolic Ge'Geo,,Sio 3 Non-parabolic

Bands 111/32 A Bands

-2
%
1.46 1.46 ;
F P
a,
a,
r C
w w
c
0
1.18 1.18 :?
ln
C
F
k

Flc. 12. Comparison between the calculated transition energies of the Eg multiplet of a (11.1/3.2
nm) Ge/Ge0,3Si0,7 SL and those obtained from the PR spectrum (see Rodrigues ef al. (1992)). (a) Full
(dashed) lines show calculations, using constant effective masses, for zone-center (zone-edge) transitions as
a function of the valence band discontinuity. (c) Same as (b) but using energy-dependent effective masses.
(b) Experimental PR spectrum; arrows indicate critical points; horizontal dashed lines are the prolongation
of these arrows into the (a) and (b) panels.

The foregoing discussion vindicates the use of simple models based on confinement
in square wells for the optical structures associated with the Eo gap. This is a nontrivial
conclusion, as the conduction minima at r, in bulk Ge, is higher in energy than other
conduction bandstates (see Fig. 1) and intervalley mixing could occur (see the chapter
by Shaw and Jaros). The nagging question remains as to whether the same would hold
for SLs with ultrathin layers. We tackle this question in the following section. Before
coming to that, let us examine the part of the spectrum of Fig. 11 associated with the
El and El +A1 transitions. No multiplets are observed here. In fact the spectrum of
the SL and that of bulk Ge are almost identical, except for a small shift in the lines of
the former towards higher photon energies, which increases as the width of the Ge-QW
(L) decreases (52 MeV for d = 11.1 nm and 72 MeV for d = 10.2 nm) (Rodrigues et
al., 1993a). This argues in favor of confinement effects, even for optical gaps such as
those that extend through a large portion of the BZ (Yu and Cardona, 1995). The actual
confinement of the electronic states is confirmed by resonant Raman results, which
shall be discussed in Section 111.5. However, it is far from obvious how this concept
applies to electronic states with such a large energy-width that they overlap with many
other states in the BZ. This complex situation precludes the use of square-well models
to treat this confinement. In fact, the very concept of confinement becomes dubious,
 5 OPTICALPROPERTIES 243

TABLE11. Transition energies obtained both for experimental ER

data and from an envelope-function calculation (including non-
parabolicities in the conduction band) for the Ge/Ge,Sil-, .. SL of
~

Fig. 12, with AE, z 0.14 eV.

Transition energy (eV\ ~ ~~~~

Line Experimental Theory Assignment

0.953 1 hr
A 0.948
0.957 1 hl7
0.962 1 lr
B 0.963
0.978 1 zn
1.099 1 hn
C 1.102
1.111 2 hr
D 1.136 1.136 2 zn
E 1.176 1.177 2 zr
1.308 3 hT
F 1.324
1.330 3 hn
G 1.547 1.548 4 hn
H 1.595 1 .595 4 hr
~~ ~

Here nh(nl) denotes the transition between the nth confined level
of the heavy (light) hole band and the corresponding level at the
conduction band. The label r(n)corresponds to transitions at the
minizone center(edge). Adapted from Rodrigues et af. (1992).

especially for SLs with very thin layers. This discussion will be taken up in the next
section, devoted to optical results in Ge,Si, SLs.

4. OTHER OPTICAL TRANSITIONS

IN G E ~ S I ,QUANTUM
WELLS
A N D SUPERLATTICES

In Section 11.2 we discussed some aspects of the ER-spectra of ultrathin Ge,Si, SLs
( n , m 5 5 ) , namely, the existence of low photon-energy spectral lines that had been
attributed to pseudo-direct transitions at the folded fundamental gap. A representative
ER-spectrum from a Ge4Si4 (Hybertsen et al., 1988) is reproduced in Fig. 4(a). Be-
sides the line assigned to this pseudo-direct transition, other strong ER-lines appear
at higher photon-energies. These are assigned to direct transitions between electronic
states originating in bulk-Ge states modified by the superlattice potential. A more com-
244 FERNANDO
CERDEIRA

plete study of ER in this type of materials was later reported by Pearsall et al. (19894.
In this work the spectra of Ge,Si, SLs (grown commensurately on Si substrates) with
n = m = 1 , 2 and 4 are discussed in detail. The spectrum of Fig. 4(a) is representative
of those of these samples. The sample with n = m = 4 shows several lines that are
attributed to Eo or El transitions. Because the Ge layers are biaxially compressed two
EOlines are expected, corresponding to transitions between the strain-split heavy and
light hole valence bands and the confined state (only one for very thin layers) of the
conduction band. The members of this doublet are called Eo(1) and Eo(2), in order of
increasing energy. This doublet (at 2.20 and 2.38 eV, respectively) is identified in the
ER spectra of Pearsall et al. (19894. Also present in their spectra are two doublets, one
strong (at 2.60 and 2.82 eV) and one weak (at 3.04 and 3.22 eV), which are assigned
+
to El and El A ] , respectively, modified by the superlattice potential. The nature of
these modifications is not made clear by Pearsall et al. They also discuss the spectra
for samples with n = m = 1 , 2 , assigning spectral lines with the assumption of perfect
interfaces. In view of the fact that interface roughness extends at least one monolayer
on each side of the interface, these assignments are not likely to be reliable.
Photoreflectance (PR) measurements by Dafesh et al. (1990) and Dafesh and Wang
(1992), performed on a strain-symmetrized 60-period Ge32Sis SL, are shown in Fig. 13.
The thick Ge-QW should produce a multiplet for each one of the two strain-split Eo
gaps, in a manner analogous to that of the upper curve in Fig. 11. Instead, only two
strong lines, associated with the n = 1 transitions of Eo( 1) and Eo(2), respectively, ap-
pear in the spectra of Fig. 13 (lines B and C, respectively). A series of weak structures
(D through P) also appear in the spectra. They are identified as higher transitions of

, I . . I I . I I I I I I . 1 . , . . I . . . .
0 1.00 1.50 2.00 2.50 3 I0
Photon Energy ( eV )

FIG. 13. PR spectrum of a strain-symmetrized Gej2Sig SL. The inset shows an enlargement of the
structures labeled B and C. The label A designates a photon energy region where indirect transitions could,
in principle, be observed. Adapted from Dafesh et al. (1990)with permission.
 5 OPTICAL
PROPERTIES 245

+
the Eo multiplets, El and El A 1 transitions from the Ge layers or transitions in the
thick, strained-relaxed, alloy buffer layer. The label A in Fig. 13 designates a photon-
energy region where indirect transitions might appear. None are reported by the authors
(Dafesh et al., 1990). The assignments are made exclusively on the basis of the photon
energy of a given line. It is not clear, for instance, why the line attributed to the El
transition is so weak, knowing that this transition is responsible for the strongest line
of the optical spectrum of bulk Ge in this photon-energy range (see Fig. 2). On the
other hand, SLs with such thick Ge-layers may have poor interfaces (see the chapter by
Bean), so it would not be surprising if these weaker lines are related to defects rather
than to the interband transitions of a perfect structure. In any case, there are a good
number of these lines in a photon-energy range where different electronic transitions
overlap, so a more detailed knowledge of the bandstructure of the SL would be required
in order to make reliable assignments of optical structures.
The forementioned combination of detailed band calculations with a sensitive op-
tical technique is present in the work of Schmidt et al. (1990). These authors report
ellipsometric measurements, both at room temperature and at T = 10 K, performed
on a Ge4Sis strain-symmetrized SL. They compare the second derivative of E ~ ( w ) ,
obtained by numerical differentiation of experimental data, with that generated by a
linear-muffin-tin-orbital (LMTO) ab inirio calculation. In Fig. 14a and b, respectively,

-400 , , ...........................
2 3 4 5
Photon Energy ( eV )

FIG. 14. Experimental and theoretical results for a strain-symmetrized Ge4Si6 SL. (a) Second deriva-
tive of the imaginary part of the dielectric constant [numerically obtained from ellipsometric measurements
of q (o)]: lowest (second lowest) curve for T=10 K (300 K). Theoretical simulations with different broad-
enings: top and second-from top curves. (b) Calculated electronic structure. Adapted from Schmidt er al.
(1990) with permission.
246 FERNANDO
CERDEIRA

we show the comparison between their experimental and theoretical optical spectra
and their results for the bandstructure calculation. Each interband transition indicated
in Fig. 4(b) produces a peak in the theoretical optical spectra of Fig. 4(a) (arrows).
Comparison between the experimental and theoretical optical spectra is excellent, once
the theoretical photon energy is given a uniform 0.1 eV shift to account for a sys-
tematic artifact of the calculation (Schmidt et al., 1990). Also, note that experimental
spectra can only be obtained after the sample has become opaque to the incoming light
(hw 1 2.7 eV). At lower photon energies the optical spectra are dominated by inter-
ferences produced by multiple internal reflections. This is a feature that affects most
optical measurements based on reflectivity to a larger or lesser degree. Several tech-
niques have been developed to remove the effects of these interferences (Rodrigues et
al., 1993a), but it is always an ultimate limiting factor to the accuracy of reflectivity-
based measurements in multilayer systems. Taking these limitations into account, we
can summarize the main conclusions of this work as follows:

0 The lowest direct energy gap occurs at the r-point (- 1.1 eV). This gap appears
as a result of zone-folding (see Section 1.2), but gives no significant contribution
to the optical spectra because of its negligible oscillator strength.

0 -
Strong absorption starts at 2.3 eV and it is associated with transitions along
the r - N line in the mini-Brillouin zone. This is a multiplet that originates in
bulk El transitions, modified by the effects of the superlattice potential through
zone-folding and confinement. They are named EY(a = a , b, c and d ) .

0 The first transition at the r-point of the mini-zone that gives a significant con-
tribution to the optical spectrum occurs at 2.6 eV and originates in bulk-Ge Eo
transitions, shifted to this high energy by the effects of quantum confinement.

0 In addition to the bulk-like features already discussed here, Fig. 14a shows a
series of weak peaks, labeled S i ( i = 1 - 6). These are attributed to transitions
from the bulk-like valence band to folded conduction band states.

Subsequent theoretical (Schmidt et al., 1991) and ellipsometric (Schmidt et al.,

1992) work confirms these results and traces the evolution of these optical structures
for different sample parameters.
The foregoing discussion exemplifies the importance of having a reliable band cal-
culation when interpreting the optical spectra of Ge,Si, SLs. In this spirit, subsequent
ER-measurements (Rodrigues et al., 1993b) in a series of strain-symmetrized SLs were
examined within the general scheme of optical transitions illustrated in Fig. 14b. In
Fig. 15 we display their ER-spectra, taken at T = 77 K, for samples with different layer
thicknesses. Each spectrum shows a large number of structures, which result from a
variety of transitions with overlapping critical energies. The authors assumed that the
number of critical points were those of the LMTO calculation for the n = m = 5
 5 OPTICALPROPERTIES 247

Ge,Si, ' ,, , '

E, a E O E,bA%C ,L,d

I .5 2.0 2.5 3.0

Photon Energy (eV)

FIG. 15. ER spectra of strain-symmetrized Ge,Si, SLs. Circles represent experimental data while the
continuous line is the best fit with Eq. (1) for seven critical points (A through G). Component lines of a given
fit are shown below each spectrum. Critical energies from the LMTO calculation of Schmidt (1991). for
n = m = 5 , are shown with arrows on top. Also indicated are the Eo critical points given by an envelope-
function calculation. Adapted from Rodrigues et al. (1993b).

case (Schmidt et al., 1991) and fitted their experimental data with this number of stan-
dard ER-lineshapes [Eq. (l)]. The continuous lines in Fig. 15 represent the best fit to
the data (open circles). The individual lineshapes composing each fit are shown below
each spectra and the arrows indexed A, B, . . . , etc., are the critical energies obtained
from these component lines. The upper arrows indicate the critical energy and assign-
ment of the LMTO calculation for a GesSiS SL (Schmidt et al., 1991). Also indicated
in Fig. 15 are the calculated positions of the strain-split Eo doublet, calculated by a
248 FERNANDO
CERDEIRA

TABLE111. Critical point energies of Ge,Si,, strain-symmetrized SLs from the fittings of the ER spec-
tra (77 K) with Eq.(l); assignments of the LMTO calculation by Schmidt er al. (1991) and the envelope
calculations for the & optical gap.
Sample Experimental Assignment Theoretical
Cj r, E j ( e V ) LMTO EF
Eabs(eV) Ej (eV) EO(eV)

GeqSi4 0.49 0.10 2.31 2.30 E" 2.31 2.3 I

0.59 0.12 2.42 EO 2.35
0.59 0.15 2.58 E: 2.48
0.69 0.14 2.80 Ef 2.68
1.OO 0.16 3.03 E? 3.01
Ey ,Eb 3.26
GesSig 0.50 0.20 2.30A 2.43 E4 2.23 2.25
0.69 0.10 2.50B Eo(hh) 2.25
0.69 0.10 2.55C Eo U h ) 2.3 1
1.13 0.17 2.64D E: 2.72
0.81 0.12 2.82E Ef 2.79
1.00 0.15 3.05F Ef 2.93
0.64 0.16 3.36G Eb
Ge(jSi6 0.27 0.20 2.30 2.59 E" 2.30 2.56
1.130.102.60 EOW) 2.55
0.93 0.10 2.66 EoQh) 2.60
1.43 0.17 2.73 Ei 2.75
I .20 0.12 2.94 E; 3.00
1.000.15 3.07 Ef 3.1 I
0.53 0.14 3.37 E:,
Eabs is the onset of strong absorption in these samples determined from the interface pattern. Adapted from
Rodrigues er al. (1993b).

simple Kronig-Penney model with energy-dependent effective masses (Rodrigues et

al., 1992). Table 111 summarizes the numerical results of these assignments for the
samples with short periods ( n + m 5 10). Here we also list the onset of strong absorp-
tion (EabS) in these samples, obtained from the exponentially decaying envelope of the
interference oscillations that precedes it, in the manner explained by Rodrigues et al.,
(1993b). Extending the same analysis to samples with larger periods, the evolution of
these optical transitions as a function of period-length can be studied. The main results
can be summarized as follows:

0 The spectra always contain a feature whose origin can be traced to confined bulk-
Ge Eo transitions. This feature is very sensitive to the thickness of the Ge layer
 5 OPTICAL
PROPERTIES 249

3.9

3.6

3.3

3.0

2.7

2.1' '
5
' "
I '

10
' '' I ' "
15
I ' ' 1
20
Number of Ge monolayers (n)

FIG.16. Dependence of the critical point energies of the El multiplet with the thickness of the Ge layer.
Arrows indicate positions of critical points for strained bulk Si and Ge. The continuous lines are guides for
the eye. The inset shows the evolution of the Q critical point. Adapted from Rodrigues ef al. (1993b) with
permission.

and its position is wellkxplained by simple Kronig-Penney-type models. This

is illustrated in the inset of Fig. 16, where the experimental transition energies
from ER-spectra (open circles) are plotted against the predictions of such a model
(open diamonds and continuous line) and those of the LMTO calculation (full
diamonds). For n + m 2 10, this transition defines the onset of strong absorption
in these materials. For smaller periods, the Eo transitions move up in energy and
fall among the members of the El-multiplet (to be discussed next). In this case
one of the members of this multiplet defines the onset of strong absorption.

As already discussed, the El -transitions of the bulk materials originate a multi-

plet as a result of the modifications imposed on them by the superlattice potential.
The evolution of the members of the multiplet as the thickness of the Ge layer in-
creases is shown in Fig. 16. This figure suggests that this multiplet is composed
mainly of a Ge-like doublet (ET and E;) and a Si-like one (EF and Ef), which
+
evolve towards the El and El A1 transitions of bulk Ge and Si, respectively,
as the Ge layers become thicker.
250 FERNANDO
CERDEIRA

0 The E7-transition of thin-layered SLs ( n 5 6) is responsible for the most in-

tense line of the ER-spectrum and constitutes the onset of strong absorption in
these SLs. As the Ge layer thickness increases this line evolves continuously
towards the bulk-Ge E I transition, but it always occurs at a higher photon en-
ergy than the latter. This is true even for very thick Ge layers, such as those of
the Ge/Ge,Sil--x SLs discussed in the previous subsection. Although this might
suggest confinement of a bulk-Ge state, this energy increase could also result
from an admixture of Si-like states, which diminishes progressively as the thick-
ness of the Ge layer increases. With the data discussed so far it would not be
possible to distinguish between these two alternatives.

The last point in the foregoing discussion could be clarified by studying how the
EI multiplet is generated as the number of Ge-quantum wells increases from a single
QW to a full superlattice, for fixed thicknesses of the Si and Ge layers. In the case of
admixture of Si and Ge wavefunctions we would expect a weak dependence of these
structures on the number of periods, as this admixture depends mostly on the relative
thicknesses of the Si and Ge layers. On the other hand, confined states would develop
into multiplets with the wavefunction of its members still mainly confined in one or
the other layer. An experiment of this type was attempted by Rodrigues et al. (1993a),
who report PR measurements on three samples containing one (1 QW), two (2 QW)
and six (6 QW) Ge quantum-wells. The samples were grown lattice-matched on Si
(001) substrates. The Ge QWs have a thickness of five monolayers. In the samples
with multiple QWs these are separated by 5 MLs of Si. Each structure is repeated
between 10 and 25 times and each unit is separated from the next by a 30-nm thick
Si spacer-layer. Low-temperature (77 K) PR and room-temperature resonant Raman
scattering (RRS) experiments were performed on these samples.
Their PR-spectra are shown in Fig. 17a, where open circles represent expenmen-
tal data and the solid curve is a fit with the standard lineshapes of Eq. (1). Each line
composing a given fit is shown below the respective spectrum. We see a continuous
evolution in the spectra of the NQW samples, from one line for N = 1, to two for N = 2
and four for N = 6, respectively. If we identify the spectral line in the single-QW as
El, then the splitting of this feature into two components for the double-QW (A and
B in Fig. 17a) is analogous to the splitting of a given electronic state into a symmetric
and an antisymmetric component by the double well, while the multiplet generated by a
fully periodic superlattice would already appear for 6 QWs. This assignment coincides
with that made by Freeouf el al. on the basis of ellipsometric and RRS experiments per-
formed on thin (- 0.7-nm) Ge-layers buried in a Si matrix (Freeouf et al., 1990). The
evolution of this structure as the number of Ge QWs increases is illustrated in Fig. 17b,
where the data for the strain-symmetrized Ge5Si5 SL from Rodrigues et al., (1993b)
was included ( N = 150). The arrows at the side of this inset indicate the El and
El + A1 transitions of biaxially strained bulk Ge and strain-free bulk Si, respectively.
There is a remarkable agreement between the multiplet of the 6 QW sample and that of
 5 OPTICAL
PROPERTIES 251

I a, - 1
ER T d 7 K Si-bulk E,
-
t .... ............................ ........ JL-
'.... '.,
i1 3.3
t
unstrained E',

-I

c
W
Ge-bulk
strained
2.4

2.1
1.5 2.0 2.5 3.0 0 2 4 6 150 180
Photon Energy (eV) Number of Ge quantum wells (N)

FIG.17. (a) ER spectra (open circles) of the NQW-samples fitted with the lineshapes of Eq. (I), contin-
uous line. Arrows indicate critical-point energies from the fit. (b). Critical energies for El -like transitions vs
N. Arrows indicate the value for this critical points in strained (unstrained) Ge (Si). Adapted from Rodrigues
er al. (1993a) with permission.

the SL. This agreement is even more impressive when we consider that both samples
have different strain profiles. In order to say something about the actual confinement of
the electronic states involved in these transitions, we turn to the RRS results. The exact
manner in which this technique gives information about wavefunction confinement will
be described in Section 111.5. Here we mention only that the Raman cross section of a
vibration, known to be localized in a given layer, is enhanced only when the incoming
(or outgoing) beam is in resonance with an electronic transition among states localized
in the same layer. In Table IV we list the photon energy and assignments of the lines
in the PR-spectra, as well as the degree of confinement of the electronic states derived
from the resonant Raman experiments. These results support the idea of wavefunction
confinement for the electronic states involved in the El transitions.
Those parts of the discussion in the last two sections that were centered around
spectral features in Ge single and multiple quantum wells attributable to either & or
El transitions of the bulk materials can be summarized as follows:

0 Multiplets associated with the Eo transitions are clearly observed in QWs and
SLs with relatively thick Ge layers (- 10 nm) and alloy barriers. As these layers
become thinner, this rich multiplet structure becomes obscured. This happens
252 FERNANDO
CERDEIRA

TABLEIV. Transition energies (Ej) and broadenings (rj)of the

lines in the ER spectra of NQW samples.
Sample ER(77 K) Assignment Confinement
E j (rj)
(in eV)
1 QW 2.83(0.11)A El Ge
2 QW 2.72(0.17) A E: Mostly Ge
2.98(0.18) B EL Mostly Si
6 QW 2.43(0.12)A E;" Mostly Ge
2.59(0.10) B El; Mostly Ge
2.74(0.15) C EE Mostly Si
2.97(0.12) D E! Mostly Si
Assignments are shown in the third column while the last column
lists the degree of confinement of the electronic states participating
in the transition from RRS data. Adapted from Rodrigues et al.
(1993a).

both because narrower wells have fewer confined states and also because inter-
face imperfection becomes more important in thinner wells, leading to broader
spectral lines. Another complicating factor is that confinement shifts these peaks
into the region of the stronger El -multiplets. However, in all cases the lines iden-
tifiable as Eo transitions have a strong dependence on layer thickness that can be
quantitatively explained with simple square-well models.

0 In single Ge-QWs confinement of the A-line states of bulk Ge occurs. This is not
obvious, as these states cover a wide range of energies that overlaps (although
at different k-vectors) with states along the same line in the barrier material.
In a superlattice, these lines split into two doublets with wavefunctions mostly
confined into the Ge (Si) layers for the doublet at lower (higher) photon energy.
These doublets appear as a consequence of zone-folding and the manner in which
this happens cannot be described by simple square-well models.

The results of this section were discussed within the framework of electronic cal-
culations performed for microstructures with perfect interfaces. As we shall see in
Section 111.5, actual interfaces always have disordered layers that affect at least fl ML
around the Ge/Si interface, and frequently present larger-scale roughness in the form of
terracing an island formations. These real interfaces might have a decisive influence on
the optical spectra which might, in turn, lead us to revise the previous assignments. The
subject of electronic states in imperfect structures, and their influence in their optical
properties, is amply discussed in the chapter by Shaw and Jaros.
 5 OPTICALPROPERTIES 253

111. Raman Scattering

1. GENERALCONSIDERATIONS

Inelastic light scattering by phonons has been used for several decades to obtain in-
formation about the electronic and vibrational states of semiconductors. Among the
numerous reviews on the subject, we cite two representative examples: that of Cardona
(1982) for bulk semiconductors and that of Jusserand and Cardona (1989) for semicon-
ductor quantum wells and superlattices. In what follows we shall give a brief summary
of the elementary concepts and equations that we shall use throughout this section to
describe the applications of this technique to GelSi microstructures.
The scattering event consists of an incoming photon of well-defined energy ( h w ~ )
and momentum (hkL), which is scattered inelastically into another photon ( hws, hks)
by creating or annihilating a phonon of energy ho and crystal-momentum fiq. Let
us focus on the process of creation of a phonon (Stokes line). Energy and crystal-
momentum conservation require that

Experiments are usually performed with lasers emitting in the visible or near infrared
parts of the spectrum so, normally: OL 2: u s >> w. In opaque semiconductors most
experiments are performed in backscattering (kL 2 - ks), which results in a phonon
wavevector given by
q = -4nrl (3)
1L
-
where q is the refractive index of the material and h t ( 500 nm) the incident laser
wavelength (in vacuo). Phonon wavevectors are measured in terms of the length of
the Brillouin zone (lT/L, for a superlattice of period L ) , so, for most cases of interest,
q 2 0. Because acoustical phonons in bulk materials, at these small wavevectors,
have very small frequencies, scattering by these phonons (Brillouin scattering) is not
observable in normal Raman scattering experimental arrangements. Hence, first-order
Raman scattering in bulk semiconductors probes only the q E 0 optical phonons.
When dealing with superlattices with a periodicity L , it is often useful to define a
reduced wavevector
Q=--4 - - 4rlL
(4)
qmax AL
which is measured in terms of the BZ-length along the growth direction. By an appro-
priate selection of L and L L , it is possible to probe both the optic and acoustic branches
at arbitrary points along this BZ-axis.
The incoming and scattered photons are closely correlated, both in polarization and
in energy. The intensity of a Raman line, associated with the creation of a given phonon
254 FERNANDO
CERDEIRA

of the o;-branch is given by

where e L (es) is a unit vector in the direction of the polarization of the incoming
(scattered) light and Rj is the Raman tensor (a tensor determined by the symmetries of
the material and that of the j t h vibrational mode). For Si, Ge and their alloys the triply
degenerate q 2 0 optical modes have Raman tensors given by

0 0 0 O O d O d O

In Eq. (6) d is a constant and x, y and z define the direction of the vibrational eigen-
mode in terms of the cubic axes. Thus, for QWs and SLs grown along the (001) direc-
tion ( z ) , the first and second tensors correspond to in-plane vibrations, while the last
one corresponds to vibrations along the growth axis. Raman scattering configurations
are usually specified in the notation: x1 (x2, x3)x4, where the first (last) xi designates
the direction of the incoming (scattered) photon, while the first and second letters in
the parentheses define the polarization of the incoming and scattered beams, respec-
tively. Inspection of Eq. (6) reveals that the combination of polarizations ( x y ) selects
scattering events by phonons vibrating along the growth axis while in-plane phonons
are visible in configurations (x,z) and ( y , z ) .
In archetypal GaAs/AlAs SLs acoustical branches are very similar in both materials,
while optical branches do not overlap in frequency. Here the dispersion relations for
the SL-phonons can be visualized by folding the average bulk acoustic branches into
the reduced Brillouin zone of the SL and confining the optical vibrations within each
layer. This procedure is schematically shown in Fig. 18 for the longitudinal branches
of a hypothetical A2B2 SL, made up of two zinc blende or diamond-type bulk semi-
conductors A and B . The optical branches of an A , B , SL are virtually dispersionless
and obey the confinement conditions

In Eq. (7) 6 accounts for the fact that the atomic displacement, instead of vanishing at
the last A or B atom of a given layer, has a small penetration into the adjacent layer.
Notice that the confined optical mode vibrating along the growth axis (perpendicular to
it) is always derived from the dispersion relation of the bulk LO-modes (TO-modes),
irrespective of the direction of propagation of the phonon. This happens because these
vibrations are longitudinal or transverse in relation to the quantized q-vector defined
in Eq. (7b), which is more important in defining the T or L-character of the phonon
 255

LOB(1)
LOB(2)

h
LOA(1)
0-
v LOA(2)

3 M(4)
M(3)

M(2)

M(1)

0 “la 0 “la 0 =14a

9
FIG.18. Schematic representation of the folding of the phonon branches in the mini-BZ for hypothet-
ical A2 B2 SL grown along the (001) direction. ‘

than the small propagation wavevector. The first experimental demonstration of this,
for GaAdAlGaAs, was given by Zucker et al. (1984a) for SLs.
The acoustic modes of the A,, B, SL are obtained by zone-folding of the average
bulk acoustic branches. The difference between both materials manifests itself at the
minizone edge and center, where gaps appear when these folded branches cross (see
Fig. 18). For a given laser wavelength, several peaks appear in the Raman spectrum
at the points of the dispersion satisfying Eq. (3). This is illustrated in Fig. 18(c) by a
dashed vertical line at this q-value. Symmetry allowing, each intersection of this line
with the dispersion relation of the SL (open circles) generates a peak in the Raman
spectrum.
Various models can be used to calculate the lattice vibrations of the SL. The most
general type consists of building a cubic supercell (SC) containing several periods of
the A,B, structure and building up the dynamical matrix of this supercell by using
force constants between the different types of atoms’. This dynamical matrix is then
diagonalized, yielding eigenvectors and eigenvalues, which can then be placed in a
minizone scheme such as that of Fig. 18. The force constants are chosen so as to
reproduce the dispersion relations of the bulk material, when the atoms of the supercell
are either all A or all B . These calculations yield accurate results, but they can be
very complex. An alternative for obtaining dispersion relations and eigenmodes for
longitudinal vibrations, for SLs grown along the (001)-direction, is to treat each plane
as an “atom” of mass mA or me and use interplanar force constants so as to reproduce
the bulk dispersion relations along the growth axis. These linear-chain (LC) models
give very good results and are easy to handle. These models are wellkiescribed by
Jusserand and Cardona (1989). More details about them shall be given when discussing
actual results for Ge/Si SLs.
256 FERNANDOCERDEIRA

200
100

r X r X r X
Wavevector
FIG. 19. Dispersion relations, along the T - X axis, for longitudinal modes in bulk Ge (right), Ge,Sif ~x
(center) and Si (left). Adapted from Schorer et al. (1994a) with permission.

The description given here of the vibrational modes of SLs is appropriate for sys-
tems in which the optic branches of one of the bulk constituents do not overlap with
any of the branches of the other. In the Ge/Si system this is not exactly the case. In
Fig. 19 we reproduce the bulk dispersion relations of Si, Ge and of a Geo.5Sio.s alloy
for longitudinal modes (Schorer et al., 1994a). This figure shows that, although the Si-
optic branch is truly isolated, that of Ge has a region of overlap with the longitudinal-
acoustic branch of Si. Thus, it is not clear that the concept of confinement, exemplified
in Eq. (7), applies to all the optic modes of SLs made up of layers of Ge alternating
with those of Si or Ge,Sil-,. We shall examine this question in more detail in the
following subsections.

2. RAMANSCATTERING IN BULK GE,SIj-, RANDOMALLOYS

Experimental results reported by several authors (Feldman et a/., 1966; Renucci et

al., 1971; Brya, 1973; Lannin, 1977; Alonso and Winer, 1989), show that the Raman
spectrum of a random Ge,Sil-, alloy is composed of three main peaks, which, for
x -0.5, appear at frequency shifts of -
290 cm-'(Ge - Ge), 407 cm-'(Si -Ge)
and 480 cm-l(Si - Si). Subsidiary, weaker structures are seen between the last two
main peaks. These spectra obey the same selection rules as those of bulk Si or Ge
and the main peaks shift as a function of strain in a manner similar to the peaks of
their bulk constituents. In fact, Cerdeira et al. (1984) used the shift of the Si-Ge peak
to determine quantitatively the biaxial strain in alloy layers deposited by MBE on Si
substrates. A representative spectrum of a bulk, 50% alloy is shown in the lower curve
of Fig. 20(a).
Several theoretical models have been used to describe the Raman spectrum of ran-
dom Ge,Sil-, alloys (Alonso and Winer, 1989; Lockwood et al., 1987; Wilke et al.,
 5 OPTICAL
PROPERTIES 257
I I I
1
Si, Ge, expt.

Si, Ge, rough

U
f

300 500
o(cm-’>
FIG.20. (a) Raman spectra of bulk Geo.sSio.5 (A) experimental and (B) calculated. Curves C and D
are calculated spectra of a GeqSi4 SL with rough and perfect interfaces, respectively, while curve E shows
the experimental spectrum of a strain-symmetrized GeqSiq SL. (b) Calculated eigenvibrations for this SL.
Adapted from Alonso et al. (1989) with permission.

1990; Gironcoli and Baroni, 1992; Keating, 1966). The most consistent descriptions
of the spectra are given by supercell calculations (Alonso and Winer, 1989; Gironcoli
and Baroni, 1992). Alonso and Winer use a 216-atom supercell (a0 = 1.62813 nm)
of Si and randomly place Si or Ge atoms at the different sites with an abundancy ratio
dictated by the alloy composition. Their force constants are derived from the Keat-
ing model (1966). Diagonalization of the dynamical matrix yields the eigenvalues and
eigenvectors of the vibrational modes of this supercell. The latter are used, in con-
junction with a bond-polarizability model (Alben et al., 1975), to generate the Raman
spectra numerically. These spectra are compared by Alonso and Winer with experi-
mental ones, obtained from thick (1- 5pm) alloy layers grown by liquid-phase-epitaxy
(LPE) on Si (1 11) substrates. This comparison is illustrated in the two bottom curves
of Fig. 20(a), taken from Alonso et al. (1989). The calculation gives a good reproduc-
tion of the three main Raman peaks, as well as of the subsidiary structures appearing
between the Si-Ge and Ge-Ge peaks. Although these subsidiary structures were taken
by Lockwood et al. (1987), to be signatures of partial ordering in these alloys, Alonso
and Winer show that, on the contrary, they are a signature of randomness. In fact, these
258 FERNANDO
CERDEIRA

structures arise from localized vibrations of the Si-Si bond when surrounded by Ge
atoms, as the later calculations of de Gironcoli and Baroni (1992) prove conclusively;
in the same way, they also show that the three main peaks arise from the vibrations of
Ge-Ge, Si-Ge and Si-Si bonds.

3. RAMANSCATTERING
BY OPTICMODESIN GE,SI, QWs A N D SLs

The discussion in Section 111.1 would lead us to expect that the contribution of the
optic modes to the Raman spectrum would be composed of lines around 300 cm-'
(500 cm-l) originating in vibrations confined within the Ge (Si) layers with a possible
extra peak between these two, due to vibrations localized around the Ge/Si interface.
Such spectra were first reported by Menendez et al. (1988) in Ge4Sij SLs grown com-
mensurately on Si (001) substrates. These authors observe thee peaks in their spectra
at 313, 421 and 509 cm-', respectively. The first (last) peak is attributed to an optical
vibration confined into the Ge(Si) layer with a downward shift, of 9 cm-' (12 cm-')
due to confinement [Eq. 71 and an upward shift of 17 cm-' due to the biaxial strain in
the Ge layers. The middle peak, however, bears a remarkable similarity to the Si-Ge
peak of a Ge,Sil-, random alloy. This led the authors to suspect that interdiffusion
could produce a thin alloy layer ( f l ML) around the Ge/Si interface. Other authors
report similar results (Friess et al., 1989; Brugger et al., 1988). These suggestions were
firmed up by Alonso et al. (1989), who measured and calculated the Raman spectra of
several strain-symmetrized GertSi, superlattices. Their measurements were performed
in backscattering with light propagating along the (001)-growth axis, so their spectra
contain only longitudinal vibrations.
Figure 20(a) shows the experimental spectrum of a Ge4Si4 (curve E), and com-
pares it with the spectrum simulated by a supercell model similar to those previously
used for calculating the spectra of random alloys (Alonso and Winer, 1989) (curve D).
The eigenvibrations of the modes producing the three theoretically predicted lines are
shown in part (b) of this figure. We see that the first (last) peak in curve D of Fig. 20(a)
are produced by optic modes confined in the Ge (Si) layers. The agreement between
the calculated and experimental spectra for these lines is good. This is also true of the
spectra of the other samples measured and calculated by Alonso et aZ. (1989). There
is, however, a large disagreement between theory and experiment when it comes to the
middle line of the Raman spectrum (- 410 cm-' in curve E). Theory predicts a mode
at much lower frequency shifts (- 358 cm-I), in which Si and Ge atoms vibrate in
opposition across the interface [Fig. 20(b)]. The peak in the experimental spectrum
coincides, both in shape and position, with that produced by the Si-Ge vibrations of
a random alloy (curve A in the same figure), which seems to reinforce the idea that a
region of alloying exists around the interface. To test this idea Alonso et al. (1989) in-
cluded disorder in the two layers at each side of the Si/Ge interface. This was done by
exchanging Si and Ge atoms in these two layers to obtain an average Geo.5Sio.scompo-
 5 PROPERTIES
OPTICAL 259

sition. The resulting spectrum (obtained by averaging several calculations for different
random configurations in the interfacial layers) is shown in curve C of Fig. 20(a). This
calculated spectrum is in much better agreement with the experimental one (curve E)
than that calculated for perfect interfaces (curve D). Thus, the idea that roughness on
the atomic scale exists at the GeISi interface, in the form of disordered alloy layers
spreading on both sides of it, was vindicated. This notion was later reinforced by
Schorer et al. (1991), who showed that the alloy Raman peak increases pronouncedly
its intensity when the interfaces are smeared by annealing.
The most complete proof of the issue discussed here was given by de Gironcoli
et al., who compare thorough experimental Raman results with an accurate supercell
calculation, which uses first-principles force constants (de Gironcoli et al., 1993). The
Raman microprobe technique is used to obtain spectra of both longitudinal (along the
growth axis) and transverse modes (in-plane vibrations), by performing backscattering
experiments both from the sample surface and from one of its cleaved or polished
edges. In the calculation, an alloy plane is included at each side of the Si/Ge interface.
Their calculation is explained in great detail in a previous publication (de Gironcoli,
1992), where it is also shown that the exact composition of the alloy layers has little
effect on the main results. Their results for 50% alloys are very similar to those already
shown in Fig. 20(a). However, two notable differences must be pointed out:(i) the T-
polarization is also obtained, and, (ii) the contribution of the individual atomic layers to
each feature in the Raman spectrum (local density of states) is calculated for a GesSis
SL. The latter is shown in Fig. 21 for both longitudinal (left-hand side) and transverse
(right-hand side) modes. The longitudinal Si-Ge mode is seen to be localized in almost
one single interfacial alloy layer. In contrast, the TO-mode leaks into both the Ge and Si
layers. This happens because in this case, the line is a superposition of an alloy mode
with an interfacial mode, which occurs for the TO-polarization in a SL with perfect
interfaces. This mode for a perfect interface does not exist for the L-polarization.
Therefore, the appearance of this line in the experimental spectra can be taken as a
signature for the existence of atomic-scale roughness at the GeISi interface.
Two additional pieces of information can be obtained from Fig. 20: (i) the Si mode,
originating the Raman peak close to 500 cm-‘, is strictly confined within the Si-layers;
and (ii) the Ge LO-modes are very nearly confined within the Ge layers, so the overlap
of the bulk Ge optical and the Si acoustical modes for L-vibrations does not produce
a significant leak of this mode into the Si layers (no such overlap exists for the T-
polarization, so Ge TO-modes are strictly confined). In a subsequent publication by
the same group (Schorer et al., 1994) these points receive confirmation. Here they also
study the Si-confined modes in detail in samples with several layer thicknesses and
successfully “unfold” these modes according to Eq. (7).
Similar results were reported by other authors, interpreted with a much simpler
linear-chain model (Dahrma-Wardana et al., 1990; Araujo Silva et a!., 1996a). Al-
loying at the interfaces was introduced by substituting the masses of Si and Ge planes
on both sides of the interface by weighted averages of both. Similar averages of the
260 FERNANDO
CERDEIRA

Si Ge
Si Ge
Ge
Ge
Ge
Ge
8 Ge
Ge
9 SiGe
SiGe
Si
Si
Si
Si
Si
Si
300 400 50CI 300 400 500
w ( cm-l) w ( crn-l)

FIG.21. Local density of states (LDOS) for L and T modes on the atomic planes along the (001) axis
of a GegSig SL with two intermixed Ge0.5Si0.5 atomic layers at the interfaces. Reprinted from Gironcoli
et at. (1993) with permission.

force constants were taken, thus creating an “alloy atom” (or plane) at each side of
the interface. Although this procedure reproduces the results of the more complete
SC-model for the Si and Ge mode, the exact symmetries it presupposes makes it inade-
quate to represent disorder. Consequently it does not reproduce the Si-Ge Raman peak
either in position or lineshape (Araujo Silva et al., 1996a). On the other hand, when its
limitations are well understood, the LC-model can be a very useful tool for interpreting
experimental spectra of features that are not induced by disorder. In particular, Araujo
Silva et al. (1996a) use it to prove confinement, according to Eq. (7), in both the Si and
the Ge optical vibrations. More shall be said about this in Section 111.5.

4. RAMAN SCATTERING BY ACOUSTICAL

PHONONS I N SI/GE
MICROSTRUCTURES

As previously explained (Section 111.l), the acoustic branches of a superlattice can be

obtained by folding the average bulk dispersion relation into the mini-Brillouin zone
(Fig. 18). Quantitative results can be obtained by an elastic continuum model, orig-
inally developed by Ryotov (1956) to explain the propagation of sound waves in a
layered medium. For a two-component SL made up of alternating layers of A and B
 5 OPTICAL
PROPERTIES 261

layers (of thicknesses dA and d g , respectively, and period L = d A + d g ) , the dispersion

relation, w (q),of these superlattice acoustic modes is given by Jusserand and Cardona
(1989)

cos ( q L ) = cos ($) cos ($1 -

2Y
sin (%) sin ($1 (8)

where U A (PA) and UB ( p ~ are

) the sound-velocities (densities) of the bulk materials
and
y=- P B ~ B (9)
P A UA
Raman-scattering experiments using different laser wavelengths (AL) probe these
branches at different q-values [see Fig. 18 and Eqs (3) and (4)]. A large variety of
Raman experiments performed by different authors in Si/Ge,Sil-, SLs allowed quanti-
tative mapping of the folded acoustic branches (Brugger et al., 1986; Dahrma-Wardana
et aE., 1986; Zhang el al., 1992a). These experiments were well explained by the model
of Eq. (8). One of the most impressive results was the observation of unklapp processes
(Dahrma-Wardana et al., 1986), made possible by choosing h~ and L in such a way as
to obtain reduced wave vectors [Eq. (4)] Q > 1 .
The Ryotov model assumes an infinite number ( N -+ m) of superlattice periods
and phonon wavelengths much larger than the thickness of the layers. The first condi-
tion is not always met in highly strained structures. In addition, the use of bulk sound
velocities and densities in Eq. (9) only gives good results for relatively thick layers. In
Ge,Si, SLs these quantities must be considered adjustable parameters in order to ob-
tain good agreement between the predictions of Eq. (8) and experiment (Zhang et al.,
1992a; Zhang et al., 1992b). Also, high-resolution Raman spectroscopy shows addi-
tional spectral features, appearing in the spectra of thick-layer Si/Ge,Sil-, SLs, which
are not predicted by Eq. (8) (Zhang et al., 1992b; Lockwood, 1992; Zhang et al., 1993;
Dahrma-Wardana et al., 1993).
In order to explain these features, Dahrma-Wardana et aZ. resorted to a linear-chain
model with first-principles interplanar force constants and up to fourth-neighbor inter-
action (Dahrma-Wardana et al., 1993). This model contains no adjustable parameters
and translational invariance (ie., N + 00) is not assumed. They simply diagonalize a
+ +
dynamical matrix of dimensionality Ntot = Nsubs N ~ LNcap,where N S L is the total
number of atomic planes of the superlattice and Nsubs (Ncap)are the number of these
planes in the substrate (capping layer). The authors compare the predictions of both
the Ryotov and the LC models with their experimental results in the frequency-shiftre-
gion w d 50 cm-' for a Si/Ge0.48Si0.52(20.5nm/4.9 nm) SL with N = 15 repetitions,
using several laser lines. This comparison is shown in Fig. 22(a), where the positions
of the main peaks in the Raman spectrum (full circles) and the LC-model calculations
(crosses) are plotted on the dispersion relation predicted by the Ryotov model (contin-
uous lines). Both models reproduce well the experimental results for the main Raman
peaks, but the latter uses several adjustable parameters while the former uses none.
262 FERNANDO
CERDEIRA

FIG. 22. (a) Comparison of experiment and theory for the positions of the major Raman peaks, for
different A L S , in the folded acoustic modes of a Si/Ge0,48Si0,52SL: Full circles are experiment, crosses are
results of the LC-model while the solid curves are calculated with the Ryotov model. (b) Raman spectra,
simulated with the LC-model, of the same SL for a finite number of periods (N). Reprinted from Dahrma-
Wardana rt ui. (1993) with permission.

Most importantly, the Ryotov model predicts only these main Raman peaks, whereas
the LC-model also predicts subsidiary structures that appear in the experimental spec-
tra. These additional peaks result from the finite character of the sample. In Fig. 22(b)
we reproduce the spectra generated by Dahrma-Wardana et al., with the LC-model, for
samples containing different repetitions of its basic period ( N ) . The spectrum evolves
towards that of an infinite superlattice (coinciding with the Ryotov model) as N in-
creases. The final folded modes are produced by the accumulation of a high density
of states at the Ryotov positions with increasing N . The lower curve (N = 15) cor-
responds to the sample used in their experiment. This curve shows, besides the main
Ryotov peaks, fine structure appearing in the experimental spectra (not shown). Hence,
the LC-model gives a better description of the spectra, while maintaining a relatively
simple calculation scheme. Recently, a numerical variation of the elastic-continuum
model has been proposed, which can account for finite size and capping layer effects by
imposing appropriate boundary conditions (Pilla et al., 1994). Many subsidiary peaks,
as well as structure appearing within the forbidden gaps of the dispersion relations,
observed in the spectra of Si/Ge,Sil-, SLs, are explained with this model (Lemos et
al., 1995). However, the model uses several adjustable parameters.
For ultrathin Ge,Si, SLs the elastic continuum model is not adequate, both be-
cause of the thinness of the layers and also because they frequently contain a very
small number of periods. Moreover, the Ge,Si, portions of the sample are nested
within more complex structures containing buffer, spacer and capping layers. These
structures contain Raman peaks in the low-frequency side of the spectrum that are un-
related to the folded modes of the G e n s & SL. The LC-model is able to deal with this
complexity, without losing its simple calculational structure. This is illustrated in the
examples reported by Lockwood et al. (1988) and Araujo et al. (1996b). In the latter,
 5 OPTICAL
PROPERTIES 263

high-resolution Raman spectroscopy was used to study the low-frequency part of the
spectrum (w 5 100 cm-I) and ordinary Raman spectroscopy was used for the remain-
ing parts of it. The samples, grown by MBE on Si (001) substrates, had a complicated
n ~ Mx] p. Here n , m and M
structure, which can be described by: [(Gen S i m ) ~ - l G e S
are layer thicknesses in monolayers (ML) and N and p are the numbers of repetitions
of a given unit. The samples used in the experiments had 12 2: 5 , m 2 5 or 7, M = 200
and p 2 10 - 20. Thus, they contained two periodicities: the smallest period ( n m ) +
is that of the GenSi, unit, while the largest ( D = N x n ( N - 1) x m M )is that of + +
the unit in square brackets. The lower-frequency part of the spectrum (o5 100 cm-')
contains peaks that arise from this larger period, the structure in the intermediate part
of the spectrum (100 cm-' 2 o 5 250 cm-') arises from the smaller periodicity and
the high-frequency part of the spectrum originates in the confined optic modes.
By applying the LC-model to these structures Araujo et al. (1996b) were able to
determine in which parts of the sample the vibrational amplitude of a given mode is
confined. They find that the vibrations originating in the low-frequency part of the spec-
trum spread throughout the whole structure, while those giving rise to the intermediate-
frequency part of the spectrum are concentrated within the Ge,Si, strings and are, in
fact, the folded acoustic modes of an infinite Ge,Si, SL. Finally, for high frequencies
the optic modes dominate the spectrum. This part of the spectrum is totally insensi-
tive to variations in N or M , that is, these complicated samples yield the same spectra,
in the optical phonon region, as that of infinite Ge,Si, SLs already discussed in the
previous subsection.
In Fig. 23 we show the calculated (a) and experimental Raman spectra (b) of these
samples in the low-frequency region. This part of the spectrum is very sensitive to
variations in N or M , as both alter the greater period D. The latter controls peak
positions, as shown in Fig. 23(c), thus providing a good way to determine this structural

[ 10 1 (a ) Calculation ( b ) Experiment 1

C
2 QW
mC

a
1 QW
Q

0 10 20 30 40 50 60 0 10 20 30 40 50 60
o (cm-') w(m-')

FIG.2 3 . (a) Calculated and (b) experimental spectra for NQW-samples; (c) calculated dispersion rela-
tions (lines) compared to experimental peak positions (circles) for the 1 QW sample and AL = 496.5 nm and
A L = 514.5 nm. Reprinted from Araujo Silva er al. (1996b) with permission.
264 FERNANDO
CERDEIRA

( a ) Linear Chain model ( b ) Experimental Results

kL=514.5 nm
r = 10 cm-' .-d
c
v)
.-
Y 3
c
3
Pm
Pm
. .
2
.-
0 c
In
0)
Ie
n I
.-
C
9 c
.-C m
E
m E
w
z
E,

I 3 150 200 250 300 350 100 150 200 250 300 350
o ( cm-')

FIG. 24. Intermediate frequency region of the Raman spectrum: (a) calculated, (b) experimental.
Reprinted from Araujo Silva et at. (1996b) with permission.

parameter. In Fig. 24 the same is done for the intermediate-frequency part of the Raman
spectrum. In Fig. 24(a) the calculations produce a Raman peak originating in the folded
acoustic modes of the Ge,Si, SL. The position of this peak is insensitive to variations
of both N or M , but its intensity depends strongly on the former. The same trend is
observed in the experimental spectra [Fig. 24(b)]. The shift in the lower curve ( N =
100) is due to the fact that this is a strained symmetrized SL and, therefore, has a
different strain profile than the other samples (commensurately grown on Si). The
interesting aspect of Fig. 24 is that the folded acoustic mode is present in the spectrum,
although weakly, even when the basic Ge,Si, unit appears only three times.
Raman scattering by folded acoustic modes was observed in strain-symmetrized
Ge,,Si, samples containing many periods (Schorer et al., 1994; Alonso et al., 1989).
A representative example of these results is shown in Fig. 25. The left-hand side of
this figure shows the dispersion relations for the longitudinal and transverse acous-
tic modes of a Ge4Si4 SL, calculated with the SC-model (Alonso et al., 1989). The
circles on four of these curves correspond to the modes observed in the Raman spec-
trum [Fig. 25(b)]. The most prominent feature in this spectrum is the peak produced
by the LJ = f l folded LA modes. Higher-order folded LA-modes are observed in
the other SLs [see Fig. 2S(b)]. In all cases simulated spectra are in good agreement
with experimental ones. The asymmetry in the Raman peak of the lowest curve in
Fig. 25(b) is produced by the appearance of the forbidden Raman peak originating in
 5 OPTICALPROPERTIES 265

! NZiL I

0 I00 200

FIG.25. (a) Dispersion relations of a GeqSiq SL for L-(solid lines) and T-acoustic modes (dotted lines).
Circles are peak positions in the Raman spectrum. (b) Experimental (upper curve) and calculated spectra for
several Ge,Si, SLs ( T = 300 K and A L = 568.2 nm). Reprinted from Alonso etal. (1989) with permission.

the B1, mode. This peak is forbidden for q = 0. The nonzero value of q in the actual
experiment [Eq. ( 3 ) ]weakly induce the appearance of this peak (Alonso et al., 1989).

5. RESONANT
RAMANSCATTERING

a. Introduction

The subject of resonant Raman scattering in semiconductors is exhaustively re-

viewed by Cardona (1982), who discusses in-depth its usefulness and the subtleties
of the interpretation of the experimental results. The Raman cross section is also di-
dactically explained in chapter 7 of the textbook by Yu and Cardona (1995). For a good
understanding of the subject we refer the reader to these general references. Here we
266 FERNANDO
CERDEIRA

shall briefly sketch the aspects of this technique that are relevant to the analysis of the
results reported for Si/Ge microstructures.
The Stokes Raman cross section results from an infinite sum of terms originating in
processes that involve the virtual absorption of a photon ( h w ~ )creating
, an electron-
hole pair, the emission of a phonon ( h w ) via electron-phonon interaction at the initial
or final state of this transition, and a recombination of the resulting electron-hole pair
with the emission of a photon ( f i w ~in) such a way that the conservation laws of Eq. (2)
are satisfied. One of these processes is shown schematically in Fig. 26(a) and its con-
tribution to the Raman cross section is given by

c( IF;:
( u I H e - r I c')(c' I H e - p I C)(C 1 ~ e - t

[fiwr. - (EL - E d ] [hws - (E'! - E " ) ]

Iu)
+. . I 2
(10)

In Eq. (10) He-,. and He-pare the Hamiltonians of the electron-radiation and electron-
phonon interactions respectively, while E, ( E , ) is the energy of the electronic conduc-
tion (valence) band state. In the cases where the photon energy of either the incoming
or outgoing beams coincides with that of an interband transition with a significant
joint density of states (i.e., one of the singular points in the optical spectra discussed
in Section II), one, or both, of the energy denominators of Eq. (10) vanishes and the
contribution from this particular term dominates the Raman cross section. This results
in an enhancement in the intensity of the Raman peak. Thus, one might expect that
plotting the intensity of the Raman peaks as a function of the photon energy of the
incoming beam, spectra similar to those obtained by modulation spectroscopy should
be obtained. Here the modulating agent is one of the vibrational modes of the material.
Even if this naive interpretation were invariably true, the process of data gathering is

( a ) A typical Ramam ( b ) A typical

process PL-process

FIG.26. Schematic representation of: (a) a two-band term in the resonant Raman cross section; and (b)
a PL process involving band-to-band recombination in a direct gap semiconductor.
 5 OPTICAL PROPERTIES 267

cumbersome, as many individual Raman experiments must be performed for different

laser wavelengths. The data also have to be normalized to correct for changes in align-
ment or laser intensity between these successive experiments, as well as to account
for the fact that both the incoming and scattered beams are partially absorbed as they
traverse the material (Cardona, 1982).
Returning to Eq. (lo), we note that each matrix element in this equation represents a
selection rule that must be obeyed if the scattering process is to have nonzero probabil-
I
ity. In particular, the element ( c He-pl c’) corresponds to electron-phonon interaction
involving the electronic states that mediate the scattering event. Hence, the electronic
and vibrational states involved must have spatial overlap for this matrix element to be
different from zero. This is of crucial importance in an A / B SL, where both the elec-
tronic and the vibrational states may be confined in either the A or B layers. In this
case, a phonon localized in layer A cannot receive a contribution to its Raman cross
section from optical transitions between states localized in layer B, and vice versa.
Hence, no resonance effect will be observed in the cross section for this phonon when
~ W isL in resonance with such a transition. On the other hand, resonant enhancements
will occur when both the electronic states and the phonon are localized in the same
layer. In the same way, vibrational modes that extend through both layers will have
enhanced cross sections for resonance with any electronic transition and an electronic
transition between extended electronic states will provoke enhancement in all Raman
lines. These facts were first demonstrated by Zucker et al. (1984b) in resonant Raman
scattering (RRS) experiments performed in GaAs/AlGaAs SLs. This characteristic
makes RRS a very useful complementary technique to the forms of differential spec-
troscopy reviewed in Section 11. While the latter provide very accurate information
about the energy of critical points, RRS furnishes information about the localization of
the electronic states participating in a given optical transition.
One cautionary note must be made concerning the analogy between RRS and mod-
ulated spectroscopies: The photon-energy position of the maxima in the RRS cross
section often differs significantly from those of the singular points in the joint density
of states that originate them (and, consequently, from the position of the corresponding
peaks in the optical spectra), even for scattering processes involving only two bands,
as is the case for the one illustrated in Fig. 26(a) (Cardona, 1982). The exact origin of
these discrepancies (which could be as much as 50 MeV) are not fully understood, but
the Raman cross section depends on the exact nature of the electron-phonon interaction
which, in turn, cannot be exactly formulated in most cases of interest. This discrepancy
becomes serious when the phonon has a symmetry such that it can couple two bands
that lie close in energy. The contribution from these three-band processes can lead to
complex lineshapes with maxima and minima (resulting from interferences between
two- and three-band terms), which bear no easy relationship to the energy position of
the associated critical points. As an example of this, the resonant Raman cross section
of bulk Ge, in the region of the El and El + A 1 critical points, is shown in Fig. 27, from
the data of Cerdeira et al. (1972). In this figure the full symbols represent experimental
268 FERNANDO
CERDEIRA

- T=3OO”K

19 2.0 2.1 2.2 23 2.4 2.5 26 2T

FIG. 27. Resonance in the room-temperature Raman cross section for bulk-Ge (full circles and
triangles). The dashed curve is a guide for the eye while the solid one is a phenomenological represen-
tation of the contribution of three band terms. Adapted from Cerdeira et al. (1972) with permission.

data, the dashed line is meant to guide the eye, and the arrows represent the positions
of these two critical points, as given by measurements of modulated reflectivity. The
Raman cross section presents only one, very broad peak at a photon energy more or
less midways between the two ER-peaks. This happens because, in this case, the cross
section is dominated by three-band terms, resulting from the coupling that the phonon
introduces between the closely spaced valence bands of Ge along the A-axis of the BZ.
The solid curve is a phenomenological estimate of this contribution. The good agree-
ment shown in the figure was obtained by shifting this theoretical curve by 45 MeV
towards higher energy. The q ? 0 optical phonon of Ge also couples the strain-split
valence bands at the zone-center, when the strain has a symmetry axis along the (001)
direction, as is the case of Ge layers grown lattice-matched on Si (001) substrates. In
that case Eo transitions could produce resonant Raman cross sections very similar to
those of Fig. 27.
The coupling already described here results from the r15 symmetry of the zone-
center phonon. A phonon of symmetry, for instance, would not produce this cou-
pling. The cross section of this phonon would show two distinct peaks, one for each
critical point. Such a phonon exists in the folded acoustic branches of a GeISi SLs or in
the totally symmetric part of the two-phonon spectrum of bulk Ge. This is indeed seen
in the Resonant cross section of the totally symmetric part of the 2TO(L) spectrum of
bulk Ge (Renucci et al., 1974). But even here the peaks in the Raman cross section are
+
shifted in relation to the positions of the El and El A1 critical points.
The foregoing discussion should warn us against assigning optical structure on the
basis of the positions of peaks in the resonant Raman cross section alone. This is partic-
ularly true when several transitions fall in the same photon-energy range. In this case
the coupling introduced by the phonon between the states participating of these transi-
tions can result in complicated resonant lineshapes with maxima and minima that bear
 5 O P T I C A L PROPERTIES 269

no immediate relationship to the energy position of the individual critical points. On

the other hand, RRS has the unique property of giving direct experimental information
about the localization of the electronic states participating in a given optical transition
(or group of transitions).

b. Resonant Raman Scattering in Si/Ge Quantum Wells and Superlattices

The first observation of RRS in this type of structure was made in Si/Ge,Sil-, SLs
of relatively large periods (Cerdeira et al., 1985). These results, displayed in Fig. 9,
were already discussed briefly in section 11.3. This figure shows broad single peaks
in the resonant cross sections, in the general photon energy region where the El and
El +A1 critical points of the unstrained alloy should be. Moreover, the general shape of
the resonant peaks is similar to that of the El resonance in bulk Ge (Fig. 27). However,
strain and confinement should produce another doublet in this photon-energy region
[Eo(1) and Eo(2)], which would also be coupled by the phonon, giving rise to a similar
peak in the Raman cross section. On the basis of the dependence of this peak with
layer thickness, Cerdeira et al. (1985) attributed this resonance to the &-doublet. This
assignment proved to be controversial and similar structures in the resonant Raman
cross section of related Si/Ge materials were attributed alternatively to either one or
another of these two doublets (Cerdeira et al., 1985; Rodrigues et al., 1993a; Cerdeira
et al., 1989; Schorer et al., 1994b; Schorer et al., 1995).
In Fig. 28 we display RRS results for the LO and LA modes of several strain-
symmetrized Ge,Si, SLs (Cerdeira et al., 1989). For the SLs with larger periods, two
-
distinct peaks are observed in the Raman cross sections of these modes at f i o ~ 2.3
and 2.9 eV respectively. The lower photon-energy peak is produced by electronic tran-
sitions between states confined in the Ge layers. This can be deduced from the fact
that, at this photon energy, only the cross sections of the Ge-optic mode (confined in
the Ge layers) and that of the folded LA-mode (extending through the whole SL) show
enhancements, while that of the optical mode confined in the Si layers does not. In
contrast, at the higher photon energy all modes are enhanced, that is, this transition (or
group of transitions) involves electronic states with nonvanishing components in both
layers. As the layer thickness decreases both peaks show a tendency to merge. The
first group of optical transitions could either be associated with states derived from the
bulk Ge El or EOdoublets. Cerdeira et al. (1989) favor the first choice, without totally
discarding the second.
More recently, Schorer et al. (1994b and 1995) performed very careful RRS exper-
iments, where both longitudinal and transverse modes could be studied by exploiting
the micro-Raman technique in order to perform backscattering experiments from the
cleaved or polished sample edges. Their main results are summarized in Fig. 29, in
which the resonant cross sections of the first Ge and Si confined modes are displayed
together with that of the alloy-like Si-Ge mode. In all cases a strong resonance is ob-
270 FERNANDO
CERDEIRA

3.0

FIG.2 8 . Raman cross section for LO and LA modes of several Ge,Si, as a function of laser photon
energy. Adapted from Cerdeira ef ul. (1989) with permission.

served in the cross section of the Ge-modes, which is absent in that of the Si-modes,
in the photon-energy range around 2.2 eV, signaling the presence of electronic tran-
sitions between states confined in the Ge layers. This resonance is more pronounced
in the L-modes, involving light polarized in the plane of the layers, than in the T-
modes, involving light polarized perpendicular to the layers. These anisotropies are in
agreement with the results of a dielectric function calculation based on a tight binding
approach (Tserbak et al., 1991). These authors calculate the dielectric constant for light
polarized both in the layer planes E I (~w ) and perpendicular to them EL ( w ) separating
the contributions from Ge and Si bulk states to this response function. This decompo-
sition is shown in Fig, 30, where it is clear that in ~ 2 1 the
1 Ge and Si contributions are
well separated in energy while this separation is blurred for ~ 2 1 The
. most prominent
contribution to the in-plane dielectric constant, in the photon-energy region being dis-
cussed, comes from the El states of bulk Ge. Thus, there is a striking analogy between
the calculations of Q ( W ) and the results of RRS for L- and T-modes. This analogy also
favors the interpretation of the RRS results in terms of bulk-Ge El transitions, even if
 5 OPTICAL
PROPERTIES 271
150

100

50

L 8W

f
(P
600

tY 4w
400

200
200

0 0
1.6 2.0 2.4 28 1.6 2.0 2.4 2.8

FIG. 29. Raman efficiency of Gel (squares), Sil (circles), and Si-Ge modes (triangles) of several
GenSim SLs and one Ge7Si3 SL for in-plane backscattering geometry from polished (1 10)-sample edges.
Full symbols denote y’ (x’x’)y’ (light polarized Ito the layers). Adapted from Schorer et al. (1995) with
permission.

in their first report Schorer et al. (1994b) were inclined to attribute this resonance to
Eo-like states.
Finally, resonant Raman results, combined with those of modulation spectroscopy,
performed on single and multiple Ge5 QWs reinforce the notion that the most important
contributions to the optical response functions in this photon-energy range originate
in confined electronic states traceable to the bulk Ge E l transitions (Rodrigues et al.,
1993a; Araujo Silva et al., 1995). The origin of these discrepancies in the interpretation
of RRS results lies in the fact that the position of the maxima in the broad features of
the resonant Raman cross sections (produced by scattering processes involving 2- and
3-band terms) are insufficient for making an identification of the optical transitions
involved in the resonance.
272 FERNANDO
CERDEIRA

FIG.30. Calculated E2(w) for a strain-symmetrized GegSig SL, decomposed into contributions from
Ge (Ge-Ge) and Si (Si-Si) atoms. Solid lines are ~ 2 1(w)
1 and dashed ones E ~ L ( w )Adapted
. from Schorer et
al. (1995) with permission.

The preceding discussion was centered mainly on the resonant cross sections of
optic modes. Schorer et al. (1994b) report in detail RRS results from several orders
( u = 1,2, 3 and4) of folded LA-modes in a GelzSil2 SL (see Fig. 31). Because
these modes transform according to totally symmetric representations of the SL point-
group, 3-band terms should not contribute to their resonant cross sections. Hence, two
well-resolved peaks should be observed when the resonance is produced by a doublet.
This effect is indeed seen in the cross section of the LA1-modes displayed in Fig. 31
as full triangles, which shows two distinct, albeit broad, peaks at ~ W L 2.1 and
2.4 eV, respectively. The resonant cross sections of higher-order TAU modes show
-
one main peak, followed by a shoulder, which shifts towards higher photon-energies
as the folding index u increases. Qualitatively, this could be explained by assuming
that the resonance is produced by a multiplet which results from confined electronic
states with different confinement indices, and that resonances are stronger when both
confinement indices (that of the phonon and that of the electronic states involved in the
transition) are equal. In this case, higher-order folded phonons resonate preferentially
with higher confined electronic transition, thus explaining the energy shift of Fig. 3 1.
This explanation, attractive as it sounds, has no theoretical underpinning, as both the
nature of the electronic transition and the details of the electron-phonon interaction are
not known.
All of the preceding discussion was centered on interpretations based on perfect
superlattices. As we shall see in the following subsection, this technique is also useful
in establishing the presence of certain types of interface roughness.
 5 OPTICAL PROPERTIES 273

FIG. 3 1. Resonant cross sections of LA-modes in a Gel2Sil2 SL (300 K). Adapted from Schorer et al.
(1994b) with permission.

c. Detecting Long-Range Inter$ace Roughness by Resonant Raman Scattering

In Section 111.3 we discussed the role of Raman scattering in determining atomic

scale roughness in the SifGe interfaces of Ge,Si, SLs, in the form of random-alloy
-
layers, existing in a region of f l ML about each interface. There is another type of
roughness (terracing) that has been observed at the interfaces of some SLs composed
of 111-V materials (Gammon et al., 1991; Brasil et al., 1993). These terraces, having
lateral dimensions of the order of 10 nm or more, produce splittings in the luminescence
line produced by exciton recombination at the direct gap of these materials. It would
be difficult to use luminescence to detect such terraces in SifGe systems, due to their
indirect gaps and the resulting complexity of the luminescence spectra (see Section IV).
However, resonant Raman measurements have recently provided evidence of terracing
in Ge,Si, SLs (Brafman et al., 1995). The samples used in the experiments of Brafman
et al. (1995) were already discussed in Sections 111.3and 111.4. They consist of N-Ge5
214 FERNANDO
CERDEIRA

quantum wells separated from one another by 5 MLs of Si. Each sample contains up
to 20 repetitions of a basic unit (with thick Si-spacer layers between them) which has
N = 1,2, or 6 and is designated by NQW. The Raman spectra of these samples are
studied, both for L- and T-modes, using several discrete lines of argon- and krypton-ion
lasers.
In Fig. 32 we show their results for the longitudinal Ge-confined optic mode. The
upper part of the figure [Fig. 32(a)], displays the off-resonance spectra of the three
samples, while part (b) of the figure shows the same part of the spectrum of the sex-
tuple QW taken with laser lines of different photon-energies. We see that in the off-
resonance spectra, the position and lineshape of this mode are different for each sample.
This is surprising, as this line originates in a mode entirely confined within the Ge lay-
ers (see Section 1111.3) and, therefore, insensitive to the number of layers-that is, all
three lines should be identical. Moreover, Fig. 32(b) shows that this line, for the same
sample, changes in position and lineshape as the wavelength of the incoming laser is
changed. This means that we are in the presence of a resonant effect. These changes
occur because the observed line is a superposition of Raman lines produced by phonons
confined in Ge quantum wells of different thicknesses. These QWs are produced by
terraces within a given Ge layer. To produce the effect of Fig. 32(b), the lateral dimen-

250 300 350

o (cm-1)

FIG. 3 2 . (a) Off-resonance spectra of the Gel LO-mode of the three NQW samples and (b) the same
spectrum for the 6QW sample taken with different laser lines. Reprinted from Brafman et al. (1995) with
permission.
 5 OPTICALPROPERTIES 275

sions of these terraces must be at least of the same order as the radius of the exciton
involved in the resonance-that is, d 2 10 nm. Thus, the laser beam ( D 2 1 p m )
samples a large number of these terraces-that is, a large number of QWs of different
widths. Each one of these QWs contributes to the Raman spectrum with a line centered
around a different frequency [Eq. (7)],in such a way that wider wells contribute to the
higher-frequency part of the composite line and vice versa. For low values of AWL,
resonant conditions are met for the wider wells, increasing the intensity of the high-
frequency side of the composite Raman line, which causes an apparent shift towards
higher energy. As the laser photon-energy increases narrower wells meet the resonance
condition, causing the low-frequency part of the composite line to increase its inten-
sity, which produces the asymmetric broadening and shift of its maximum towards the
lower frequencies seen in Fig. 32(b). Why does this happen in the 6QW sample and not
in the others? Because terracing becomes more pronounced as the number of quantum
wells increases. This explains the differences observed in the off-resonance spectra of
the different samples [Fig. 32(a)].
The preceding conclusions were put on a more quantitative basis by comparing the
experimental spectra with those generated by a linear-chain model, in which terracing
was simulated by superimposing the Raman lines of QWs with different widths (Araujo
Silva et al., 1996a). In Fig. 33(a) we show the result of fitting the experimental Raman
line, for a given laser line, of the 6 QW sample with a simulation using terraces with
three different Ge thicknesses (3,4 and 5 MLs). By performing such a fit for each laser
line, the resonant cross section of each terrace, (Y, ( w L ) , is obtained. This is shown in

o 70 L ~r,( = 12.0 m-l)

0.01 L ~r
,( = 9.0 m-1)
0 5 1 L ~r
,( = 7.0 ~ m - '

I I 1 I 1
260 280 300 320 340 5
o ( cm-')

FIG. 33. (a) Raman spectrum of the Gel TO-mode in the 6 QW sample fitted with contributions from
wells of different thicknesses (3,4, and 5 MLs) and (b) the resonant cross section an(o[,)for each of these
contributions (circles, squares and diamonds) fitted to Lorentzian lineshapes (lines). The inset shows the po-
sition of these Lorentzian lines vs Ge layer thickness (circles) compared to an envelope-function calculation
(line) for Eg-like states. Reprinted from Araujo Silva ef a[. (1996a) with permission.
276 FERNANDO
CERDEIRA

Fig. 33(b), where the dots, squares, and diamonds represent the Raman cross-sections
of the phonons confined within the QWs of 3, 4, and 5 MLs, respectively, and the
curves (dashed, dotted, and solid) are least-square fits to these points with Lorentzian
lineshapes. The results are consistent with the previous analysis, as they predict opti-
cal transitions that decrease in photon energy and linewidth as the QW becomes wider.
This is consistent with the confinement of the electronic states involved in the transition
(higher transition energies for narrower wells) and with the fact that microroughness
is more important in broadening the line as the well becomes narrower. Finally, the
change in the transition energy is plotted (full circles) as a function of QW-width in the
inset of Fig. 33(b) and compared with the predictions of an envelope-function calcu-
lation (solid line) for an Eo optical transition (section 11.4). The experimental confine-
ment shifts are much smaller than those predicted by theory, which lends support to the
El (rather than Eo) assignment for the optical transitions responsible for this resonance.
The method outlined here was recently used to study the evolution of short and long
range roughness in Ge, single quantum-wells of different thicknesses ( n = 3 , 4 , 5, and
6), separated by 70 MLs of Si (Narvaez et al., 1997). These authors find that alloying
at the Si/Ge interface occurs always, regardless of the Ge layer thickness. For n 5 5

it stabilizes at x-
the alloy layer has an average Ge molar fraction that grows steadily as n increases until
0.5 for n 2 5. This is probably due to Ge segregation occurring
at low values of n, which results in terrace formation. This terracing is visible in the
dependence of the confined Ge Raman line on the wavelength of the exciting laser for
the samples with n = 3 and 4, but absent in the samples with n = 5 and 6. Thus, a
transition from terracing to layers of uniform average thickness seems to occur in these
samples at some value between 4 and 5 MLs.
The foregoing discussion shows yet another application of Raman scattering to the
structural characterization of quantum wells and superlattices.

6. SUMMARY

The preceding discussion shows that, when the results of experiments are comple-
mented by lattice dynamical calculations, Raman scattering can provide important in-
formation about vibrational and electronic states. It also gives quantitative estimates for
several structural parameters (such as strain, period length, layer thicknesses, etc.) as
well as detecting short- and long-range interface roughness. While the best picture of
what goes on in a given microstructure is always given by the rather complex supercell
calculations, simpler models, such as linear-chain or elastic continuum ones, are often
sufficient to give an enlightening interpretation of the experimental data. Resonant Ra-
man scattering has the unique property of giving direct experimental information about
the localization of the electronic wavefunction at critical points in the Brillouin zone.
This aspect makes RRS a supplementary technique to those discussed in Section 11.
However, its limitations must be understood in order not to incur misinterpretations.
 5 PROPERTIES
OPTICAL 277

One of these limitations is that the peaks in the Raman cross sections do not always co-
incide with the energy of the critical point that originates it. The mechanism by which
the phonon interacts with the electronic states involved in the transition must be known
before conclusions are drawn on the basis of the photon-energy position of peaks in the
Raman cross section.

IV. Photoluminescence

1. INTRODUCTION

In a photoluminescence (PL) experiment an electron-hole pair is created by the ab-

sorption of an incoming photon, the created electron and hole thermalize rapidly to en-
ergy minima and recombine from there by emitting a photon of lower energy. Because
the emission occurs after a multiple scattering process, there is usually no correlation
between the polarizations of the incoming and emitted photons. The idealized process
of PL by band-to-band recombination is shown schematically in Fig. 26(b), for a di-
rect bandgap semiconductor. This process bears a certain superficial resemblance to
that of resonant Raman scattering, shown schematically in part (a) of this figure. In
the latter, however, both the photon absorption and emission are virtual processes and
no loss of correlation between them occurs. Also, in the Raman process the frequen-
cies of the incoming and outgoing photons are related to one another through Eq. (2),
while in the PL process of Fig. 26(b) the outgoing photon always has the energy of the
bandgap, regardless of the energy of the incoming photon (as long as it is greater than
the bandgap).
In an indirect bandgap semiconductor, such as Si and Ge, recombination must be as-
sisted by large wavenumber phonons in order to conserve crystal momentum. Hence,
the intensity of the emission lines in indirect gap semiconductors is always much
smaller than those in direct gap ones. In real semiconductors, especially at low temper-
atures, the recombination energy may not coincide with the bandgap. First,
electron-hole interaction (excitons) modifies this. Second, excitons can be localized
by impurities and defects and recombine from there, producing a rather complex PL-
spectrum. This complexity is increased by the fact that the intensity of a given PL line
depends much more on the efficiency of the recombination channel than on the con-
tribution of the recombination centers to the overall density of states. Thus, emission
lines from electronic states with a very small density of states can, in certain cases, be
the dominant features of the PL-spectrum.
A technique related to PL is that of photoluminescence excitation spectroscopy
(PLE). Here, the spectrometer is set at the maximum of a given PL-line while the
photon energy of the incoming radiation is varied in a continuous manner around the
region of the absorption edge. As the number of electron-hole pairs created at a given
incident photon-energy (Ti@,) is proportional to the number of absorbed photons, the
278 FERNANDO
CERDEIRA

intensity of the resulting PL line will be roughly proportional to the absorption coef-
ficient ~ ( w L ) In
. microstructures composed of direct bandgap semiconductors PLE
spectra show very sharp structure related to transitions between quantum-confined lev-
els associated with the direct bandgap (Liu et al., 1989). For indirect bandgap systems,
such as the ones in which we are interested, the PLE spectrum does not show peaks,
but rather an absorption edge below which the response is zero and above which it
increases monotonically (Sturm et al., 1991).
In the following subsections we discuss the application of this techniques to bulk
Ge,Sil-, alloys and to QWs and SLs obtained by alternating layers of Si, Ge, or alloy
with one another.

2. PL FROM BULKG E , S I ~ -ALLOYS

~

Well-resolved free-exciton (FE) and bound-exciton (BE) PL have been observed in

bulk Ge,Sil-,r alloys by several groups (Benoit B la Guillane et al., 1974; Gross et
al., 1973; Rentz and Shlimak, 1978; Mitchard and McGill, 1982; Lyutovich ef al.,
1985; Dismukes et al., 1964) culminating in the comprehensive work of Weber and
Alonso (1989). In Fig. 34 we display their low temperature (4.2 K) PL-spectra of
bulk alloys with different compositions. The spectra exhibit several lines assigned to
recombination of excitons bound to shallow donors and acceptors. The lines are labeled
X:, where j indicates whether the recombination is phonon assisted or not (NP) and i
specifies the nature of the phonon when it is. The phonons of the alloy are labeled as
Ge-Ge, Si-Ge or Si-Si, according to the classification explained in section 111.2. They
also observe free exciton lines in the PL-spectra taken at higher temperatures. The
most prominent feature of the spectra in Fig. 34 is the no-phonon recombination line
( X N P ) , which appears as a consequence of a disorder-induced process and does not
conserve crystal momentum. The ratio of the intensities of the no-phonon line to that
of the phonon-assisted ones scales approximately as the number of Si-Ge pairs in the
alloy
INP
- x(1 - x) (11)

and the relative intensities of the phonon-assisted lines are given by

-
The full-width at half-maximum (FWHM) of the X N P lines also depends on x , varying
from 4 to 8 MeV (in the best samples), as opposed to 0.3 MeV for the same line in
bulk Si. Finally, the position of this line as a function of x allows Weber and Alonso
(1989) to obtain an accurate expression for the dependence of the indirect energy gap
 5 OPTICALPROPERTIES 279

Ge,

x = 0.93

x = 0.08
I I I

Photon Energy (eV )

FIG. 34. Near-bandgap PL-spectra for bulk Ge,Sil-, alloys. The optical transitions are labeled X:
where j = N P when the transition is not phonon-assisted and nothing when it is and i specifies the type of
phonon. Reprinted from Weber and Alonso (1989) with permission.

as a function of Ge molar fraction and to determine the cross-over (from A to L) of the

conduction bandedge at x = 0.85.
Another interesting feature is observed in the PL spectra of some lower-quality
samples: a broad feature on the low-energy side of the X N P line (Weber and Alonso,
1989). This line had been previously labeled as the “L-line” by other authors (Mitchard
and McGill et al., 1982), who interpreted it as a bound-exciton recombination at an In-
acceptor. This interpretation is revised by Weber and Alonso (1989), who attribute this
broad PL-line to recombination occurring in a dense electron-hole plasma gathering
in potential wells formed by large compositional fluctuations (probably in the vicinity
of dislocations or other defects). A similar line is observed in the PL-spectra of some
MBE-grown Si/Ge,Si I-, QWs. We shall discuss this in the following subsection.
280 FERNANDO
CERDEIRA

3. PL FROM SI/GE,SI~-, MICROSTRUCTURES

First reports of PL measurements in MBE-grown Si/Ge,Sil -, structures show spec-

tra that are significantly different from those of bulk alloys (Noel et al., 1990). The
low-temperature spectra of these samples show a broad PL structure near the alloy
bandgap, rather than the sharp phonon-resolved structures of Fig. 34. By comparing
PL and PLE measurements for their samples, Noel et al. (1990) determined that the
center of this broad PL structure lies slightly below the indirect absorption edge of
the alloy and tracks this gap as x varies. This is illustrated in Fig. 35, where the low
temperature (4.2 K) PL-spectra of three samples with different compositions and layer
thicknesses are displayed.
Observation of phonon-resolved near-bandedge PL from strained Si/Ge, Si 1-,y lay-
ers were later reported both in MBE-grown samples (Terashima et al., 1990) and in
samples grown by rapid-thermal-chemical deposition (RTCVD) (Sturm et al., 1991).
The spectra of Sturm et al. (1991) are dominated by no-phonon recombination, at-
tributed to the annihilation of excitons bound to shallow impurities at T ^" 2 K, and
to free exciton recombination at higher temperatures. As in the bulk case, peaks due
to phonon-assisted recombinations are also observed. In fact, their spectra are almost
identical to those of bulk alloys (Fig. 34), except for photon-energy shifts, which can
be quantitatively related to strain and quantum-confinement. They also perform PLE-
measurements to determine the absorption edge of the alloy QWs and use the difference
in position between this and the PL line to determine the binding energy of the excitons.
Both these measurements and those of the decay times (- 0.4 ps) of the main PL peak

T = 4.2 K
x = 0.47 1, = 514.5 nm
d = 5.0 nm

QE=5%
3 -

d=Z3nm x

.-
E
v)
c
c
K
x = 0.12
$ d=l30nm
A x 4 I

650 750 850 950 1050

Photon Energy ( eV )

FIG. 35. The PL-spectra at 4.2 K, after rapid thermal annealing, of Si/Ge,Sil-, QWs of different
widths (d) and compositions (x). Adapted from Noel et af. (1990) with permission.
 5 OPTICAL
PROPERTIES 281

at 2 K are consistent with the assignment of this line (recombination of excitons bound
to shallow impurities). These authors also use the relative intensities of the phonon-
assisted lines [Eqs. (1 1) and (12)] to draw conclusions as to the actual confinement of
these excitons. They determine that, when the width of the QW (d) is larger than the
-
exciton radius (aexc 4 nm), the wavefunction is entirely contained within the alloy
layer while, when d 5 aexc,the exciton wavefunction penetrates into the Si-bamer
region.
Similar results were reported later by other authors in samples grown by MBE or
CVD (Fukatsu et al., 1992; Usami et al., 1992; Xiao et al., 1992). The clearest demon-
stration of quantum confinement in these QWs was given by Xiao et al. (1992), whose
results we reproduce in Fig. 36. The left-hand side of this picture shows their PL spec-
tra at 4 K for QWs of different well-widths ( d ) ,while part (b) of this figure shows a plot
of the position of the no-phonon PL-line for two different temperatures (full triangles
and squares) compared to the predictions of an envelope-function-type model (solid
lines), which include the effects of strain and confinement in the valence band states
of the alloy and assume negligible confinement for the conduction band electrons (Van
de Walle and Martin, 1986; People and Bean, 1986). The excellent agreement between
theory and experiment confirms the assignment of this PL-line.
The preceding discussion shows that two distinct types of behavior are seen in the
PL spectra of Si/Ge,Sil-, QWs and SLs: well-resolved luminescence of the same type
observed in bulk alloys (Fig. 36) and a broad PL-line, also associated with the indirect
bandgap of the alloy-layer (Fig. 35). The broad PL-line seems to be present only in
some (but not all) of the samples grown by MBE (Usami et at., 1992; Terashima et al.,
1991; Spitzer et al., 1992; Noel et al., 1992; Glaser et al., 1993; Wachter et al., 1993;
Brunner et ~ l . 1992),
, but not in those grown by CVD (Sturm et al., 1991; Dutrarte et

- theory -
n
m
-
c
'0
n
m

FIG. 36. (a) PL spectra, at 4 K, of four Si/Ge0,8Si0,2 QWs of different widths ( d ) and, (b) bandgap
vs d at 4 K (triangles) and 77 K (squares). The solid line is an envelope function calculation for each case.
Reprinted from Xiao er 01. (1992) with permission.
282 FERNANDO
CERDEIRA

al., 1991; Robbins et al., 1992). Several authors tried to correlate the appearance of
this line with growth parameters such as layer-thickness, Ge-molar fraction, number of
repetitions of the QWs, and growth temperature. This gave a rather confusing picture,
where contradictions abound. Rowell et al. (1993) give a good review of these attempts.
The main findings about the appearance of this broad PL-feature can be summarized
as follows (we discuss low-temperature PL measurements, T 5 4K, unless otherwise
specified):

0 The maximum of this broad (- 80 MeV FWHM) PL peak lies at lower en-

indirect gap of the alloy (always -

ergy than the NP-line in the sharp, phonon-resolved, spectrum, but it tracks the
10 MeV below) as alloy composition or
QW-widths change. This shows that this feature is also related to a no-phonon
emission process across the fundamental gap (Noel et al. 1990).

0 Terashima et al. (1991) studied the evolution of the PL-spectrum of QWs grown
by MBE at low-growth temperature (TG 2 400 "C) as a function of annealing

discussing. Upon annealing in a N2 atmosphere at temperatures TA 600 - -

temperature. Initially their samples exhibit the broad PL-feature we have been

700 "C, this line increases its intensity by factors of between 5 and 10. Annealing
at higher temperatures (TA = 800 "C) transforms the PL-spectrum into a sharp
phonon-resolved one similar to that observed in bulk alloys or in CVD-grown
QWs (although greatly reducing the overall PL-intensity). The NP-line of this
new spectrum lies at slightly higher photon energies than that of the maximum
of the broad PL-line.

0 Spitzer et al. (1992) report PL measurements in samples of different alloy com-

positions grown by MBE at low temperatures (TG = 325 - 450 "C). The thick-
nesses of these coherently strained Ge,Sil-, layers (up to 500 nm) greatly ex-
ceeded their equilibrium values (see the chapter by Hull). While some as-grown
samples present the broad PL line, others exhibit sharp phonon-resolved spec-
tra. No correlation was found between layer thickness and the type of PL-
presented by the as-grown samples. The broad PL-line disappears upon anneal-
ing at TA ? 600 "C, when strain-relaxation sets in. After annealing both types
of samples show narrow phonon-resolved PL-spectra.

Noel er al. (1992) and Rowell et al. (1993) present some results that conflict
with those of the previous item. They grew, by MBE, Si/Ge,Sil-, MQWs de-
signed to be metastable at the growth temperature (TG = 600 "C). Their samples
had three different QW-thicknesses (d = 2.7, 5.2, and 6.8 nm, respectively) and
two different molar fractions (x = 0.15 for the first two and x = 0.19 for the
last one). Their results are displayed in Fig. 37, which shows a steady increase
of the broad PL-line over the phonon-resolved PL as the QW-thickness and Ge
molar fraction increase. Observation of images by transmission electron (TEM)
 5 OPTICAL
PROPERTIES 283

< MBE Sil.,Ge,

m
v
broad PL band
x
.-
c

( a ) d=2.7nm

850 900 950 1000 1050 1100 1150

Photon Energy ( rneV )

FIG. 37. PL spectra, at 2 K, of several Si/Ge,Sil-, QWs grown by MBE at 600 OC: (a) d = 2.7 nm
and x = 0.15, (b)d = 5.2 nm and x = 0.15 and (c) d = 6.8 nm and x = 0.19. The broad minimum near
890 MeV is instrumental. Reprinted from Noel et al. (1992) with permission.

and Normansky phase-contrast microscopies suggest that the broad PL-feature

is associated with the formation of platelets within the alloy layer, having lateral
dimensions of I 5 1.5 nm and a few MLs in thickness, oriented with their nor-

-
mal along the growth direction. These platelets seem to grow in number (up to
7 x lo8 cm-*) as x or d increase and are envisaged as Ge-rich regions within
the alloy layers. Because they constitute regions of lower energy-gap, excitons
would drift towards these platelets and recombine there. This explains the lower
photon-energy of the broad PL-line when compared with the NP-recombination
from the regions of average alloy composition. The width of the PL feature is ex-
plained in terms of the wide size-distribution of these platelets, with their accom-
panying different confinement shifts. This interpretation is reinforced by their
time-resolved PL measurements, which show that the decay time of the phonon-
resolved PL is about 100 times faster than that of the broad PL feature. Notice
that this explanation is very similar to the one given by Weber and Alonso (1989)
for the “L-peak” of bad-quality bulk-alloy samples (Section IV.2). The transition
from sharp to broad PL as x or d increase is explained by Rowel1 et al. in terms
of a strain energy model, which predicts the existence of a “transition thickness”
( d c ) ,and which decreases as x increases. For d 2 dc. excess strain energy is
284 FERNANDO
CERDEIRA

relieved by the formation of platelets. This explains the fact that in samples with
many QWs the platelets seem to appear only in the outermost QWs. This was
established by Rowell et al. by using selective etching in a MQW sample that
exhibited broad PL before treatment. As successive QWs were etched away, the
PL evolved towards sharp phonon-resolved luminescence. The mechanism pro-
posed by these authors also explains the change-over from broad to sharp PL
upon annealing (Rowel1 et al., 1993).
0 An alternative interpretation of the broad PL-feature is offered by Glaser et al.
(1993), on the basis of experiments that combine PL with optically detected
magnetic resonance. They associate it with donor-acceptor pair recombination,
which would explain the lower peak position as well as the larger width of this
peak. The latter would result from the variations in the binding energy of the
donor-acceptor pair depending on their position within the alloy-QW.
0

-
Another piece of this puzzle is provided by Wachter et al. (1993), who grew
Si/Ge,Sil-, (x 0.19 - 0.24) QWs of different widths (d
MBE using different growth temperatures (TG -
- 2 - 30 nm) by
350 - 600 "C). Only sharp
phonon-resolved PL was observed by these authors in as-grown samples, which
seems to indicate that the formation of the type of defects that lead to the broad
PL-line depends on how the MBE machine is run, rather than being a predictable
characteristic of MBE-growth.
In an attempt to clarify the relationship between the method of growth and the
appearance of broadband PL, Sturm et al. (1994) performed a series of exper-
iments on RTCVD-grown Si/Ge,Sil-, QWs subjected to ion implantation and
posterior thermal annealing. Their results for one of their samples (x = 0.20
and d = 6 nm) are displayed in Fig. 38. The topmost curve shows the low-
temperature (2 K) spectrum of the as-grown sample, showing the sharp phonon-
resolved spectra characteristic of CVD samples. This spectrum is preserved
when a piece of this sample is annealed (T, = 600 "C), as shown in Fig. 38(c).
The luminescence disappears when the as-grown sample is subjected to ion im-
plantation with Si29+ ions at dosages between 1O'O and 10l2 cm-2 [Fig. 38(b)J.
Annealing of the ion-implanted sample at 600 "C brings back the luminescence,
but in the form of the broadband PL thought to be characteristic of MBE-grown
samples [Fig. 38 (d)-(01. Finally, annealing another piece of the ion-implanted
sample at a higher temperature recovers the sharp phonon-resolved PL of the
as-grown sample, although with weaker intensity [Fig. 38(g)]. It is also to be
noted that the broadband PL is not observed in similarly treated Si-substrates or
Si layers deposited on Si substrates, that is, this PL is definitely associated with
the Ge,Sil-, layers. The properties of the broad PL in these CVD samples are
identical to those previously observed in some of the MBE-grown samples. This
is illustrated in Fig. 39, where the spectra of as-grown and treated samples are
 5 OPTICAL PROPERTIES 285

Implant ( To
Anneal
a) none
none

b) 10'' none

I I I I I , , ,

800 900 1000

Photon Energy ( meV)

FIG.38. PL spectra, at 2 K, of one Si/Ge,Sil-, QW (d -6 nm, x = 0.20) (a) as-grown, (b) after
!O'O cmP2 SO Kev Sif29 implant, ( c )after 10 min annealing at 600 OC (no implant), (d) after same anneal of
the implanted sample, (e) after 10" cmP2 implant followed by 600 OC anneal, (0 after 10l2 c r C 2 implant
followed by 600 O C anneal, and (g) after !OIO cm-' implant followed by anneal at 800 OC. In (9) the Si PL
was suppressed by a filter. Adapted from Sturm ef al. (1994) with permission.

displayed together for different sample parameters. The broad PL band follows
the sharp PL, remaining always at slightly lower photon-energy. The appearance

centration of unwanted impurities of only 10" ~ m - rules -

of broadband PL in samples with very small implant doses, equivalent to a con-
~ , out the mechanism
of donor-acceptor pairs that was previously discussed (Glaser et al., 1993).

The different, and often contradictory, results outlined here can be summarized as
follows: broadband PL is associated with no-phonon recombination across the indirect
bandgap of the alloy layer. This type of PL appears in samples containing a relatively
high density of point defects or defect clusters. The formation of platelets, richer in
Ge than the average alloy composition, could be associated with these point defects.
286 FERNANDO
CERDEIRA

I 1 I I I I

800 900 1000

Photon Energy (rneV)

FIG.39. PL, at 2 K, of Si/Ge,Sil-, QWs with 600 "C anneals both directly after growth (dashed lines)
and after implant (solid lines). Reprinted from Sturm et al. (1994) with permission.

The broad PL-line would result from the superposition of emission from platelets of
different sizes. It is not clear why these defects appear in some of the MBE-growths,
but it seems unlikely that there is a mechanism inherent to the growth process itself that
would result automatically in the formation of these defects or defect clusters.

4. PL FROM ULTRATHIN GE,SI, QWS AND SLS

The first observations of PL in Ge,Si, SLs reported a broad emission line, which
was attributed to recombination from the folded pseudo-direct gap (Zachai et al., 1990;
Meczingar et al., 1993). These results were already discussed in Section 11.1 and are
displayed in Figs. 5 and 6. These spectra bear an uncanny resemblance to the broad-
band PL ones from Si/Ge,Sil-, structures shown in Fig. 35. In view of the discus-
sion in the preceding sections of this chapter, it is probable that the PL features of the
Ge,Si, SLs are greatly influenced by recombination in alloy layers inevitably present
at the Si/Ge interfaces of these samples, regardless of whether they were grown strain-
symmetrized on a partially relaxed Ge,Sil-, buffer layer or directly on Si. As this
interfacial alloy forms spontaneously as a result of interdiffusion, it must be inhomo-
geneous both in strain profile and composition, resulting in the type of defects that are
seen to produce broadband PL in the Si/Ge,Sil-, structures. This would explain the
lineshape and intensity of the observed PL-line.
The more recent work of Sunamura et al. (1995) on Ge,Si, QWs focuses on using
low temperature PL spectra to diagnose Ge segregation at the Si/Ge interface (Suna-
mura e l al., 1995). Their samples were grown on Si (001) substrates, at 700"C,
 5 OPTICAL
PROPERTIES 287

by gas-source MBE and consisted of Ge, QWs embedded between thick Si layers.
Samples were grown with different average thicknesses of the Ge layers ( n -
12 MLs). They studied the PL spectra of these samples at 22 K. For small values of n
1-

they observe sharp phonon-resolved luminescence, which they attribute to recombina-

tion in the Ge QWs. The peak of the no-phonon line shifts towards lower energy as n

-
increases. This is attributed to the diminishing of the confinement shift with increas-
ing n. At n 4 an abrupt change occurs. The now familiar broad PL appears and gains
in intensity with increasing n, while the sharp PL gradually fades away. Beyond this
point peak positions in both the broad and sharp PL lines remain insensitive to further
changes in n. Sunamura et al. interpret this as a transition between 2D and 3D growth
-
occurring at n 4. The sharp PL lines would originate in 2D regions while the broad
PL is attributed to recombination in 3D islands created by Ge segregation for larger
values of n. The number of these islands would increase as n increases at the expense
of the 2D regions, while the average size of both regions would remain constant. This
would explain both the increasing (decreasing) intensity of the broad (sharp) PL line
as n increases beyond 4 MLs and the fact that PL lines do not suffer any further shifts
in their peak position. Their analysis does not include the formation of alloy interfa-
cial layers, such as those observed in similar (MBE-grown) samples by Narvaez et al.
(1997) (see Section III.5.C). The latter observe smoother 2D layers for n = 5 and 6
than for lower values of n. The difference in these results may be a consequence of the
different growth method.
On the other hand, in view of the discussion of Section IV.2, it is also possible
that the alloy layers are present in the samples of Sunamura et al. (199s) and that the
PL-lines they observe in their samples are strongly influenced by those layers. This
is in line with the theoretical results of Turton and Jaros (1996) (see the chapter by
Shaw and Jaros), which predict that alloy scattering is the predominant mechanism for
recombination in these materials. In this case, the results of Sunamura et al. (1985) and
those of Narvaez et al. (1997) might be brought into closer accord, as the composition
of this alloy layer seems to vary with n in the MBE samples of the latter. For low
QW-thicknesses the interfacial alloy layers of the MBE samples have a low average Ge

of defects. As n increases the molar fraction also increases, stabilizing at x

for n
-
molar fraction. Because of this they should not be very strained or have a large density

- 6. This change in alloy composition and strain of the alloy layer could be
0.5

partly responsible for the evolution of the PL spectra as a function of n reported on

the gas source samples. On the other hand, it is also possible that the two different
growth methods produce a different evolution of the Ge/Si interface as the Ge coverage
increases. Further experimental and theoretical work is needed in order to clarify this
issue.
The discussion in this section shows that, in good quality Si/Ge,Sil-, structures,
well-resolved near bandedge PL is observed. The PL spectra from these samples are
similar to those of bulk alloys when appropriately modified by strain and confinement.
Defects, whether spontaneously arising during growth or deliberately induced by pos-
288 FERNANDO
CERDEIRA

terior treatment, produce a broad PL line also associated to the alloy bandgap. In fact,
this line is rather ubiquitous, because it appears in bulk alloys as well as in Ge,Si, SLs
and QWs. Hence, care must be taken when interpreting PL data from these thin-layer
systems in order not to attribute to SL these effects, (such as zone-folding) features,
that may arise from the inevitable roughness of the Si/Ge interface.

V. Concluding Remarks

In this chapter we have reviewed the optical properties of SUGe QWs and SLs. Tech-
niques based on the absorption or reflection of light produce spectra with peaks at crit-
ical points in the joint density of states for interband transitions. Many experimental
results can be explained in terms of the electronic bandstructure of the constituent ma-
terials, suitably modified by the effects of strain and confinement. For samples with
relatively thick layers these effects can be calculated using elastic theory for strain and
simple Kronig-Penney-type models for confinement. As the layers become thinner (on
the monolayer scale), more complex band calculations are needed in order to interpret
optical spectra. One common feature of these spectroscopies is that, as the dielectric
constant depends on the joint density of states, they are less sensitive to interface qual-
ity or end effects than are those of other forms of spectroscopy such as Raman or PL.
Because of this, calculations based on perfect interfaces often provide a good descrip-
tion of the major spectral features. On the other hand, PL spectra are very sensitive
to interface effects (see Section IV). Here, model calculations for real interfaces are
needed to give a correct interpretation of the spectra. This is discussed in detail in the
chapter by Shaw and Jaros. The Raman spectrum is also sensitive to interface effects.
Fortunately these effects can be simulated using relatively simple models. This makes
it possible to use Raman scattering as a tool to characterize interface roughness.
Finally, some of the foregoing results may be applicable to the rapidly developing
field of Ge or Si quantum dots (QDs). For example, optical absorption spectra of Ge
nanocrystals embedded in an A1203 matrix (Tognini et al., 1996) are well described
by the calculation, based on perfect crystallites, of Wang and Zunger (1994). On the
other hand, the Raman spectra of Si nanocrystals in porous Si is strongly dependent
on the boundary conditions at the interface between them and the matrix in which they
are embedded, as the analysis based on a linear-chain model of Ribeiro et al. (1997)
shows. While it is beyond the scope of this chapter to present a discussion of the results
obtained in this rapidly expanding field, it is safe to assume that a combination of op-
tical spectra and model calculations will be decisive in unveiling the optical properties
of this new generation of SUGe microstructures.
 5 OPTICAL
PROPERTIES 289

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 SEMICONDUCTORSAND SEMIMETALS. VOL. 56

CHAPTER6

Electronic Properties and Deep Levels in

Germanium-Silicon
Steven A. Ringel
THE O H I O STATE UNIVERSITY,
DEPARTMENT
OF ELECTRICAL ENGINEERING
OHIO
COLUMBUS.

Patrick N. Grillot
HEWLETT
PACKARD
OPTOELECTRONICS
SAN JOSE, CALIFORNIA

I. INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
11. D E E P L E V E L S IN Ge,Sil-, .................................. 295
1. DLTS Identification and Analysis of Extended Defect States
in Ge,Sil-, ........................................ 296
2. Electron Traps in GexSil-, Alloys f o r x = 0 - 1 . . . . . . . . . . . . . . . . . . . . . 303
3. Hole Traps in GexSil-, from x = 0 - 1 . . . . . . . . . . . . . . . . . . . . . . . . . . 309
111. INFLUENCE OF DEFECTS
ON ELECTRICAL PROPERTIES O F Ge,Sil_, ALLOYS. . . . . . . 319
1. Doping Compensation in Reluxed Ge,Sil-, Layers . . . . . . . . . . . . . . . . . . . . 319
2. Currier Generation-Recombination in Reluxed
Ge,Sil-, Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
IV. C A R R I E R TRANSPORT PROPERTIES OF Ge,Sil_, ...................... 326
1. Carrier Mobilities in Strained and Unsrrained Bulk Ge,Sil-, . . . . . . . . . . . . . . . 321
2. Two-Dimensional Carrier Transport in GeSi/Si Heterostructures . . . . . . . . . . . . . 334
3. Minority Carrier Lifetimes and Diyusion Coeficients . . . . . . . . . . . . . . . . . . . . 339
V. CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 1
REFERENCES. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343

I. Introduction

The electronic properties and quality of semiconductors depend strongly on the pres-
ence of deep electronic states within the bandgap of semiconductors. Deep levels are
ubiquitous in that they are a consequence of unintentional impurities, intrinsic point
defects, and a variety of extended defects such as dislocations, grain boundaries, inter-
faces, and general crystalline disorder. Deep levels can affect device performance in
Copyright @ 1999 by Academic Press
All rlghta of reproduction tn any form reserved.
ISBN 0-12-752164-X
0080-8784/99 $30.00
294 STEVEN A. RINGELAND PATRICK
N.GRILLOT

a variety of ways, from limiting carrier lifetimes and mobilities, to providing both un-
wanted current paths across junctions via generation and recombination processes, and
pathways for nonradiative transitions that can limit optoelectronic device efficiency.
Great strides have been made to eliminate many physical defects responsible for deep
levels in order to achieve optimum electronic properties and nowhere has this been
more significant than in Si Very Large Scale Integration technology. This has occurred
over several decades of intense process research and development where the purity and
control of wafer generation, cleaning procedures, and subsequent planar processing
have been perfected such that electrical properties can be tailored with unsurpassed
precision over large diameter Si wafers. During this effort, deep levels not only were
detected and studied using very sensitive and quantitativetechniques, but their physical
sources were identified and subsequently removed from (or at least highly controlled
in) the Si fabrication process.
However, in contrast to bulk Si technology, Ge,Sil-, devices are based on epi-
taxial growth methods in which Ge,Sil-, layers of different alloy compositions (x)
and lattice constants are used to form heterostmctures, primarily on Si. Hence, the
electronic properties and quality of Ge,Sil-, materials also depend on additional fac-
tors such as interfaces, strain, mismatch-related defects such as threading and misfit
dislocations, alloy composition, etc., all of which must be understood to control the
characteristics and performance of Ge,Sil-, devices. By engineering the lattice mis-
match between the epitaxial Ge,Sil-, layer and the Si substrate, as well as the m i s -
matches between individual Ge,Sil-, layers of different compositions, a plethora of
new electronic properties and advanced devices based on bandgap and strain engineer-
ing have been enabled, as covered within this volume and elsewhere (People, 1986;
Beam, 1992; Kaspar and Schaffler, 1991; Ismail et al., 1995; Fitzgerald, 1995; Kasper
et al., 1994; Jain, 1994; Stoneham and Jain, 1995). Many of these devices require a
“virtual” substrate with an adjustable lattice constant to provide the appropriate mis-
fit strain to achieve specific properties (Fitzgerald et al., 1992; Fitzgerald, 1989). For
example, a typical n-channel GeSi Modulation Doped Field Effect Transistor contains
a thin, strained Si layer (channel) that may be grown on a relaxed, Ge,Sil-, buffer
layer having a Geo.3oSio.70 surface composition, which has a lattice constant approx-
imately 1.2% larger than that of Si. The Si channel is under tensile strain (so long
as it is below the critical thickness), and the desired band offsets and carrier confine-
ment for high-speed two-dimensional carrier transport are enhanced. Whereas relaxed,
Ge, Sil -, layers are commonly used as lattice-mismatched templates for strained layer
overgrowth, they can also be used to provide a lattice constant that is matched to an
overlayer, where strain-free integration, rather than strain-engineered electronic prop-
erties, is the motivation for adjusting the lattice constant. For example, the equilibrium
lattice constant of Ge is very close to that of GaAs, and the possibility of integrating
GaAs-based epitaxial devices with Si wafer technology via a graded Ge,Sil_, buffer
layer terminated by a relaxed Ge layer is attracting interest for optoelectronic integra-
tion (Fitzgerald et al., 1992; Sieg et al., 1997).
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 295

In any of these applications, realizing the theoretical benefits of strain-induced

changes in electronic structure andor lattice matching depends upon the practical
achievement of Ge,Sil-, heterostructures with low defect concentrations. From a
structural perspective, maintaining controlled pathways for strain-relaxation within
Ge,Sil-, buffer layers so that smooth, uniform layers can be achieved coupled with
minimization of threading dislocationsis critical to realizing ideal heterojunctionprop-
erties. However, from strictly an electrical perspective, defect control is equally crucial.
For instance, threading dislocations in field-effect transistor structures can cause vari-
ations in the threshold voltage, increased power consumption due to leakage paths be-
tween the source/drain and substrate, and enhanced diffusion paths (Xie et d., 1994). In
heterojunction bipolar transistors (HBTs), misfit dislocations cause excess
recombination-generation at either junction, which reduces gain (King et aZ., 1989).
For optoelectronics, any such defects can also reduce both efficiency and responsiv-
ity through the introduction of competing nonradiative current paths. Thus, much of
the recent progress in Ge,Sil-, device technology is directly attributable to the sub-
stantial improvements in the quality of relaxed Ge,Sil-, layers due to an improved
understanding of strain-relaxationin lattice-mismatched thin films.
In this chapter, recent experimental results on the electronic properties of Ge,Sil-,
alloys are reviewed. Particular attention is devoted to deep levels resulting from strain-
relaxation and their influence on the electrical properties of Ge,Sil-, layers. The role
of alloy composition, bandgap, and growth parameters of Ge,Sil-, layers on these
properties are considered as these have both fundamental and technological implica-
tions on electronic properties. Issues important for carrier transport, such as scatter-
ing and recombination are discussed and comparisons between unstrained and strained
properties are made. Related issues such as electronic band structure, band lineups and
strained layer physics are discussed elsewhere in this volume. Throughout the remain-
der of this chapter, Ge,Sil-, alloys will in general be referred to as GeSi, unless a
specific composition is noted.

11. Deep Levels in Ge,Sil-,

As in any semiconductor, deep levels in GeSi can result from either intrinsic or ex-
trinsic sources. Compared to Si and many 111-V semiconductors,very little information
is available on the detection and presence of deep levels in GeSi materials. This is due,
in part, to the common difficulty in identifying deep levels in alloys due to broaden-
ing effects, and in particular, due to difficulties in analyzing deep levels associated with
spatially extended defects such as dislocationsthat arise due to lattice mismatch. In this
section, the current state of knowledge concerning the detection and analysis of deep
levels associated with extended defects by deep level transient spectroscopy (DLTS) is
reviewed.
296 STEVEN A. RINGELAND PATRICK N. GRILLOT

1. OF EXTENDED
DLTS IDENTIFICATION AND ANALYSIS DEFECTSTATES
IN Ge,Sil-,

Since dislocations are inevitable within GeSi heterostructures, it is useful to first

review measurement and analysis considerations for DLTS as applied to the case of
extended defect states. Conventional DLTS measurements rely on the detection and
subsequent analysis of junction capacitance transients induced by repetitively applying
an appropriate voltage pulse on a reverse-biasedjunction. If a deep level present within
the original depletion region is filled with a free carrier by the voltage (filling) pulse,
then a capacitance transient develops once the filling pulse is removed as the deep level
emits the trapped charge and the capacitance returns to its original, quiescent value.
The time constant of the capacitance transient for simple, noninteracting traps directly
yields the deep level emission rate, from which the energy level and cross section of
the trap can be obtained (Miller et aE., 1977). Figures 1 and 2 schematically show the
pulse timing and subsequent carrier capture and emission along with the ideal resulting
junction capacitance behavior.
Mathematically, the correlation between the observed capacitance transient and trap
emission rate can be developed by starting with the simple, general rate equation for a
concentration of ideal point defects NT generating a single deep level with an energy

Electron trap level electrons

B .**.**

FIG. 1. Schematic representation of the depletion region of a p+t, junction during a DLTS experiment
that contains a uniform concentration of a single electron trap. (a), (b), ( c ) ,and (d) correspond to the quies-
cent steady state, the application of the trap filling pulse ( V p ) ,trap emission after V , is removed, and return
to the steady state, respectively.
 6 ELECTRONIC
PROPERTIES AND DEEP LEVELS 297

FIG. 2. A representation of the voltage bias timing diagram and corresponding junction capacitance
behavior during a conventional majority carrier DLTS experiment for a p + n junction. (a), (b), (c), and (d)
correspond to the conditions shown in Fig. 1 and the voltage sign is with respect to the p+ contact.

ET, as given by

where n T , NT, en, c p , en, and ep are the concentration of defect states occupied by
an electron, the total concentration of the given defect state, the electron and hole
capture rates, and the electron and hole emission rates, respectively. For simplicity of
explanation, we will assume the case for an electron trap in n-type material throughout
this discussion. During the filling pulse application the capture rates will far exceed the
emission rates and Eq. (1) reduces to

which has a solution given by

As can be seen from this last expression, for long filling pulse times n t ( t ) = NT and
all traps are filled. For DLTS fill pulse times such that the traps are not saturated, we
may substitute t = tp in Eq. (3) to obtain the trap occupation during the DLTS fill pulse
time according to
298 STEVEN A. RINGELAND PATRICK N.GRILLOT

Similar expressions will result for hole traps. Once the filling pulse is removed, emis-
sion processes become important now that traps are filled, and the rate equation be-
comes
dnT/dt = Cn(Nr - n T ) - ennT (5)
from which the well-known emission rate expression for an electron trap can be de-
rived, viz. (Lang, 1974),

Here, N , is the effective conduction band density of states, a,,is the electron capture
cross section, (v,) is the average electron thermal velocity, E , is the trap activation
energy (E, - ET) for an electron trap, and k is the Boltzmann constant.
The theoretically derived emission rate can now be connected to the measured ca-
pacitance transient that can be expressed as

C ( t ) = Co exp(-e,t) (7)

This capacitance expression can be rewritten in terms of the doping concentration (as-
suming an n-type, one-sided junction material as in Fig. 2) as

where A is the junction area, E is the dielectric constant, q is the electronic charge, Vo
is the built-in junction voltage, and V is the applied voltage.
The idealized approach outlined here assumes no local band distortion, no interac-
tion between traps, and no involvement of traps with different energy levels, and the
simple, single exponential capacitance transient is easily analyzed to extract trap pa-
rameters. However, these simplifying assumptions are often violated during detection
of traps associated with extended defects by at least two key issues: local charging
effects that distort the band diagram in the vicinity of the defect (Omling et al., 1985;
Wosinski, 1989), and the formation of deep level bands rather than isolated energy lev-
els (Schroter et al., 1980). The result of these complications for DLTS measurements
are the observation of both peak broadening and nonexponential trapping kinetics (i.e.,
a violation of Eq. (4)), which cause significant difficulty in correctly measuring trap
concentrations and activation energies. Moreover, the fact that dislocations can in-
teract with point defects makes the exact identification of the physical sources for
observed DLTS peaks in mismatched systems such as SiGe/Si ambiguous and is an
area of current research (Ringel and Grillot, 1997; Grillot et al., 1996b; Schroter et
al., 1995; Mooney et al., 1997). Hence, in the absence of additional information, one
can only categorize deep states associated with dislocations generally as dislocation-
related, whether they are due to the dislocation core itself or to point defects trapped
within a dislocation strain field at a dislocation core.
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 299

In spite of the ambiguity with regard to the physical origin of dislocation-related

states (to be discussed), the nonexponential trapping kinetics coupled with peak broad-
ening can be used to discriminate between traps associated with dislocations and those
associated with non-interacting point defects. The nonexponential kinetics have been
widely observed for dislocation-related states in a number of semiconductors, includ-
ing GeSi/Si heterostructures (Ringel and Grillot, 1997; Grillot et al., 1996b; Schroter
et al., 1995; Mooney et al., 1997; Grillot et al., 1994; 1995a; 1995b), relaxed InGaAs/
GaAs (Watson et aZ., 1992), plastically deformed bulk Si (Omling et al., 1985; Kimer-
ling and Patel, 1979; Kimerling et al., 1981; Kveder et al., 1982; Alexander, 1989) and
GaAs (Wosinski, 1989), and has been attributed to local charging of extended defects
during the application of the DLTS filling pulse. The accumulation of charge during
the filling pulse results in the formation of a local, time-dependent potential that in-
hibits the capture of additional charge by the extended defect during the filling pulse
by effectively reducing the local free carrier population available for trapping. Such
a time4ependent potential is schematically shown for a majority carrier electron trap
in Fig. 3. It has been suggested that this potential barrier modifies the carrier capture
rate given earlier by Eq. (2) during a DLTS filling pulse of duration t p according to
(Wosinski, 1989)

for the case of electron traps. Here, $ ( t p ) is the time-dependent coulombic barrier (as
shown in Fig. 3), which, assuming a linear distribution of defect sites can be expressed
as (Wosinski, 1989)
4 @ p ) = 4onr(tp)/nTo (10)
In these expressions, $0 and nTO are the equilibrium value of the barrier height and
the equilibrium trap occupation, respectively, and as seen, the barrier increases until
n~ = N T . As this potential barrier is time-dependent, it will alter the capture kinetics
previously shown to be exponentially dependent on t p for ideal point defects as shown
by Eq. (4). The solution to Q. (9) instead results in a logarithmic time dependence

conduction
band edge

valence
band edge

FIG. 3. Schematic illustration of a coulombic barrier that occurs during capture of electrons by a ma-
jority canier electron trap due to an extended defect in an n-type semiconductor. The barrier height $ ( t )
impedes carrier capture during a DLTS filling pulse.
300 STEVENA. RINGELA N D PATRICKN. GRILLOT

according to (Omling et al., 1985; Grillot, 1996)

where t is a parameter that reflects the time required for charge capture to begin influ-
encing the potential barrier. Equation (1 1) demonstrates the slow, logarithmic capture
kinetics commonly observed for broadened DLTS peaks attributed to extended defects,
and this behavior can be exploited to identify whether a deep level is due to a point
or extended defect. For instance, Fig. 4 shows a comparison of the trapping kinetics
behavior for the well-known EL2 point defect and what is presumed to be a disloca-
tion state in a plastically deformed, bulk GaAs sample (Wosinski, 1989). Note the
logarithmic dependence that is observed only for the dislocation-related state. In con-
trast, additional analysis would show that the EL2 kinetics in fact is purely exponential,
as expected from Eq. (4). Obviously, this slow, logarithmic trapping kinetics will in-
fluence significantly the filling pulse time necessary to saturate extended defect states.
Hence, determination of total trap concentration N T , which is often assumed by simply
noting the maximum value for the DLTS signal, should account for the dependence of
n~ on t p ,noting that longer filling pulses are needed to saturate such traps. More detail
on the formation of the local potential barrier and its consequences on GeSi deep level
analysis can be found in the literature (Grillot et al., 1995b, 1996; Brighton, 1994).
While it is generally accepted that the logarithmic trapping kinetics is a result of de-
fect charging, DLTS peak broadening as a function of the applied filling pulse duration
can arise due to the presence of a band of states such as theoretically predicated for
the dislocation core, or from a distribution of localized states at an extended defect,
the latter perhaps due to point defect clouds within a dislocation core region (Schroter

12 6

FIG.4. Comparison of the DLTS filling pulse dependence for a well-known point defect, EL2 in GaAs
vs a dislocation state ED1 in GaAs. The slow, semilogarithmic dependence for the extended defect state is
readily apparent. Reprinted with permission from Wosinski (1989).
 6 PROPERTIES A N D DEEPLEVELS
ELECTRONIC 301

et al., 1995). Localized band bending resulting from the time-dependent coulombic
barrier might be expected to have an effect, although it has been shown that the DLTS
lineshape is nearly independent of this barrier (Schroter et al., 1995). Hence, DLTS
peak broadening is generally indicative of the density of defect states spread over a
certain energy range.
The presence of deep energy bands has a major influence on DLTS measurements
and data interpretation and continues to be a source of theoretical and experimental
research interest (Ringel and Grillot, 1997; Schroter et al., 1995). Figure 5 shows
a DLTS scan of a dislocation-related electron trap detected in a relaxed Geo.30Sio.70
layer measured using various filling pulse times but with identical rate windows and
bias conditions. The DLTS peak in the figure asymmetrically broadens on the low
temperature side with increasing values of t p , causing the DLTS signal maximum to
shift toward lower temperatures while the high temperature sides for each filling pulse
virtually coincide. In fact, the characteristic DLTS peakwidth, which can be defined

maximum, that is, F W H M / T p , increases from -

by the ratio of the full width at half maximum (FWHM) to the temperature at the peak
0.08 to 0.15 as t p increases from
50ps to 5ps for the trap shown in Fig. 5. Such behavior is not characteristic of ideal
point defect traps where the effect of increasing the filling pulse time is simply to sat-
urate the peak maximum without either a shift in the peak position nor a change in
FWHM/T,, which for an ideal trap is approximately 0.1, independent of t p (Lang,

-800

FIG. 5 . DLTS signal from an electron trap at E(0.63) due to an extended defect in a 30% GeSi layer
obtained for various fill pulse times with all other measurement settings kept constant. Reprinted with per-
mission from Grillot et al. (1995a).
302 STEVEN A . RINCELAND PATRICK N.GRILLOT

1986). This can be understood by considering the presence of a distribution of deep

states where the lowest energy states available are preferentially filled for short t p val-
ues. As t p increases, higher energy states which are closer to the conduction band
become filled. The filling of states closer to the conduction band generates DLTS sig-
nals detected at progressively lower temperatures (for the same rate window settings)
due to the reduced activation energy for carrjer emission (i.e., increased emission rate)
and a broadened DLTS signal will be observed due to multiple emission events from
within the defect band to the conduction band. Hence, the conventionally measured
trap activation energy determined by the position of the peak maximum is actually an
average of the emission processes from filled states within the band, weighted by the
density of filled states, N(E). This notion is supported by the series of Arrhenius plots
shown in Fig. 6, that were obtained for the trap shown in Fig. 5 for each filling pulse
time. Analysis of the slopes of these lines yields the “apparent” electron trap activation

from - 0.9 eV to -
energy ( E , - E r ) , and it is found that the activation energy systematically decreases
0.6 eV as t p is increased from 5 0 ~ tos 5 p . Thus, the defect
band density of states is essentially being scanned by the filling pulse and the strong
dependence of trap parameters on t p highlights the need to account for the complete
measurement conditions when comparing extended defect DLTS data for the purpose
of data correlation.

FIG. 6 . Activation energy plots obtained by analysis of the DLTS spectra obtained for various rate
windows at each fill pulse condition listed in Fig. 5. The systematic decrease in slope as t p is increased from
50 p s to 5 ms corresponds to a decrease in apparent trap activation energy from 0.9 to 0.6 eV. Reprinted with
permission from Grillot et al. (1995a).
 6 ELECTRONIC
PROPERTIES AND DEEP LEVELS 303

2. ELECTRON
TRAPSIN Ge,Sil-, ALLOYSFOR x = 0 - 1

Now that the general DLTS features which characterize deep levels associated with
extended defects have been summarized, we turn to a discussion of deep levels present
within relaxed, GeSi epitaxial layers. Deep levels detected in GeSi have been variously
assigned to the dislocation core (kink sites) (Grillot et al., 1995b), clusters of intrinsic
point defects associated with dislocation motion that are trapped by dislocation fields
(Ringel and Grillot, 1997; Grillot et al., 1996b; Grillot and Ringel, 1996a), clusters
of extrinsic point defects trapped by dislocations (Mooney et al., 1997; Brighten et
al., 1994), as well as isolated impurity defects (Nagesh et al., 1990a, 1990b), all of
which are discussed later in this chapter. The assignment of a physical source to a
detected deep level is quite complex, and systematically controlled growth and pro-
cessing experiments, in addition to the evaluation of trapping kinetics as discussed in
the previous section have been performed to reveal potential deep level sources. In this
section, electron traps detected in relaxed GeSi epitaxial layers are reviewed for the
entire alloy composition range. Compared to hole traps, which are discussed in the fol-
lowing section, very little work has been done concerning the detection and evaluation
of electron traps in GeSi to date. Nevertheless, an important purpose of this section is
to provide a convenient compilation of deep level data obtained for GeSi layers grown
and processed by various methods.
The DLTS measurements have been performed on GeSi layers grown by ultrahigh-
vacuum chemical vapor deposition (UHVCVD), rapid thermal chemical vapor depo-
sition (RTCVD), molecular beam epitaxy (MBE) and other CVD methods. Figure 7

0 100 200 300

Temperature (K)

FIG.7. Electron trapping spectra of constant composition, n-type GeSi layers for the alloy compositions
indicated. Each layer was grown on a 10% Ge/pm step-graded GeSi buffer on Si except for the 15% Ge
sample, which was a single heterostructure. A 5-ms fill pulse time was used for these measurements and a
single lOOO/s rate window is shown for all cases. Reprinted with permission from Grillot et al. (1996~).
304 STEVEN A. RINGELAND PATRICK N.GRILLOT

shows a collection of DLTS scans obtained for relaxed, n-type GeSi epitaxial layers,
grown by UHVCVD at high-growth temperatures (850 or 9OO0C), that were part of
a systematic study of deep level behavior as a function of alloy composition (Grillot
et al., 1996~).To obtain these spectra p + n diode test structures were fabricated US-
ing a thin p + layer grown onto a lightly doped, thick, n-type layer of a fixed GeSi
composition to allow DLTS probing of the n-type region. A low donor concentration
in the low 1014cm-3 range was used to enhance the sensitivity of DLTS so that trap
densities as low as l O " ~ m - ~could be detected in these relaxed layers that were grown
on a compositionally graded buffer to ensure low threading dislocation densities. A
representative TEM cross section of a heterostructure used for DLTS studies is shown
in Fig. 8 for a Geo.3oSio.70 structure, which indicates that dislocations are essentially
confined to the graded buffer region beneath the 30% Ge cap layer and that threading
dislocations in the cap are present only below the TEM statistical limit. Larger area
electron beam induced current measurements revealed that this sample has a threading
dislocation density in the mid 105cm-2 range within the cap layer. The same grading
rate (10% Gelkm) was used in the buffer layer of each structure and x-ray rocking
curve measurements indicated that each structure was 90% or more relaxed. For the
largest mismatched layer consisting of pure Ge, the threading dislocation density in
the Ge cap was approximately 8 x 106cm-* using the same grading rate and high-
temperature growth. Thus it is important to note at the outset of this discussion that the
rich deep level spectra in Fig. 7 do not imply poor electronic material quality for these
films. Indeed the total trap density in these layers is only in the 10'2cm-3 range or
less, consistent with the low density of threading dislocations and also the high purity
of these layers from the viewpoint of background impurities.

relaxed Ge,,Si,,cap I graded composition buffer I Si wafer

FIG.8. The TEM cross section of a representative 4-pm thick 30% Ge layer grown on a step-graded
buffer. A threading dislocation density in the ~nid-lO'cm-~ range was measured by EBIC.
 6 ELECTRONIC
PROPERTIES A N D DEEP LEVELS 305

Figure 7 indicates the presence of a few electron traps at each composition. For
samples having a Ge composition of less than 73% for which the Si-like bandstructure

(AE, -
is still dominant and the conduction band energy changes only slightly with Ge content
0.05 eV between Si and Geo.73Si0.27),two main electron traps, E(0.37) and
one near midgap at - E(0.51) are consistently detected for each composition with
little variation in activation energy. Both of these levels closely match electron trap data
obtained for plastically deformed bulk Si (PD-Si), which is an important observation
that is discussed in detail later (Grillot and Ringel, 1996a). The relative concentrations
of these levels were found to depend on growth temperature and the degree of lattice
mismatch. Both states are apparent in the DLTS spectrum of the 73% Ge sample shown
in Fig. 7, whereas only the E(0.37) is detected for these particular 30% and 15% GeSi
layers, although the broadness of these DLTS peaks may include contributions from
both levels since their emission rates have been shown to be very similar. Indeed a
detailed study of 30% Ge layers that were grown and processed at lower temperatures
(65O0C-800"C) do reveal the presence of the midgap electron trap in these materials
as well (Grillot et al., 1996b). Trapping kinetics studies indicate that the E(0.37)
level displays the logarithmic capture kinetics and broadened peak features that are
characteristicof extended defects as discussed in the previous section. The midgap trap
also displays the extended capture kinetics associated with extended defects. However,
as discussed later, the fact that this level is removed by annealing or growth at high
temperatures whereas the E(0.37) level is thermally stable implies a different physical
source for these states. In addition to these levels, a small concentration of shallow
electron traps (the E(0.07) level for the 30% Ge sample in Fig. 7) and traps at E(0.20)
and E (0.33) have been occasionally detected in these materials. However, annealing
or growth in excess of 850 "C eliminates these levels, except for the shallow E(0.07)
level whose source is not known.

For high Ge content films (x > 0.85) such that the bandstructure appears "Ge-like"
where the conduction bandedge is defined by the (111) minima (Braunstein et al.,
1958), two electron traps have been detected with activation energies that are signifi-
cantly different from those at lower Ge compositions. As shown in Fig. 7 for UHCVD-
grown samples, these electron traps have activation energies of 0.28 eV and 0.42 eV. As
in the case for lower Ge content films whose DLTS spectrum are quite similar to those
of PD-Si, the electron traps in heteroepitaxial, relaxed Ge layers closely match deep
levels detected in some early work on bulk, n-type PD-Ge (Baumann and Schroter,
1983) and Ge bicrystals (Broniatowski, 1983). In fact, if the change in the conduction
band minimum energy is accounted for as a function of GeSi composition for the elec-
tron traps discussed thus far, the E(0.28) and E(0.42) levels in the pure Ge layers map
into the E(0.37) and E(0.50) levels, respectively, found for samples with Ge contents
of less than 73%. This observation coupled with the data on PD Si and Ge suggests
the presence of compositionally independent defect states and implies similar physical
sources may be responsible for these electron traps.
306 STEVEN N.GRILLOT
A. RINGELAND PATRICK

Electron traps have also been detected by DLTS in GeSi grown by techniques other
than UHVCVD. A single, deep electron trap at E (0.63) was detected in RTCVD-grown
Geo.3oSio.70 films using a 20% graded buffer layer on Si (Grillot et al., 1995a, 1995b).
This level has been detected as both a majority carrier trap in n-type layers and as a
minority carrier trap in p-type layers, and the DLTS spectrum for this level was actually
shown earlier in Fig. 5. Similar to the electron traps discussed thus far, the E(0.63)
states displays the logarithmic capture kinetics and defect banding properties indicative
of an extended defect source. It should be noted that this particular material had a more
complex (less-ordered) dislocation network and a higher threading dislocation density
(- 107cm-2) that the UHVCVD material described in the foregoing, and that this trap
was also detected very occasionally in certain UHVCVD samples but only for those
samples that exhibited a high threading dislocation density with significant dislocation
interaction. Hence, it was concluded that this was not a trap specific to the RTCVD
growth technique. Electron traps were also observed in n-type GeSi heteroepitaxial
layers grown by a C1-based CVD process (Nagesh et al., 1990a, 1990b). The DLTS
spectra in that work resemble the spectra shown in Fig. 7. For these CVD materials
a midgap electron trap was identified as the dominant feature although an additional
shallow electron trap was detected but without determination of its energy state. This
work was in fact the first published DLTS work on GeSi (Nagesh et al., 1990a, 1990b).
Table I summarizes the electron traps detected by various groups in relaxed, GeSi
layers. The similarities in trap energies detected in the various materials suggest the
possibility of common sources for these states. In fact, if the details of the bandstruc-
ture are considered with respect to the trap levels, the dominant electron states appear
at a fixed energy position for all compositions, independent of the conduction band-
edge. This is clear from Fig. 9 where the energy levels of the dominant electron traps
as detected by DLTS (using identical filling pulse conditions to avoid ambiguity in
data interpretation due to band filling) are plotted within the relaxed GeSi bandgap as
a function of composition. Note that for x < 0.85, the conduction bandedge is es-
sentially flat and the dominant E(0.37), E(0.50) and E(0.63) levels (squares, circles
and triangles in the figure) in the 30% Ge layers have essentially the same activation
energies for PD-Si, 15% and 73% Ge (note that the E(0.63) trap was not detected for
the 15% and 73% samples but has been observed in PD-Si). For pure relaxed Ge, the
conduction bandedge is lowered by approximately 0.1 eV with respect to Si, and as
seen the E(0.42) and E(0.28) traps now fairly coincide in energy with the E(0.50)
and E(0.37) traps for the lower Ge content samples. Such a decrease in the thermal ac-
tivation energies of these traps as the conduction bandedge is reduced with increasing
Ge content is consistent with a vacuum-level reference model that has been suggested
for deep traps within a variety of semiconductors, in the absence of lattice relaxation
effects (Caldas et al., 1984; Neuhalfen and Wessels, 1992; Langer and Heinrich, 1985;
Ledebo and Ridley, 1982).
Of course to make such a correlation for deep levels detected at various composi-
tions implies that each correlated level is due to the same physical source. While this
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 307

TABLEI. Summary of electron traps reported in GeSi materials to date

Ge mol Energy level E ( x x )
fraction ( x ) (xx = E, - E r ) Comments Reference(s)
0.0340.08* E(0.484.50) Series of thick, low Ge content layers;
C1-based CVD; concentration (Nagesh et al., 1990a, b)
increases with anneal-process related
0.149* E(0.5 1) Same as previous; process-related (Ibid.)

0.15* E(0.07) UHCVCD (Gnillot e f al., 1996c)

E(0.37) UHVCVD; dislocation core state (Ibid.)
E(0.51) C1-based CVD growth (Nagesh e f al., 1990a, b)
0.30 E(0.07) UHVCVD (Grillot ef al., 1996b, c)
E(0.20) UHVCVD; point defect complex (Ringel and Grillot, 1997:
Grillot ef al., 1996b)
E(0.37) UHVCVD; dislocation core state (kink site) (Grillot er al., 1996b,c)
E(0.50-0.51) UHVCVD; point defect complex (Ringel and Grillot, 1997;
Grillot etal., 1996b)
E(0.63) p-type;RTCVD; minority carrier trap (Grillot ef al., 1995a, b)
0.73 E(0.51-0.52) UHVCVD (Grillot er al., 1995~)
1.00 E(0.28) UHVCVD; probable dislocation core state (Ibid.)
E(0.42) UHVCVD (Ibid.)
*Denotes constant composition GeSi layers grown directly onto Si, without a graded buffer. Electron traps
closely match IeveIs found in both PD-Si (for x c 0.73) and PD-Ge (for the pure Ge layer) as discussed
in the text. All are majority carrier traps unless specified. Comments are from individual references. Trap
concentrationscan be found in individual references.

4.5
E,

0 0.25 0.50 0.75 1.00

Ge mole fractlon, x

FIG.9. Position of dominant electron traps within the GeSi bandgap as a function of alloy composition
in relaxed material as measured by DLTS. The data for 0% Ge (PD-Si) are from (Kimmerling and Patel,
1979; Kimmerling er al., 1981). The values for the electron traps in the 100% Ge layer match those reported
for bulk PD-Ge in (Baumann and Schroter, 1983; Broniatowski, 1983). The different symbols correspond to
specific trap levels. Reprinted with permission from Ringel and Grillot (1997).
308 STEVENA. RINGELAND PATRICK
N. GRILLOT

has not yet been proven, some convincing evidence supporting this notion is provided
by comparing the electron traps detected in PD-Si, for which a significant amount of
analysis as to their physical origin has occurred, with the electron traps detected in the
30% Ge samples. For PD-Si, electron traps displaying the logarithmic capture kinetics
indicative of an extended defect source were detected at E(0.37-0.38), E(0.48-0.51)
and E(0.60 - 0.63), all of which are close in energy to the dominant electron traps in
Geo.3oSi0.70, noting that the conduction band offset between these compositions is less
than 0.02 eV (People, 1986). The detailed Arrhenius behavior of these electron traps
in these two materials is compared in Fig. 10. Such detailed Arrhenius analysis is often
used as a means of verifying the common origin of deep levels in different crystals,
as the Arrhenius behavior of a given trap results from a unique combination of appar-
ent capture cross section and activation energy. A common origin for these E(0.37),
E(0.50), and E(0.63) traps in Geo.3oSi0.70 and bulk Si is indeed implied due to the
nearly identical Arrhenius behavior observed for saturating fill pulse times >_ 1 ms.
These results suggest that a quantitative relationship exists between strain relaxation
induced deep levels in Geo.3oSio.7o/Si and plastic deformation induced deep levels in
bulk PD-Si. The Arrhenius results have significant implications regarding these deep
levels in GeSi alloys, as they allow one to correlate results on GeSi/Si heterostruc-
tures to the extensive literature on bulk PD-Si. In particular, the E(0.37-0.38) state
in PD Si has been attributed to the theoretically predicted dislocation kink site state at
Ec - 0.4 eV (Kmerling eb al., 1981). From the forementioned Arrhenius compari-
son, the E(0.37) state in the Geo.3oSio,7ofSisamples is also most likely associated with
electron capture at the dislocation kink sites in the relaxed alloy layers. Moreover, the

40 45 50 55 60 65
l/kT (eV")

FIG. 10. Comparison of Arrhenius behavior of electron traps near E(0.37), E(0.50) and E(0.63) in
relaxed UHVCVD-grown Ge0.30Si0.70 layers and bulk PD-Si. The solid lines are a best fit to the GeSi data
while the dashed lines and the d a s h & lines are taken wirh permission from Kimerling and Pate1 (1985)
and Kveder et a!.,(1982), respectively.
 PROPERTIES AND DEEPLEVELS
6 ELECTRONIC 309

connection of this level to the E(0.28) trap in the relaxed Ge layer, coupled with the
correlation of this state with the E(0.29) state in PD-Ge imply that this lunk core state
is present in the entire GeSi alloy system. Origins for the E(0.50) and E(0.63) traps
are less clear, although they have been found to be thermally unstable in both GeSi and
PD-Si and hence are not pure dislocation states. While they cannot be ruled out with-
out more detailed studies, extrinsic sources for these states do not appear likely due
to their presence in materials prepared by different growth techniques (bulk Cz crys-
tal growth, UHVCVD, RTCVD, C1-based CVD) and in materials deformed by vastly
different methods (heteroepitaxy,bulk deformation by bending, twisting, compression,
tension, etc.). Instead, detailed work in PD-Si has identified the thermally unstable
E(0.50) and E(0.63) levels as being related to point defect clusters that form as a con-
sequence of dislocation motion and interaction, and that these clusters are likely to be
influenced by their association with a dislocation core or strain fields (Kimerling and
Patel, 1979; Kimerling et al., 1981; Kisielowski-Kemmerich et al., 1985). The similar
annealing behavior and Arrhenius results described here support a similar conclusion
for the GeSi alloys.

3. HOLETRAPSIN Ge,Sil-, FROM x = 0 - 1

Compared to electron traps, far more work has been documented with regard to hole
traps and their effects on GeSi properties. Hole traps have been detected and analyzed
by DLTS and other techniques in GeSi materials grown by UHVCVD, RTCVD, and
MBE. Various levels have been attributed to dislocations in addition to intrinsic and
extrinsic point defect sources, and these have been found to have a major impact on
the bulk GeSi electrical properties, which is the subject of the next section. Similar to
electron traps, the presence of hole traps is highly dependent upon growth temperature
and other conditions and there is a strong correlation between the GeSi results with
bulk PD-Si (Ringel and Grillot, 1997; Kimerling and Patel, 1985). Prior to discussing
the impact of growth and processing conditions on the hole trapping spectrum how-
ever, the various hole traps detected in Ge,Sil-, alloys are considered and compiled.
Figure 11 shows hole trap spectra obtained by DLTS under minority carrier injection
conditions for the same UHVCVD layers used to reveal the electron trapping spectra
of Fig. 7 (Grillot et al., 1996). For these high temperature-grown layers, one minority
carrier hole trap is detected, at concentration in the 10'2cm-3 range or lower for each
composition. Note that the hole trap energy decreases systematically with increasing
Ge mole fraction. Just as in the case for the electron traps, the decrease in activation
energy with increasing Ge content is accounted for by the change in the relevant band-
edge, which in this case is the increasing valence band energy with increasing Ge con-
tent. Other than this systematic study of compositional dependence, all other reports
of hole traps considered GeSi samples having a Ge content of 30% or less. The first
report of hole traps in any type of GeSi layer (Soufi et al., 1992; Bremond et al.,
310 STEVEN A. RINGELAND PATRICK N. GRILLOT

100 150 200 250 300

Temperature(K)

FIG. 1 1. Minority canier hole trap spectra for UHVCVD-grownGeSi layers having the compositions
indicated. All layers were grown at high temperature (either 850 or 9OOOC). Reprinted with permission from
Grillot et al. (1996).

1992) revealed a midgap trap at H(0.51), and a trap at H(0.38) for RTCVD-grown
GeSi layers containing Ge up to a 20% mol fraction. These structures consisted of a
single heterostructure with no graded buffer layer which, while not optimum from the
viewpoint of dislocation reduction, did allow for the unambiguous characterization of
a single interface. By performing depth-resolved measurements in these relaxed layers
and through the interface region, the midgap H (0.51) trap was associated with misfit
dislocations at the GeSi/Si interface whereas the H(0.38) level was proposed to be
associated with the associated 60" threading segment. The trap spectra are shown in
Fig. 12. Neither of these levels was detected in strained GeSi layers that were grown for
comparison and the association of the H(0.38) state with threading dislocations is con-
sistent with the H(0.34) defect band previously assigned to 60" dislocations in p-type
PD-Si (Pate1and Kimerling, 1979). Later work on p-type RTCVD Geo.3oSio.70,which
did include a graded composition buffer supports these assignments,where 2-hole traps
of similar activation energies were detected (Grillot et al., 1995a). Moreover, depth-
resolved DLTS measurements were correlated with depth-resolved plan-view EBIC
contrast, indicating the connection between these 2-hole traps and dislocations. Each of
these levels exhibited the logarithmic capture kinetics expected for dislocation-related
deep levels.
Hole traps were also observed in MBE-grown GeSi heterostructures. One DLTS
study of metastable strained Si/Ge, Sil -,IS heterostructures for Ge contents ranging
up to 20% indicated the presence of a broadened distribution of deep levels in the vicin-
ity of the H (0.51) and H (0.38) levels, in addition to a distribution of shallow hole traps
(Brighten et al., 1994). The effects of a local repulsive potential and distributions of
deep levels on DLTS spectra were considered using a Gaussian modeling routine from
which it was shown that distorted peak broadening observed for these traps resulted
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 311

FIG. 12. The DLTS spectra of relaxed, RTCVD-grown 15% GeSi/Si single heterostructures showing
hole traps associated with interface misfit dislocations H(0.51) and threading dislocations H(0.38). Spec-
trum a was obtained for a 290-nm thick 15%GeSi/Si single heterostructure in which both the interface and
relaxed GeSi layer were probed. Spectrum b was obtained from a 500-nmthick GeSi/Si heterostructure in-
dicating only the presence of H(0.38) and spectrum c was obtained from the same sample as b in which only
the interface region revealed the H(0.51) misfit state. Reprinted with permission from Souifi et al. (1992).

from the buildup of a local repulsive potential during hole capture by defect bands.
In these films, however, Fe contamination was present, which was suggested to have
originated from the solid Ge source during MBE growth, and the detected hole traps
may be associated with Fe-decorated dislocations. In an earlier study of deep levels
present within undoped, GSMBE-grown GeSi/Si single heterostructures, shallow hole
traps were detected with activation energies less than 0.1 eV as well as a hole trap near
H(0.3-0.4) for a series of films with Ge compositions ranging from 6%-26% (Li et
al., 1993). However, the origins of these levels were not identified.
The most detailed reports of deep levels within GeSi layers have focused on p-type
Geo,3oSio,;lolayers grown by UHVCVD (Ringel and Grillot, 1997; Grillot et al., 1996b;
Mooney et al., 1997; Grillot and Ringel, 1996a; Grillot et al., 1996~).In these studies,
a primary consideration was the effect of growth andor post-growth annealing tem-
perature, as changes in these conditions have a profound effect on the presence and
concentration of deep levels. Figure 13 shows DLTS spectra obtained for relaxed, 30%
Ge layers grown in an identical fashion as shown in Fig. 8, but with the important dif-
ference that a much lower growth temperature of 650°C was used for this study. The
evolution of the spectrum with post-growth annealing is also shown. Before contin-
312 STEVENA . RINGELAND PATRICKN . GRILLOT

Temperature (K)

5
- en 50/s

,.,--.
-..
' ~ O C R T A

8M) o c RTA ------ tP=5ms

0 100 200 300

Temperature (K)

FIG. 13. The DLTS spectra for UHVCVD 30% GeSi layers on graded GeSi/Si grown at 6 S O O C with no
post-growth annealing and after annealing at the conditions shown in the figure. Fig. 13(a) includes spectra
prior to complete conductivity type reversal from p to n-type and Fig. 13(b) includes spectra after complete
reversal to n-type conductivity due to removal of shallow, acceptor-like traps. Reprinted with permission
from Grillot et al. (1996).

uing, it is important to note that this low growth temperature results in a low p-type
background conductivity, in spite of the intentional 1014cm-3 n-type Si doping within
the cap layer that was apparent in the last section for the layers grown at higher tem-
peratures. This type conversion effect, and its dependence on the DLTS spectrum, is
discussed in the next section. As seen in the figure, a number of hole traps were de-
tected in the as-grown samples, all of which are present in very low concentrations in
the l O " ~ m - ~to low 10'2cm-3 range, consistent with a threading dislocation density
in the mid 10scm-2 range for this sample. The H(0.38) and H(0.49) states, which
were earlier associated with dislocations, are weakly present in the DLTS spectrum.
The dominant feature in the DLTS spectrum of the as-grown layers are a series of
 PROPERTIES A N D D E E P LEVELS
6 ELECTRONIC 313

shallow hole traps at H(0.05), H(0.15), H(0.20) and H(0.30). These shallow hole
states are thermally unstable and are removed by rapid thermal annealing as indicated
in the figure. Indeed as these states are removed, the electron traps that were earlier
associated with the dislocation kink site, E(0.37), and E(0.50) now appear as minority
carrier traps. Annealing at yet higher temperatures was found to convert the as-grown,
p-type material to n-type due to the removal of the compensating shallow, acceptor-
like states, which is discussed later. Hence, after conversion to n-type material, the
dislocation-related electron traps are now detected as majority carrier traps, consis-
tent with UHVCVD material initially grown at a higher temperature of 850 or 9OO0C,
(discussed in the previous section). Hence from these annealing dependencies, it was
concluded that the shallow hole traps cannot be pure dislocation core states and must
consist of some type of point defect complex that anneals out at a moderately high
temperature. Figure 14 compiles the Arrhenius data for each of the traps detected in

0
I

-10’ I
0 50 100 150 200 250
1lkT (eV”)

01

E(0.50) t
I E(0.07)

\
E 0.37) (b)
0 100 200 300
Ilk1 (eV”)

FIG. 14. Summary of DLTS Arrhenius data for (a) hole traps and (b) electron traps present in UHVCVD
30% Ge layers shown in Fig. 13. Reprinted with permission from Grillot er al. (1995).
314 STEVEN A. RINGELAND PATRICK N.GRlLLOT

these UHVCVD Ge0.3oSio.~olayers for all annealing conditions, using a 5-ms. filling
pulse to ensure complete saturation has occurred.
Potential physical sources for these traps were considered in some detail by evalua-
tion of the annealing characteristics. The assignment of the thermally stable, E(0.37)
trap to kink sites along the dislocation core was supported by the observation that its
concentration saturates for annealing temperatures of 850°C and above, at a value of
2 x l O " ~ m - ~and
, matches the results in PD-Si as was discussed in more detail in the

of electrically active dislocation core sites estimated to be -

previous section. This concentration is consistent with the theoretical concentration
1 x 1011cm-3 for GeSi
layers having a threading dislocation density of 7 x 105cm-2. This estimate is obtained
by assuming that 1% of all dislocation core sites is electrically active due to substantial
core reconstruction along dislocation lines (Kimerling and Patel, 1985). While this is
only a rough estimate, the close agreement with the concentration of the E (0.37) trap
nevertheless demonstrates a correlation between the DLTS and TEIWEBIC results. In
contrast, the strong annealing dependence of the shallow trap concentration seen in
Fig. 13 demonstrates that these are not dislocation core states. However, these levels
do display the logarithmic capture kinetics, implying that these are not simple point
defects. In addition, the relatively high annealing temperatures necessary to remove
these defects would suggest that these complexes are probably associated with the dis-
location core, that is, located within the dislocation strain field.
Similar to the case for the electron traps, the hole-trap spectrum for Geo.30Sio.7o
bears a remarkable similarity to that of PD-Si. Figure 15 shows the as-grown DLTS
spectrum from Fig. 13 now replotted alongside a DLTS spectrum obtained for p-type
float zone PD-Si. As indicated in the figure, by uniformly translating the entire GeSi

0.8

0 100 200 300

Temperature (K)

FIG. 15. The DLTS spectrum of the 650OC as-grown GeSi sample of Figure 6.13(a) plotted with the
DLTS spectrum of PD-Si from Kimerling and Patel (1985). The indicated 70 K difference in temperature
corresponds to 0.12 eV, equivalent to the valence band offset between these two compositions. Reprinted
with permission from Grillot and Ringel (1996).
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 315

spectrum by 70 K, the main spectral features almost completely overlap. This tem-
perature shift translates to an energy shift of approximately 0.12 eV, equivalent to the
increase in valence band energy as one moves from Si to relaxed, 30% Ge alloys (Gril-
lot and Ringel, 1996a). This implies that the difference in the two DLTS spectra may
be entirely due to the valence band offset, and not necessarily due to the introduction
of different defect states, an interpretation that is identical to the situation for electron
traps discussed in the previous section where defects states were shown to be invariant
with respect to GeSi composition and the corresponding bandstructure. This is quanti-
fied in Table 11, where the energy level of each hole trap detected for the Geo.3oSio.70
layers are given in the left-hand column. By adding the valence band offset of 0.12 eV
to each level, the expected trap activation energy for each state in PD-Si can be calcu-
lated by this simple model and these values are listed in the second column. The third
column lists the actual measured data for PD-Si, and the close match with the theoret-
ically predicted values based on the measurements in the 30% Ge layers for each hole
trap is evident. Figure 16 summarizes the tabulated data where the smooth increase
in the valence bandedge with increasing Ge mol fraction and the resulting decrease in
the measured trap activation energies for the GeSi layer as compared with the PD-Si
is apparent from this figure. As was explained for compositionally invariant electron
traps, such a connection between corresponding hole traps in each material implies that
each correlated state has a common source.
The identification of the source, however, remains a challenge. The work on PD-Si
concluded on the basis of detailed deformation and annealing studies that the shallow
acceptor-like traps are due to intrinsic point defect complexes at the dislocation core,
probably vacancy-related, that form due to dislocation motion and interaction during
deformation at moderate temperatures (Kimerling and Patel, 1979; Kimerling et al.,
1981). These hole traps in PD-Si were also found to anneal out in a very similar

TABLE II. Comparison of hole trap energies measured in 30% Ge relaxed GeSi alloys with hole traps
measured in PD-Si
Measured hole trap in Ge0.30Si0.70 (eV) Corresponding hole trap in PD Si (eV)
Average trap energy Predicted Measured Difference
0.49 f0.02 eV 0.61 0.63 -0.02
0.43 f0.02 eV 0.55 0.56 -0.01
0.38 f 0.02 eV 0.50 0.49 0.01
0.30 f0.02 eV 0.42 0.40 0.02
0.20 f0.02 eV 0.32 0.33,0.35 -0.01,-0.03
0.15 f0.02 eV 0.27 0.26 0.01
0.065 f0.02 eV 0.17 0.21 -0.04
The predicted hole traps in PD-Si are determined by adding the 0.12 eV valence band offset to the measured
trap energy in GeSi (From Ringel and Grillot, 1997; Alexander, 1989; Kisielowski-Kernmerich et al., 1985;
Kimerling and Patel, 1985).
316 STEVEN A. RINGELAND PATRICK N . GRILLOT

0 0.2 0.4 0.6 0.8 1.0

Ge mole fraction, x

FIG. 16. Position of hole traps within the GeSi bandgap as a function of alloy composition in relaxed
material. PD-Si data is from Kimerling and Patel (1985) with permission. The different symbols refer to
specific trap levels. From Ringel and Grillot (1997).

fashion as the hole traps shown in Fig. 13. Additionally, as will be explained in the
next section, the presence of the shallow acceptor levels in both materials was observed
to cause a high degree of dopant compensation and even type conversion for lightly
doped n-type material, which was alluded to previously in this section. Hence, these
very similar observations coupled with the DLTS data of Table I1 and Fig. 16, provide
considerable support to the possibility that the sources for the hole traps in the GeSi
layer are identical to those identified in PD-Si, which were associated with intrinsic
point defect complexes formed by dislocation interactions. Note, however, that the
configurations of the various possible point defect clusters responsible for these states
are not known.
Significant dislocation interactions are certainly expected within the step-graded
GeSi structures used in this study. One possible dislocation interaction mechanism
is premised on the fact that lattice mismatch in these step-graded structures is slowly
relieved in a series of closely spaced interfaces. Hence, any misfit dislocation that is
pushed out of its ideal misfit plane may have one or more other misfit planes with which
to interact. Based on the complicated dislocation networks that are typically observed
in compositionally graded films, such dislocation repulsion events are not an uncom-
mon occurrence (LeGoues et al., 1991). In fact, from strain-relaxation kinetics, it can
be shown that these individual layers are, in general, not fully relaxed prior to growth
of the next alloy layer; the goal of compositional grading is simply to suppress disloca-
tion nucleation processes by avoiding the buildup of excessive misfit strain (Fitzgerald
et af., 1992; Tersoff, 1993; Watson et at., 1994). As these lower layers are not fully
relaxed prior to growth of the next layer, some residual strain-relaxation must occur
in these lower layers as the upper layers begin to relax. Hence, dislocations gliding
 6 ELECTRONIC
PROPERTIES A N D DEEPLEVELS 317

in the next interface plane can be “injected” downward into the previous layer in or-
der to relax the remaining strain. In so doing, misfit dislocations must cut through
orthogonal dislocations to glide down to the previous interface, and the resulting “jog
motion” of the dislocation will generate nonequilibrium concentration of intrinsic point
defects. At typical growth temperatures, these defects have sufficient energy to migrate
together and form extended complexes of point defects which, for the case of vacancy
generation, reduces the total dangling bond energy. These defect complexes can then
disperse throughout the film to reach a convenient sink, such as dislocation cores or
the sample surface. It is noted that the shallow traps shown in Fig. 13 anneal out at
temperatures that are somewhat higher than for usual point defect complexes. It is
therefore quite likely that these complexes are located at, or influenced by the dislo-
cation core, as has been suggested previously in PD-Si for dislocation-related vacancy
clusters (Ibsielowski-Kemmerich et al., 1985).
The annealing dependence of the shallow acceptor-like levels demonstrates their as-
sociation with point defect clusters that are probably situated near or within the disloca-
tion core region. But neither the exact configuration nor the identity of the constituent
defects is known. In the preceding scenario, the defects are assumed to be intrinsic
based on the correlation with the PD-Si results. However, extrinsic constituents can
certainly play a role, particularly for low trap concentrations where even trace amounts
become important. Indeed in a later study, shallow hole traps were also reported in
UHVCVD Geo.30Sio.70 layers that were grown at even lower temperatures of 500°C
and 560°C (Mooney et al., 1997). In that work, two shallow hole traps at H(0.06) and
H(0.14) were detected, consistent with two of the hole traps shown in Fig. 13, and
were found to be even more dominant as they are present at concentrations approach-
ing the mid 10’4cm-3 range. Deeper hole traps were also observed, although their
exact energy levels were not reported. However, these deeper states exhibited DLTS
signatures similar to the dislocation-related H(0.49-0.5 1) and H(0.38) levels already
discussed here, and the concentrations of these traps were reported to be 1&20% of the
shallow trap concentration, that is, in the 10i3cm-3 range. The overall higher trap con-
centration is consistent with the higher threading dislocation density of 2-4x 107cm-2
in these samples as compared with the UHVCVD layers discussed above, indicating
the correlation of the trap spectrum with the presence of threading dislocations. These
two shallow acceptor-like states were found to anneal out and displayed logarithmic
capture kinetics, similar to the study cited here. However, the concentrations of the
H(0.06) and H(0.14) states were also found to correlate with the oxygen content in
these films. Based on this correlation, it was concluded that the point defect complexes
giving rise to these states are likely to contain oxygen impurities and are located at
dislocation cores.
Table 111 summarizes the hole traps detected by DLTS in GeSi materials to date.
Similar to the case for electron traps, there is a general consistency in the hole traps
detected in the variously grown and processed materials, and the differences in trap
activation energies as a function alloy composition tend to track the change in va-
318 STEVEN A. RINGELAND PATRICK N. GRILLOT

TABLEIII. Summary of hole traps reported in GeSi to date

Ge mol Energy level E ( x x )
fraction ( x ) ( x x = ET - E , ) Comments Reference(s)
0.15 H(0.38) RTCVD; single heterostructure; (Soufi et al., 1992;
associated with threading Bremond et al., 1992)
dislocations
H(0.51) RTCVD; single heterostructure; (Ibid.)
associated with misfit dislocations
0.03.0.12.0.20 broad 99% strained GeSi; MBE; (Brighten et al., 1994)
distribution Fe contamination
0.14 H(0.029) GSMBE single heterostructure (Li et al., 1993)
H(0.065) GSMBE; single heterostructure (Ibid.)
H(0.3 14) GSMBE; single heterostructure (Ibid.)
0.19,0.20 H(0.041) GSMBE; single heterostructure (Bid.)
H(0.2) GSMBE; single heterostructure (Ibid.)
H(0.261) GSMBE; single heterostructure; (lbid.)
Possible impurity-vacancy complex
H(0.45) Gas-source MBE; (Ibid.)
single heterostructure;
Possible impurity-vacancy complex
0.274.32 H(0.05)* UHVCVD; thermally unstable (Grillot et al., 1996b;
Grillot and Ringel, 1996a)
H(0.06)** UHVCVD; thermally unstable (Mooney et al., 1997)
H(0.14)** UHVCVD; thermally unstable (Ibid.)
H(O.15)* UHVCVD; thermally unstable (Grillot et al., 1996b;
Grillot and Ringel, 1996a)
H(0.17)** UHVCVD (Mooney et al., 1997)
H(0.20)* UHVCVD; thermally unstable (Grillot et al., 1996b;
Grillot and Ringel, 1996a)
H(0.30)* UHVCVD; thermally unstable (Bid.)
H(0.38)* RTCVD; UHVCVD; (Grillot et al., 1994, 1995a, 1996b;
thermally unstable Grillot and Ringel, 1996a)
H(0.43) RTCVD; UHVCVD, (Grillotet al., 1995a; Grillot, 1996;
minority carrier trap Grillot et al., 1996c)
H(0.494.5 1)* UHVCVD; thermally unstable (Grillot et al., 1996b;
Grillot and Ringel, 1996a)
H(0.63) UHVCVD; minority carrier trap; (Grillot and Ringel, 1996a)
thermally stable;
possible dislocation core state
0.73 H(0.30) UHVCVD; minority carrier trap (Grillot er al., 1996c)
1.oo H(0.18) UHVCVD growth (Ibid.)
minority carrier trap
*Associated with point defect complexes at dislocations formed by dislocation interactions (Ringel and Gril-
lot, 1997; Grillot et d., 1996b; Grillot and Ringel, 1996a).
**Associated with oxygen-containing point defect complexes at dislocations (Mooney et al., 1997).
All hole traps are majority carrier traps unless specified. Comments are derived from individual references.
Trap concentrations can be found in individual references.
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 319

lence band energy. It remains of interest to determine unambiguously the origin of

the shallow hole traps, especially as just discussed, in light of their strong dependence
of growth and anneal temperature, and due to their significant impact on the overall
electronic properties of the GeSi layers as a whole (to be presented in what follows).

111. Influence of Defects on Electrical Properties of Ge,Sil-, Alloys

High defect concentrations will of course degrade semiconductor quality, and dislo-
cation density must be kept to a minimum in relaxed GeSi layers for any viable device
technology. Therefore this section focuses both on measurements of electrical prop-
erties of high structural quality, relaxed GeSi layers, that is, those with dislocation
densities in the 10scm-2 to 107cm-2 range, and how these properties are influenced
by any remaining deep levels. Properties are found to correlate with the presence of
specific deep levels as outlined in the previous sections.

1. DOPINGCOMPENSATION IN RELAXEDGe,Sil-, LAYERS

Intentional doping of GeSi layers as well as the ability to achieve regions of very
low background doping concentration are important because they establish a baseline
for implementation of device designs. Achieving extremely low background doping
within the carrier channel region of GeSi/Si MODFETs are of particular importance
for highest mobilities (to be discussed). Thus, growth issues that affect the ability to re-
produce controlled doping concentration must be understood. For instance, it has been
found that growth temperature and/or post-growth annealing of relaxed GeSi layers
grown on graded buffers have a major impact on the background doping concentra-
tion and conductivity type (Grillot et al., 1996b). This is apparent from Fig. 17, which
shows spreading resistance profiles obtained for two, identically grown Gq.30Sio.70
layers grown on a 10% Ge/pm graded buffer on n+Si with the only difference being
that one sample received a 5 min, 900°C anneal in vacuum after growth. The growth
temperature in both cases was 650°C. For each sample, the constant composition cap
layer consisted of a thin, p + emitter grown on a lightly (mid 10'4cm-3) Si-doped base
and the same Si doping was used throughout the buffer region. As seen in the figure, in
spite of the intentional Si doping, the background conductivity of the as-grown film is
actually p-type, with a nearly constant hole concentration of 1014cm-3being measured
below the p+ contact layer down to a position well within the graded layer. Below this
point the film becomes n-type down to the n+Si wafer. This unexpected type conver-

-
sion in the upper part of the structure was consistently observed for structures grown
at temperatures less than 800 "C using graded buffers, unless significantly higher Si
doping concentrations were used. Figure 17 shows that after annealing, the layer con-
ductivity reverts to the desired n-type conductivity, although for the profile shown, the
320 STEVENA. RINGELAND PATRICK
N. GRILLOT

1 I_

.r cap I graded region

-g lo'*
t it
f 10'~
0hole concentration
electron concentration
-as-grown
--_-__- annealed

I"

0 4 8 12
Sample depth, z (microns)

FIG. 17. Spreading resistance profiles for a 650°C-grown Ge0,30Si0,70/gradedGeSi/Si sample prior to
and after a 900°C rapid thermal anneal. Reprinted with permission from Gnllot et al. (1 995).

concentration is still lower than expected. Homoepitaxial Si layers were grown under
the same conditions in the same UHVCVD reactor, and the expected n-type concen-
tration in the mid-10'4cm-3 range was measured indicating that the source of the type
conversion is a characteristic of the GeSi structure. These layers were found to revert
to the expected n-type conductivity after either conventional or rapid thermal anneal-
ing at temperatures above 800 "C for the structures grown at 650 "C. In addition, layers
that were initially grown at 850°C or above did not display the unexpected p-type con-
ductivity. From these observations, an obvious possible cause for the observed p-type
conductivity in as-grown layers is donor compensation by acceptor-like states.
This was confirmed by additional electrical measurements. Figure 18 shows the
zero bias capacitance of the Geo.3oSio.70 diodes as a function of measurement tem-
perature for an as-grown 650°C diode and after various anneals. The capacitance of
the as-grown and low temperature annealed samples display considerable temperature
dependence with large shoulders present, which is indicative of the participation and
freeze-out of electrically active deep states. This dependence is flattened out by an-
nealing at higher temperatures as shown, indicating the removal of these states with
increasing annealing temperature. Note that this temperature dependence of both the
type conversion and the C-T scans precisely matches the annealing behavior of the
series of shallow hole traps described in the previous section and shown in Fig. 13.
The behavior of these hole traps as acceptor-like levels that control the background
conductivity was confirmed by resistivity measurements. The results obtained using a
Van der Pauw contact arrangement are shown in Fig. 19. Arrhenius analysis indicates
that an acceptor level with an activation energy of 0.05 eV controls the conductivity
for temperatures below approximately 250 K, which gives way to a deeper level with
an activation energy of approximately 0.3 eV for temperatures near 300 K and above.
Note that these both match the H(0.05) and H(0.30) hole traps detected in Fig. 13,
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 32 1

ig 200

100
as-grown and

750 'C RTA

1
' C RTA
a

0 1
0 100 200 300
Temperature (K)

FIG. 18. Zero bias capacitance-temperature data for the Gq.30Si0.70/graded GeSi/Si structures that
were post-growth processed at the annealing conditions indicated in the figure. The temperature dependence
for the as-grown and 700°C annealed structures indicates the participation of deep states for these samples.
Reprinted with permission from Grillot er al. (1995).

which is a good indication that these states dictate the background resistivity and cause
the observed type conversion. In fact, by considering the Fermi level position for the
-
background hole concentration of 2 x 10'4cm-3, which is calculated to be 0.25 eV
above the valence band for Ge0.30Si0.70, any level significantly above E , 0.25 eV +
would have insignificant electron occupation in equilibrium, and such a level could

36.5

36.0

---
35.5
Q
E

35.0

34.5

34.0
40 50 60
l/kT (eV-')

FIG. 19. Temperature-dependent resistivity measurement of a 650'C-grown Ge0.30Si0.70/graded

GeSi/Si structure prior to annealing indicating the presence of acceptor-likedefects at H(0.30) and H((0.05)
that dictate sample conductivity.
322 STEVEN A. RINGELAND PATRICK N. GRILLOT

lOOr

- 90,
s
*El- 8o

8 70

8
d 6o

50,

Temuerature MI

FIG. 20. Temperature-dependent hole mobility obtained from the 650°C-grown Gq,30Si0,70/graded
GeSi/Si structure prior to annealing. The solid line fit indicates a T-'.69 dependence above 250 K.

not be responsible for compensation of the Si donors. This Fermi level argument is
consistent with the DLTS, C-T and resistivity measurements that imply one or more of
the shallow hole states are responsible for the type conversion. Further evidence for
the specific dominance of the H(0.05) and H(0.30) traps is revealed by comparing the
inflection point temperatures of the C-T scan with the DLTS peak positions, as DLTS
signals can be qualitatively interpreted as the derivative of the C-T signal. As seen, the
inflection temperatures from the C-T scan near 50 K and 130 K for the as-grown sample
correspond roughly to the locations of the H(0.05) and H(0.30) levels of Fig. 13.
A good indicator of the impact of defects on material quality is carrier mobility.
Figure 20 shows the temperature dependent hole mobility of the as-grown, relaxed
Geo.3oSio.70 layer. The low room temperature hole mobility of 60 cm2/V-s (carrier
density of 2 x 1014cm-3)suggests a defect scattering mechanism. Fitting to the temper-
ature dependence indicates that mobility varies as T-1.69 over the fitted region shown,
which indicates that phonon scattering does not exclusively dominate mobility up to
at least 320 K. More details on carrier transport properties is discussed later in this
chapter.

2 . CARRIER GENERATION-RECOMBINATION
IN RELAXED
Ge,Sil-, LAYERS

Generation-recombination currents are present within defective diodes, and these

can be expected to be problematic for any relaxed GeSi diodes due to the presence
of even relatively low densities of threading dislocations that cause junction leakage
and device degradation. For instance, in the case of GeSi HBTs, inadvertent relaxation
of the strained GeSi base has been found to contribute generation-recombination cur-
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 323

:0.50 ev

I
Pure Oe. E- I0.63 eV

-2
25
15% Ge, E, g0.51 eV
30 35
1
40
1lkT rev')
FIG. 2 1. Arrhenius plot of the reverse current measured at a constant reverse bias of 1 V as a function
of temperature for various relaxed, constant composition GeSi diodes grown on graded buffers on Si by
UHVCVD. The activation energies of the dominant generation center for each composition is indicated.
Reprinted with permission from Grillot et al. (1996).

rents at the base-emitter and base-collector junctions within the HBT structure (King
et al., 1989). In this section, the generation-recombination behavior of low dislocation
density, relaxed GeSi diodes are described.
Figure 21 shows the dependence of the reverse bias current, measured for a fixed re-
verse voltage of 1 v, against temperature, obtained for a series of UHVCVD-grown
GeSi p+n diodes of a range of alloy compositions grown on 10% Ge/pm graded
buffers (Grillot et al., 1996~). All layers were almost completely relaxed and the
threading dislocation density ranged from the low 1@cm-2 range for layers with Ge
contents of 15-30% to the mid 106cm-2 range for relaxed, 100% Ge diode layers. A
growth temperature of 850-900 "C was used for these samples in order to avoid the type
conversion problem and the presence of shallow acceptor traps as already discussed
here, so that the base doping in each case was n-type in the low 1 0 ' 4 ~ m -range.
~ Ar-
rhenius analysis of this I-V/T data yields a nearly constant activation energy of 0.50 eV
for all compositions with x 5 0.73. This result is consistent with the DLTS results
presented earlier where a dominant midgap trap was detected for GeSi layers grown by
a wide variety of growth methods under various conditions with an activation energy
at midgap. These I-V/T results demonstrate that the midgap level is present in all films
with x I0.73, and that this level is a much more efficient recombination-generation
center than the various other deep levels in these materials, including theE(0.37) dis-
location kink site level, for these low dislocation density layers. This is consistent with
the work of Ross et al. (1993) who showed that recombination-generation processes
at dislocation cores cannot explain the large leakage current observed during disloca-
tion introduction and that other sources, perhaps associated with defects surrounding
dislocations, are dominant.
324 STEVEN A. RINGELAND PATRICK
N. GRILLOT

In contrast to the close agreement between DLTS and I-V/T results for x 5 0.73,
the situation is markedly different for the relaxed, heteroepitaxial Ge diodes grown on
graded GeSi/Si (Grillot ef al., 1996~).As shown in Fig. 21, a reverse current activation
energy of 0.63 eV is observed for the Ge diode, which does not match the E(0.42),
E(0.28) and H(0.18) DLTS traps reported for the Ge diode in the previous sections
but agrees quite well with the bandgap energy of Ge over the measured temperature
range. This suggests that reverse bias generation in these relaxed heteroepitaxial Ge
diodes is dominated by intrinsic, band-to-band generation, and not by decp levels in
the depletion region, which can be understood by considering the complete expression
for reverse current density given by (Sze, 1981)

where the first term represents a space charge generation component and the second
term represents the ideal Shockley diode (saturation current density) in reverse bias.
For the generation term, Ea represents the activation energy of the dominant gener-
ation center within the bandgap. For the relaxed Ge layers, the ideal diode (second
term) is dominant due to its small bandgap and enhanced intrinsic generation, whereas
for lower compositions below the Ge = 85% conduction band crossover point, space
charge generation via defects (first term) is dominant. This was confirmed by per-
forming a series of reverse I-V/T experiments as a function of reverse bias voltage on
the graded Ge/GeSi/Si structures so that as the bias is increased, the defective graded
layer, which contains progressively lower Ge content away from the surface, becomes
incorporated into the depletion region. The results are shown in Fig. 22 where for small

c
Y

4. v (0.53 ev)

2’
I -0.1 V /
(0.63 eV)
>l V (0.57 eV)

25 27 29 31 33 35
I l k 1 (eV”)

FIG. 22. Arrhenius plot of the reverse current measured as a function of temperature for a heteroepi-
taxial Ge diode grown on a graded GeSi/Si substrate, for various values of applied reverse bias. Activation
energies are in parentheses. Reprinted with permission from Grillot et al. (1996).
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 325

reverse biases that incorporate only the 100%Ge top layer within the depletion region,
an activation energy of the Ge bandgap is observed. As the bias voltage is increased,
the activation energy decreases and approaches the E(0.42) DLTS electron trap energy
observed in the high Ge content layers, which is close to midgap for x > 85% (i.e., the
constant composition cap plus the top few layers of the graded buffer), consistent with
the dominant midgap trap for low Ge content layers. This indicates that the leakage
current is dominated by generation via deep states within the depletion region for re-
verse biases in excess of 4 v. This interpretation was confirmed by considering Fig. 23,
which demonstrates a linear dependence of the square of the reverse current on reverse
bias for voltages beyond 4 V as expected for generation-dominated current according
to the first term of Eq. (12). No such voltage dependence is expected for the ideal diode
saturation current term. The physical reasons are clear from the cross-sectional TEM

-
micrograph of Fig. 24 that shows the 2pm Ge cap layer, in which the doping concentra-
tion was 5 x 1014cm-3 yielding a zero bias depletion width of l p m . As the reverse
bias increases to 1 V, the Ge layer is nearly fully depleted, and for voltages greater than
4 V, the depletion region extends well into the graded buffer. Hence, with increasing
reverse bias, regions of higher bandgap and higher defect density are simultaneously
incorporated within the depletion region, which from Eq. (12) has the dual effect of
reducing the contribution from the ideal saturation current term due to the increas-
ing bandgap, while simultaneously increasing the contribution from generation centers
through increased trap density. It is interesting to realize from this that even though the
relaxed Ge layers have a higher threading dislocation density than the low Ge content
layers due to the higher lattice mismatch, the substantial decrease in bandgap beyond
a Ge content of 85% is a more dominant current source. Thus. the constraint on the

Diode bias (4)

FIG. 23. The square of the reverse current of this figure is found to vary linearly with respect to the
applied reverse bias for voltages in excess of 4 V,indicating that deep generation centers within the depletion
region dominate the reverse current in this voltage range. Reprinted with permission from Grillot et al.
(1996).
326 A. RINGELAND PATRICK
STEVEN N. GRILLOT

FIG. 24. The TEM cross section of a relaxed, Ge/graded GeSi/Si heterostructure. The 2-hm thick Ge
cap layer has an n-type doping concentration of 5 x 10’4cm-3.

critical defect density above which defects dictate reverse leakage currents is relaxed
for Ge, and Ge layers on GeSi/Si appear more “defect-tolerant.’’ This may have im-
plications for building Ge devices such as 1.55pm infrared photodetectors directly on
Si as a simpler alternative to GeSi quantum well detectors (which involve considerably
more complexity) because somewhat higher defect densities may be tolerated.

IV. Carrier Transport Properties of Ge,Sil-,

The ability to control defect introduction and maintain high-quality interfaces in

GeSi/Si heterostructures has allowed the realization of theoretically predicted perfor-
mance enhancements over conventional Si electronics by virtue of engineering band
offset energies, strain energy, and alloy composition. The most important transport
property benefiting from these enhancements is the carrier mobility, and the demonstra-
tion of record high electron and hole mobilities in GeSi/Si heterostructures is largely
attributed to advances in epitaxial growth and defect control in lattice-mismatched sys-
tems since the late 1980s and early 1990s (Bean, 1992; Kasper and Schaffler, 1991;
Ismail et al., 1995; Fitzgerald, 1995; Kasper et al., 1994; Jain, 1994; Stoneham and
Jain, 1995; Fitzgerald et al., 1992; Fitzgerald, 1989). High mobilities have trans-
lated into the development of high-speed heterojunction bipolar transistors (HBTs),
and n-channel and p-channel GeSi/Si MODFETs. For the usual npn GeSi HBT that
utilizes a p-type pseudomorphic GeSi base, increased hole mobilities reduce the RC
time constant, which yields higher operation frequency. For MODFETs the speed of
operation is determined to a large extent by the speed at which carriers can cross from
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 327

the source to drain through a two-dimensional channel. The obvious importance of

carrier mobilities in every electronic device has therefore led to detailed considerations
of scattering mechanisms, both fundamental and otherwise, that limit carrier mobilities
so that the ultimate performance of GeSi/Si devices can be realized (Chun and Wang,
1992; Monroe et at., 1993; Krishnamurthy and Sher, 1985). Carrier scattering in GeSi
crystals can generally occur via interactions with the lattice (acoustic and nonpolar
optical phonons), neutral and ionized impurities, alloy fluctuations, and strain distribu-
tion. For twdimensional transport, interface roughness is a concern as are threading
dislocations when using relaxed GeSi buffer layers in MODFET structures. This sec-
tion provides an overview of mobility results in both bulk GeSi (relaxed and strained)
and two-dimensional carrier gases in Ge-Si and concludes with a brief overview of car-
rier lifetime and diffusion coefficients due to their importance in the operation of both
HBTs and photodiodes.

1. CARRIER MOBILITIES
IN STRAINED AND UNSTRAINED BULKGe,Sil-,

a. Bulk Hole Mobility

Bulk GeSi includes relaxed (i.e., unstrained) and strained material where transport is
three-dimensional. For relaxed GeSi, the bulk carrier mobility is isotropic, whereas the
mobility in strained GeSi has two components, one in the growth plane (the so-called
in-plane or transverse mobility), generally labeled pxx = pyyand one perpendicular
to the growth plane (i.e., in the growth direction or so-called longitudinal direction),
which is denoted as pzz.We first consider the hole mobility, which for strained layers
can be expressed in its tensor form according to

The components are shown in the diagram of Fig. 25 (an analogous expression can
be written for the electron mobility). For relaxed GeSi when no strain is present,
p x x= pyy= pzz= p p . As a starting point, it is useful to review what is known of car-
rier mobilities in bulk, relaxed GeSi alloys. To provide a reference for GeSi camer mo-
bilities, room-temperature mobility and effective mass values for bulk Si(x = 0) and
Ge(x = 1) are listed in Table IV. Complete information on the temperature and doping
dependence of mobilities in Si and Ge can be found in other publications (Landolt-
Bornstein, 1982, 1989; Klaassen, 1992a, 1992b). In contrast, very little information on
transport properties of bulk, relaxed GeSi currently exists. This is due to two factors:
(1) the dominant technological interest in pseudomorphic strained layers, and (2) the
fact that bulk GeSi crystal growth with homogeneous Ge content and uniform doping
328 A. RINGELAND PATRICKN.GRILLOT
STEVEN

FIG. 2 5 . A schematic illustration of the mobility components in a GeSi layer on Si. The terms
pcxx= wyl corresponds to the in-plane (transverse) mobility; pLzz
corresponds to perpendicular (longi-
tudinal) mobility components.

remains a significant challenge. Earlier in this chapter, Fig. 21 showed how the Hall
hole mobility varied with temperature for a p-type, relaxed 30%GeSi layer grown at
low temperature, which was found to contain a background of conductivity-controlling
shallow acceptor defects. In that case, the high-temperature mobility exponent of 1.69
indicated that factors such as alloy scattering or possible defect participation may be
important, which was also consistent with the low hole mobility reported for that sam-
ple. In a recent systematic study of transport in bulk p-type GeSi single crystals
and polycrystalline material grown by the Czochralski method, hole Hall mobilities
were measured as a function of Ge content up to 50% (Mchedlidze et al., 1995). The
temperature-dependent Hall mobility decreased as a function of increasing Ge content
for the range of compositions tested. Fitting of this data led the authors to conclude that
alloy scattering influenced the mobility even at room temperature, as the measured dis-
location densities (< 105cm-*) in these wafers were too low to influence the mobility.
However, they also noted the presence of shallow, acceptor-like levels that controlled
the undoped conductivity of these bulk crystals, whose concentration increased with

TABLEIV. Electron ( b e and

) hole ( L L ~ drift
) mobilities for intrinsic, bulk Ge and Si at 300 K along with
effective mass data
Ile Ilh
(cm*/V-s) (cm2/ V-s) mt * /mo m l * /mo mhh * /mo mih * /m o ~ $ * 0/m o

Ge 3900 1800 0.082 1.59 0.284 0.044 0.095

Si 1450 505 0.191 0.916 0.537 0.153 0.234
The terms mt*,mi*,mhh*, mlh* and m,,* refer to the transverse electron, longitudinal electron, heavy
hole, light hole and split off effective masses, respectively, and mg is the free electron rest mass (Landolt-
Bfirnstein, 19821989).
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 329

Ge content and probably appeared as a consequence of cooling the CZ GeSi crystal af-
ter growth. The presence of these additional defects is consistent with the discussion of
acceptor-like point defect complexes in relaxed, heteroepitaxial GeSi layers grown at
low temperatures (discussed earlier in this chapter). It is quite possible then that point
defects may have limited the mobility in these samples. The trends observed in this re-
cent study of bulk crystals agree with the very early experimental transport studies that
were done on polycrystalline bulk GeSi material where the Hall mobility was not only
found to degrade strongly as a function of Ge composition up to a mol fraction of 30%
for both n and p-type material, but exhibited a general U-shaped mobility dependence
on alloy composition where the mobility increases for Ge concentrations in excess of
80% (Levitas, 1955; von Busch and Vogt, 1960; Braunstein, 1963). However, neither
the absolute values for the measured mobilities nor the dependence on alloy compo-
sition for these early measurements agree with theoretical calculations that predict an
expected increase in hole mobility for GeSi as compared to Si due to the lower ef-
fective hole mass and lifting of the heavy and light hole band degeneracy (Takeda et
al., 1983; Manku and Nathan, 1991). The disagreement between early experiments
and theory has been variously attributed to alloy scattering, grain boundary scattering
as well as scattering via other uncontrolled defects present in these relaxed, polycrys-
talline materials (Schaffler, 1995). The possible role of point defects is supported by
a recent report in which the hole mobility was found to increase as growth tempera-
ture increases, implying a point defect annealing process may be present (Smith et aZ.,
1991).
Similar discrepancies between experiment and theory exist for bulk hole mobility
in strained GeSi layers, where theoretical work has argued that the large reduction in
the hole effective mass due to both increasing Ge content and strain should increase
mobility with increasing Ge composition (Chun and Wang, 1992). In fact, based on
Monte Car10 calculations it was predicted that the bulk hole mobility within strained
GeSi layers should reach the bulk Ge value at a composition of only 40% Ge within
the strained alloy (Hinckley and Singh, 1990). However, much like the case for relaxed
alloys, significant differences exist when theory is compared with early experiments,
indicating that more work needs to be done on high-quality materials having a wide va-
riety of compositions with varying amounts of strain to reconcile these differences. For
instance, Manku et al. (1992) first calculated the doping dependent hole drift mobility
values over a limited composition range based on a measurement of sheet resistance
from the SiGe base of a single HBT. From this single data point, they predicted that
a monotonic decrease in the hole drift mobility as a function of Ge content could be
expected as the Ge content in the base was increased from 0% to 10% over a wide
doping range. However, this result is contradicted by a later, but far more systematic
experimental study by the same group using a similar approach to extract hole drift mo-
bility but now using sheet resistance measurements made on a statistically much wide
range of HBTs with Ge content ranging from 0% to 30% (Manku et al., 1993). In that
work a monotonic increase of the in-plane hole drift mobility for low Ge content lay-
330 STEVEN A. RINGELAND PATRICK N. GRILLOT

ers as compared with Si was measured, for a doping concentration of 2 x 10'9cm-3,

which now agrees with the theoretically predicted trend. In general, the higher hole
drift mobility in these strained layers has been attributed mainly to the reduced hole
effective mass as a result of strain-induced compression of the valence band, which is
now consistent with the earlier models. Moreover, as the compression is anisotropic,
the in-plane mobility component was found to be larger than the component in the
growth direction, although both directional mobilities are increased with respect to re-
laxed alloy layers (Chun and Wang, 1992; Manku et al., 1993). An increase in hole
drift mobility was also predicted and experimentally observed for relaxed layers, al-
though the enhancement over Si was less than in the strained layer case because there
is no strain-induced change in the valence band for the former. These general conclu-
sions can be summarized by Fig. 26, which shows the dependence of the directional
mobilities of strained GeSi layers on doping concentration for a range of alloy com-
positions at room temperature. Also included are the calculated and measured bulk Si
and Ge mobility data of Chun and Wang (1992) and references therein, from which
the mobility enhancement of the GeSi layers are clear. Similar mobility dependencies
were calculated by Manku et a/. (1993) using a different approach to calculate the drift
mobility with both approaches leading to the conclusion that at room temperature, alloy
scattering does not appear to limit the hole drift mobility in GeSi and phonon scattering
is dominant [although alloy scattering can be expected to become important at lower
temperatures (Chun and Wang, 1992)l. This however, contradicts other studies where
alloy scattering was proposed as the dominant scattering mechanism (Venkataraman et
a/., 1993; Li eta/., 1993) as well as the early measurements on polycrystalline bulk
material (Levitas, 1995) for which the low mobilities were attributed to alloy disorder
(although grain boundary scattering clouds quantitative conclusions from those mate-
rials).
Some of the early discrepancies may also be related to the different methods used to
extract experimental mobility values as most measurements made on bulk crystals were
by the Hall technique, whereas most theoretical calculations as well as measurements
on HBTs are concerned with the in-plane drift mobility. The differences between Hall
and drift mobility have recently been considered by a few groups. McGregor et al.
(1993) reported that for heavily doped p-type, strained GeSi, the measured hole Hall
mobility decreases with increasing Ge mol fraction up to 20%, whereas the measured
drift mobility (derived from sheet resistance measurements) increases over the same
compositional range. Thus the Hall scattering factor given by w(Hall)/w(drift) is not a
constant for GeSi and decreases strongly with increasing Ge content. For strained lay-
ers, the Hall scattering factor was found to reduce from around 0.7-0.8 for GeSi layers
with less than 10% Ge down to 0.3-0.4 for Ge contents near 25%. This discrepancy
was also reported and analyzed in detail in a more recent work by Carns et a/. (1994),
where the same divergent behavior for the drift and Hall mobilities was measured as
a function of Ge content over a doping range of 10'8cm-3-1020cm~3. These results
were compiled together with the experimental and theoretical mobility work of other
 6 ELECTRONIC
PROPERTIES AND DEEP LEVELS 331

Old' Id' Id' Id' lo" Id' LO'* Id'

Doping CQncentratlan (cm-')

FIG.26. Room temperature hole mobility of strained GeSi grown on (001) Si as a function of carrier
concentration for (a) the in-plane component and (b) the perpendicular component. Also shown in (c) are
the bulk unstrained hole mobilities for Ge and Si (and references therein). Reprinted with permission from
Chun and Wang ( 1992).

groups and it was found that the compiled room temperature, in-plane hole drift mo-
bility could be reasonably well fitted by the usual empirical doping dependence for Si
mobility given by (Arora et al., 1982)

where a = 0.90, Pref = 2.35 x 10'7cm-3 (assumed to be the same as bulk Si for this
composition range), and p p is the in-plane hole drift mobility. The terms Vfin and /IO
depend on Ge mol fraction ( x ) and are expressed as (Carnes et al., 1994)
332 STEVEN A. RINGELA N D PATRICK N . GRILLOT

vmin +
= 44 - 2 0 ~ 8 5 0 ~ ~
po = 400 + 29x + 4 1 3 7 ~ ~
While the scatter in the actual data is large due in part to the difficulty in obtaining ac-
curate drift mobility measurements, this nevertheless provides a means to estimate the
in-plane hole drift mobility behavior in p-type strained GeSi that is confirmed exper-
imentally and follows the theoretically predicted characteristics. However, compared
to theoretical values, the experimental drift mobility values are still somewhat low, and
this may be due to uncertainty in determining the exact alloy scattering potential as
well as the lack of consideration of heavy doping effects in the theoretical calculations.
The dependence of the room-temperature hole Hall mobility on doping and Ge mol
fraction up to 20% was compiled in a similar fashion. For Hall measurements there is
considerably less measurement uncertainty compared to drift mobility measurements
and Carns et al. (1994) obtained fits to Eq. (13) with Vmin and po now given by

urnin = 37 - 6 1 ~
go = 440 - 6 3 2 ~

In this case, p p in Eq. (14) is the hole Hall mobility. From the drift and Hall mobility
results, the strong decrease in the Hall scattering factor rh as Ge content increases is
apparent within the GeSi composition range (0-2.5% Ge) considered. However, the
fundamental reason for this decrease in rh is not yet clear but may be a consequence of
strain-induced changes in the valence band structure and density of states, which may
have different effects on Hall and drift mobilities. More accurate determination of the
valence bandstructure and factors affecting the scattering times as a function of both
GeSi composition and strain are needed for full understanding of the hole mobility
behavior.

b. Bulk Electron Mobility

Compared with the hole mobility, somewhat less work has been done on electron
transport in relaxed or strained bulk GeSi due largely to the significant valence band
offset and negligible conduction band offset for compressively strained GeSi layers
grown on Si that has made p-type GeSi the material of choice for the GeSi HBT
structures. The most obvious effect of GeSi composition on the electron mobility for
unstrained alloys is due to the crossover from Si-like conduction bandstructure with
6 equivalent minima near the X-point to a Ge-like conduction with eight equivalent
L-point minima for alloy compositions above 85% Ge (Braunstein et al., 19.58). For
strained layers, however, the alloy may remain Si-like up to 100%Ge (Van de Walle and
Martin, 1986). The major effect of the bandstructure crossover, which is qualitatively
supported by experimental data, is the lower electron mobility for compositions below
85% Ge compared with alloys of higher Ge compositions due to the sharp increase
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 333

in the electron effective mass as the dominant conduction bandedge becomes Si-like.
However, within the Si-like bandstructure range itself, that is, below 85% Ge, the trend
is less clear. For compositions ranging from 0% to 30% Ge, Monte Carlo simulations
(Hinckley et al., 1989; Pejcinovic et al., 1989; Kay and Wang, 1991) and analytical cal-
culations (Manku and Nathan, 1992) all indicate a gradual decrease in the bulk electron
mobility with increasing Ge content relative to Si for relaxed alloys, which results from
the increase in alloy scattering. For strained layers a similar decrease in the in-plane
electron mobility in strained GeSi layers compared with Si was also found, while the
perpendicular mobility was enhanced (Hinckley et al., 1989; Pejcinovic et al., 1989;
Kay and Wang, 1991; Manku and Nathan, 1992). One of these studies also considered
the dependence of these trends on doping concentration, from which it was found that
the perpendicular drift mobility component for the strained layers was slightly higher
than the Si mobility only for doping concentrations in excess of 10'7cm-3 (Manku and
Nathan, 1992). For lower doping concentration, both components are reduced in com-
parison to Si and these findings are summarized in Fig. 27. Also shown are results of
Monte Carlo simulations indicating a general agreement for these trends. The reduced
mobility observed for low doping was attributed to the dominance of alloy scattering,

'si 1500t 1 , 0 0 0 1 ,

,@pq -.---

0.00 0.05aio 0.15 0.20

Ge FRACTION, x Ge FRACTION, x

FIG. 27. Calculated room temperature electron mobility components as a function of GeSi alloy com-
position for a donor concentration of (a) 10i5cm-', (b) 10'7cmp3, (c) l O ' * ~ m - and
~ (d) 10'9cm-3. The
solid lines are the unstrained bulk electron mobilities, the dot-dashed line are the perpendicular mobilities
and the dashed lines are the in-plane mobilities as calculated from (Kay and Wang, 1991). The symbols
represent the calculations of the same mobility components by Monte Carlo methods (Kay and Wang, 1991).
Reprinted with permission from Manku and Nathan (1992).
334 STEVEN A. RINGEL A N D PATRICK N. GRILLOT

whereas for higher doping impurity scattering limits mobility is relatively independent
of alloy composition. While the various models for mobility trends may differ in some
basic assumptions regarding details of the scattering mechanisms, there is a general
agreement between the various methods.

2. CARRIER TRANSPORT
TWO-DIMENSIONAL IN GeSi/Si HETEROSTRUCTURES

The utilization of modulation doping in which a SiGeISi heterojunction is used to

separate the mobile carriers from their parent dopant atoms has resulted in extremely
high two-dimensional mobilities within MODFET structures. In MODFET structures,
carriers are confined to a narrow channel defined by an appropriate heterojunction pair
and both two-dimensional electron gases (2DEG) and hole gases (2DHG) are possible,
enabling n-channel and p-channel MODFET devices, respectively, and the potential
for complementary, CMOS-like functionality. For 2DEGs, the channel is typically
within a strained Si layer with barriers consisting of relaxed GeSi, which places the Si
in tension (Abstreiter et al., 1985). For 2DHGs the channel is within a compressively
strained GeSi (or Ge) layer with either lower Ge content GeSi or possibly Si barrier
layers (Pearsall and Bean, 1986). Note that while strain is needed to develop a large
enough conduction band offset to achieve electron confinement in these structures, this
is not a necessary condition for hole confinement within the lower bandgap GeSi layer
due to the large valence band offset in GeSi/Si heterostructures, although pseudomor-
phic channels are typically employed to exploit the favorable strain-induced valence
band deformation and to minimize the presence of dislocations.
In contrast to the HBT case discussed in the previous section where bulk mobilities
are critical, MODFETs rely on the transport of charge in a two-dimensional sheet that
is confined within a narrow region of the strained layer in close proximity to a hetero-
junction. Carrier transport occurs parallel to the growth plane within quantized states
confined by the band bending within the channel and the heterointerface. Extremely
high electron and hole mobilities are made possible by the combination of both quan-
tization effects and the physical separation of the mobile carriers from their parent
dopant atoms. Figure 28 shows representative schematics of high mobility 2DEG and
2DHG structures with the 2D carrier gas regions identified. Critical to the success of
these structures are (1) extremely low defect density, relaxed buffer layers used to pro-
vide the desired lattice constant on which to commence pseudomorphic growth of the
MODFET structure, as discussed earlier in this chapter and elsewhere in this volume,
and (2) appropriate doping setback or spacer layers to control the distance between the
doping spikes and the conducting channel in order to optimize the tradeoff between
maximizing carrier transfer to the channel and minimizing ionized impurity scatter-
ing. As two-dimensional transport is in the growth plane, a critically important issue
is interface roughness, which introduces an additional scattering mechanism for these
lateral transport structures.
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 335

Si substrate Si substrate

2DEG structure 2DHG structure

FIG. 28. Representative schematics of typical 2DEG and 2DHG structures in GeSi/Si (not to scale).
The degree of shading represents the Ge mol fraction, except for the strained channels and the delta-doped
regions. Note that the 2DHG is at the bottom interface of the Ge channel. From Xie et al. (1993) with
permission.

Historically, the initial work on 2DHG structures took advantage of the favorable
valence band offset for low (30% or less) Ge content GeSi/Si heterojunctions and
consisted of psuedomorphic GeSi channels grown directly on Si, which do not require
graded buffer layers to provide additional strain adjustment (Fitzgerald, 1995). These
structures relied on both their simplicity and the expected increase in hole mobility due
to strain to achieve high-performance devices. However, as the graded, relaxed, GeSi
buffer layer technology has matured to the point where very low threading dislocation
density layers on Si became a reality, this opened the possibility of utilizing high Ge
content alloys and even pure Ge as the transport channel (with the additional advantage
of an intrinsically lower hole effective mass and in which even higher mobilities can be
expected). Measured mobilities for both types of structures are shown in Fig. 29.
For structures utilizing the low Ge content GeSi channel, while gradual improve-
ments in low-temperature mobility are evident in the figure due to improvements in
growth methods, room-temperature mobilities are well below those of undoped Si. In
contrast, extremely high hole mobilities have been achieved using strained Ge chan-
nel structures grown on graded GeSi buffers on Si as seen in Fig. 29. Xie et al. (1993)
have reported 2DHG mobilities as high as 55,000 cm2/ V-s at 4.2 K. This improvement
was explained as resulting from two important findings. First, temperature-dependent
Shubnikov-de-Haas (SdH) measurements revealed a concentration-dependent hole ef-
fective mass of less than 0 . 1 for~ the strained Ge layer, which is substantially lower
336 STEVEN A. R I N G E L AND PATRICK N. GRILLOT

Gechannel
0
-
0
0 0

V D
VV" 0
0 0 0 0

-
0 .
V
GeSi channel
0
0 after[86]
v after[87] 0
0 after1881 0
o afteriegj

FIG. 29. Representative measurements of two dimensional Hall hole mobility vs temperature of p-type
MODFET structures using strained Ge (Xie et al., 1993; Konig and Schaffler, 1993) or GeSi (Wang et al.,
1989; Whall et al., 1993) channels for the 2DHG transport.

than the hole density of states effective mass for Ge of 0.29mo (Xie et al., 1993), con-
sistent with the theoretically expected lighter mass due to valence band deformation
under strain. Second was the key observation that the interface between the upper GeSi
cap and the strained Ge channel was rough, which is depicted by the TEM image shown
in Fig. 30. Undulations having a period on the order of hundreds of angstroms are evi-

FIG. 30. Cross-sectional TEM image of a strained Ge channel grown between Ge0.60Si0.40 barrier
layers on (001) Si, where the undulation at the top interface due to compressive strain is apparent. From
Fitzgerald (1995) and Xie et al. (1993) with reprint permission from Fitzgerald.
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 331

dent at the upper interface, which were explained to be short enough to cause effective
hole scattering and likely limit the mobility of these structures (this is not the same as
the well-known cross-hatch undulations which occur at a period on the order of 1pm
and hence do not interfere with carrier transport). This realization prompted Xie et al.
(1993) to move the 2DHG region to the smoother, bottom interface, and after suffi-
ciently increasing the Ge channel width to increase the separation between the 2DHG
and the rough interface (but so thick as to cause strain-relaxation), the highest mobili-
ties were achieved. The highest hole mobilities at room temperature of 1300cm2/ V-s
were also achieved using a similar, graded buffer scheme and a strained Ge layer to
supply a 2DHG region (Konig and Schaffler, 1993). This value approaches that of
bulk, intrinsic Ge and additional improvements can be expected because the saturation
of the mobility at lower temperatures implies the presence of additional scattering, such
as by interface roughness or other unintentional scattering mechanisms.
In contrast to the 2DHGs, the situation for achieving similar 2DEGs within GeSi/Si
heterostructures was initially complicated by the lack of a natural conduction band
offset between low Ge content (30% Ge or less) GeSi and Si. To achieve a useful
conduction band offset for electron confinement required placing a Si layer in biaxial
tension to achieve the necessary type I1 band alignment. Relaxed GeSi buffer layers
can be used to achieve this condition by providing lattice constant larger than that of
Si for subsequent Si growth. This was first reported by Abstreiter et al. (1985) where
a thin, strained Si layer was sandwiched between two partially relaxed GeSi layers of
uniform composition. This structure suffered from a high density of threading disloca-
tions as a result of the lattice relaxation and the low-temperature 2DEG mobilities in
the Si channel were low. It was only after substantial reductions of threading disloca-
tion density were achieved via the advent of well-controlled, compositionally graded
GeSi buffers on which fully relaxed, uniform composition GeSi layers could be grown
that high mobility 2DEGs within strained Si layers were possible. The impact of im-
proved buffer layers and dislocation reduction on the 2DEG mobility is apparent from
Fig. 31. Threading dislocation densities were reduced from above 1 x 10' cm-2 for
single step (i.e. uniform composition) GeSi buffer layers grown on Si, to less then
1 x 106 cm-* using compositionally graded buffers (Kasper and Schaffler, 1991; Is-
mail et al., 1995a; Fitzgerald, 1995; Fitzgerald et al., 1992; Fitzgerald et al., 1991;
Tuppen et al., 1991). The reduction in defect density translated into dramatic increases
in the low-temperature 2DEG mobility over a few year window of optimization in the
-
early-mid 1990s, starting at 17,000-19,000 cm2/ V-s (Ismail et al., 1991; Schuberth
et al., 1991), reaching 96,000-125,000 cm2/ V-s in 1991 (Mii et al., 1991), and even-
tually reaching the 170,000-180,000 cm2/ V-s range by various groups (Fitzgerald et
al,, 1992; Schaffler et al., 1992) with the highest report of 520,000 cm2/ V-s occurring
in 1995 (Ismail et al., 1995a, 1995b). The significance of these results is apparent upon
comparison with the highest 4.2 K electron mobility ever reported for a Si MOSFET
of 41,000 cm2/ V-s (Kukushkin and Timofeev, 1988), which is about an order of mag-
nitude lower than the GeSi/Si 2DEG mobility. The fundamental mechanism for this
338 STEVEN A . N.GRILLOT
RINGELA N D PATRICK

0 ~7 after (5,9]
o after (951
o after1951
Q v vcV P 0 after[96]
with graded buffers A V J
vF
7
0
9 0
ka
with single step buffer 2 0

01 1 10 100 1000
Temperature (K)

FIG. 3 1. Two-dimensional Hall electron mobility vs temperature of n-type MODFET structures using
strained GeSi channels for 2DEG transport. Also shown is a comparison between data from stmctures using
a single step buffer (open circles) and graded buffers.

improvement is primarily from the substantial reduction in the electron effective mass
and the population of only two electron valleys (as compared with 6 degenerate con-
duction band valleys for bulk Si) due to strain-induced band ordering, which reduces
intervalley scattering, in addition to the reduction in ionized impurity scattering via
the use of modulation doping in the GeSijSi heterojunction system. The mobility en-
hancement is maintained at room temperature, where room temperature mobilities of
up to 2600 cm2/ V-s were reported (Nelson et al., 1993), as compared with MOSFET
mobilities of about 1000 cm2/ V-s.
These results have prompted considerable interest in identifying the mobility-
limiting mechanisms of the high mobility 2DEG GeSi/Si structures. Scattering sources,
such as remote dopants, impurities, interface roughness, alloy scattering, strain fluctu-
ations, cross-hatch morphology, misfit, and threading dislocations have all been con-
sidered. As mentioned here, the well-known crosshatch pattern present in high-quality,
relaxed graded buffers does not impact carrier transport due to the small wavevector
of these undulations (- 1 pm) as compared with the Fermi wavevector of 2DEGs,
resulting in negligible large angle scattering (Xie et al., 1994). Monroe et al. (1993)
have concluded from both theoretical calculations and comparison with experiment that
scattering from remote dopants, interface roughness, background impurities and alloy
fluctuations are the remaining possible limitations on the 2DEG mobility, and for Si
layers in excess of the Matthews-Blakeslee critical thickness, Ismail et al. (1994) have
shown that the formation of in-plane misfit dislocations at the lower Si/GeSi interface
is an important mobility-limiting factor. It is clear that spacer thickness and channel po-
 6 ELECTRONIC
PROPERTIES AND D E E P LEVELS 339

sitioning are critical, and theoretical calculations support the possibility of long-range
impurity scattering as being the limiting factor for optimally designed structures.

3 . MINORITYCARRIER LIFETIMES
AND DIFFUSION
COEFFICIENTS

Compared to carrier mobilities, little information is explicitly available on minority

carrier lifetimes in GeSi materials and the first direct measurements have only occurred
since 1990 in spite of the use of GeSi within minority carrier devices such as HBTs
and photodiodes. Nevertheless, the minority carrier lifetime is of great importance for
minority carrier devices that invariably depend on the collection efficiency of minor-
ity carriers and are, therefore, extremely sensitive to defects via Shockley-Read-Hall
(SRH) recombination. In fact to obtain device-quality Si with even modestly long life-
-
times of SO ps, deep level concentrations must be less than 1 part in 10" (Higashi
et al., 1990) which highlights the extreme sensitivity of minority carrier lifetime to
material quality and SRH recombination.
Direct comparisons between GeSi-based HBTs and similarly fabricated Si homo-
junction bipolar transistors indeed show evidence of increased base recombination ef-
fects within the GeSi HBT (King et al., 1988). Based on earlier reports showing sig-
nificant oxygen incorporation within CVD-grown strained GeSi layers as compared to
Si layers [41], King et al. (1989) investigated the dependence of the minority carrier
recombination lifetime within GeSi on oxygen content. The measured I-V characteris-
tics of p + n and p + in GeSi test diodes containing various concentrations of oxygen as
determined by SIMS were fitted using a device model by including the minority carrier
lifetime as an adjustable fitting parameter, from which a strong, inverse correlation be-
tween lifetime and oxygen content was observed for a given Ge content. Moreover, the
lifetime was found to be only weakly dependent on Ge content for oxygen-containing
layers, which indicates the extreme sensitivity of lifetime to oxygen content. These
results are summarized in Fig. 32, which also includes lifetime values extracted from
simulations of GeSi HBTs for comparison. This data clearly shows the necessity of

reduced from 10 ns for an oxygen concentration of

range for oxygen concentrations in excess of lo2' cmp3.
-
minimizing the oxygen content within GeSi devices as the minority carrier lifetime is
- 10'' cm-3 down to the ps

Another study of minority carrier lifetime was done in MBE-grown Si/GeSi het-
erostructures in which the minority carrier lifetimes were directly obtained using a
contactless photocarrier lifetime measurement (Higashi et al., 1990) instead of being
obtained by parameter-fitting. For this case, the minority carrier electron recombina-

-
tion lifetime was found to degrade from SO-100 ps for a Si layer grown on an optimally
cleaned Si substrate, to 100 ns for a fully processed GeSi HBT device. It should be
noted, however, that the lifetime values for the MBE-grown Si layer were obtained
directly from the contactless probe, whereas the lifetime after HBT processing was
calculated from the zero bias current of the emitter-base junction. The degradation
340 STEVEN A. RINGEL
AND PATRICK N . GRILLOT

T--------

1 0 - ’ 2 L -
1Oq8 10’’ 1oZ0 lo2’
oxygen concentration ( ~ r n - ~ )

FIG. 32. Minority carrier lifetime as a function of oxygen content in GeSi layers for x = 0.15 - 0.31
indicating a strong (but scattered) dependence on oxygen concentration. The two endpoints were measured
from GeSi pin diodes and the other data points were extracted from simulations of HBTs. Reprinted with
permission from Ghani et al. (1991).

was attributed to the presence of the GeSi layer or to processing steps used in HBT
fabrication, although oxygen impurities may have played a role (as already described
herein).
Another method of obtaining the minority carrier lifetime is the pulsed MOS ca-
pacitor technique where the recovery of the device capacitance after pulsing into deep
depletion can be related to the carrier generation lifetime (Schroder and Guldberg,
1971). To accomplish this, Schwartz and Sturm (1989) fabricated an MOS capacitor
on Si in which a thin, strained GeSi layer was sandwiched between Si layers, beneath
Si02. Following Shockley-Read-Hall (SRH) theory, as outlined earlier in this chapter,
the rate of carrier generation (G) from within a depletion region via a single, midgap
trap level can be simply approximated as

where tg is the generation lifetime. Under these approximations tg = 2t0 where

to = ( ~ N uth)-l
T is the low-level injection minority carrier lifetime. Hence, the char-
acteristic response time of the capacitance transient after pulsing into deep depletion
as well as the total recovery time can be related to the carrier lifetime. However, be-
cause in this structure the GeSi is within the Si depletion region, the smaller bandgap
and larger intrinsic carrier concentration of the GeSi layer must be accounted for in
the Zerbst analysis, which effectively derives the generation lifetime from the relation
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 341

between the generation rate and the generation volume (i.e. the recovery time). Hence
by properly accounting for the generation volume within the GeSi layer, a generation
lifetime of 1 p s was obtained for a strained, 18% Ge layer. This was similar to com-
parably processed all-Si MOS capacitors, which led to the conclusion that for these
CVD-grown samples, the GeSi and Si layers have comparable trap densities and prop-
erties, thereby implying the favorable application of GeSi materials for minority carrier
applications. Note that the relation between generation lifetime and actual minority
carrier recombination lifetime depends upon the deep level characteristics (trap energy,
cross section and density), which can be obtained via DLTS-type measurements. In the
simplest case of midgap trap, however, the recombination lifetime would be half of the
generation lifetime as just described.
In addition to carrier lifetimes, the diffusion coefficient is also an important trans-
port parameter for minority carrier devices. The predicted increase in the perpendicular
mobility component over that of bulk Si as described in the previous section suggests a
higher diffusion coefficient can be expected for strained GeSi HBTs as compared with
Si bipolar transistors. Patton ef al. (1988) however, found that the diffusivity of elec-
trons through the p-type GeSi base is instead reduced by 2630% for strained 12% Ge
layers based on analysis of the HBT I-V characteristics. This reduction was supported
by the work of King et al. (1989) who, by measuring the effect of changing the base
width on the collector current of HBTs, were able to extract the diffusion coefficient.
They obtained an electron diffusivity (D,)of 4.4 cm2/s, 6.2 cm2/s, and 7.1 cm2/s,
for 31% Ge, 21% Ge and 0% Ge (i.e. pure Si) GeSi layers, respectively. This sur-
prising decrease was attributed either to a large concentration of oxygen within the
Ge-containing layers or to alloy scattering. Later however, Grivickas et al. (1991) mea-
sured the ambipolar transport properties of strained, p-type GeSi layers for 0% to 50%
Ge using an optical transient grating method which measures only in-plane transport.
The ambipolar diffusion coefficient in this case was found to increase systematically
with increasing Ge content as compared with bulk Si, as shown in Fig. 33. For 50% Ge
alloys, the diffusion coefficient is increased by approximately 50%, consistent with the
theoretically predicted enhancement of the in-plane mobility.

V. Conclusions

In this chapter, the electronic properties of relaxed and strained GeSi materials and
heterostructures were reviewed with an emphasis on the properties and sources of deep
levels within GeSi materials and their impact on electronic transport properties. The
presence of deep levels and their association with dislocations were described in some
detail for both n and p-type, relaxed GeSi materials grown by a variety of methods. Us-
ing DLTS, traps associated with the dislocation core were identified, as were deep lev-
els, which result from other extended defects, such as point defect clusters introduced
either by dislocation interactions during relaxation or by extrinsic impurities that are
342 STEVEN A. RINGELAND PATRICK N. GRILLOT

13 ,
I

6 1 I I
I I
0 0.1 0.2 0.3 0.4 0.5 0.6

Ge mole fraction ( x )

FIG.3 3 , Ambipolar diffusion coefficient as a function of Ge mol fraction for MBE-grown GeSi samples
with moderate doping concentrations. The vertical bars represent the range values including measurement
error. Reprinted with permission from Grivickas, et al. (1991).

associated with the dislocation core. Many of these deep levels were detected in GeSi
materials prepared by a wide range of methods and in GeSi layers of various composi-
tions. There appears to be a general consistency throughout the full range of GeSi alloy
compositions for both electron and hole traps that correlates with deformation-induced
states in plastically deformed bulk Si and Ge. The most dominant deep levels for high-
quality (threading dislocation densities < lo6 cm-2), relaxed material appear to be
a series of shallow acceptor-like states present for relaxed GeSi layers grown at tem-
peratures below 700 "C, which cause significant dopant compensation and even type
conversion for lightly doped materials. These levels are not due to the dislocation core
but instead result from point defect complexes associated with the dislocation core,
which indicates that defects other than threading dislocations must also be considered
in the pursuit of optimum relaxed material quality. However, for high Ge content alloys
such that the energy bandstructure is Ge-like, the constraint on maximum threading dis-
location density is significantly reduced by the small Ge bandgap and it was shown that
reverse bias diode currents of relaxed Ge p-n junction diodes grown on graded GeSi/Si
substrates were dictated by intrinsic generation for layers having threading dislocation
densities as high as 8 x lo6 cm-'. This indicates the potential of relaxed Ge layers
on Si as an active device material in its own right for applications such as I .55 wrn
photodetectors.
Carrier transport properties in strained and unstrained bulk GeSi, as well as two-
dimensional GeSi/Si heterostructures were also reviewed. For bulk transport in relaxed
material, the hole mobility is generally observed to decrease initially with respect to
 6 ELECTRONIC
PROPERTIES AND DEEPLEVELS 343

bulk Si as Ge content increases due to alloy scattering andor the contribution of de-
fects, but then increases at high Ge compositions due to the significant reduction hole
effective mass. For bulk strained layers, the hole mobility increases with Ge content;
however, the enhancement is more pronounced for the in-plane directional component
than the perpendicular component due to the anisotropic compression of the strained
layer. Various groups have attributed the limiting scattering mechanisms for hole trans-
port in the strained bulk layers to either phonon scattering at room temperature or alloy
scattering. It was also noted that there are differences between the hole Hall vs drift
mobility behavior with alloy composition, with the Hall scattering factor decreasing
dramatically with increasing Ge content. For the bulk electron mobility, the in-plane
mobility is reduced with respect to bulk Si, whereas the perpendicular component is
increased with increasing Ge content for layers having a doping concentration in ex-
cess of l O I 7 ~ m - At
~ .lower doping concentrations, alloy scattering immediately limits
electron mobility.
For twdimensional carrier gases, extremely high 2DEG electron and 2DHG hole
mobilities have been achieved by appropriate engineering of the relaxed buffer layers
and band offsets. For holes, the highest mobilities reported were 55,000 cm2/ V-s at
4 K (Wang et al., 1989) and for electrons, the highest reported value is 520,000 cm2/ V-
s at 0.4 K (Ismail et al., 1995b). The high hole mobility is due primarily to the very
small 2DHG hole mass, whereas the high electron mobility results from the reduced
intervalley scattering and reduced ionized impurity scattering. Both achievements are
only possible due to the low defect density relaxed barrier layers necessary to provide
the appropriate band lineups. Finally, although little information is available, carrier
lifetimes and diffusivities in GeSi were briefly reviewed.

ACKNOWLEDGMENTS

The authors gratefully acknowledge E.A. Fitzgerald (MIT) and Y.H. Xie (Lucent
Technologies) for many stimulating discussions and their valuable input. This work
was supported by NSF grant DMR9458406 and ARO grant DAAG55-91-0111.

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Schroter, W., Scheibe, E., and Schoen IV, J. (1 980). J. Microscopy, 118, 23.
Schroter, W., Kronewitz, J., Gnauerr, U.L., Riedel, F,, and Seibt, M. (1995). Phys. Rev., 52, 13,726.
Schuberth, G., Schaffler, F., Besson, M., Abstreiter, G., andGornik, E. (1991).Appl. Phys. Lett., 59, 3318.
Schwartz, P.V. and Sturm, J.C. (1989). Appl. Phys. Lett., 55,2333.
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 SEMICONDUCTORS AND SEMIMETALS, VOL. 56

CHAPTER 7

Optoelectronics in Silicon and Germanium Silicon

Joe C. Campbell
UNIVERSITY OF TEXAS
MICROELECTRONICS
RESEARCH
CENTER
TX
AUSTLN,

I. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
11. PHOTODETECTORS ....................................... 348
1. Avalanche and p-i-n Photodiodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
2. Resonant-Cavity Photodiodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
3. Metal-Semiconductor-Metal Photodiodes . . . . . . . . . . . . . . . . . . . . . . . . . . 356
4. Integrated Optical Receivers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
111. LIGHTEMITTERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
1. Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
2. Erbium-doped Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
3. Si~-,Ge, Quantum Wells and (Si),(Ge), Strained Layer
Superlattices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
IV. GUIDED-WAVE DEVICES. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
1. Waveguides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 1
2. Integrated and Active Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 375
v. CONCLUSIONS ......................................... 380
REFERENCES. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380

I. Introduction

Photonics technology relies on optoelectronic devices to generate, modulate, switch,

and detect optical signals. To date, essentially all optoelectronic devices and circuits
have been fabricated from 111-V compounds while Si has been the dominant material
for electronic circuits. The goal of combining Si-integrated circuit technology and op-
toelectronics has been a tantalizing and, to a great extent, elusive objective for decades.
However, the current course of technological evolution is making this quest more ur-
gent and, simultaneously, providing the technological tools for its realization.
Silicon has not been widely used for optoelectronic applications for the following
reasons: (1) Si has an indirect band structure, which severely restricts its application

. . . . 0 1999 by Academic Press

Copyneht
All nghts of reproduction m any form reserved.
ISBN 0-12-7521M-X
0080-8784/99 $30 00
348 JOE C. CAMPBELL

for emitters such as lasers and LEDs; ( 2 ) Si does not exhibit an electro-optic effect;
and ( 3 ) the bandgap of Si is too large for photodetection in the wavelength range
( k 2 1.0 pm) for long-haul fiber optic transmission systems. Recent advances in the
synthesis of Ge, Sil-, epitaxial layers (both single layers and superlattice structures)
on Si substrates have opened the possibility of fabricating long-wavelength photode-
tectors, active waveguide devices such as modulators and switches, and light-emitting
devices. The addition of Ge to Si reduces the bandgap and thus extends the sensitivity
range for photodetectors to approximately 1.6 pm. Furthermore, this reduction of the
bandgap energy can be enhanced by incorporating strain.
Most of the early work on waveguide modulators, switches, and active filters em-
ployed the electro-optic effect to change the phase of the propagating wave. However,
for many applications, especially those where speed is not a driving factor, other effects
such as the themo-optic effect and plasma dispersion can be used to realize Si-based
modulators and switches. The most promising approaches for practical light emit-
ters appear to be nanostructures and impurity incorporation, for example, Er doping.
Numerous nanostructures, including Sil-, Ge, quantum wells and superlattices and
porous Si/Sil -,Ge,, have demonstrated room-temperature electroluminescence.

11. Photodetectors

In the area of Si/Sil -,Ge, optoelectronics, photodetectors are the most advanced
and widely deployed devices. Several types of Si and Si/Si1-,GeX photodetectors,
including p-i-ns, metal-semiconductor-metal (MSM) photodiodes, and avalanche pho-
todiodes have been reported. Due to their low dark current, favorable ionization coef-
ficients, and compatibility with Si integrated circuit technology, Si photodiodes are the
most widely used photodetectors for applications in the wavelength range h 5 1 pm.
On the other hand, the bandgap of Si renders it transparent at the wavelengths where
optical fibers exhibit minima in material dispersion and attenuation, namely, 1.3 pin
and 1.55 Fm. To address this deficiency, photodiodes with Sil-,Ge, absorbing layers
have been developed.

1. AVALANCHE
AND P-I-N PHOTODIODES

A p-i-n photodiode consists of a single p-n junction designed to respond, without

gain, to photon absorption. It has become the most ubiquitous photodetector because
of its ease of fabrication and excellent operating characteristics. Avalanche photodi-
odes are, in many respects, similar to p-i-ns, except that they are operated near break-
down where gain, or multiplication, is achieved by impact ionization. With regard to
responsivity, in an ideal photodiode, each incident photon would result in the charge
of one electron flowing in the external circuit. In practice, there are several physical
 7 OPTOELECTRONICS IN SILICON AND GERMANIUM
SILICON 349

effects, such as incomplete absorption, recombination, reflection from the semiconduc-

tor surface, and contact shadowing that tend to reduce responsivity. In the absence of
recombination and to the extent that band-to-band absorption dominates, the external
quantum efficiency is given by qe = (1 - R) x (1 - e-OLd),where CY is the absorp-
tion coefficient, d is the length of the absorbing region, and R is the reflectivity at the
detector surface. Owing to their relatively high index of refraction, semiconductors
reflect approximately 30% of the incident light. However, antireflection (AR) coatings
consisting of single or multiple dielectrics such as SiN, Al2O3, Pb2O3, ZnS, or MgFz
can routinely reduce this optical power loss to less than 5%. As a result, the quantum
efficiency of most p-i-n photodiodes is determined by a and d.
For a photodiode in which diffusion has been minimized, the bandwidth is deter-
mined by the RC time constant and the time it takes for the carriers to traverse the de-
pletion region, referred to as the transit time. By proper scaling of the detector area, it
is possible to optimize the tradeoff between the RC and transit-time limits. In essence,
this is accomplished by reducing the depletiodabsorption layer thickness to achieve
the requisite transit time; the device diameter is then constrained by the condition that
the RC time constant should not exceed the transit time. A reduction of the transit time
through the use of very thin absorption layers, however, usually results in a significant
penalty in quantum efficiency because a large fraction of the light is transmitted without
being absorbed. Unfortunately, the absorption coefficients of indirect bandgap semi-
conductors such as Si and Ge are much smaller (-lox) than those of direct bandgap
111-Vcompounds. As a result, in order to achieve high quantum efficiency, Si-based
materials require long absorption thicknesses. This leads to long transit times and low
bandwidths. The most successful approach to improving the speed has been to develop
structures that increase the optical path while maintaining a narrow depletion width
and, consequently, a short transit time. Two such structures that decouple the transit-
time component of the bandwidth from the responsivity are the waveguide photodiode
and the resonant-cavity structure. Figure 1 shows generic, schematic cross sections of
these two structures.

a. Waveguide Photodiodes

In the waveguide photodiode light is incident from the edge and propagates parallel
to the heterojunction interfaces. The photogenerated carriers, on the other hand, travel
perpendicularly to the optical signal across a thin depletion region. In order to optimize
the performance there are several design considerations that must be addressed. If the
input coupling loss is to be maintained at an acceptable level, the waveguide must be
designed with a large enough optical mode to facilitate coupling from a lens or optical
fiber. The length of the device is selected to be long enough to absorb essentially all
of the input signal, which is determined, to a great extent, by the optical confinement
factor, but no longer than necessary so as to keep the capacitance low.
350 JOE C . CAMPBELI

FIG. I. Schematic cross sections of (a) waveguide and (b) resonant-cavity photodiodes

The waveguide-type structure that has achieved the best overall performance to date
is the Ge,Sil-,/Si rib waveguide avalanche photodiode (Pearsall et al., 1986; Temkin
et al., 1986). A schematic cross section of this device is shown in Fig. 2. The wafers
from which these devices were fabricated were grown by molecular beam epitaxy. The
structure is that of a Ge,Sil-,/Si strained-layer superlattice (SLS) absorbing region
beneath a Si avalanche photodiode. The SLS absorbing region, which also served as the
waveguide core, consisted of 20 pairs of Geo.&0.4(30 A) and Si(290 A). The bandgap
of strained Geo.6Sio.4 layers would permit absorption to wavelengths as long as 1.7 p m
but, to date, all of the work on these devices has been carried out at 1.3 pm. Light
was coupled from the edge into the SLS region where it was absorbed as it propagated
along the waveguide. The photogenerated electrons were injected into the p-type Si
layer above the SLS where gain was achieved by impact ionization. This approach
has the potential for low-noise gain and high gain-bandwidth products because of the
favorable ratio of ionization coefficients in Si. The responsivity of these photodiodes
is the product of the input coupling efficiency, typically < 25%, the internal quantum
efficiency, and the avalanche gain. In the absence of significant scattering or other
 7 OPTOELECTRONICS IN SILICON AND GERMANIUM
SILICON 351
rAI METALLIZATION

AVALANCHE
REGION
.XIS!
.ATTICE ,ABSORPTION
REGION
THICK

I p'St SUBSTRATE AND BUFFER LAYER I

I I
A1 METALLIZATION

(a)

FIG.2. (a) Schematic cross section of SilPxGex/Si strained-layer-superlattice photodetector. (b) Light-
coupling geometry for single-mode optical fiber input. Reprinted with permission from Temkin er al.( 1986).

distributed losses, the internal quantum efficiency is given by (1 - e-rrL)where e is

the effective absorption coefficient and L is the device length. It was found that a was
in the range 50-100 cm-', which gave internal efficiencies in the range 20% to 70%
for lengths of 100 pm and 500 pm, respectively. The maximum gains observed before
the onset of microplasmas were in the range 12-17. As the depletion layer thickness in
this type of structure can be much thinner than that of conventional normal-incidence
photodiodes, higher bandwidths would be projected. The highest speed achieved to
date was 8 GHz at M = 6. A transmission experiment utilizing these APDs achieved
a receiver sensitivity of P = - 26.4 dBm at 800 Mbitsh over 45 km of single-mode
optical fiber. A normal-incidence version of this photodiode, which had a Geo,sSio,s
SLS, was reported by Huang et al. (1995). The measured quantum efficiency was 17%
at 0.85 p m and 1% at 1.3 Fm. The lower efficiency of the normal-incidence structure
is due to the shorter optical length.
352 JOEC. CAMPBELL

2 . RESONANT-CAVITY
PHOTODIODES

The resonant-cavity structure (Fig. lb) increases the absorption through multiple re-
flections between two parallel mirrors in a Fabry-Perot cavity whose length is usually
less than one wavelength (Chin and Chang, 1991; Unlu et aZ., 1990). The lower mirror
is typically an integrated Bragg reflector consisting of alternating k / 4 “high” and “low”
refractive index layers. It is common for these Bragg reflectors to have a reflectivity
> 99%. The top mirror is usually a high-reflectivity dielectric stack that can be de-
posited after fabrication and initial characterization.
In 111-V compound semiconductor systems, the mature materials technologies com-
bined with clever designs and the availability of a wide variety of lattice constants and
refractive indices has enabled the fabrication of high-reflectivity (> 95%), wide band-
width (-50 nm) epitaxial mirrors. However, for Si-based materials, it has been much
more difficult to fabricate high-quality mirrors. One approach, reported by Kuchib-
hotla et aZ.(1993), used alternating layers of GeSi (high index layer) and Si (low index
layer). A difficulty with this approach is that the lattice mismatch between Ge and
Si imposes severe constraints on how thick the layers can be grown. In fact, if the
GeSi layer is grown to h / 4 thickness, the layer relaxes and the resulting high density
of dislocations results in very poor reflectivity. An asymmetric mirror (Murtaza et al.,
1994) has been developed to overcome this problem. In this mirror every other re-
flection is perfectly in phase with the first one from the semiconductodair interface,
but the intermediate reflections are slightly out of phase depending upon the deviation
from the quarter-wavelength thickness. Such mirror structures have a lower peak re-

““’ I -Measured

in0 750 8 0 850 900

Wavelength (nm)

FIG. 3. Simulated and measured reflectivities of a forty-five period Ge0.33SiO.67 (250 A)lSi(800 8)
Bragg mirror. Reprinted with permission from Murtaza et aL(1994).
 7 OPTOELECTRONICS IN S I L I C O N AND GERMANIUM
SILICON 353

flectivity as well as a smaller bandwidth than a conventional quarter-wave stack with

the same number of periods. Nevertheless, mirrors with reflectivity in excess of 90%
have been achieved. Figure 3 shows the simulated and experimental reflectivity of a
GeSi/Si mirror designed to operate at 800 nm. When these mirrors are used for visible
and near-infrared, the reflectivities are reduced somewhat due to absorption. On the
other hand, this absorption in the mirror can be more than compensated by the larger
refractive index step available at the shorter wavelengths.
A mirror similar to that shown in Fig. 3, except peaked at -600 nm, was incorporated
into a resonant-cavity photodiode (Murtaza et al., 1996). The lower Bragg reflector had
40 Geo.3Sio.7(225 A)/Si(570 A) periods. The absorbing region was a 1.03 pm, intrin-
sic Si layer. On top of this was a 0.2 pm, p-doped (1 x lo1*cmP3) Si layer followed
by a 200 A, 5 x lo'* cm-3 p-type Si contact layer. The peak quantum efficiency
was found to be 67% at 608 nm. In order to achieve the same quantum efficiency
with a conventional Si p-i-n structure, approximately 6 p m absorption region thick-
ness would be needed. This would, in turn, reduce significantly the bandwidth. The
point corresponding to the measured efficiency and the designed normalized absorption
coefficient (ad 0.8) is shown in Fig. 4. The frequency response of a GeSi/Si photo-
diode that had a resonance of 780 nm and an n-doped mirror is shown in Fig. 5. The
bandwidth was approximately 15 GHz, a significant improvement (-lox) compared
to commercially available Si p-i-n photodiodes.
The resonant-cavity photodiodes with GeSi/Si mirrors demonstrated the performance
advantages that can be achieved with the resonant-cavity approach. This has led to the

I""

Normalized Absorption Coefficient (ad)

FIG.4. Calculated quantum efficiency vs the normalized absorption coefficient a d for resonant cavity
photodetectors with different top (R1) and bottom (Rz) mirror reflectivities. The data point was obtained for
-
a Sil-,Ge,/Si resonant-cavity photodiode where cud was estimated to be 0.8, R1 0.35, and R2 * 0.9.
Reprinted with permission from Murtaza ef al.( 1996).
354 JOE C. CAMPBELL

5
s o
2 -3
Op -6
2ln-9
.-g
-12
-
5 -15
Q)
a
0 2.3 4.6 6.9 9.2 11.5 13.8 16.1 18.4 20.7 23
Frequency (GHz)

FIG.5 . Frequency response of Sil-,Ge,/Si resonant-cavity photodiode. Reprinted with permission

from Murtaza eta!. (1996).

development of a photodiode that is more compatible with standard Si IC processing.

The structure, shown in Fig. 6, consists of an interdigitated, polysilicon p-i-n that is
grown by MBE on top of the Sit302 layer. Conventional polysilicon deposition tech-
niques yield photodiodes that exhibit high dark current (typically > 1 pA at 1 V)
and low quantum efficiencies (Diaz et al., 1996). Bean et al. (1997) have developed
a new MBE procedure for growth directlyon Si02 that yields superior device-quality
polysilicon films. The p-i-n photodiodes fabricated from this polysilicon have exhib-
ited a 1OOx decrease in dark current and an improvement in peak external quantum
efficiency to 50%. Figure 7 shows the dark current vs bias voltage. At bias voltages
of - 10 and -25 V, the dark current was 60 nA and 500 nA. It may be that even lower
dark current and higher quantum efficiencies will be achieved by post-growth defect-
passivation techniques such as hydrogenation. The bandwidth of a 12 p m x 18 p m
Si/SiO2 photodiode with a 0.5-pm thick absorbing layer was determined by analyzing
the photocurrent spectrum produced by excitation with a mode-locked Timpphire laser
that was tuned to the peak of the responsivity. A bandwidth of approximately 10 GHz
was observed (Fig. 8). To date, these structures have been demonstrated €or an ab-
sorbing layer of polysilicon. However, as the “substrate” is amorphous Si02, it should

. - - - - - - -a --
 7 OPTOELECTRONICS IN SILICON AND GERMANIUM
SILICON 355

10-3 1
h 104 I
a,
t 10-7
3
0 10"

FIG. 7. (a) Dark current vs bias voltage for photodiode shown in Fig. 6. Reprinted with permission
from Bean et al. (1997).

be straightforward to incorporate Ge into the p-i-n in order to extend its operation to

longer wavelengths.
Ishikawa et al. (1996) have developed a novel technique for fabricating Si/SiO2
Bragg reflectors by multiple separation-by-implanted oxygen (SIMOX). This approach
has the advantage that the Si layers, including the top layer of the mirror, are single
crystalline. The finished mirror is "epitaxy-ready" for additional crystal growth or de-
vice fabrication on top of the mirror. The SiO2 layers were created beneath the Si
surface by low-energy oxygen ion implantation. After each implant, the wafer was an-
nealed to form the Si02 layer. This was followed by growth of an additional Si layer by
MBE, which was subsequently implanted. This process was repeated until four or five
Si/SiOz pairs were formed. The highest reflectivity reported was 92% with a stopband
> 3000 cm-l.

8 14
h

v
P) '2
E0 10
$ 8
a"6
.-c$ 4
-m 2
$ 0
10' 108 109 10'0 1011
Frequency (Hz)

FIG. 8. Frequency response of photodiode shown in Fig. 6 . The 3 dB bandwidth is approximately

10 GHz. Reprinted with permission from Bean er al. (1997).
356 JOE C . CAMPBELL

3. METAL-SEMICONDUCTOR-METAL
PHOTOPIODES

The metal-semiconductor-metal (MSM) photodiode (Sugeta et al., 1980) has de-

veloped into one of the most promising photodetectors for arrays and optoelectronic
integrated circuits (OEICs). Structurally, it is a planar device with two interdigitated
electrodes on a semiconductor surface (Fig. 9). These electrodes are deposited so as to
form back-to-back Schottky diodes. Light is usually incident from the top and absorp-
tion occurs between the electrodes. The positive attributes of MSMs are nui.lerous. The
principle advantage, which derives from the simplicity of the planar contact configu-
ration, is its compatibility with transistor circuitry. In addition, MSM photodiodes are
relatively easy to fabricate, they do not add significantly to the complexity of circuit,
and, typically, they exhibit very low capacitance per unit area. The low capacitance is
important because: (1) it permits relatively large-area devices, which facilitates cou-
pling to optical fibers; and (2) its contribution to the total front-end capacitance of an
optical receiver is negligible. The bandwidth can be very high for sufficiently narrow
electrode spacing, if there is no photoconductive gain.
The two fundamental limiting factors in the performance of MSMs are dark current
and quantum efficiency. It has frequently been difficult to obtain low dark current in
an MSM because the lateral current flow can be significantly influenced by the semi-
conductor surface. For Si MSMs this is not a concern because excellent passivation
techniques and a mature Schottky technology are available. For SiGe structures, on
the other hand, passivation and Schottky contacts may require further development. In
recent years there have been several studies of Schottky contacts on P-type Sil-,Ge,
layers. One of the more thorough investigations, conducted by Nur et at. (1996), in-
cluded measurements of the electrical properties of Pd, Pt, Ir, and Fe contacts for Ge
concentrations in the range 0 5 x 5 0.24. It was found that the Schottky barrier height
for each metal decreased with increasing Ge fraction. The energy vs concentration, x ,
slope was the same for all metals and the change in barrier height with x directly cor-
related to the valence band discontinuity at the Si/Sil -,Ge, heterojunction. Recently,
very similar results have been reported for A1 on Sil-,Ge, (Jiang et aE., 1996). The

I SUBSTRATE
I/
FIG.9. Schematic diagram of a generic MSM photodiode.
 7 OPTOELECTRONICS
IN SILICONA N D GERMANIUM
SILICON 357

degradation in the quantum efficiency of MSMs that is caused by electrode shadowing

can not be completely eliminated. There are, however, fabrication techniques such as
the formation of submicron electrodes that can reduce the effect of contact shadowing.
The indirect bandgap of Si poses an additional challenge in that it gives rise to
low absorption coefficients and, consequently, long absorption lengths. For example,
at wavelengths of 800 nm, 830 nm, and 850 nm the absorption lengths are 9 pm,
13 pm, and 15 pm, respectively. Numerous techniques have been adopted to deal
with this problem. The most straightforward solution is to operate at short wavelengths
(-400 nm) where the absorption length is only 100 nm. In this wavelength regime,
the transit-time component of the bandwidth is determined by the spacing between the
fingers instead of the absorption depth. Liu et al. have reported bandwidths as high
as 110 GHz with “short-wavelength” Si MSMs that had finger separation and width
of 200 nm. The quantum efficiency of these MSM photodiodes was approximately
12% (Liu et al., 1993). The operation of Si MSMs can be extended to wavelengths in
the near infrared by using SO1 substrates (Canham, 1993; Richter et al., 1991). The
motivation is to prevent carriers generated out of the shallow depletion region from
slowly diffusing to the junction where they contribute to the optical signal but they also
greatly reduce the bandwidth. In effect, this approach trades off responsivity for speed.
Wang et al.(1994) reported Si MSMs with finger width and spacing down to 200 nm
that were fabricated on silicon-on-sapphire substrates. They observed that the pulse
response was relatively independent of wavelength but that the quantum efficiency de-
creased from approximately 20% at A = 400 nm to < 1% for h x 900 nm. Liu et
nl. (1994) fabricated similar photodiodes on SIMOX substrates; the top Si layer was
thinned to 100 nm. These photodiodes achieved a record bandwidth of 140 GHz at
780 nm but, again, the efficiency was low (-2%).
Another approach that has proved successful in increasing the speed of Si MSM pho-
todiodes has been to decrease the carrier lifetime through ion implantation. Sharma et
al. (1994) reported that both the quantum efficiency and the bandwidth of Ni-Si-Ni
MSMs could be significantly enhanced by using ion implantation of 19F+ to create
a damaged, highly absorbing region approximately 1 p m below the Si surface. The
quantum efficiency at 860 nm and 1060 nm was 64% and 23%, respectively. It was
not clear whether photoconductive gain played a role in the responsivity. Compared to
unimplanted devices, the pulse response decreased by approximately a factor of 6 to
100 ps (FWHM). Dutta et al. (1997) have used a similar approach and have obtained
bandwidths as high as 6 GHz, compared to 300 MHz for similar unimplanted photodi-
odes, albeit with approximately 3 to 5 times lower quantum efficiencies (-10%) than
the unimplanted devices.
Textured surfaces provide a novel and effective method to increase the optical path
length for absorption while maintaining short carrier transit distances. The basic idea
is to use scattering to “trap” light inside the semiconductor. Yablonovitch and Cody
(1982) first used this technique to enhance the conversion efficiency of solar cells. More
recently, Lee and Van Zeghbroeck (1995) applied texturing to photodiodes designed to
358 JOE c. CAMPBELL
be incorporated into optical receivers. A schematic cross section and a photomicro-
graph of this device is shown in Fig. 10. The membrane was formed by etching the
wafer from the back to thicknesses in the range 3-7 pm. Texturing was accomplished
in an Ar/CF4 plasma. It was determined from transmission experiments at 830 nm
that the effective reflectivity of the black-textured surface was 86%. For comparison,
untextured and ideally textured surfaces should have reflectivities of 30% and 98%,
respectively. The internal and external quantum efficiencies were 61% and 25%, re-
spectively. Prior to formation of the textured membranes the bandwidth was limited
to -300 MHz by the light penetration depth. After forming the thin membrane, the
bandwidth was > 3 GHz. Levine et al. (1995) have used texturing in conjunction with
an SO1 substrate to fabricate a CMOS-compatible Si MSM. The SO1 prevented carrier
diffusion from deep within the substrate and a textured surface provided light trap-
ping that enhanced the efficiency by a factor of 3.6 to 27% compared to an untextured
surface.
A structure that uses a vertical array of “membranes” or ridges has been developed
by Ho and Wong (1996a, 1996b). They have employed reactive ion etching to form Si
ridges with electrodes inside the interdigitated trenches. A cross-sectional view and an
SEM micrograph are shown in Fig. 11. An SO1 substrate was used to eliminate carriers
generated below the ridges. Light is absorbed in the ridges; the electrodes on the sides
ensure that the field is relatively uniform throughout the absorbing regions and that the
transit distance is short enough to allow high speed, even for those carriers generated
several microns below the surface. The responsivity was 0.12 A/W at 800 nm, cor-

FIG. 10. (a) Cross-sectional diagram of a textured Si MSM photodiode. (b) SEM photomicrograph of
the textured back surface. Reprinted with permission from Lee and Van Zeghbroeck (1995).
 7 OPTOELECTRONICS IN SILICON AND GERMANIUM
SILICON 359
SW2W nm TiWiAu Si Rdgc Si Trench

si r--pq
2.75 urn 1.25 urn 6

FIG. 11. (a) Cross section of an SO1 MSM formed with Si trenches. (h) Edge-view SEM photomicro-
graph of the photodiode. The trenches are 6 ,urn deep, 2.75 brn wide, and spaced 2.75 wm apart. Reprinted
with permission from Ho and Wang (1996b).

responding to an internal quantum efficiency of -90% and an external efficiency of

-20%. An instrument-limited bandwidth of 2.3 GHz was reported.

a. Infrared Photodetectors

For long-wavelength infrared (LWIR) applications, Si and SiGe photodiodes have

been widely accepted. Technologies that have been developed include PtSi/Si (Ho
and Wang, 1996b) and IrSi/Si Schottky-barrier photodiodes (Pellegrini et al., 1982),
SiGe/Si heterojunction internal photoemission (HIP) photodetectors (Lin and Maser-
jian, 1990; Lin et al., 1991; Tsaur et al., 1991; Park et al., 1994; Jimenez et al., 1995),
SiGe/Si quantum well infrared photodetectors (QWIPs) (People et al., 1992; Park et
al., 1992; Karunasiri et al., 1992; Robbins et al., 1995; Carline et al., 1996; Kruck
et al., 1996), and doping-spike PtSi/Si detectors (Lin et al., 1993; Lin et al., 1995).
The best overall device characteristics, including detectivity, have been obtained from
narrow-bandgap semiconductors such as InSb and HgCdTe. However, it has been diffi-
cult to fabricate large, uniform two-dimensional arrays from these materials. For array
applications (1024 x 1024 elements), silicide Schottky-barrier devices such as IrSi and
360 JOE C. CAMPBELL

PtSi have been implemented. Unfortunately, however, these photodiodes have a long-
wavelength cutoff of -5 prn. Strained Sil-,Ge, has been used to extend the response
of this type of photodiode to the 8-10 E;c.rnwavelength range.

b. SiGe/Si Heterojunction Internal Photoemission Photodetectors

The operation of the SiGe/Si heterojunction internal photoemission (HIP) photodi-

odes is illustrated and contrasted to the PtSi/Si Schottky barrier in Fig. 12. It can be
seen that the response of the PtSi/Si photodiode is determined, to a great extent, by the
height of the hole barrier. Lin et al. (1993; 1995) have used p-type doping spikes to
lower the effective barrier height, through the image-force effect and the electric field
due to ionized dopants in the depletion region, to extend the cutoff to -7.3 Wni.
The concept of using a HIP structure in place of the PtSi/Si Schottky barrier was first
proposed by Shepherd et al. (1969). The first Sil -,Ge,/Si HIP was reported by Lin and
Maserjian (1990). The structure consisted of P+-Sil-,Ge, layers grown by MBE on
p-type Si substrates. The operating principle involves absorption in the degeneratedly
doped Sil _,Ge, layer, primarily by free carrier absorption, and subsequent internal
photoemission of photoexcited holes over the Sil -,Ge,/Si heterojunction barrier into
the Si substrate. The effective barrier height is determined by the Sil-,Ge,/Si valence
band discontinuity A E , and the Fermi level in the Sil-,Ge, layer. By tailoring the Ge
concentration to modify A E, and the doping to alter the position of the Fermi level,
the barrier height, and thus the cutoff wavelength, can be tailored over a wide range of
infrared wavelengths. Lin and Maserjian (1990) achieved cutoff wavelengths between
2 ,um and 10 p m for Ge concentrations in the range 0.2-0.4, respectively, and for a p
doping level of -lo2' crnp3. The efficiency decreased from -3% to 1 % with increas-
ing wavelength in initiaI devices. In subsequent work, optimization of the thickness and
doping of the Sil -,Ge, layers yielded efficiencies of 3-596 in the wavelength range 8-
10 Wm (Lin et al., 1991). Tsaur et aL(1991) extended this technology by fabricating

PtSi

FIG. 12. Energy level diagrams of (a) a PtSi/Si Schottky barrier and (h) a P+: SiGeRSi heterojunction
internal photoemission photodetector.
 7 OPTOELECTRONICS I N S I L I C O N AND GERMANIUM
SILICON 361

400 x 400 focal plane arrays of Si0,5&e0.~/SiHIP photodiodes with a cutoff wave-
length of 9.3 p m and monolithic CCD readout circuitry. These arrays exhibited a high
degree of pixel-to-pixel uniformity (< 1% rms variation) and the overall performance
at 50 K was reported to be superior to that of IrSi arrays.
The external quantum efficiency of HIP photodetectors is determined by the amount
of absorption in the Sil-,Ge, layers and the efficiency with which the photogenerated
holes surmount the heterojunction barrier. There is a tradeoff involving the thickness
of the Sil-,Ge, layers. Thin layers yield improved barrier transport because scattering
is less detrimental but there is also less absorption in thin layers. Park et al. (1994)
proposed to use stacks of thin ( 5 5 0 A) Sio.7Geo.3 layers to enhance the absorption
without degrading the transport efficiency. Strong response in the wavelength range
2-20 p m was achieved; the quantum efficiencies were 4% and 1.5% at 10 p m and
15 pm, respectively.
Using a PtSi/SiGe/Si HIP, Jimenez et al. (1995) have demonstrated a tunable re-
sponse. The relative heights of the two barriers, the PtSi/SiGe Schottky barrier and the
SiGe/Si heterojunction barrier, are very sensitive to the applied voltage. It was found
that the effective barrier height could be varied from 0.3 eV at zero bias to 0.12 eV at
2.4 V bias for a 450-A thick Sio.gGeo.2 layer. The tunability is achieved at the price
of reduced quantum efficiency at the shorter wavelengths because the carriers must
traverse the Sio.gGe0.2 layer prior to being collected. Nevertheless, the tunability may
permit spectral analysis of infrared images by altering the bias condition.

c. SiGe/Si Quantum Well Infrared Photodetectors

An alternative approach to HIP photodiodes is the quantum well infrared photode-

tector (QWIP) (People et al., 1992; Park et al., 1992; Karunasiri et al., 1992; Robbins
et al., 1995; Carline et al., 1996; Kruck et al., 1996). GaAs/AlGaAs QWIPs have
exhibited detectivities comparable to those of HgCdTe (Levine, 1993). These devices
rely on intersubband absorption in conduction band quantum wells. Figure 13 il-
lustrates the bandstructure and the detection process for QWIPs. Unfortunately, for
these devices, a quantum mechanical selection rule prohibits intersub-band absorp-
tion for light polarized perpendicular to the growth direction (i.e., normal incidence).
This complicates input coupling and restricts available device architectures. Extend-
ing the QWIP approach to Sil-,Ge,/Si quantum wells would have the advantage that
the detector arrays match thermally with Si readout electronics and can be flip-chip
bonded to Si multiplexer circuits. Furthermore, for p-type Sil-,Ge,/Si QWIPs nor-
mal incidence absorption is strong because strong mixing of heavy and light hole
states enables hole intersub-band transitions. To date, however, the performance of
Sil -,Ge,/Si QWIPs has been limited by relatively low responsivities and high dark
currents. Kruck et al.( 1996) have reported a normal-incidence QWIP that operates in
the wavelength range 3-8 p m with a peak responsivity of 76 mAlW and a detectivity
as high as D* = 2 x 10" cm(Hz W)'I2. As this material system becomes more mature
362 JOE C. CAMPBELL

CONDUCTION
BAND
(n-DOPED)

I
I
I
Eg
Eg (BARRIER)
(WELL)

I
VALENCE
BAND
(p-DOPED)

FIG.13. Quantum well bandstructure. This diagram illustrates both electron (for N-type) and hole (for
P-type) interband absorption. Reprinted with permission from Levine (1993).

and new processing techniques evolve, it is anticipated that the Sil -,Ge,/Si QWIP will
prove to be a practical imaging device.

4. OPTICAL
INTEGRATED RECEIVERS

Optical receivers for long-haul transmission systems that require high speed and
high sensitivity have primarily been implemented in the 111-V material systems. How-
ever, there are many high-volume applications that require low-cost, high-reliability
components with proven manufacturability. Integration of an optical receiver on Si
using the well-established Si transistor fabrication technology for use with 870-nm
laser transmitters can fulfill these requirements. There have been several reports of
Si-MOS receiver circuits with hybrid photodiode interconnection techniques such as
wire-bonding or epitaxial-liftoff demonstrating that optimized Si-MOS preamplifiers
can provide the required performance for short-distance optical data links (Fraser et
al., 1983; Abidi, 1984; Steyaert et al., 1994; Lee et al., 1996).
Ultimately, it will be advantageous in terms of cost and performance to integrate op-
toelectronic devices and electrical circuits. Lim et al. (1993) and Kuchta et al. (1994)
have reported an integrated optical receiver with a CMOS preamplifier and a vertical Si
p-i-n photodetector fabricated using a Bi-CMOS manufacturing process. That receiver
had an optical sensitivity at bit error rate (BER) of - 14.8 dBm at 531 Mb/s with
850 nm optical input. The photodiode structure in that work used an N- absorption
layer that was much thinner than the optical absorption depth at the operating wave-
length. The authors cited the advantage that the device can be depleted with a low bias
voltage while maintaining hig-speed performance. However, another result of the thin
 7 OPTOELECTRONICS IN SILICON AND GERMANIUM
SILICON 363

f 10-7 $
b
\
4" MBiVs

FIG. 14. Bit error rate (BER) vs average received optical power, qP,at 155 Mbit/s and 300 Mbit/s for
Si NMOS integrated receiver. The inset shows an eye diagram at 250 MBids. Reprinted with permission
from Qi et al.( 1997).

absorption layer is that the photodiode had a low responsivity of 0.7 A/w. A recent
integrated receiver implemented in a silicon bipolar process using epitaxial layers to
integrate a p-i-n photodiode, while demonstrating high bandwidth, also demonstrated
low photodiode efficiencies (Wieland et al., 1994). Qi et al. (1997) have achieved an
overall improvement in performance using a novel approach to integrate a Si-NMOS
preamplifier with a planar p-i-n Si photodiode structure that ameliorates the design
tradeoff between the efficiency and bandwidth of the photodiode while causing far less
disruption to a standard silicon MOS fabrication process. The p-i-n photodiode was a
planar interdigitated structure that exhibited a dark current of 0.1 nA at 5 V and quan-
tum efficiencies of 84% and 74% at 800 nm and 870 nm, respectively. Both depletion-
and enhancement-mode MOSFETs were used in the preamplifier; the effective channel
length of the MOSFETs was 0.6 pm. A transimpedance of 6.5 kR and a bandwidth
of 130 MHz was obtained from the preamplifier circuit. Figure 14 shows the BER vs
average received optical power. The sensitivities for a BER of were -33 dBm
and -25.5 dBm at bit rates of 155 MBit/s and 300 MBit/s, respectively.

111. Light Emitters

1. POROUS SILICON

Owing primarily to the dominance of Si in integrated circuit technology, there has

long been a desire for a practical Si-based light emitter to provide an interface between
microelectronics and optoelectronics. Consequently, light emission from Si, Sil-,Ge,,
364 JOE C. CAMPBELL

and SiGeC has been the subject of intensive research for several years. Many of these
topics have been reviewed by Canham (1993). It is clear from this that light emis-
sion from Si-related materials is actually quite common. Unfortunately, the efficiency
of essentially all of these mechanisms is still relatively low. There are, however, a
few exceptions including hydrogenated amorphous Si, siloxene, and porous Si. In this
section, we will describe some of the more promising approaches for practical electro-
luminescent devices in Si-based materials.
The technology that has achieved the highest performance as an LED is porous Si,
a form of Si that is formed by anodization in an HF solution. It has nanometer-sized
columnar crystallites separated by pores of similar dimensions. Photoluminescence ef-
ficiencies, for red light emission, in excess of 10% have been widely reported. There
have been numerous reviews that detail the fabrication procedures and the lumines-
cence characteristics of porous Si. In addition there are numerous papers that address
the physical effects responsible for the luminescence, namely, whether quantum con-
finement is the dominant physical effect and the role of surface states. These topics are
beyond the scope of this chapter, which will concentrate on recent progress in electro-
luminescent devices.
While very high photoluminescence (PL) efficiencies have been achieved with por-
ous Si, the extension to practical electroluminescent (EL) devices has not been straight-
forward. The most serious difficulty has been that the EL efficiencies are at least
100 times lower than the best PL results. In addition, initially, the EL was unsta-
ble, degraded in periods of minutes to days, and was very sensitive to environmental
conditions. Passivation techniques have been developed that have solved these latter
problems but the issue of low EL efficiency remains.
The first porous Si EL devices were relatively simple structures consisting of a top
electrode, such as Au, Al, ITO, or conducting polymers, placed directly on top of the
porous Si layer and a bottom electrode on the Si substrate (Richter er al., 1991; Koshida
and Koyama, 1992; Maruska et a/., 1992; Koshida et al., 1993). These devices exhib-
ited very high series resistance, had lifetimes of only a few minutes, achieved quantum
efficiencies -lop6 and had high threshold voltages ( 2 10 V) and current densities
(< 10 mA/cm2). Threshold is defined as the bias condition at which EL is detectable.
Furthermore, light emission was frequently observed for both forward and reverse bias.
There are several reasons for the low efficiencies of these structures. The first is related
to charge transport. The porous Si structure is a honeycomb of crystalline nanostruc-
tures. The top electrical contact connects directly to only a small fraction of these
crystalline clusters that are at the top of the film. There is a strong impediment to trans-
porting through the film to the lower regions as evidenced by the low carrier mobility
(- c m 2 N s). Another factor is that the low thermal conductivity of porous Si
leads to severe heat dissipation problems.
A significant increase in emission efficiency was achieved with a p-n structure devel-
oped by Steiner et al. (1993) and Lang et al. (1993). This device utilized the fact that
the structural and luminescence characteristics of porous Si are strongly influenced by
 7 OPTOELECTRONICS I N S I L I C O N AND GERMANIUM
SILICON 365

cu resoporous
p+ layer 1 5pm
ranoporous
nsilicon l o r n
macroporous
p'
0'

6 1 j
-5 ' "
-40
" i "
-20
I
0
" ' ) '
2c
"
40
'
voltage (V)

FIG. 15. Schematic cross section (inset) and current-voltage characteristic of porous Si light-emitting
diode. Reprinted with permission from Steiner et aL(1993).

the carrier type and the carrier density. The device had a "double-heter0structure"-type
configuration in which the n-type nanoporous emitting region was sandwiched between
a pf mesoporous cap layer and a macroporous n-type substrate. Figure 15 shows the
current-voltage characteristic and a schematic cross section of the structure. In order
to achieve the three different types of porous Si regions, an n+ substrate was initially
implanted with boron and annealed. This produced a 1.5-pm thick p+ layer at the top
with a thin, compensated n-type layer near the p-n junction on top of the underlying n+
substrate. When anodized the pf region became mesoporous with crystalline regions
having dimensions on the order of 50 to 100 nm. This region did not contribute to
the luminescence but it did provide: ( 1 ) an improved interface for the top electrode;
(2) lower resistance; ( 3 ) better heat dissipation; and (4) displacement of the porous Si
region beneath the surface, which has both mechanical and environmental advantages.
The nanoporous light emitting region was formed in the n-type layer underneath the
pf layer. Under forward bias, electrons and holes are injected into this layer from
the adjacent regions. This approach has resulted in quantum yields as high as
Unfortunately, these devices exhibited rapid degradation. The potential of this type of
structure for high luminescence efficiencies, however, was demonstrated under pulsed
conditions by Linnros and Laic (1995). Using a structure with an optimized p+ layer
and an improved ohmic contact they achieved peak efficiencies of -0.2% with 20-V
pulses of 200 ps duration and with a period of 4 s between pulses.
Loni et al. (1995) reported cw efficiencies of 0.1% with a structure consisting of an
IT0 contact deposited directly on the porous Si layer. This device demonstrated record
low threshold current density (10 A/cm2) and voltage (2.3 V). Degradation remained a
problem, however, in that these results were achieved with the devices under vacuum.
366 JOE C. CAMPBELL

When exposed to air, the efficiency dropped by more than a factor of 100 in a few
minutes.
Recently, stability has been greatly improved with a passivated p-n emitter developed
by Fauchet et al. (1996; Tsybeskov et al., 1996). This device was fabricated as follows:
First a p+ layer was diffused into a p-type Si substrate. The wafer was then anodized
to form a porous Si layer approximately 0.5 p m thick. The porous Si emitting region
was successfully passivated by annealing at 800-900 "C in an inert atmosphere (N2) or
in oxygen, The anneal effectively replaced the hydrogen that covers the surface after
anodization with a low-defect Si02 interface. After anodization, an n-type poly-Si
film was deposited on the wafer and A1 contacts were formed. The threshold of these
devices was 2-3 mA/cm2 at 1.5 V and the quantum efficiency was estimated to be
approximately 0.1 %. The passivation resulted in stable operation over a time period of
weeks (at the time of publication) and a faster pulse response. Devices with a rise time
of less than 100 ns and a fall time of -2 p s were demonstrated. As an illustration of
the performance of these passivated LEDs, Fig. 16 shows a 7-segment display in room
light. The number 2 is clearly visible (Collins et al., 1997). These LEDs have also been
integrated with a Si bipolar drive circuit (Hirschman et al., 1996). Figure 17(a) shows
a schematic cross section of the LEDhipolar transistor combination, an equivalent
circuit, and a photomicrograph of the fabricated structure. The circular LED region
has a diameter of 400 p m . The emitter (E), base (B), and collector (C) terminals

FIG. 16. An array of porous Si displays, each composed of seven elements. The height of each display
is 4 mm. Reprinted with permission from Collins et al.( 1997).
 7 OPTOELECTRONICS IN S I L I C O N AND GERMANIUM
SILICON 367

FIG. 17. (a) Micrograph and schematic of an integrated porous Si LED and bipolar transistor structure.
The 400 pm-diameter LED is in the center of the structure. (b) Luminescence of an LEDhipolar transistor.
Reprinted with permission from Hirschmann et al.( 1996).

surround the LED. The photograph in Fig. 17(b) demonstrates the luminescence of the
LEDhipolar transistor. The emission is relatively uniform over the active LED surface.
While porous Si EL devices are not yet in position for widespread deployment in
circuits and systems, significant progress toward practical devices has been achieved
and there is basis for optimism. Useful efficiencies have been demonstrated, passiva-
tion techniques have been developed, and response times have been reduced. Future
research will undoubtedly focus on further improving performance in these areas.

2. ERBIUM-DOPED
SI

Another area that has demonstrated potential for practical EL devices is rare-earth-
doped Si and Sil-,Ge,. The rare-earth element that has emerged as the clear favorite
is erbium (Er). This is due in part to its relatively narrow emission near 1.5 pm, an
important wavelength for communications applications. The Er atoms are incorpo-
rated into Si in a 3+ charge state. In this state a transition from the excited 4 1 1 3 p
state to the 4115p level results in emission at 1.54 pm. Ennen et al. (1983; 1985)
first reported the incorporation of Er in Si and its associated PL and EL. At 77 K they
observed sharply structured PL spectra from ion-implanted structures and EL from
forward-biased erbium-doped Si junctions that were grown by MBE. Much of the sub-
sequent work on Er-doped Si has focused on PL of the recombination lifetime, thermal
quenching, and power saturation. In general, it has been found that co-doping with
oxygen improves the luminescence characteristics because it increases the solubility of
Er (Coffa et al., 1993), inhibits Er segregation (Coffa et al., 1993; Custer er al., 1994),
increases the luminescence efficiency (Michel et al., 199 1 ;Favennec et al., I990), and
368 JOE C. CAMPBELL

reduces thermal quenching (Yablonovitch and Cody, 1982). For example, the PL from
samples without oxygen typically decreases by three orders of magnitude as the tem-
perature is raised to room temperature. In the oxygen-doped samples, on the other
hand, the decrease is only about a factor of 10 to 50 (Coffa et a/., 1994). While there
is a consensus on the physical mechanism responsible for PL, namely, bound exciton
recombination with transfer of energy to the Er atom, there are still several compet-
ing models to explain the thermal quenching (Coffa et al., 1994; Priolo et al., 1995;
Anderson, 1996).
Recently, it has been demonstrated that it may be possible to avoid thermal quench-
ing with EL structures. The first room-temperature electroluminescence from an Er-
doped Si light emitting diode was an oxide passivated mesa structure with an emission
region formed by coimplantation of Er and 0 (Zheng eta/., 1994). Under forward bias
these devices exhibited the same thermal quenching as PL (-5Ox lower at room tem-
perature than at 100 K). Subsequently, it was shown by Franzo et al. (1997) that much
higher intensities (> 20) could be achieved by operating the devices under reverse bias.
The reason for the higher output is that in forward bias, excitation occurs by electron-
hole recombination at an Er-related level in the Si bandgap. DLTS measurements show
that only a fraction (- 1/10) of the Er atoms participate in this type of recombination,
thus severely restricting the number of luminescent sites. Furthermore, nonradiative
processes such as auger de-excitation reduce the carrier lifetime in forward bias. In
reverse bias the Er atoms are excited by hot carrier impact. All of the atoms in the
depletion region are excitable and Auger-type processes are inhibited. Stimmer et a/.
(1996) have observed similar differences between forward and reverse bias operations
in Er-0-doped diodes grown by MBE. Figure 18 shows the luminescence intensity for

T (K)
300 250 200 150

: y Forward Elas 9 5 A i m 2
0 Reverse Bias, 8 5 A/cm2

3 4 5 6 7 8 9 1 0 1 1
1 O O O R ( 1/K)

FIG. 18. Electroluminescence intensity vs temperature for an Er-doped Si light emitting diode. The
forward bias curve (square data points) is multiplied by a factor of 30. Reprinted with permission from
Stimmer et aZ.( 1996).
 7 SILICON
OPTOELECTRONICS IN SILICON AND GERMANIUM 369

forward and reverse bias vs temperature. Under forward bias the intensity was 30x
lower than under reverse bias at low temperature and exhibited strong thermal quench-
ing. However, at reverse bias, essentially no thermal quenching was observed between
4 and 300 K. The estimated external quantum efficiency of these devices was >

3. S I I - ~ G E ,QUANTUM
WELLS AND (SI),(GE), STRAINED LAYER
SUPERLATTICES

In recent years Sil -xGex quantum wells and (Si),(Ge), strained-layer superlattices
(SLS) have attracted a great deal of attention. The original motivation for studying
(Si), (Ge), SLS was to create a quasi-direct bandstructure by using the periodicity of
the superlattice to fold the Brillouin zone (Gnutzmann and Clausecker, 1974; Pearsall
et al., 1987). If the period of the superlattice is approximately 10 monolayers, the 2-
fold degenerate A minima that are perpendicular to the epitaxial layer planes, which
are at 0.85 in the r-X direction of the Brillouin zone in Si, are folded back to the
r position. Compared to the indirect bandgap transition in bulk Si, the quasi-direct
transition between the folded A states and the valence band is projected to have an
enhanced oscillator strength. In the initial stages of this work, defect-related emission
that was linked to the very high densities of dislocations masked bandgap luminescence
from the (Si),(Ge), SLS (Zachai et al., 1990). By using Sil-,Ge, buffer layers with
graded Ge concentrations and utilizing a monolayer of Sb to suppress segregation of the
Ge atoms during growth by MBE, well-defined bandgap PL (Menczigar et al., 1993)
and EL (Engvall et al., 1993) were achieved. The PL of wafers grown in this way have
demonstrated several intriguing characteristics.
Figure 19 shows low-temperature PL spectra for a (Si)6(Ge)4 SLS wafer at different
annealing temperatures. The as-grown spectrum exhibited two strong emission peaks;
the strongest signal was identified as a no-phonon, interband transition and the other
was a phonon replica (labeled LEN‘ and LET’, respectively, in the figure). The total lu-
minescence intensity was much greater than that of an “equivalent” Sio.sGe0.4random
alloy. As the (Si)6(Ge)4 SLS wafer was annealed to higher and higher temperatures to
create more intermixing of the Si and Ge layers, the as-grown (Si)6(Ge)4 SLS spectra
evolved into that of the Sio.6Geo.4 alloy. Unfortunately, similar to the luminescence
from Er-doped Si, there is significant drop in intensity with increasing temperature.
While these results clearly show that the (Si),(Ge), SLS can achieve enhanced lumi-
nescence at low temperature relative to a Sil-,Ge, alloy, the oscillator strength is still
two to three orders of magnitude lower than that of direct-bandgap 111-V compounds
such as GaAs. Further, there is still uncertainty whether the enhancement is caused by
zone folding or symmetry breaking due to the presence of the Si-Ge interfaces. Turton
and Jaros (1990) have proposed that the rapid change of the microscopic potential at
the interface breaks the bulk nodal structure of the wave function. This, in turn, alters
the selection rule and thus creates an allowed transition across the bandgap.
370 JOE C . CAMPBELL

-
3,Ge,
32416
:=5 K

a
0
C

Y
c:
2

0.75 0.80 0.85 0.90 0.95 1.00 1.05

Energy (eV)

FIG. 19. Photoluminescence spectra ( 5 K) for a (Si)h(Ge)4 strained-layer-superlattice. Spectrum (a)

was obtained on the as-grown sample and spectra (h), (c), (d), (e), and (f) correspond to one hour anneals
at 550 OC, 600 O C , 650 O C , 700 OC, and 750 OC, respectively. Spectrum ( 9 ) shows the emission after a
complete anneal. Reprinted with permission from Menczigar et uI.( 1993).

Strong PL and EL have also been observed from pseudomorphic and Sil_,Ge, quan-
tum wells. There was some ambiguity in the interpretation of initial SiGe quantum
wells because the emission energies were below the projected bandgaps and, in some
instances, the emission peaks were close to those identified with dislocations. Recent
advances in crystal growth techniques have led to significantly improved luminescence
characteristics. Sturm ef al. (1993) have observed well-resolved bandedge lumines-
cence in strained Sil-,Ge, quantum wells grown on Si(100) by rapid thermal chemical
vapor deposition. A schematic cross section of this structure is shown in Fig. 20(a). The
luminescence was identified as due to shallow-impurity bound excitons at low tempera-
tures and to free excitons or electron-hole plasmas at higher temperatures. Electrolumi-
nescence was achieved above room temperature but for high temperatures ( 5 200 K),
the luminescence intensity decreased exponentially with an activation energy close to
that of the valence band offset. Figure 20(b) shows the EL spectrum at 300 K. At room
temperature, the estimated internal quantum efficiency was approximately 2 x 1Ow4.
Another type of Si 1-,Ge, heterojunction has achieved room-temperature photolumi-
nescence (Gail et al., 1995). These structures consist of Ge,Si,Ge, quantum wells
 Oxide
\
7 OPTOELECTRONICS IN S I L I C O N A N D

n type Sl svbrlralr
I1)
i Ti
-
sds,(;,~\lI,n
10prtOlid.
;!y
-.e_
v
c
.%

c
c
c
-
w
i
v)
0)
~

---
-
-

-
"
GERMANIUM
" i
SILICON

~ ~

sir,
" l ~

l l l l # l * l . , l l , , , l . ~
~
371
" i ~

embedded in Sil-,Ge, alloy. For m = 4 and n = 20 the drop in the luminescence

intensity from 77 K to room temperature was only about 20%. While there are still
questions regarding the physical mechanisms that are responsible for the luminescence
(Turton and Jaros, 1996) and electroluminescence has yet to be demonstrated, temper-
ature stability is encouraging.

IV. Guided-Wave Devices

Both active and passive Si-based guided-wave devices, including Sil-,Ge, struc-
tures, have been reported. Soref (1993) and Schuppert et al. (1996) provide good
reviews of work in this area. The passive structures usually contain straight sections
of waveguides with some combination of bends, couplers, andor '3"' branches. These
"building blocks" have been used to fabricate directional couplers, star couplers, grat-
ing feedback elements, multimode interference couplers, Mach-Zehnder interferome-
ters, optical power dividers, and spatial multiplexers.

1. WAVEGUIDES

The insertion loss for guided-wave structures is determined primarily by four factors:
(1) proper preparation of the end facets; (2) Fresnel losses at the input and output facets;
(3) attenuation in the waveguide; and (4) the mode mismatch between the waveguide
and that of the VO components, for example, optical fibers, End preparation is more
difficult for Si-based waveguides than for their 111-V compound counterparts because
372 JOE C . CAMPBELL

Si does not reproducibly cleave with smooth, vertical facets. Consequently, the ends
are typically polished, a time-consuming process that might be difficult to adapt to
mass production. Nevertheless, optical quality facets can be obtained. Antireflection
coatings with net reflectivity of less than 5% are routinely deposited by evaporation.
From a materials perspective, the passive waveguides can be grouped into three
broad categories: lightly doped Si on heavily doped Si (Soref and Lorenzo, 1985;
1986; Splett and Pettermann, 1994), Sil-,Ge, on Si (Soref et al., 1990; Schmidtchen
et al., 1994; Splett et al., 1990; Namavar and Soref, 1991b; Pesarchik et al., 1992;
Schmidtchen et al., 1992; Meyer et at., 1991), and Si on insulator (Soref et al., 1991;
Schmidtchen et al., 1991; Zinke et al., 1993; Rickman et al., 1994; Evans et al., 1991;
Emmons et al., 1992; Namavar and Soref, 1991a; Trinh et al., 1995; Rickman and
Reed, 1994; Fisher et al., 1996). Structurally, the two principal waveguide types are:
the rib waveguide and the diffused Sil-,Ge, buried channel. Schematic representa-
tions of these structures are shown in Fig. 21. The use of lightly doped Si on heavily
doped Si relies on the fact that the free carrier contribution to the refractive index is
negative. For n-type doping, which is most common for this type of waveguide, the
change in the refractive index achieved by heavy doping is given by the expression

N+:Si Si

SitSi SiGe/Si
L - 3-5dB/cm 1, - 0.6 dB/cm
(4

-42 Si
SiOz
Si Si
sits01 Ge Indiffused
L- 0.1 dB/crn L- 0.3 dBlcrn
(C) (d)

FIG. 2 1 . Schematic diagrams of four types of Si-based waveguide structures: (a) lightly doped Si on
heavily doped Si; (b) Sil-,Ge,/Si; (c) SUSOI; and (d) Ge-indiffused. A rib structure is used to achieve
lateral confinement in (a), (b), and (c). The Ge diffusion produces a buried channel waveguide.
 7 OPTOELECTRONICS IN SILICON AND GERMANIUM SILICON 373

where q is the charge on the electron, n is the refractive index of pure Si, EO is the per-
mittivity of free space, and N is the electron carrier concentration. These waveguides
are easy to fabricate and they are very compatible with conventional Si processing tech-
niques but the optical attenuation tends to be quite high (- a few dB/cm) due to free
carrier absorption of the evanescent field in the cladding region. Splett and Petermann
(1994) showed that this loss mechanism could be reduced by using thick (-20 pm)
N - layers. Waveguide losses in the range 1.2 to 1.5 dB/cm for both TE- and TM-
polarization at wavelengths of 1.3 p m and 1.55 p m were reported.
The addition of Ge to Si increases the refractive index, thus making epitaxial layers
of Sil -,Gex attractive candidates for Si-based waveguide devices. Assuming a linear
relationship between the refractive indices of Si and Ge (3.5 and 4.3, respectively,
at 1 = 1.3 pm), the refractive indices for small Ge concentrations is given by the
relation nS,Ge +
3.5 0 . 8 ~(Soref et al., 1990; Schmidtchen et al., 1994). It has
also been determined empirically (Soref and Lorenzo, 1986), that for strained layers,
IZSiGe X 3.5 + +
0 . 3 ~ 0 . 3 2 ~ From
~ . these relations it is clear that Sil-,Ge, wave-
guiding layers can be formed with only a few percent of Ge. The upper limit on x is
probably determined by the fact that the bandgap decreases with increasing Ge content
and the bandgap energy of the waveguiding layer needs to be greater than the photon
energy of the optical signal.
Sil-,Ge, rib waveguide structures have been fabricated from epitaxial layers grown
by MBE and by CVD. The lowest loss reported to date, for this type of waveguide,
was 0.6 dB/cm (Pesarcik et al., 1992). The core region, a 6.5-pm thick Sio.9xxGeo.olz
layer, was clad on both sides with Si, below by the Si substrate and above by a 3 wm
Si epitaxial layer. The mode size was approximately 8 p m in height with a width of
14 pm. As this profile is well matched to that of a single-mode fiber, low insertions
losses would be expected.
A diffusion technique, similar to that employed for Ti:LiNbOs, has been developed.
This approach has the advantage of utilizing conventional processing on commercial
Si substrates without the added cost and complication of epitaxial growth. In this case,
Ge is diffused from a Sil-,Ge, source that has been evaporated onto the surface and
patterned into the desired channel configuration. Typical diffusion conditions are 65 h
at 1200 "C. As this fabrication technique has been developed, the losses have contin-
ued to decrease; the champion values are currently in the range 0.3 dB/cm at 1.3 p m
and 1.55 p m for TE- and TM-polarizations. The diffusion process creates a refrac-
tive index profile that is relatively well-matched to a single-mode optical fiber. Using
the approximation of Gaussian mode profiles an overlap-integral calculation predicted
coupling losses of approximately 1 dB per facet.
Another approach for Si-based optical waveguides that has been very successful is
silicon-on-insulator (SOI) (Fig. 21c). One of the first structures of this type was silicon
374 JOE C. CAMPBELL

on sapphire (Namavar and Soref, 1991a). More recently, SO1 prepared by zone melting
recrystallization (ZMR), separation by implantation of oxygen (SIMOX), or bond and
etchback (BE) wafers have been used. Optical confinement in the vertical direction
is achieved because of the large refractive index differences between silicon and air
(on the top) and the Si02 layer (on the bottom). Figure 22 shows reported losses for
different SO1 materials (Zinke et al., 1993). As a result of the fact that they tend to have
lower defect densities, SIMOX and BESOI appear to be better suited than ZMR for this
application. The rib height and the roughness of its edges also significantly affect the
waveguide losses. By developing processing procedures that yield very smooth rib
edges, losses < 0.2 dB/cm have been reported for reactive ion etching (Trinh et al.,
1995; Rickman and Reed, 1994) and isotropic chemical etching (Fischer el al., 1996).
In order to attain low insertion losses, it is advantageous to maintain single-mode
operation. Fischer et al. (1996) have determined that the conditions for single-mode
profiles in the horizontal and vertical directions are

r
r = -t > 0.5 and
W
- <0.3t ~

h - h - d z 7
where h is the thickness of the Si overlayer and t and w are the height and width of
the rib, respectively. With BE-SO1 waveguides having h = 11 pm, t = 5.5 pm,
w = 8 pm, and length of 6 cm, they have obtained total fiber to waveguide to fiber
insertion losses of 0.9 dB, of which 0.3 dB, 0.1 dB, and 0.5 dB were estimated to be due
to the field mismatch, Fresnel reflections at the end faces, and waveguide attenuation,
respectively.

V ZMR
Ci SIMO:

1 10
top-layer thickness H, vrn
FIG.22. Optical attenuation of waveguides formed in three different types of SO1 (A = 1.3 pm).
Reprinted with permission from Schiippert ef aL( 1996).
 7 OPTOELECTRONICS IN SILICON AND G E R M A N ~ USILICON
M 375

2. INTEGRATED AND ACTIVECOMPONENTS

The Si-based waveguide structures described in the previous section have been used
to build devices that do more than simply route light. In order to combine waveguide
elements or to combine with active devices it is usually necessary to introduce bends.
The allowable bend radius is determined by the waveguide parameters such as the
effective lateral refractive discontinuity. Typically, it is found that bend radii of a few
tens of millimeters have acceptable bend losses (Schmidtchen et al., 1994; Rickman
and Reed, 1994).

a. Directional Couplers

Directional couplers are fundamental components for optical modulators and

switches. The first SiGe/Si directional coupler was reported by Mayer et al. (1991).
The coupler consisted of two adjacent Geo.4Sio.96 rib waveguides. The interaction
length was varied between 3 and 7 mm and the spacing between the waveguides was
varied from 1.5 to 3 Fm. For an interwaveguide gap of 3 p m the coupling coeffi-
cient was 3.9 cm-' and the coupling length was 0.46 cm. Ge-indiffused couplers have
also been fabricated and characterized for different coupling lengths and waveguide
spacings (Schmidtchen et al., 1994). As illustrated in Fig. 23, nearly polarization-
independent operation was obtained at 1.55 gm. A 3-dB coupler using BESOI was
demonstrated by Trinh et al. (1995). The waveguide attenuation was 0.2 dB/cm and

+-
a
v
\
N
a

coupling length L . r n n t

FIG. 2 3 , Coupling characteristics of a directional coupler fabricated with Ge-indiffused waveguides

(A = 1.55 pm). Note that almost complete transfer between waveguides is observed and that the coupling is
almost identical for TE- and TM-polarizations. Reprinted with permission from Schmidtchen et al.( 1994).
376 JOEC . CAMPBELL

the total insertion loss was 1.9 dB. To achieve 3-dB coupling with 2.5 p m waveguide
separation, the interaction length was approximately 400 pm.

b. Optical Modulators and Switches

The development of optical modulators and switches in Si-based materials has been
restrained by the absence of a linear electro-optic effect in column IV materials, a
direct result of the inversion symmetry of the centrosymmetric lattices. Although other
mechanisms, primarily free-carrier injection and the thermo-optic effect, have been
used to realize modulation and switching, the speed of these devices is much lower
than that of 111-V compound electro-optic devices.

Thermo-optic devices Thermo-optic devices make use of the temperature depen-

dence of the refractive index. As the bandwidth of thenno-optic devices is limited, it is
anticipated that they will be used in applications where switching speed is not a crucial
characteristic. For silicon, an,/aT = 2 x (Nazarova et al., 1988); compared to
other semiconductors this value is relatively high, which means that large changes in
the refractive index can be achieved at low drive power. Furthermore, because the ther-
mal conductivity of Si is very high, the induced heat can be quickly removed, which
enhances switching speeds. In addition, simplicity of their structures makes thermo-
optic devices attractive from both the cost and integration perspectives.
Treyz (1990) fabricated a thermo-optic modulator based on a multimode Mach-
Zehnder interferometer on SOI; a phase shift was induced in one arm of the interferom-
eter by modulating the current in a Ni0.8Cr0.2 heater that was deposited on top of that
arm. A maximum modulation depth of approximately 40% was achieved with a drive
power of 30 mW. The bandwidth was 20 kHz. Fischer et al. (1994) reported improved
performance with a similar structure. The primary difference in their device was that
the waveguides were single mode, which resulted in better extinction ratios and better
coupling to optical fibers. On-off ratios of 13 dB for TE and 9 d 3 for TM polariza-
tion were obtained and the switching time was 5 JLS. Higher speed was accomplished
with a thin-film thermo-optic Sio.96Geo.04Mach-Zehnder interferometer (Meyer et al.,
1991). The rib waveguides of this structure were fabricated by reactive ion etching and
NiCr thin-film heaters were formed on one arm of the interferometer by evaporation
and lift-off. The maximum extinction ratio was 8 dB for an applied power of 245 mW.
The bandwidth was determined to be 88 kHz by measuring transmission as a variable-
frequency ac signal was applied to the heater. Cocorullo et al. (1995) have used the
thermo-optic effect in a Fabry-Perot waveguide modulator. For this device, facets that
served as the mirrors of the Fabry cavity were formed in an N - N + Si waveguide by
RIE; the cavity length was 100 p m . Polysilicon heaters were patterned on the top of the

-
ribs. A maximum modulation depth of 60% was achieved for switching pulse energies
of 0.2 pJ and the 3-dB bandwidth was 700 kH.
 7 OPTOELECTRONICS IN SILICON AND GERMANIUM
SILICON 377

Free-carrierinjection devices Free-carrier modulators utilize the perturbation in the

refractive index that results from modulation of the carrier concentration in a semi-
conductor, which is frequently referred to as plasma dispersion. The value for the
carrier-induced change in the refractive index An is given by the classical Drude the-
ory (Eq. (1) with N representing the injected electron density). An alternate expression
that was determined empirically via Kramers-Kronig analysis of experimental data is
given by the expression A n = -8.8 x A N at h = 1.55 ,xrn (Soref and Bennett,
1986). For reasonable current densities relatively large values of A n can be achieved
but, as carrier injection frequently leads to local heating, plasma dispersion is usually
coupled to and opposed by the thermo-optic effect. Nevertheless, carrier injection has
been successfully used for several modulation schemes including in-line phase modu-
lation (Tang et al., 1994; Tang and Reed, 1995), active Fabry-Perot (Xiao et al., 1991),
reflective interference (Solgaard et al., 1990, 1991), optical absorption (Treyz et al.,
1991), a digital optical switch (Liu et al., 1994), and a Mach-Zehnder (Schmidtchen et
al., 1994; Fischer et al., 1994).
Tang and Reed (1995) have demonstrated that free carrier injection can be a very
efficient means of changing the refractive index, and thus the phase of the optical sig-
nal. For phase modulators, the figure of merit q is the induced phase shift per volt
bias per millimeter of length. Using a straight SO1 rib waveguide, the value of 17 was
found to be approximately 200 "Nlmmand was obtained at a drive current of 10 mA.
This is comparable to that obtained in similar 111-V compound modulators. Xiao et
al.( 1991) have introduced the carrier-injection phase change into a Fabry-Perot cavity
to achieve amplitude modulation. The basic structure, which could be integrated into
two-dimensional arrays, was very similar to that of resonant-cavity photodiodes except
without absorption within the cavity. The p-i-n was formed on SO1 and, for normal
incidence, the lower mirror was the Si/SiO;! interface of the SO1 substrate and the top
mirror was a polysilicon/SiO2/Si multilayer stack. A modulation depth of 10%was ob-
tained for a drive current density of 6 x lo3 Ncm2 and the bandwidth was 40 MHz. A
normal-incidence interference modulator, shown in Fig. 24, was reported by Solgaard
et al. (1990, 1991). Light is incident through the Si substrate where it impinges on a
split reflecting region. One side of the reflector has a p-n junction that can be forward-
biased to inject high carrier densities underneath one of the reflector sections. The
reflected wave comprises reflections from the passive section and the phase-modulated
section. For specific injection levels, interference between the two sections can inhibit
coupling back into the input fiber. A modulation depth of 24% with a 3-dB bandwidth
of 60 MHz and an insertion loss of 5 dB were reported.
Digital optical switches have been widely used for modulation and switching in
111-V compound optoelectronic circuits (Yanagawa et al., 1990). Liu et al. (1994) have
developed a similar device (Fig. 25) in Si using N - / N + rib waveguides. Each of the
branching waveguides has a p' junction (dark region in the figure) to permit carrier
injection. For a passive, symmetric Y junction the power will be coupled equally into
each arm. However, when one of the p-n junctions is forward-biased, the refractive
378 JOE C. CAMPBELL

m Aluminum

Slltcon a8vxiQI

Silicon Chlp with

&ubtor

FIG.24. Schematic cross section of Si interference modulator. Half of the incident signal is reflected
from the mirror on the left side. Beneath the right mirror, there is a p-n junction that can be forward biased
to change the refractive index beneath that reflector. The resulting phase modulation can create interference
and change the amplitude of the total reflected signal that is coupled into the fiber. Reprinted with permission
from Solgaard et al.( 1990).

output waveguide

input waveguide

FIG.2 5 . Silicon 1 x 2 digital optical switch. Reprinted with permission from Liu et aL(1994)
 7 OPTOELECTRONICS IN SILICON AND GERMANIUM
SILICON 379

index in that waveguide will decrease. If the plasma effect cancels the initial confine-
ment, that section will cease to be a waveguide and all of the power will emerge from
the other arm. By this technique, the incident signal can be switched between the two
outputs. This modulation technique has the advantage that it is relatively insensitive to
polarization or wavelength. For a current level of 290 mA, Liu et al. (1994) reported
22.3-dB extinction, insertion loss of 8.2 dB, and switching time of 0.2 ps.
A Mach-Zehnder modulator that used plasma dispersion was fabricated with Ge-
indiffused waveguides (Schmidtchen et al., 1994; Fischer et al., 1994); both the top-
view and cross section of a device with lateral p-n diodes are shown in Fig. 26. The
ordoff ratio was 16.5 dB at 1.3 p m for 200 mA switching current. It was determined
from time domain measurements that plasma dispersion and a significant thermo-optic
effect coexisted. The time constant associated with the plasma effect was 25 ns but
the thermal effect limited the bandwidth to 160 kHz. - -
c. Integrated Waveguide/Photodetectors

For some applications where cost is a driving factor, it may be advantageous to

integrate a photodiode with waveguide devices. To date, Sil-,Ge, photodiodes have

L- =4mm

-<=+-
4 L
-rTt

-n+
Ge-nddfused waveguide
fd)

SiO, Al-contact

Ge-indiiusedwavtaguide

p Si-substrate
(hi

FIG. 26. (a) Top-view and (b) cross section of Mach-Zehnder interferometer fabricated from Ge-
indiffused waveguides. Reprinted with permission from Fischer et al.( 1994).
380 JOEC . CAMPBELL

been integrated with SO1 (Kesan et al., 1990) and Sil-,Ge, waveguides (Splett et al.,
1994). Kesan et al. (1990) showed that SiGe photodiodes can be integrated with SO1
rib waveguides. The SLS Sio.4Geo.6 photodiodes had internal and external quantum
efficiencies of 50% and 12%, respectively, at 1.1 p m and 10 V bias. The RC-limited
bandwidth was 200 ps.
Splett et al. (1994) have fabricated an all SiCe circuit consisting of a 2.5 pm-thick
Sio.98Ge0.02 waveguide beneath an SLS SiGe photodiode. The absorbing region of
the photodiode consisted of 20 periods of 30 nm Si and 5 nm Si0.55Geo.45. The ex-
ternal quantum efficiency for a single-mode fiber input was -
11%. Taking into
account the losses due to fiber-to-waveguide coupling, attenuation in the waveguide,
and waveguide-to-photodiode coupling, it was estimated that the internal quantum ef-
ficiency was - 40%. The measured time response showed two components: a fast
response due to the RC time constant (- 2 GHz) and a slow response that was caused
by hole trapping in the quantum wells (- 50 ns). It was projected that the slow response
could be eliminated by using triangularly shaped barriers to facilitate hole transport out
of the wells.

V. Conclusions

Si-based approaches to emitters, photodetectors, and guided-wave modulators and

switches have been described. At present, most of these optoelectronic devices and cir-
cuits have not demonstrated performance comparable to state-of-the-art 111-V optoelec-
tronics. Nevertheless, the potential impact that results from leveraging Si-integrated
circuit technology is enormous. While there is little prospect that a Si/Sil-,Ge, tech-
nology will displace 111-V compounds for high-performance optoelectronics, there are
numerous factors that make a Si-based integrated circuit technology very attractive for
multiuser networks and high-density applications where manufacturability and cost are
key factors. Within the last decade great strides have been made in this area. All of
the essential components have been demonstrated and the remaining challenges will
encompass refinement of the device types and structures and improvement of overall
performance.

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SILICON 383

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 SEMICONDUCTORS AND SEMIMETALS, VOL. 56

CHAPTER8

Si1-,C, and Si~-,-,Ge,C, Alloy Layers

Karl Eberl, Karl Brunner and Oliver G. Schmidt
MAX-PLANCK-INSTITUT
FUR F E S T K ~ R P E R F O R S C H U N G

STUTTCART. GERMANY

I. INTRODUCTION ........................................ 387

11. GENERAL REMARKSO N T H E MATERIALC O M B I N A T I O N O F SI, GE A N D c . . . . . . . . . 390
111. P R E P A R A T I O N OF SI[-,C, A N D S I I - - + - ~ G E - + C ~LAYERS
B Y MOLECULAR
BEAMEPITAXY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
IV. STRUCTURAL PROPERTIES .................................. 394
1. Thermal Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
2. Local Strain of Substitutional C in Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
V. O P T I C A L PROPERTlES ..................................... 401
I . Si1-,C, Alloy Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
2. SiGeCAlloy Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
3. Si/Ge/Sil_,Cy Quantum Wells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
4. Carbon-Induced Ge Quantum Dots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
VI. ELECTRICAL TRANSPORT PROPERTIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
VII. SUMMARY/DEVICES ...................................... 418
REFERENCES. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419

I. Introduction

The fundamental properties and possible device applications of Si/SiGe heterostruc-

tures have been discussed extensively in the previous chapters. The lattice constant of
Ge is about 4% larger than in Si (see Table I and Kasper and Schaffler (1991)). There-
fore, a thin SiGe film is laterally compressed to match the in-plane substrate lattice
when grown epitaxially on Si (see Fig. l a and Fig. 2). This is also called pseudo-
morphic growth. Pseudomorphic Si/SiGe heterostructures are clearly advantageous for
device applications such as heterobipolar transistors and photodetectors. Additional
flexibility in the design of device structures is achieved by using thick relaxed SiGe
buffer layers as a virtual substrate, which allows one to adjust the strain (see Fig. lb).
This concept made it possible to prepare high mobility electron and hole channels in

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ISBN O - I Z - ~ ~ Z I ~ - X
0080-8784/99 $30.00
388 KARLEBERL,KARLBRUNNER
A N D OLIVER G . SCHMIDT

TABLEI. Properties of some group IV elements

Property Diamond /I-Sic Si Ge
Covalent radius (A) 0.077 - 0.1 I7 0.122
Lattice constant (A) 3.567 4.36 5.43 1 5.657
Lattice mismatch to Si -0.52 -0.246 - 0.040
f =t ~ -m
aSi)/afilrn
Bandgap at 4.2 K (eV) 5.48 2.2 1.19 0.66
Thermal conductivity (W/cmK) 20 5 1.56 0.6
Saturation drift velocity (107cm/s) 2.7 2.5 1 .o 0.6
Electron mobility (cm2Ns) 1800 - 1500 3900
Hole mobility (cm2Ns) 1600 - 450 1900
Dielectric constant 5.66 6.5 11.9 16
Table Data from Landolt-Bornstein (1982) and Ismail et al. (1994).

Si SiGe Si Si SiGe Si SiGe Si Si,,C, Si Si SiGeC Si

.... . .

CB
EB- ---lJ-
CB

- -u---

FIG. 1. Schematic illustration of the lattice structure and the alignment in the valence and the conduc-
tion hand in Si/SiGe heterostructures and recently realized C containing alloy layers on (100)-oriented Si
substrate: (a) Pseudomorphic SiGe layer on Si substrate and capped with a Si layer. The intrinsic lattice
constant of SiGe is larger than in Si. Thus, due to the Poisson effect in a pseudomorphic layer on Si the
lattice becomes tetragonally distorted. In other words, the lateral compression causes a lattice extension per-
pendicular to the layer. In this heterostructure there is a large band offset in the valence band. (b) A thin Si
layer grown on top of a thick strain-relaxed SiGe buffer layer is under tensile strain. In this case a significant
potential well can he realized for the electrons in the conduction hand. (c) Pseudomorphic Sil_?.CYlayers
on Si are also under hiaxial tension and provide an electron confinement potential. (d) SiGeC alloys are
lattice matched to Si if the Ge:C ratio is about 8.2 : 1. The bandgap of SiGeC is smaller than in Si.
 8 sI~-,c, AND S I 1 - x - - y G ~ x CALLOY
y LAYERS 389
b, h.
I I

- -film
_---
substrate

FIG. 2. Two-dimensional sketch of strained Sil-*Ge, and Sil-,C, on Si. The difference in lattice
constant is accommodated by tetragonal deformation of the epilayer. The upper part shows surfaces of
constant energy in k-space for the conduction band. It illustrates the influence of lateral strain on the 6-fold
degenerate A-valleys in Si. The two A-minima in growth direction become the conduction band minima in
Sil_,C, due to the lateral tension.

tensely strained Si (Ismail et al., 1994) and compressively strained Ge quantum wells
(Xie et al., 1993), respectively. An overview of this subject was given by Schaffler
(1997). The main problems of strain-relaxed buffer layers, however, include several
micron total film thickness, very high defect density, and characteristic surface rough-
ness.
A new concept towards strain adjustment was suggested by adding C into the Si/SiGe
material system. Carbon is much smaller than Si (see Table I) and, therefore, when in-
corporated onto substitutional lattice sites it reduces the intrinsic lattice constant. In
other words, the lattice constant of a Sil-,C, alloy is expected to be smaller than that
of Si. The first pseudomorphic Si1-,,Cy layers with tensile strain (see Figs. Ic and 2)
and Sil-,-,Ge,C, films (see Fig. Id) with reduced compressive strain directly on Si
were reported by Iyer et al. (1992), Eberl et al. (1992a), and Eberl et al. (1992b).
Before that, Posthill et al. (1990) published the first epitaxial growth of Sil-,C, alloy
layers on Si, but the films were very heavily dislocated, probably because they used rel-
atively high substrate temperatures during growth. Since that time, several groups have
prepared Si and SiGe films with substitutional C by molecular beam epitaxy (MBE)
(Osten et al., 1994; He et al., 1995) and different chemical vapor deposition (CVD)
and gas source techniques (Regolini et al., 1993; Atzomon et al., 1994; Lanzerotti
390 KARLE B E R L . KARLBRUNNER
AND O L I V E R G. SCHMIDT

et al., 1994; Rim et al., 1995; Mi et al., 1995; Todd et al., 1995a; Todd et al., 1995b;
Hiroi and Tatsumi, 1995; Kusunoki et al., 1996). Acetylene, methylsilane (SiCH4),
and C(SiH3)4 are used as C precursors. Other preparation methods include solid phase
epitaxy, which means room temperature co-deposition or implantation and subsequent
annealing (Strane et al., 1993; Kantor et al., 1997; Lu et al., 1995; Lu and Cheung,
1995; Boulmer et al., 1997), laser induced melting and solidification (Kramer and
Thompson, 1996), crystallization of Sil-,C, films by eximer laser annealing (Boher
et al., 1997), and ion-beam-induced epitaxial crystallization of ion-beam implanted
layers (Kobayashi et aZ., 1996).
The MBE- and CVD-grown pseudomorphic Sil-,C, and Sil -,-yGe,C, alloy lay-
ers on Si have demonstrated good crystal quality and are essentially free of extended
lattice defects when prepared under appropriate conditions. Tensile strain in Si l-yCq.
and strain reduction or strain compensation in Sil-,-,Ge,C, on Si has been observed
by many research groups in X-ray diffraction. Raman spectroscopy measurements
by Tsang et al. (1992), Rucker et al. (1994 and 1996), Dietrich et al. (1994), and
Mentndez-Lira et al. (1996) indicated that there is considerable local lattice deforma-
tion around the C atoms. Demkov and Sankey (1993) discussed the influence of local
strain around C atoms in the Si matrix on the basis of a first principles model calcula-
tion and predicted that the fundamental bandgap in unstrained Sil-yC, is reduced for
small amounts of C in the Si lattice. As a consequence of that the questions arise: What
are the effects on the electronic and optical properties, and how are camer mobilities
affected?
In this contribution we provide a review of recent experimental results on the struc-
tural analysis and thermal stability, lattice dynamic properties, photoluminescence (PL)
and electrical transport properties of pseudomorphic Sil-,C, and Sil-,-,Ge.,C, alloy
layers on Si (100).

11. General Remarks on the Material Combination of Si, Ge and C

Over the whole range of compositions Si and Ge are miscible with the average equi-
librium lattice constant of the SiGe alloy varying approximately linearly between that
of pure Si and Ge (as already outlined in preceding chapters). The solubility of C in Si
is only about 3.5 x 10'7cm-3 at the melting point (Landolt-Bornstein, 1982). Silicon
carbide (Sic) is the only stable compound. The original motivation of adding C into
the Si/SiGe heterostructure system was very much driven by the idea of achieving a
larger bandgap material on Si and by strain compensation. For example, researchers
have tried for a long time to grow Sic on Si in order to use it as a wide gap emitter in a
heterobipolar transistor. However, large lattice mismatch of 24.6% between Si and S i c
leads to formation of misfit dislocations, which deteriorate the device properties. The
hope was to reduce the problem of dislocation formation by incorporating only a small
amount of C in the few percent range in Si. It turned out, however, that the C forms
 8 sI~-,c, AND SI1--x--yG~xCyALLOYLAYERS 391

S i c precipitates very easily in the film when grown at high substrate temperatures.
The Sil-,C, alloys with 0 < y < 0.5 are thermodynamically metastable and can,
therefore, only be synthesized in a growth process that is not controlled by the thermo-
dynamic equilibrium of the whole crystal but rather by surface kinetics. Examples are
MBE and low-temperature CVD.
Carbon is a much smaller atom than Si and Ge (see Table I). The lattice mismatch
between Si and diamond is in fact 52% compared to only -4% between Si and Ge. In
other words, a pseudomorphic diamond film on Si would have to be laterally extended
by 52% to match the Si substrate. This means also that only a very small amount
of substitutional C in Si is necessary to introduce large average tensile strain in the
pseudomorphic epilayer. Assuming a linear dependence of the intrinsic lattice constant
ao(x, y) of Sil-,-,Ge,C, on the composition x and y between Si, Ge, and diamond
one gets the following expression:

aO(x, Y) = aSi -k (aGe - a S i b -k ( a C - aSi)y (1)

where uc is the lattice constant of diamond. Based on this linear interpolation it turns
out that the compressive strain of 8.2% Ge can be compensated by 1% C in a pseudo-
morphic Sil-,-,Ge,C, layer on Si substrate (Iyer et al., 1992). Osten et al. (1994)
used a linear interpolation between Sic, Si and Ge. In this case the expression for the
lattice constant of Sil-,-,Ge,C, is:

This formula provides strain compensation for 9.4% Ge by 1% C. The difference is due
to the fact that asic is not exactly in the middle between asi and U C . Moreover, U S ~ C
+
is 0.436 nm, whereas (asi ac)/2 is 0.461 nm. Kelires (1995, 1997) calculated the
lattice constant of Sil-,C, alloys ao(y) between Si and diamond and found a bowing
effect. The slight negative deviation from Vegard’s linear rule is described by:

An interesting conclusion of this calculation is that the lattice constant of stoichiometric

disordered Sio.5Co.s alloy is larger than for zinc blende silicon carbide (B-Sic). The
alloy has mixed bonds and thus can not aquire the optimum density of the unstrained
B-Sic. The result from Kelires (1997) in Eq. 3 suggests a o ( y ) = asi - 2 . 4 2 3 9 ~for
small amounts of C, whereas the extrapolation towards diamond provides ao(y) =
u ~-i 1 . 8 6 4 ~
for Sil-,C, alloys. The measured carbon concentrations indicated in this
chapter are based on the linear interpolation between Si, Ge, and diamond as described
in Eq. 1, because there are no experimental data for the exact lattice constants and
elastic constants of unstrained Sil-,C, alloys available to date. It must be noted that
the Kelires equation would reduce the carbon concentration indicated in the following
by about 30%; however, this does not change the other statements.
392 KARLEBERL,KARLBRUNNER
A N D OLIVER G. S C H M I D T

111. Preparation of Sil-,C, and Sil-,-,Ge, C, Layers

by Molecular Beam Epitaxy

A schematic drawing from a SiGeC-MBE system is shown in Fig. 3 . A directly

heated pyrolytic graphite filament is used for C sublimation with a typical growth rate
of up to 0.002 rids. It is important that the hot filament is completely surrounded
by graphite shieldings, and that the shutter is lined with graphite shielding to reduce
problems with metal, CO, and C02 contamination. Other C sources that have been used
in MBE are electron beam evaporators with pyrolytic graphite load (Faschinger et al.,
1995; Gutheit et al., 1995) and S i c sublimated out of a high-temperature effusion cell
using a graphite crucible (Joelsson et al., 1997). An alternative to solid sources are gas
sources, such as acetylene in MBE (Powel and Iyer, 1994).
Si is evaporated in an electron beam evaporator, which is feedback controlled by a
mass-spectrometer. For Ge a feedback-controlled electron beam evaporator or a spe-
cial PBN crucible effusion cell with a Si orifice plate to reduce boron background dop-
ing can be used. Elemental B and a GaP decomposition source (Lippert et al., 1995)
or Sb are used for p- and n-type doping, respectively. Typically the active multilayer
structures are grown on a 200-400 nm thick Si buffer layer. Optimized sample quality
with respect to photoluminescence (PL) intensity for Si/Sil-,C, quantum well struc-
tures is achieved at a substrate temperature of about 550°C for typical growth rates
of about 0.1 rids. The substrate temperature window for good layer quality is about
500-600°C for 1% C incorporation and it becomes narrower for higher C concentra-
tions (Powel et al., 1993). The C atoms on the surface reduce significantly the diffusion
of adatoms and thus at substrate temperatures below 450°C twinning occurs and very

Tisubl. turbo
PUP PUP

Si& gmwth at:

Temperature:450" - 650°C

Pressure: 1 0 0 rnbar

FIG.3 . Schematic drawing of the SiGeC-MBE system. The growth chamber has a base pressure below
'
3 x lo-' mbar. During deposition the pressure is typically in the l o r 9 mbar range. The load lock chamber
is shown on the left side.
likely amorphous growth is observed. For temperatures above 600°C, S i c phases are
very easily nucleated. The result is a mixture of a diluted Sil-,C, alloy with S i c
precipitates in the layer (Powel et al., 1993).
A cross-sectional transmission electron microscopy (TEM) image from a 30-period
Sil-,C,/Si superlattice grown by MBE is shown in Fig. 4. The thickness of the pseu-
domorphic Sil-,C, alloy layer is 5 nm. The carbon concentration is 1.6%. The TEM
indicates good crystal quality with homogeneous and planar layers. No extended de-
fects are observed. The composition and structural properties of the samples are also
determined by double-crystal high-resolution X-ray diffraction (XRD) and by compar-
ing the data with dynamical simulation results, which are based on Vegard's law and
linearly interpolated elastic constants. An example is shown in Fig. 5 , which shows
the XRD spectrum from a sample with three different layers on Si (100). A 200-
nm thick Sio.992Co.00~layer is followed by a 200-nm Si0.973Geo.063 and a 200-nm
Si0.93Ge0.063C0.008layer. The layers are fully strained to match the Si substrate. The
upper curve shows the measured spectrum; the lower curve shows the simulated data.
The Si0.992Co.oog peak is shifted to larger angles indicating tensile strain, in contrast
to the Si0.973Ge0.063 peak, which indicates lateral compression in the film. For illus-
tration see also Fig. 1, which shows the schematic lattice structure of pseudomorphic
Sil-,Ge, (a), Sil-,C, (c) and strain-compensated SiGeC (d) on Si. The XRD peak
from the Si0.93Geo.063C0.~8 layer falls together with the Si substrate peak. That means
the strain is compensated and the layer has about the same equilibrium lattice constant

200 nm Si Cap Layer

-100 nm

Multi-Layer Structure
30 Periods with
~ 5 . nm
2 S~,,,CO~~~
\15.6 nm SI

Bi-Substrate

FIG.4. Cross-sectional TEM micrograph from a 30-period Si0.984Co.o16/Sisuperlattice on Si (100)

substrate.
394 KARLEBERL,KARLBRUNNERAND O L I V E R G. SCHMIDT

105

h
u)
c 104
C
3

$
Y lo3
F-:
Id
w
I-
z
;3 10'
CK
X
1oo

-1800 -1200 -600 0 600 1200 1800

ANGLE (arcsec)

FIG. 5. Double crystal X-ray diffraction spectrum and simulated spectrum from a sample with three
different layers on Si (100). A 200-nm thick Si0,992C0.~8layer followed by a 200-nm Si0.973Ge0.063 and
a 200-nm Si0,93Ge0,063C0.~8layer is grown on a Si buffer layer.

as Si. The C content measured by XRD agrees well with the C nominally deposited and
calibrated by secondary-ion mass spectroscopy (SJMS) analysis. Within the absolute
uncertainty in SIMS, which is about lo%, we find a complete substitutional incorpo-
ration of C in Si layers within a fairly large range of growth temperatures in MBE at
growth rates of about O.lnm/s. A pronounced dependence of the substitutional C in-
corporation on growth temperature is not observed within the temperature range from
400 to 550 "C for C concentrations of about 1% (Zerlauth et al., 1997). For higher tem-
peratures or higher C concentrations the percentage of substitutional carbon drops and
a pronounced tendency to island growth is observed. Former results indicated a rather
small percentage of C on substitutional lattice sites for considerably lower growth rates
(Osten et nl., 1996).

IV. Structural Properties

1. THERMAL
STABILITY

Thermal stability of pseudomorphic Sil-,C, and Sil-,-yGe,Cy layers is important

for device processing conditions, which often involve high temperature annealing steps.
 8 sI1_,cy ALLOYLAYERS
AND SI1--x--vG~nCy 395

Usually metastable alloy films relax by diffusion and/or misfit dislocation formation
to reduce both, chemical modulation and strain (Iyer and LeGoues, 1989). Sil-,C,
alloys have an additional possible mode for relaxation, which is S i c precipitation. S i c
is the only thermodynamically stable compound for these structures as the solubility of
carbon in Si is extremely low. Therefore Sil-,C, and Sil-,-,Ge,C, strained layers
may be unstable against not only diffusion and dislocation formation, but also S i c
precipitation.
Figure 6a shows an X-ray rocking diffraction curve of a 10 period Si0,99Co,ol/Si
superlattice with individual layer thicknesses of 10 nm and 13.5 nm, respectively. Also
shown is a dynamic simulation fit to the data. The main peak at A@ = 0 is the [004]

- b)
I
I " ' -
sio.!&o.ol/si
10 periods

1ooooc

9oooc

8OO0C

7OO0C

-2000 0 2000 4000

-
5
? lo3
ds& Onwdspl 3.5nm

Gy Id
Y
?!
i
210'
X

FIG. 6. (a) Double crystal X-ray diffraction from (004) lattice planes and simulated spectrum from a
pseudomorphic IGperiod 10 nm Sio.99Co,o1/13.5 nm Si superlattice on Si. (b) X-ray diffraction data for
the sample shown in (a) after one hour annealing at 700 OC, 800 OC, 900 "C, lo00 'C and 1100 OC.
396 KARLEBERL,KARLBRUNNERAND OLIVER G. SCHMIDT

diffraction from the substrate. The zero order peak originating from the superlattice
structure is shifted to A@ = 360 arcsec. This indicates the average tensile strain in the
superlattice. The good crystal quality of the sample is reflected in the strong intensity
of the high order superlattice peaks, in the small line width and the clearly observable
Pendelosung fringes between the main peaks.
The thermal stability of this multilayer is investigated by annealing different pieces
of the sample shown in Figure 6a for one hour at 700,800,900, 1000 and 1100°C. The
corresponding X-ray diffraction spectra are shown in Figure 6b. No significant change
is observable up to 800°C. After 900°C the superlattice peaks disappear completely,
which is due to considerable interdiffusion of the individual layers. At the same time
the zero order peak shifts slightly towards the substrate peak at A @ = 0. This indicates
the beginning of strain reduction. For higher annealing temperatures of 1000°C the
epilayer peak continues to move towards the substrate peak. The spectrum for 1100°C
looks almost like bulk Si. Obviously the C disappears almost completely from the Si
lattice sites and forms precipitates, which are clearly visible in cross-sectional TEM
for extensive annealing at temperatures above 900°C (Fig. 7). The precipitates are
localized entirely to the layers that contained substitutional C initially, and they are a
few nanometers in diameter (Powel et al., 1994).
More detailed X-ray diffraction studies (Goorsky et ~ l . ,1992; Eberl et al., 1994;
Fischer et al., 1995; Osten et al., 1996; Fischer and Zaumseil, 1995) provide the fol-
lowing picture for Sil-,C, layers: Regardless of the large tensile strain introduced
by substitutional C, the SiI-,C, alloy layers are stable up to extended annealing at
800°C. Beyond this temperature the C interdiffuses. For temperatures of about 900°C
and higher the C diffuses to regions of high C concentration and forms S i c precipitates.

FIG. 7. Cross-sectional TEM micrograph from the sample shown in Fig. 6(h) after 1 h annealing at
1000 'C. The C in the Si0.99Co.ol layers diffuses during the annealing process towards C-rich places and
forms S i c clusters, which are marked by arrows. Misfit dislocations are not observed in TEM even after
extended 1100 " C annealing.
 8 sI1-,c, AND S11-,,-,GExCY ALLOYLAYERS 397

The strain in the pseudomorphic Sil-,C, alloy layer is not reduced by introduction of
misfit dislocations. In contrast to the mechanism of strain relief in Sil-,Gex in com-
parably strained Sil-&, layers the relaxation process is precipitation.
The annealing behavior of pseudomorphic Sil-,-,Ge,C, layers and superlattice
structures has been investigated in the temperature range from 750 to 900°C (Fischer
et al., 1997) and between 1000 and 1130°C (Warren et al., 1995). Carbon incorpora-
tion changes the thermal stability of SiGe layers significantly. As for pseudomorphic
Sil-,C, layers the plastic relaxation is suppressed by the dislocation pinning effect
of C. No relaxation of Si0.597Ge0,391C0,012/Simultilayers was observed during anneal-
ing at up to 875°C for 3 h. For comparison a reference SiGe sample without C relaxed
by misfit dislocation nucleation at 800°C. However, C strongly increases the interdif-
fusion of Ge in Si. The activation energy of this Ge diffusion process for a Ge content
of 40% decreases from about 4.8 eV for SiGe to about 2 eV for SiGeC with 1.2% C
(Fischer et al., 1997). For annealing temperatures of above 1000°C the substitutional
C diffuses and forms S i c precipitates. The perpendicular lattice constant of pseudo-
morphic strain-reduced or even strain-compensated Sil -,-,GexCy layers increases,
which is due to the decreasing C concentration in the lattice. That means that com-
pressive strain increases as the amount of substitutional C decreases by forming S i c
precipitates.
Osten et al. (1997) have reported a significant reduction of boron diffusion in SiGe
layers with very small amounts of substitutional C in the 10'9cm-3 range. This effect
is very useful for SiGe heterobipolar transistors, because it allows higher and sharper
boron doping in the SiGe base layer and increases the overall process margins, which
leads to more freedom in device design.

2. LOCALSTRAIN OF SUBSTITUTIONAL c IN SI

The covalent radius of carbon atoms is much smaller than for Si as was already men-
tioned. Therefore, it is obvious that substitutional carbon atoms in a diluted Sil-,C,
alloy introduce a considerable amount of local strain. Raman spectroscopy measure-
ments by Tsang et al. (1992), Rucker et d.(1994, 1996), Dietrich et al. (1994), and
Menkndez et al. (1995) clearly indicate that there is a local lattice deformation around
the C atoms in Si and SiGe. An overview of this discussion is provided by Jain et al.
(1995).
A typical Raman spectrum of a 200-nm thick Sio.g9sCo.~slayer on Si (100)is shown
in Fig. 8. The presence of a small amount of C adds mainly one peak at 604 cm-',
which is the isolated substitutional C vibration. There is no sign of defect-activated
acoustic phonon scattering or a Sic-like phase in the range of frequency shifts from
10&1000 cm-' . The scattering cross section per C atom is independent of the Sil-,C,
alloy concentration for y < 2%. A second C-induced peak is observed near 475 cm-'
(marked by an arrow in Fig. 8). This peak is broader than the bulk Si peak or the
398 KARLEBERL,KARLBRUNNER
AND OLIVER G. SCHMIDT

I I I I I I
h
Si
-b -
-1=488nm
T-300K
7
--
Si- C -Si -
I
E Si
cn
c - -
CQ
.-C Substrate wbtracted
S
E-
c l
I I

FIG. 8. Raman spectrum of a 200-nm thick Si0,995Co,y~5layer on Si (100) with the first-order LO
phonon symmetry allowed. The presence of a small amount of C adds mainly one peak at 604 cm-' , which
is the isolated substitutional C vibration. The linewidth of the C-peak is about 7 cm-' .

C local mode and indicates lattice relaxation around the substitutional C atoms in Si
(Tsang et al., 1992; Rucker et al., 1996). The atomic structure around a substitutional C
atom in Si calculated from the anharmonic Keating model is shown in Fig. 9 (Dietrich
et al., 1994). The first and second nearest-neighbor Si atoms surrounding the C atom
are displaced from the bulk lattice sites towards the C atom because of the shorter Si-C
bond length compared to the Si-Si bond length.
Ab initio total energy calculations from Tersoff (1 990) indicated that the most stable
position of carbon in Si is the substitutional site. This way the carbon can form strong
covalent bonds to the four nearest-neighbor Si atoms and does not introduce doping
with extra electrons or holes. This picture is confirmed by the experimental results
discussed throughout Tersoff's article (see also Zerlauth et al., 1997). The interaction
energy for two substitutional C atoms in Si is shown in Fig. 10. The interaction is re-
pulsive for first and second, but attractive for the third nearest-neighbor arrangement
(Rucker et al., 1994). The inset in Fig. 10 shows the third nearest-neighbor arrange-
ment of two carbon atoms (black). For this geometry the carbon atoms sit at opposite
corners of a 6-fold ring where they can accommodate the short Si-C bonds relatively
easily without strong bond-bending distortions. A very careful Raman analysis on
Sil-,C, alloy layers was performed by combining theoretical and experimental results
for local Si-C phonon modes (Rucker et al., 1996). Figure 1 I shows a Raman spectrum
around the substitutional Si-C vibration of a pseudomorphic Sio.994C0.006layer. The
arrow indicates the satellite peak at 625 cm-' arising from the third nearest-neighbor
C pair geometry shown in Fig. 10. Calculated spectra for a random alloy (dash-dotted
 8 sI1-,cy AND S I 1 - x - y G ~ x C yALLOYLAYERS 399

FIG. 9. Atomic structure around a substitutional C atom (gray) in Si calculated from the anharmonic
Keating model (after Dietrich et al., 1994). The ideal Si lattice sites are indicated by black underlying circles.
The normal direction of view is [ 1 101. The Si atoms surrounding the C atom are displaced from the lattice
sites towards the C atom because of the shorter Si-C bond length compared to the Si-Si bond length.

r - I

.o wP b -

] , -.2 I
2.0 4.0 6.0 8.0
C-C distance (A)
FIG. 10. Interaction energy for two substitutional C atoms in Si calculated by a Keating model. The in-
teraction is repulsive for first and second, but attractive for the third nearest-neighbor arrangement (reprinted
with permission from Riicker et al., 1996).
400 KARLEBERL,KARLBRUNNER
A N D OLIVER G. SCHMIDT

.-0
c. - Experiment
- - - . short range order
3 -.-.-.. random alloy

550 600 650

Frequency (cm-’)
FIG.1 1. Raman spectrum around the Si-C vibration of a pseudomorphic S i o . ~ ~ ~ C olayer
, o oon
~ Si( 100)
(solid line). The arrow indicates the satellite peak at 625 cm-l arising from the third nearest-neighbor C
pair geometry shown in Fig. 10. Calculated spectra for a random alloy (dash-dotted line), and for an alloy
with a 4 x enhanced occurrence of the third nearest-neighbor occupation (dashed line). The occurrence of
the second nearest-neighbor pairs was reduced by a factor of four in this case (reprinted with permission
from Rucker et al., 1996).

line), and for an alloy with a 4 x enhanced occurrence of the third nearest-neighbor
occupation (dashed line) are included. The occurrence of the second nearest-neighbor
pairs was reduced by a factor of four in this case. By comparing the theoretical spec-
tra with those obtained by Raman spectroscopy, Rucker and his co-workers (1996)
concluded that the probability of a third nearest-neighbor coordination of the carbon
atoms is considerably above that for a random alloy. The local atomic structure of strain
compensated Sil-,-,Ge,C, alloys on Si has been discussed in detail by Dietrich et al.
(1994). Local strain fields introduced by substitutional carbon broaden the Si-Si, Si-Ge
and Ge-Ge Raman peaks by elongating bonds close to the carbon atoms. The substitu-
tional carbon peak around 605 cm-’ is also broadened as compared to Sil-? C, alloys
(Eberl ef aE., 1992b). The Raman results indicate that the Si-Si bonds are not identi-
cal to those in unstrained bulk Si for strain-compensated Sil-,-,Ge,C, alloys, which
have the same average lattice constant than Si. It was found that the experimental and
theoretical results are compatible with Vegard’s law.
 8 sI1-,cy AND S I 1 - - x - y G ~ x C y ALLOY LAYERS 401

V. Optical Properties

1. S I I - , ~ , ALLOYLAYERS

The lattice mismatch between Si and Ge is only 4%, therefore the fundamental prop-
erties can be interpolated for SiGe alloys to a large degree. The intrinsic bandgap of
Sil-,C, alloys was expected to increase homogeneously with the C content, because
the band structures of Si, cubic Sic, and diamond are very similar with the exception
of the energy value of the bandgap as shown in Table I (Soref, 1991; Powell et al.,
1993). Recently, obtained PL data indicate a strong bandgap reduction for pseudo-
morphic Sil-,C, alloy films (Brunner et al., 1996a; Penn et al., 1997; Brunner et al.,
1996b; Joelsson et al., 1997).
Figure 12a shows a typical PL spectrum from a 30-period 5.2 nm Sio.99Co.01/15.6nm
Si multiquantum well (MQW) structure. The Si-TO phonon-assisted PL at 1.1 eV orig-

MQW structure
QW-NP
30 x (52A Si,aaC,ol/ 156A Si)

Si-TO
QW-TO

., Q W - F r )
QW-TA

h----kFx5

52A Sil,Cy QWs

;1.10
g! 1.08
y 1.06 fCf A(2) &&On6
W
z
1.04 1.10 w
-I

a 1.02 a
1 .oo 1.08
0.0 0.5 1.0 1.5 2.0 0 20 40 60 80 100
CARBON CONTENT y (%) LAYER WIDTH dsi, (A)

FIG. 12. a) Low temperature PL spectrum of a 30-period S ~ O . ~ ~ C Omultiple . O ~ / Squantum

~ well struc-
ture. The Si and Sil-,C, layers are 15.6 nm and 5.2 nm thick, respectively. b) Energy of the no-phonon PL
peak as a function of the carbon content. c) Energy of the no-phonon PL peak as a function of the Si0.99C0.01
layers thickness. For smaller thickness the PL peak shifts to higher energies due to the quantum confinement
effect in the SiI-,C, quantum wells.
402 KARLEBERL,KARLBRUNNERA N D O L I V E R G . S C H M I D T

inates from the Si substrate, buffer layer and 200-nm Si cap layer. The intense PL peaks
from excitons confined in the quantum wells (QWs) are the Si-Si TO phonon replica at
1.032 eV and the no-phonon (NP) transition at 1.089 eV. The linewidth of these peaks
is about 12 meV. The weak PL shoulders labeled as QW-TA and QW-(TO+Or) are
probably TA phonon and TO plus r point optical phonon-assisted recombinations of
carriers confined in the Sil-,C, quantum wells. All lines labeled with QW shift as a
function of the C content y in the Sil-yCy layers as shown for the no-phonon line in
Fig. 12b. The PL energy of the NP line shifts linearly by A E N P = - y . (5.7 eV), re-
flecting the decrease of the fundamental bandgap in the MQW structure. For the layer
thickness of 5.2 nm and a C content of about 2% or more we observe an increasing
broad emission background at low energy, which is similar to the broad PL reported
earlier (Kantor et al., 1997). In thinner Si1-,C, MQWs we observe bandedge PL for
a C content of up to about y = 6.4% (Brunner et aZ., 1996b).
Figure 12c shows the energy dependence of the NP PL peak from 30-period
Sio.99Co.ol/15.6-nm Si MQWs as a function of the Sio.99C0.01 alloy layer thickness
d s i c . The peak is shifting to higher energy by reducing the QW width dsic. This proves
that the PL lines originate from quantum-confined levels and not from defect states
related to C incorporation. The measured data follow the curve, which represents a
Kronig-Penney-Model calculation for the 2-fold degenerate conduction bandedge A(2)
and thus uses m = 0.92mo as the effective mass for the electrons and neglects any band
offset in the valence band. This and more detailed PL studies on MQW structures with
the Sil-,C, layer thickness constant and varying of the Si layer thickness indicate that
the band offset in this heterostructure is mainly in the conduction band (Brunner et al.,
1996a; Houghton el al., 1997), which is complementary to the situation for pseudo-
morphic Si/SiGe heterostructures, where the band offset is mainly in the valence band.
More recent experiments on Si/Sil -,C, heterostructures using PL energy shifts under
applied external strain (Houghton et al., 1997), admittance spectroscopy (Stein er al.,
1997) and X-ray photoelectron spectroscopy (Kim and Osten, 1997) indicate also a
small valence band offset.
This band alignment model is also supported just by looking at the strain-induced
splitting of the electron and hole valleys. Figure 13 shows a schematic diagram of
the conduction (CB) and valence bandedge (VB) for pseudomorphic Sil-,Cy layers
on Si (100). It is based on a deformation potential calculation. The tensile biaxial
strain introduced by substitutional C splits the electron valleys and thus, the twofold
degenerate conduction bandedge A(2) is shifted down in energy by about A E A ( 2 ) =
- y . (4.6 eV). In the valence band the light hole states are expected to increase only
slightly in energy with increasing tensile strain E = 0.35 . y .
Comparing the PL data with the expected energy shift caused by the tensile strain,
we get the following picture for pseudomorphic SiI-,C, alloys: For small C contents
of up to about 2.5% the optical bandgap shrinks by about A E ( y ) = - y . (6.5 eV).
This takes the electron confinement into account, which is about 8 meV for a 5.2 nm
QW as shown in Fig. 12. Because the tensile strain accounts for only about -y.(5 eV),
 403

FIG. 13. Schematic diagram of the conduction (CB) and valence bandedge (VB) for pseudomorphic
Si1-,C, on Si (100). It is based on a deformation potential calculation taking the tensile strain within the
Sii -,C, layer into account and neglecting the intrinsic effects of C on the band offset.

we conclude that the intrinsic bandgap of unstrained Sil-,C, will decrease roughly by
A E, ( y ) = -y . (1.5 eV) for small C concentrations. Exciton binding of electrons and
holes with a typical energy of 10 meV are neglected. The tentative change of the fun-
damental bandgap for unstrained and strained Si1-,C, alloys is illustrated in Fig. 17
by the continuous and the dashed curves starting from Si towards the left, respectively.
A strong bowing departure from linearity between Si and diamond was found for the
band energies of unstrained Sil-,C, alloys by Orner and Kolodzey (1997) based on
a virtual crystal approximation with linear combination of atomic orbital method. For
small carbon concentrations this calculation predicts a very small increase of the funda-
mental bandgap, which is defined by the A minimum throughout alloy compositions.
The experimentally found trend of slightly decreasing bandgap was proposed by a lin-
ear muffin-tin-orbital method with the atomic-sphere approximation (Xie et al., 1995).
However, the intrinsic shift of about -( 10 to 20) meV experimentally observed for 1%
carbon in Sil-,C, (Brunner et al., 1996a) and Sil-,-,Ge,C, (Amour et al., 1995) is
smaller than the value of about -30 meV calculated by Xie et al. (1995).
Higher energy optical interband transitions in Sil-,C, have been investigated by el-
lipsometry and electroreflectance measurements (Kissinger et al., 1994; Zollner et al.,
1995). It turns out, that the EO and E2 gaps decrease slightly with increasing carbon
concentration, whereas the El gap increases in energy. This behavior is discussed on
the basis of established deformation-potential theory by Zollner (1995). The observed
shifts of El have the expected sign and magnitude of about 40 meV per percent carbon,
but the lack of similar shifts of the EO and E2 gaps is not yet understood. Part of the
disagreement with the deformation-potential model is the assumption that homogenous
strain in the layer may be explained by local strain effects as indicated by Demkov and
Sankey (1993) and Gryko and Sankey (1995).
404 KARLEBERL,KARLBRUNNER
A N D OLIVERG. SCHMIDT

2. SIGEC ALLOYLAYERS

Figure 14 shows low-temperature PL spectra from a Sio.g4Geo.16 and two

Si0.84-yGeo.~6CyMQW structures with y = 0.008 and y = 0.01. The samples have
25 periods and the thickness of the Si0.84Ge0.16 and Si0.84-yGe0.16Cy layers is 4 nm.
The QWs are separated by 17-nm thick Si layers. The main PL originating from the
QWs are no-phonon and TO-phonon lines of confined carriers. The intense peak at
E = 1.1 eV is the TO-phonon replica from the thick Si layers. For compressively
strained Sil-,Ge, on Si the band offset is mainly in the valence band with the heavy
hole (hh) shift being about AEhh = x (0.72 eV) (Sturm et al., 1991). f

The band alignment for Si/SiGe is schematically shown in the middle part of Fig. 15.
In the conduction band there is a small offset for the A(4) electron valleys (Thewalt
et al., 1997). The PL from Sio.842Geo,l&o.oog MQWs is shifted to about 20 meV higher
energy compared to the Si0.84Geo.l6 as shown in Fig. 14. The substitutional incorpo-
ration of 0.8% c into Si0.84Ge0.16 reduces the compressive strain from E = -0.64%

-
1.10
I " " I ~ " ' 1 " " 1 -" " 1 " " ~ ~

% 1.09 -
v
40A Si ,,Ge ,& QWs-- T= 8K

Si-TO
1.08
8z 1.07
1.06
a 1.05 -
1 1 1 1 1 1 1 . 1 . 1

0.0 0.5 1.0 1.5

CARBON CONTENT y (%)
?
3 QW-NP
cd si mGe mC 01 Qw QW-TO
v
------ Si-TA
c
v)
z
W
I-
z
-I
a
0.90 0.95 1.00 1.05 1.10 1.15
ENERGY (eV)

FIG. 14. The PL spectra from a 25-period Si/Si0.84Ge0.16 and two S ~ / S ~ O . + - ~ G ~multiple O.~~C~
quantum well structures with y = 0.008 and y = 0.01. The Si and Sil_,-,Ge,C, layers are 20 nm
and 4 nm thick, respectively. The TO phonon replica and the no-phonon (NP) PL peaks labeled with QW
originate from the quantum wells. The low-intensity shoulder close to E = 1.035 eV is the TO O ( r ) +
phonon-assisted transition from the Si substrate and buffer layers. The inset shows the energy shift of the
no-phonon PL energy as a function of the carbon concentration.
to -0.36%. The PL blueshift is attributed to the strain-induced increase and a minor
intrinsic lowering of the fundamental bandgap as pointed out by Amour et al. (1995
and 1997) and Brunner et al. (1996~).For carbon concentrations in Si0.84-~Ge0.16C,
that are higher than 0.8% we find a downward shift of the PL energies as shown by the
topmost spectrum in Fig. 14 with y = 1% and, more precisely, in the inset of Fig. 14.
The bandgap increase in Sil-,-,Ge,C, is schematically illustrated in the right part
of Fig. 15. Due to partial relief of compressive strain the A(2) to A(4) and the hh to
lh splittings are reduced and would be brought back to degeneracy in case of perfect
strain compensation, which is achieved for about y = x/8.2. In addition to the strain
effect there is an intrinsic effect of carbon on the bandgap for relaxed Sil-,-,Ge,C,
as for the Sil-,C, alloys that were discussed in the last section.
The bandgap in pseudomorphic Sil-,Ge, with x < 25% is (Dutarte et al., 1991):
E g ( x ) = 1.171-1.01x+0.835x2 eV. Thus, the bandgap of strained Sio.84Geo.16 is 1.03
eV at 4.2 K, which is 140 meV smaller than that of Si. We assume that substitutional
C increases the energy gap by about A E = y ' (0.24 eV) based on the extrapolation
of the increasing NP-PL energy shown in the insert of Fig. 14 for up to y = 0.008.
As a consequence, for strain-compensated Sio.82Geo.16C0.02on Si the bandgap would
still be about 100 meV smaller than in Si. For comparison, unstrained Sio.84Geo.16
has a bandgap of about 1.11 eV, whereas the relaxed Si0.82Ge0.16C0.02film would have
a roughly 30 meV smaller bandgap of about 1.07 eV. A similar result was reported
for x = 0.24 and 0.38 by Amour et al. (1991) and by Boucaud et al. (1995). The
decrease of the NP-PL energy above y = 0.008 (see inset of Fig. 14) has not been
investigated in detail so far. It can be explained by (A2) - (A4) energy level crossing
due to confinement effects.
Just considering the effects of strain reduction and neglecting intrinsic effects, one
would expect that the VB offset decreases with increasing carbon content (see Fig. 15).

Si SiGe SiGeC

VB hh, Ih
- hh
Ih

FIG. 15. Schematic diagram of the conduction (CB) and valence bandedge (VB) for pseudomophic
SiGe and SiGeC on Si (100). The effects of substitutional C in SiGe are shown at the right side of the picture
just by considering the effect of partial reduction of compressive strain. Intrinsic effects of C on the bandgap
and the band offsets are not considered.
406 KARLEBERL,KARLBRUNNERAND OLIVER G. S C H M I D T

The continuous shift to lower energies for y > 0.01 and especially PL measurements
on coupled quantum wells (Brunner et al., 1996c), indicate a constant or slightly
increasing valence band offset in SVSiGeC. This is confirmed in X-ray photoemis-
sion spectroscopy (Powel et al., 1994; Kim and Osten, 1997). On the other hand,
there are a number of reliable experiments like intersubband absorption (Boucaud
et al., 1996; Warren et al., 1997), admittance spectroscopy (Stein et al., 1997) and
capacitance-voltage measurements on p-type MOS structures (Rim et al., 1995), and
pf Sil-,-,Ge,C, / p- Si unipolar diodes (Chang et al., 1997), which clearly indicate
a significant decrease of the valence band offset in Si/Sil-,-,Ge,rC, heterostructures.
Chang et al. (1997) have reported a value for the valence band offset reduction between
20-26 meV per percent carbon. This means that the bandgap shift in Sil-,-,Ge,C,
alloys due to carbon incorporation would be almost completely in the valence band.
Figures 16 and 17 summarize and compare the effects of substitutional carbon on
the bandgap and band alignment in Si/Sil-,C, and Si/Sil-,-,Ge,C, heterostruc-
tures. Figure 16 shows the calculated bandedge energies in strained Sil-,Cy, (a) and
(Si0,7Ge0,3)1-~C, (b) on Si( 100) using a deformation potential approach (Brunner
et al., 1997). In Fig. 16a the energy shifts caused by lateral strain of 6 = 0 . 3 5 ~in
Sil-,C, on Si are taken into account. The intrinsic influence of C is neglected. The
tensile strain splits and shifts the electronic levels as already discussed in the previous
section. The A(2) states are strongly decreasing and the lh states are slightly increas-
ing in energy. They form the bandedges and the observed PL in Fig. 12 is attributed

I. .
0 2 4 6 8 10120 2 4 6 8 1012
C CONTENT y (Yo)
FIG.16. Calculated bandedge energies in strained Sil-,,Cy, (a) and ( S i 0 . 7 G e 0 . 3 ) l ~ ~(b)
C ~on Si(100)
using a deformation potential approach. The horizontal lines at E = 0 and about E = 1.18 eV indicate the
bandedge energies in Si. The energy shifts caused by lateral strain and the band offsets introduced by Ge are
taken into account. The intrinsic influence of C is neglected.
 8 sI1-,c, AND SIl-x-yG~,Cy ALLOYLAYERS 407

1.6 I ' I ! ' I ' I ' 1

A(2) - Ih
! A(4) - hh
-
i Si (001)
W
- Si,,C, !substrate
1.2
>. unstrained/
0
elf 1.0
-- -~I.s~v
/
/'

Lu I
z strained I
/

0.8 - -y6.5eV
a
0 0.6 -
n
z
a
m
0.4

0.21'
t ' ' ' ' '
strained

' I '
I
5.3 5.4 5.5 5.6 5.7
LATTICE CONSTANT a (A)
FIG. 17. Bandgap in strained and unstrained Sii-yCj,, Sil-,Ge, and Sil-,-yGe,Cy. The PL re-
sults from strained SiI-,C, layers are shown by a dashed line. The bandgap for unstrained Sij-,CY is
indicated by the solid line. The thin full line and the thin dashed line show the bandgap for unstrained and
pseudomorphic Sil-,-rGe,Cy layers, respectively.

to spatially direct type I transitions within the Sil-,C, quantum well. The bandgap
reduction deduced from PL is attributed mainly to strain effects.
For (Sio.7Geo.3)1 -yCl, the strain-mediated influence of carbon on the bandedges is
different from pseudomorphic Si1-&,. Compensation of strain reduces the level split-
ting and opens the bandgap by about A E = y x 3.8 eV when neglecting the intrinsic
influence of C. At a carbon content of y = x / 8 . 2 where perfect strain symmetrization
is achieved, the A(2) and A(4) as well as the lh and hh states recover degeneracy as
in unstrained Si. This is achieved for y = 3.4% in the example shown in Fig. 16b.
For higher carbon concentration the (Si0.7Ge0.3)1-,C~alloy is under tensile strain and
bandgap reduction is similar as for the case of Sil-,Cy alloy layers on silicon.
Figure 17 shows the bandgap vs lattice constant for strained and unstrained Sil-yCy,
Sil-,Ge, and Sil-,-,Ge,C,. The solid curve between Si and Ge indicates the bandgap
for unstrained SiGe alloys with the characteristic kink at about 85% Ge, which is due
to the crossover from the Si-like 6-fold A minima to the Ge-like 4-fold L minima in
the conduction band (CB). The dashed line towards Ge shows the reduction of the
bandgap for pseudomorphic SiGe on Si, which is determined by the strain-degenerate
4-fold A minima in the CB and the heavy holes (hh) in the valance band (VB). The
PL results from strained Sil-,C, layers are shown by a dashed line starting from Si
408 KARLEBERL,KARLBRUNNER
A N D O L I V E R G. SCHMIDT

towards smaller lattice constants. The bandgap for unstrained Si1-,C, is indicated by
the solid line. For SiGeC alloys we find a very similar downwards bowing of the in-
trinsic energy gap such as for Sil-,C, as already discussed here. When starting from
a certain unstrained SiGe alloy composition and adding substitutional C into the layer,
the energy gap goes down by about 10-20 meV per percent C for unstrained alloys, at
least for small C concentrations. In pseudomorphic layers the carbon reduces the strain
in the films and increases the bandgap by about A E = y . (0.24 eV); however, this
increase is only part of the one that would be obtained by reducing the Ge content in
order to achieve similar strain reduction. The latest experimental data demonstrate that
SiGeC layers can be prepared on Si, which have small and adjustable lateral strain, a
smaller bandgap and a substantial band offset in the valence band (Schmidt and Eberl,
to be published).

3. SI/GE/SII-, C ~ QUANTUM
WELLS

In order to increase the light output from Si-based heterostructures it is necessary to

achieve strong confinement for both holes and electrons. Based on Si/Sil -x-pGexCv
heterostructures this is possible by putting a Sii-,Ge, layer right next to a Sil-,jC,
quantum well directly on Si. Similar concepts have been realized on a strain-relaxed
Sil-,Ce, buffer layer with a tensile-strained Si layer next to a compressively strained
Sil-,Ge,, quantum well with x < y (Usami et al., 1995 and 1996). Figure 18 shows
a cross-sectional TEM micrograph of a 25-period 4 nm Sio.84Ge0.16/3.3nm Sio.988
C0.012/17 nm Si double quantum well structure on Si (100).
The PL spectra of 3.3 nm siO.986cO.014, 4 nm Si0.84Ge0.16,and 4 nm Sio.832Geo.16
c0.008 single quantum wells (SQWs) are shown in the lower part of Fig. 19. The
upper part shows PL spectra of coupled Sil-,-,Ge,C, /Sil-& double quantum well
structures (DQWs) with x = 0.16, y = 0 or 0.009, and z = 0.012. The excitonic no-
phonon and TO-phonon PL lines originating from alloy layers are marked by QW-NP
and QW-TO, respectively.
The DQWs reveal PL lines at lower energy than the corresponding single QWs. They
are attributed to spatially indirect transitions of A(2) electron and heavy hole states lo-
calized within the neighboring siO.988CO.012 and Sio.84Geo.16 layers, respectively. The
band alignment is schematically illustrated in the insert of Fig. 20. The no-phonon line
is strongly enhanced compared to the TO-phonon line. There is a significant intensity
gain observed for the DQW with respect to the corresponding single QWs.
For optimized QW thicknesses with respect to maximum overlap of the wave func-
tions for electrons in siO.988CO.012and holes in Sio.84Geo.16 we achieve a three-orders-
of-magnitude intensity increase as shown in Fig. 20 (Brunner et al., 1996c; Brunner
et al., 1997). The strong dependence of the DQW PL on the spatial separation of car-
riers is also demonstrated by the 40% intensity decrease observed for a DQW structure
with a 0.4-nm thick Si layer in between the Si0.84Ge0.16and siO.988cO.012 layers shown
in Fig. 19.
 8 S I I - , ~ , AND S I ~ - ~ - , G E ~ALLOY
C ~ LAYERS 409

FIG. 18. Cross-sectional TEM micrographs with moderate (a) and high resolution (b) of a 25-period
4 nm Si0.84Ge0.~5/3.3nm si-O.988cO.O~2/17nm Si double quantum well structure on Si (100).

Adding C into the Sio.84Geo.16 layers results in a further PL intensity enhance-

ment. A slight downwards shift in energy of about -10 meV/%C is observed for
the Sio.84-,Geo,l6Cy/Sil-~C~double quantum wells with respect to corresponding
Sio,84Geo,~6/Sil-~C~ DQW structures. This can be assigned to an increase of the hh
valence band offset in a 4-nm Si0.84-,,Ge0.16Cy quantum well by C incorporation rel-
ative to Si. However, more detailed studies are needed to get a reliable picture of the
quantitative change of the valence band offset, as other groups found a slight decrease
as already mentioned in the last section. One has to keep in mind that confinement ef-
fects, a modified excitonic binding energy in DQWs, inhomogeneities within the layers
or impurities, may affect the quantitative PL shifts with C content.
In conclusion, we can describe the energy shifts of the PL lines for Sio.84Geo.16/
Sil-,C, and Si0.84-~Geo.l6C,/Sil-~C~ DQWs considering strain and intrinsic effects
of C on the alloy layers within the picture of the CB and VB alignments shown in the
inset of Fig. 20. An improved PL efficiency of the DQWs embedded in Si is observed
410 KARLEBERL,KARLBRUNNERA N D O L I V E R G . SCHMIDT
I i . , . , , . , ~ , i , , , , ~ ~ ~ , , i , , , , ~ ,

QW-NP T= 8K

DQWs embedded in Si
Si-TO

I
d \
\ OW-TO

siO 84Ge0 16 siO S8aC0 012

SiOMGeO 16’si‘si0988c0012

SQWs embedded in Si
QW-TO QW-NF
siO B.ZGe0 16‘O w)8

0.90 0.95 1.00 1.05 1.10 1.15

ENERGY (eV)

FIG.19. PL spectra of 3.3 nm Si0.986C0.014,4 nm Si0.84Geo 16 and 4 nm Si0.832Ge0.&0.008 single

quantum wells (SQWs) are shown in the lower par; PL spectra of coupled Si~-,,_,Ge,C,/Sil~,C, double
quantum well stmctures (DQWs) with x = 0.16, y = 0 or 0.009, and z = 0.012 are shown in the upper part.
The Sil-,_yGe,Cy and the Si1-,C, layers are 4-nm and 3.3-nm thick, respectively. The quantum wells
are repeated 25 times with 17-nm thick Si layers in between. The excitonic no-phonon and TO-phonon PL
lines originating from alloy layers are marked by QW-NP and QW-TO, respectively. A 0.4 nm thin Si spacer
layer in the Sio,8~Geo,~6/Si/Sio,988CO,012 sample separates the electrons in the Si0.988C0.012 layer from
the holes in the Si0.84Ge0.16 layer and thus causes a 40% reduction of PL intensity.

compared to single QWs. Further enhanced no-phonon transitions and even more effi-
cient capture of excited carriers may be expected for larger Ge and C contents.

4. CARBON-INDUCED
GE QUANTUM
DOTS

The Ge islands appear during Ge deposition on Si (100) according to the Stranski-

Krastanov growth model (Apetz et al., 1995; Sunamura et al., 1995; Abstreiter et al.,
1996). The island formation is observed after growth of a wetting layer, which is about
3 to 4 monolayers (ML) thick. However, the Ge islands are rather large (> 50 nm) and
size reduction is only possible by low temperature growth, which, on the other hand,
 411

40A A LR ,
0.90 0.95 1.00 1.05 1.10 1.15
ENERGY (eV)

FIG. 20. The PL spectra from DQW structures with varied layer widths
d ~ = 1.2dsic
i ~ The inset shows a schematic diagram of the conduction (CB) and valence bandedge
~ in Si.
(VB) for a pseudomorphic Sil-,Ge, layer next to a Sil- C film on Si (100). Within the Sil-,Ge, and
y ' i
the SiI-,C, layer the thicker lines indicate the 2-fold A(2) minima and the heavy hole bandedge in the CB
and the VB, respectively. The thinner lines indicate the 4-fold A(4) minima and the light hole bandedge.
The arrow indicates the PL transition from the A(2) CB states in the Sil-,C, layer to the hh VB states in
-,
the Si 1 Ge, layer.

results in a low PL output due to point defects. We reported on the formation of carbon-
induced Ge islands (Schmidt et al., 1997). A small amount of predeposited carbon
causes the formation of very small and optically active Ge quantum dots. Figure 21a
shows an atomic force microscopy (AFM) image of 0.2 ML C / 2.16 ML Ge islands
on a Si (100) surface. The carbon-induced Ge islands have a diameter of about 10 nm
and a height of 1 nm. The island density is 1 x 1011cm-2. The cross-sectional TEM
image in (b) shows the planar growth of pure 4 ML Ge deposited at Ts = 550°C
without predeposited carbon. This is in clear contrast to the structure shown in Fig. 21c,
which is a cross-sectional TEM image of 3 ML Ge on 0.2 ML carbon. The carbon-
412 KARL EBERL,KARLBRUNNER
AND OLIVER G. SCHMIDT

FIG. 21. Atomic force microscopy (AFM) image of 0.2 monolayers (ML) C / 2 ML Ge islands on Si
(a). The carbon-induced Ge islands have a diameter of about 10 nm and a height of 1 nm. The island density
is 1 x 1011cm-2. The cross-sectional TEM image in (b) shows the planar growth of 4 ML Ge deposited at
TS = 550 'C without predeposited carbon. (c) shows a cross-sectional TEM image of 3 ML Ge on 0.2 ML
carbon. The carbon-induced 3 ML Ge dots have a diameter of 14 nm and a height of about I .S nm. The
samples in (b) and (c ) have a 150-nm Si cap layer on top of the Ge layer.

induced 3 ML Ge dots have a diameter of 14 nm and a height of about 1.5 nm. The
samples in (b) and (c) have a 1 5 S n m thick Si cap layer on top of the Ge layer. The
0.2 ML carbon deposited on Si can be regarded as a thin delta-like Sil-,C, layer with
considerable surface roughness, which is induced by strong local strain surrounding
the carbon atoms. The Ge deposited on this surface has a reduced surface mobility and
thus forms a high density of small islands after more than 1.6 ML Ge growth (Schmidt
et al., 1997; Schmidt et al., 1998). The expected bandedge alignment across the Ge
dots is illustrated in Fig. 22. Spatially indirect recombination of electrons confined in
the underlying carbon-rich layer and heavy holes localized in the Ge-rich upper region
of the Ge islands are expected. We assume a gradual variation of the alloy composition
across the carbon-induced Ge quantum dots, as only very small amounts of carbon and
Ge are deposited. The situation is similar to spatially indirect structures discussed in
the previous section with additional lateral carrier localization.
Figure 23 shows PL spectra from Sio.s4Geo.l~/Sio.sssC0.0~2 DQW structures with
dSiGe = 1.2 X dsic = 3.2 nm, a single layer of 0.2 ML carbon-induced 2.2 ML Ge
quantum dots embedded in Si, and a 50x stacked 0.2 ML C / 2.4 ML Ge sample. The
Si spacer layer thickness in the stacked sample is 9.6 nm. The NP-PL intensity of the
dot samples is significantly higher than Sil-,Ge, and Sil-,C, quantum well samples,
 CB A2

HH
_I__, Growth direction
FIG.22. Schematic illustration of the C-induced Ge island structure and the expected band alignment
in the growth direction. Spatially indirect recombination of electrons confined in the underlying carbon-rich
layer and heavy hole states localized in the Ge-rich upper region of the Ge islands are assumed. Gradual
variation of the alloy composition across the carbon-induced Ge quantum dots is expected.

which may be explained by strong carrier localization effects. The integrated PL inten-
sity of the single dot-layer sample is even higher than the 25-period coupled quantum
well structure. The energy position of the 50x stacked sample is red-shifted by about
50 meV. This is due to the larger dot size for 2.4 ML Ge and partly by electronic cou-
pling between the dot layers.
It is important to note that the DQW structures presented in the previous section
as well as the carbon-induced Ge dot structures can be designed as nearly strain-
symmetrized layer sequences. This means that there are no strong overall thickness
limitations for the superlattice or stacked dots, which makes both concepts interesting
for future applications in waveguides, infrared detectors, modulators, and electrolumi-
nescence devices grown directly on Si without the need of relaxed SiGe buffer layers.

VI. Electrical "ransport Properties

Pseudomorphic Si1-,C, and Sil-,-,Ge,C, alloy layers on Si are interesting for

transistors, because strain influences the charged carrier transport properties signifi-
cantly. Ershov and Ryzhii (1994) published a theoretical study of electron transport in
strained Sil-,C, and predicted an increase of the mobility for reasonably small alloy-
scattering potentials. The first experimental results from Sb-doped Sil-,C, alloys were
reported by Faschinger et al. (1995).
We have prepared 0.5k.m thick Sio.996Co.~4and Si reference layers with nominally
the same phosphorus doping of about 3 x 1017 cm-3 (Eberl et al., 1997; Brunner
et al., 1996d). The total thickness of 0.5 wm was chosen relatively thick for the doping
level of 3 x lo" cm-3 in order to avoid misinterpretation caused by surface-depletion
effects. The Si0.996Co.004layer is fully strained as measured by XRD. The critical
thickness for pseudomorphic growth is significantly beyond O . 5 ~ mfor the small C
content used in this case. The layers described in Figs. 24-26 were grown on an n-
414 KARLEBERL,KARL B R U N N E R AND OLIVER G. SCHMIDT

0,8 or9 1,o

Photon Energy (eV)

F I G . 2 3 . The PL spectra from Si0.84Ge0,16/siO,9ggc0.012 DQW structures with d s i =~ 1.2 ~ x dS,C =

3.2 nm, a single layer of 0.2 ML carbon-induced 2.2 ML Ge quantum dots embedded in Si, and a 50x
stacked 0.2 ML C / 2.4 ML Ge sample. The Si spacer layer thickness in the stacked sample is 9.6 nm. The
NP-PL intensity of the dot samples is significantly higher than for Sil-nGe, and SiI-yCy quantum well
samples, which may be explained by strong carrier localization effects. The energy position of the 50x
stacked sample is red-shifted by about 50 meV. This is due to the larger dot size for 2.4 ML Ge and partly by
electronic coupling between the dot layers.

Si (100) substrate with a resistance of above 5000 s2 cm. A 200-nm thick undoped Si
buffer layer is deposited at 700°C before growing the doped layer. A careful chemical
precleaning is performed to keep the boron doping at the substrate interface below
5 x 10'0cm-2.
The electron density and Hall mobility from the samples described here are shown
in Fig. 24. Over the whole temperature range from 50-300 K the electron density is
essentially the same in the S ~ O . ~ ~ ~and
C Othe
. Oreference
O~ sample. No electron capture
by C or by any C-related defects is observed. In undoped Si0.996C0.004layers we find
 415

1o4

z
g 103
I- I-
0 0
i!u

FIG.24. Hall mobility and electron density (corrected for surface depletion) measured as a function of
temperature in a Van der Pauw geometry from an n-type (phosphorus) 3 x 1017cm-3 doped 0.5 Krn thick
S i 0 . 9 9 6 C o . ~layer and a reference layer without C. The doped layers were grown at 550 "C on (n-) 5000
R cm Si substrates with a 200-nm thick undoped Si buffer layer.

a high resistivity with no ohmic contacts to the layer. The electron mobility of the
Si0.996C0.004sample and the reference sample are also closely matched down to about
180 K. For lower temperatures the mobility in the Si0.996Co.004sample is getting signif-
icantly higher as compared to the Si sample with still almost the same electron density.
This is in contrast to measurements on 200-nm thick 1 x 10'7cm-3 n-type doped
Sil-,C, layers already reported (Osten and Gaworzewski, 1997). The observation of
increased mobility in thick homogeneous layers shown in Fig. 24 can be explained by
the tensile strain in the Sio.996Co.004layer, which induces a splitting of the 6-fold A
valleys, The A(2) valleys become the CB minima with the small in-plane effective
mass for the electron. The splitting of the A(4) and A(2) levels is only about 20 meV
for the small C concentration used in this sample; therefore, a mobility enhancement
is expected only for low temperatures. The results on the thick homogeneously doped
Sil-,C, alloy layers demonstrate that the samples show reasonable doping behavior
and that the mobilities do not degrade. The mobility seems to be limited by charged
dopant impurity scattering although the concentration of carbon atoms exceeds that of
the phosphorus dopants by three orders of magnitude.
Pseudomorphic Sil-,C, alloy layers on Si provide a significant band offset in the
conduction band and have a small in-plane mass mA2 = 0.2 mo. The smaller effective
mass with the A(2) levels mainly occupied should also reduce intervalley scattering.
Consequently, Si/Sil -yCy heterostructures are very interesting for n-type modulation-
doped field effect transistors (FET) (Nayak et al., 1994; Nay& and Chun, 1994; Doll-
416 KARLEBERL,KARLBRUNNERA N D OLIVER G. SCHMIDT

a) n-Si MOS-FET: b) n-Sit.$, MOS-FET

FIG. 25. Comparison of a Si (a) and a SiI-,C, (b) n-channel MOSFET. The confinement induced
splitting in pure Si MOS structures is only of the order of 10 meV. Thus, both A(2) and A(4) levels are
occupied at room temperature. In (b) a Sil-yCy alloy layer is used at the Si02 interface or close to the
interface as an inversion layer. The idea is to take advantage of the built-in tensile strain to increase the A(2)-
A(4) energy splitting and to achieve close to zero occupancy in the upper A(4) levels at room temperature.

fus and Meyer, private communication). A suggestion for an n-channel MOSFET is

schematically shown in Fig. 25b. In this case a thin Sil-,Cy alloy layer is used at
the Si02 interface or close to the interface as an inversion layer. The idea is to take
advantage of the tensile strain in order to increase the A(2)-A(4) energy splitting just
enough to achieve close to zero occupancy in the upper A(4) levels at room temper-
ature (Brunner and Eberl, U.S. Patent). The confinement-induced splitting in pure Si
MOS structures is only on the order of 10 meV, thus, both A(2) and A(4) levels are
occupied at room temperature as schematically illustrated in Fig. 25a. The same struc-
ture would be interesting for p-channel devices because of the reduced effective mass
for holes in tensile-strained Si (Nayak et al., 1994; Nayak and Chun, 1994).
In a different approach, substitutional carbon is used for strain reduction in
Si/Sil -x-yGe,Cy heterostructures. This increases the critical thickness and thus al-
lows an increase in the Ge concentration. Ideally a Gel-,C, layer would be used as a
p-channel in an FET with the C content just enough to reduce part of the compressive
strain such that a thin (> 2 nm) planar layer can be grown. The idea is to take advan-
tage of the high hole mobility in strained Ge (Manku and Nathan, 1991). However,
it turned out to be extremely difficult to prepare planar Gel-,Cy layers on Si (100)
because carbon causes Ge island formation as shown in Fig. 21. Extremely low sub-
strate temperatures of only about 300°C are necessary to avoid the island formation,
which, on the other hand, leads to low crystal quality due to incorporation of point
defects (Brunner et al., 1996e). Osten and Klatt (1994) measured an increased critical
thickness for Geo.99Co.ol layers of about 20 monolayers using an antimony-mediated
growth technique. For a discussion of the bandgap of Ge-rich Sil-,-,Ge.,C, alloys
see Orner et al. (1996).
 417

z
n

hl

E
0
W

Oo0 I
1I n--Si substrate I
!!
0 100
I 10 20 30 40 50 60
Ge CONTENT x (%)
FIG. 26. Hall mobilities measured at room temperature and 77 K in a Van der Pauw geometry from
p-channel Sil -x-yGexCy modulation doped quantum well structures. The layer sequence is schematically
shown in the inset. The growth temperature was 550 "C.

Figure 26 shows Hall mobilities measured at room temperature and 77 K in a Van-

der Pauw geometry from several p-channel Sil-,Ge, and one Si0.49Ge0.49C0.02 mod-
ulation doped quantum well structure represented by open and full symbols, respec-
tively. The layer sequence is 400-nm undoped Si, 8 nm Sil-,-,Ge,C,, 10 nm Si
spacer, a boron-doped Si layer and a 20-nm Si cap layer (see also the inset of Fig. 26).
Looking at the hole mobilities in the Sil-,Ge, QWs we observe a maximum of about
220 cm2N s at 300 K and about 2000 cm2N s at 77 K for x = 30%. For higher
Ge concentrations the mobilities degrade, which is attributed to strain-induced inter-
face roughness and misfit dislocation nucleation. The 8-nm quantum well thickness
is above the equilibrium critical thickness for pseudomorphic Si0.5Ge0.5 on Si. In the
Si0.49Ge0.49Co.02 sample the compressive strain is reduced by about 30%. In other
words, the strain is similar to a virtual Ge concentration of about 35%. The mobilities
for the Si0.49Ge0.49C0.02 QW are 185 c m 2 N s at 300 K and 2750 c m 2 N s at 77 K,
the latter being significantly improved against the corresponding sample without C.
The higher hole mobility for the Si0.49Ge0.49Co.02QW is a consequence of the reduced
strain in the layer due to substitutional C . For the Si0.5Geo.ssample we measure a hole
density of 5 x 1011cm-2at 300 K and 1.5 x 1011cm-2 at 77 K. The hole density in the
C alloyed QW is also 5 x 1011cm-2 at 300 K, but only about 0.5 x 1011cm-2at 77 K.
So far, the samples are not optimized for maximum carrier transfer from the doping
layer to the QW. The reduction of carrier density at low temperature may be a con-
418 KARLEBERL,KARLBRUNNERA N D O L I V E R G. SCHMIDT

sequence of reduced valence band offset, alloy inhomogeneities and local strain fields
around the C atoms in the Sio.sGe0.5matrix. A first p-channel MODFET with 45% Ge
and 1.2% C was demonstrated by Cluck et al. (1998). The device with 0.75 p m gate
length provided a transconductance of 62 mS/mm at room temperature.

VII. SummaryDevices

In pseudomorphic Sil-,C, layers on Si the bandgap is reduced by about 65

meV/%C. Considering the deformation potentials we find the bandgap of unstrained
Sil-,C, alloys with small carbon concentration to be smaller than in Si by about 10-
20 meV/%C. The bandgap in pseudomorphic SiGeC is increased by substitutional C
incorporation by about 24 meV percent of C. The band alignment in Si/Sil-, C, is type
I with the offset mainly in the conduction band. A strong electron and hole confinement
is achieved directly on Si in coupled Sil-xGex/Sil-yC, quantum wells, which results
in a strong no-phonon PL intensity. Carbon-induced Ge quantum dots with dimensions
in the 1Gnm range have been prepared; they provide very intensive PL intensity.
Enhanced electron mobilities are observed in thick pseudomorphic n-type doped
Sil-,C, layers at low temperatures, which are attributable to the splitting of the A
valleys with the A(2) valleys being the conduction band minima. In a modulation-
doped p-type Si0.49Ge0.49C0.02QW an improved hole mobility is observed at room
temperature and 77 K compared to a corresponding sample without carbon, which is a
consequence of the reduced strain in the layer due to substitutional carbon.
The first device-relevant work applying substitutional carbon has been published
(Huang and Wang et al., 1996; Soref et al., 1996; Soref, 1996; Lanzerotti et al., 1996;
Chen et al., 1996; Bair et al., 1996; Mamor et al., 1996; Meyer et al., 1996; Os-
ten and Bugiel, 1997; Osten et al., 1997a; Osten et al., 1997b). A first p-channel
MODFET with 45% Ge and 1.2% C was demonstrated as mentioned in the previous
section (Cluck et al., 1998). Most promising for device applications is the effect of
significantly reduced boron outdiffusion in SiGe layers with carbon incorporated in
the 1020cm-3 range (Osten et al., 1997a). Osten et al. (1997b) demonstrated SiGe:C
heterojunction bipolar transistors (HBT) with fT/fm,, of 64 / 50 GHz and typical ring
oscillator ECL gate delay times of 22.5 ps using 0.8pm design rules. Outdiffusion of
boron from the SiGe base layer especially on the collector side leads to drastic degra-
dation of the device during processing. Incorporation of a small amount of carbon into
the base layer increases the process margins and thus allows more cost-effective device
fabrication (Osten et al., 1997a). The first Sil-,-,Ge,C, HBT with carbon concen-
trations in the percent range, high enough to reduce strain significantly and change the
bandgap in the base layer, was reported by Lanzerotti et al. (1996).
Particularly interesting are Si1-,Cy, Sil-x-yGexCy layers and strain-symmetrized
Sil-,-yGexC,/Si~-,C, coupled multiquantum wells or carbon-induced Ge quantum
dot structures for the field of optoelectronic devices as already pointed out (Soref et al.,
 8 S1l-,Cy AND SI1-x-yGExCy ALLOY LAYERS 419

1996; Soref, 1996; Eberl and Brunner, Patent). A first normal-incidence epitaxial
SiGeC photodetector near 1.3pm wavelength grown on Si was reported by Huang and
Wang (1996).
The PL investigations and the Hall measurements presented provide a picture of the
influence of substitutional C on both the bandgap and band alignment. The results
demonstrate that Sil-,C, and Sil -x-yCe,C, alloys are useful semiconductor materi-
als that offer more flexibility in the design of device structures on Si substrate.

ACKNOWLEDGMENTS

It is a pleasure to acknowledge the excellent collaboration with M. Cluck and U.

Konig from the Daimler Benz Research Center in Ulm and the skillful assistance of
W. Winter, H. Seeberger, S. Schieker, and C. Lange. This work has been supported
financially by the “Bundesministerium fiir Bildung und Forschung” within the “Si Na-
noelektronik” project. The authors gratefully acknowledge the continuous support of
H. Grimmeiss, E. Kasper, and K. von Klitzing.

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 Index

A minority, 339-341
Acoustical phonons, Raman scattering by, mobility of, 3 2 6 3 3 4
260-265 Chemical vapor deposition (CVD)
Activation energy, and diffusion, 67-70 conditions for, 3-4
Adatoms contamination risk in, 4
absorption of, 62-64 kinetic processes during, 52
diffusion of, 64 Chidambarro model, of critical thickness, 125
interaction with surface steps, 71-74 Chlorides, use in RTCVD, 13
AlGaAs growth, 2 , 4 Cleaning procedures, 4-5
Antimony, as impurity in SiGe, 203,209 Climb, defined, 113
APCVD, 21-24 Conduction states, defect perturbations to, 207-210
Arsenic, as impurity in SiGe, 205-209 Critical thickness
Atmospheric pressure chemical vapor deposition models of, 120-126
(APCVD), 21-24 in multilayer structures, 128-131
Atomic bonds, elastic distortion of, 103, 104 in partial misfit dislocations, 126-128
Atomic ordering, 3 1-32
Auger processes, 214-216 D
Avalanche photodiodes, 348-35 I Deep level transient spectroscopy (DLTS), 295
Deep levels, in GeSi, 295, 31 1
B Density functional theory, 172
Blocking, of dislocations, 150, 151, 152 Diborane, 22
Buffers Dichlorosilane, 23
against dislocations, 156-157 Differential spectroscopy, 2 2 6 2 3 I
graded, 158-159 Diffusion, anisotropy of, 67
strained layer superlattices as, 159 Diffusion coefficient, 65-67
Burgers vector, 109, 110 and activation energy, 67-70
Directional couplers, 375-376
C Dislocation theory, 109-120
Cammarata-Sieradzki model, of critical thickness, Dislocations. See Misfit dislocations; Threading
125 dislocations.
Carbon Dopants, 28
boron diffusion adjustment using, 397 in APCVD, 23
as impurity, 4 in MBE, 6
induction ofdot structures by, 410-413 in RTCVD, 15
properties of, 388 in UHVCVD, 2 1
strain adjustment using, 389-390 Doping compensation, 316,319-322
substitution for Si in S i c alloy, 397-400
Carriers E
generation and recombination of, 322-326 Edge dislocations, 111, 113, 114
in GeSi/Si heterostructures, 334-339 Elastic strain, 102

423
424
Electromodulated reflectivity, 228-230
Electron transport, in bulk GeSi, 332-333
Electron traps, in GeSi, 303-309
Ellipsometry, spectroscopic, 230
Empirical pseudopotential (EPP) method, 171-172
Epitaxial films
adatom-step interaction, 70-74
coarsening of, 75
equilibrium growth modes for, 50-52
kinetic growth modes of, 53-55
kinetic processes during deposition of, 52-53
Erbium, as dopant, 367-368
F majority carrier transport in, 28-29
Filtering, of dislocations, 157-161
Fox-Jesser model, of critical thickness, 125-126
Frank-Read mechanism, 138, 140
Frank-van der Merwe growth mode, 50,51
Frank-van der Merwe model of critical thickness,
124-125
Free-carrier injection devices, 377-379
G microscopic signature of, 199-21 2
Gas source MBE, 23-24
Germanium
bandstructures of, 174, I75
collection in GeSi alloy, 90
electroreflectivity spectrum of, 228
growth of submonolayer, 79-8 1
properties of, 387-388
GeSi
atomic ordering in, 31-32
bandstructures of, 174-178, 182-188
boron diffusion ion, 396
carrier generation-recombination in, 322-325
carrier transport properties of, 326-341
deep levels in, 295-3 19
defects in, 317-326
doping compensation in, 3 19-322
electric field applied to, 215
electron transport in, 333
electron traps in, 303-309
extended defect states in, 295-301
growth of dimer vacancy lines, 82-84
growth of Ge wetting layer, 79-86
growth methods of, 2 9 4 2 9 5
hole mobility in, 326-332
hole traps in, 309-319,320
morphology of, 85-86
optical spectra of, 195-196
INDEX
photoluminescence in, 29,277-279
strain in systems, 170-171
substrates of, 4 0 4 2
GeSi alloy films, 90-94
multilayer growth in, 93-94
Raman scattering in, 256-258
roughening and islanding in, 92-93
thermodynamic characteristics of, 91
GeSi crystal growth, 2-3
APCVD, 22-24
development of, 1-2
doping in, 28
layer thickness in, 25-27
MBE, 6-13
methods of, 4-5
minority carrier lifetime and, 30
RTCVD, 13-16
UHVCVD, 16-22
GeSi interfaces
impurities at, 197-199,203-207
intermixing of atoms at, 84-85
GeSi microstructures, 179-182
experiments on, 173
GeSiC, 388
annealing behavior of, 396
coupling with S i c alloy layers, 4 0 7 4 1 0
devices made from, 4 1 8 4 1 9
electrical transport properties of. 4 1 3 4 1 8
lattice constant of, 390-391
MBE preparation of, 392-394
optical properties of, 4 0 4 4 0 8
optoelectronic use of, 418
thermal stability of, 394-397
GeSilSi, carrier transport in, 334-341
Glide planes, 112-1 15
Guided-wave devices
integrated and active components,
375-379
waveguides, 37 1-374
H
Hagen-Strnnk mechanism, 138-1 39
Harmonic generation, 216-217
Henderson method, 5
Heterojunction bipolar transistors (HBTS), 8
SiGeC, 4 1 7 4 1 8
Heterojunction internal photoemission (HEP)
photodetectors, 359-360
 INDEX 425
Hole mobility, 326-33 1 Minority carriers
Hole traps, in GeSi, 308-317, 318 diffusion coefficient of, 339-341
Hut islands, 86-89 lifetimes of, 339-341
Hydrides Misfit dislocation arrays, 107
use in RTCVD, 14 geometry of, 113-1 15
use in UHVCVD, 17-18 Misfit dislocations
Hydrogen, reactivity of, 4 annihilation of, 157
density of, 132-133
I dissociation of, 117-1 19
Image dislocation, 112 energy of, 111-1 12
Infrared photodetectors, 359-361 forces on, 112
SdSiGe superlattices in, 212 geometry of, 109-1 11
Integrated optical receivers, 362-363 interactions among, 149-152, 157-158
Interdiffusion, 105-107 motionof, 112-113, 115-117
Interface islands, impurities at, 197-199 multiplication of, 138-141
Islanding, 11, 32-38 nucleation of, 133-144
carbon-induced, 410-413 p a h l vs. total, 119-120
dependence on diffusion coefficient, propagation of, 144-149, 156
65-67 strain relaxation by, 152-155
in GeSi alloy films, 92-93 techniques for reducing, 155-161
hut, 8 6 9 0 Mixed dislocations, I l l , 112, 113
stable nuclei and, 74 MODFET structures, 334
Islands SiCeC, 418
equilibrium shape of, 76 Modulation spectroscopy, 228
formation of, 92-93 Molecular beam epitaxy (MBE), 2, 18
multilayer organization of, 93-94 conditions for, 3-4,9-13
and step energies, 76 contamination risk in, 4, 8-9
3-D, 86-90 disadvantages of, 9
dopants in, 6-7
K gas source, 24
Kinetically rough growth, 53 impurity introduction in, 4-5
Kinks, 113, 116-117 machinery for, 7-9
Multilayer structures
L critical thickness in, 128-131
Layer-by-layer growth, 54-55 step bunching in, 93-94
Limited area epitaxy, 159-161
Linear-chain model, of Raman scattering, N
261-262 Nonlinearities, in optical response, 216-219
Local density approximation, 172 Nonplanar growth
Localization atomic ordering, 31-32
at Ge impurities in Si layers, 21 1-212 islands, 32-37
interface-induced, 203-207 selective area epitaxy (SAG), 38-40
substrates for, 40-42
M wires, 32-37
Matthews-Blakeslee model of critical thickness, Nucleation
12g-123 heterogeneous, 133-1 35
accuracy of, 124 homogeneous, 135-138
Metal-semiconductor-metal (MSM) photodiodes, mechanisms of, 133, 142-144
356-359 quasi-homogeneous, 137
Metastability, 131 rates of, 141-142
426
0 Q
Optical modulators and switches, 375-379
Optical spectra, 195-196
microscopic electronic structure effects in,
2 12-21 9
nonlinearities in, 216-219
Optical transitions
in GeSi quantum wells and superlattices,
243-252
pseudo-direct, 23 1-236
in Si/GeSi and Ge/GeSi microstructures,
236-243
P in bulk GeSi random alloys, 256-258
p-i-n photodiodes, 348-349
Partial dislocations, 117-120
critical thickness and, 126-128
People-Bean model, of critical thickness, 125
Photodetectors
avalanche photodiodes, 350-35 1
heterojunction internal photoemission (HEP),
359-361
infrared, 359-360
integrated optical receivers, 362-363
metal-semiconductor-metal (MSM) photodiodes,
356-359
p-i-n photodiodes, 348-349
quantum well infrared (QWIP), 361-362
resonant-cavity photodiodes, 352-355
SiGeC, 4 18
waveguide photodiodes, 349-35 1,379-380
Photodiodes
avalanche, 350-351
metal-semiconductor-metal (MSM), 356-359
p-i-n, 348-349
resonant-cavity, 352-355
waveguide, 349-351,379-380
Photoluminescence, 277-278
from bulk GeSi alloys, 278-279
by Er-doped silicon, 367-369
by porous silicon, 363-367
by SVGe quantum wells and superlattices,
369-37 1
from Si/GeSi microstructures, 280-286
from ultrathin quantum wells and superlattices,
286-288
Photomodulated reflectivity, 228-230
Pinning, 150, 151
Plastic relaxation, 104, 107-108
Porous Si, photoemission by, 363-367
INDEX
Quantum dots, carbon-induced, 4 1 M 1 3
Quantum well infrared photodetectors (QWIP),
361-362
Quantum wells
optical transitions in, 243-252
photoluminescence from, 286-288.369-37 1
Raman scattering in, 258-260
resonant Raman scattering in, 269-273
R
Raman scattering, 253-256
by acoustical phonons, 260-265
resonant, 265-276
Rapid thermal chemical vapor deposition (RTCVD)
dopants in. 15
machinery for, 13- 16
raw materials for, 13
temperature of, 14
RCA method, 5
Relaxation
kinetic modeling of, 152-155
plastic, 104, 107-108
via 3-D cluster formation, 88-90
Resonant Raman scattering, 265-269
detecting interface roughness by, 273-276
in quantum wells and superlattices, 269-273
Resonant-cavity photodiodes, 352-355
Roughening
detecting with resonant Raman scattering,
273-276
in GeSi alloy films, 92-93
of epitaxial layer, 105
reducing activation barriers, 137-1 38
Ryotov model, 260-261
s
Sb, as impurity in SiGe, 203,207-208
Screw dislocations, 112, 113
Selective area epitaxy (SAG), 3 8 4 0
Shintani-Fujita model, of critical thickness, 126
Shiraki method, 5
Si (001],56-59
step configurations on, 76-78
Si{lll),61
Si islands
equilibrium shape of, 75-76
and step energies, 76
P-SiC, properties o f , 388
 INDEX 427

S i c alloy, 388-390 critical point energies of, 246-248

coupling with SiGeC layers, 407-410 first-principles calculations of, 200-203
electrical transport properties of, 413-418 imperfections in structure of, 189-192
lattice constant of, 390-391 optical transitions in, 193,243-252
MBE preparation of, 392-394 photoluminescence from, 286-288,369-371
optical properties of, 4 0 1 4 0 3 Raman scattering in, 258-260
optoelectronic use of, 418 resonant Raman scattering in, 269-273
thermal stability of, 394-397 strained layer, 159
Silicon Surface diffusion, 64
bandstructures of, 174, 175,348 Surface vacancies, 82-84
characteristics of, 347-348
crystal structure of, 57-61 T
electroreflectivity spectrum of, 228 Temperature, measurement of, 16
erbium-doped, 367-369 Thermal mismatch, 103
growth on Si (OOl], 62-75 Thermo-optic devices, 376
MBE of, 6-1 Threading dislocations, 110
photoemission by, 363-367 filtering of, 157-161
photoluminescence of, 29 3-D islands, 86-90
porous, 363-367 formation of, 92-93
properties of, 387-388 self-organization of, 94
self-diffusion of, 64-70
Spectroscopic ellipsometry, 230 U
Step bunching, 93-94 Ultra-high vacuum chemical vapor deposition
of 3-D islands, 94 (UHVCVD)
Step configurations advantages and disadvantages of, 19-21
bunching in multilayers, 93-94 conditions for, 1 6 1 8
on nominal surface, 76-77 dopants in, 20-21
on vicinal surface, 78 raw materials for, 17-19
Step-flow growth, 54,55,70-74
Strain V
accommodation of, 103-109, 120 Vacancies, dimer, 82-84
competition among relief mechanisms, Volmer-Weber growth mode, 50,51
108-109
metastability and, 131 w
origins of, 102-103 Wafer cleaning, 5
relaxation of, 152-155 Wall deposition, 16
Strain-relaxed GeSi, 40-45 Waveguide photodiodes, 349-35 1
Strained layer superlattice filtering, 159 Waveguides, 371-374
Stranski-Krastanov growth mode, 50 integrated with photodetectors, 379-380
Superlattices Willis model, of critical thickness, 125
bandstructures of, 174-182, 189-192 Wires, quantum, 32-37
charge densities of, 194
This Page Intentionally Left Blank
Contents of Volumes in This Series

Volume 1 Physics of 111-V Compounds

C. Hilsum, Some Key Features of 111-V Compounds

Franco Bassani, Methods of Band Calculations Applicable to 111-V Compounds
E. 0. Kane, The k - p Method
V L. Bonch-Bruevich,Effect of Heavy Doping on the Semiconductor Band Structure
Donald Long, Energy Band Structures of Mixed Crystals of 111-V Compounds
Laura M. Rorh and Petros N. Argyres, Magnetic Quantum Effects
S. M. Puri and I: H. Geballe, Tnermomagnetic Effects in the Quantum Region
W M. Becker, Band Characteristics near Principal Minima from Magnetoresistance
E. H. Purley, Freeze-Out Effects, Hot Electron Effects, and Submillimeter Photoconductivity in InSb
H. Weiss, Magnetoresistance
Betsy Ancker-Johnson, Plasma in Semiconductors and Semimetals

Volume 2 Physics of 111-V Compounds

M. G. Holland, Thermal Conductivity

S. I. Novkova, Thermal Expansion
(1. Piesbergen, Heat Capacity and Debye Temperatures
G. Giesecke, Lattice Constants
J. R. Drabble, Elastic Properties
A. U. Mac Rae and G. W. Gobeli, LOWEnergy Electron Diffraction Studies
Robert Lee Mieher, Nuclear Magnetic Resonance
Bernard Goldsrein, Electron Paramagnetic Resonance
I: S. Moss, Photoconduction in 111-V Compounds
E. Anfoncik and J. Tauc, Quantum Efficiency of the Internal Photoelectric Effect in InSb
G. W Gobeli and I. G. Allen, Photoelectric Threshold and Work Function
f! S. Pershan, Nonlinear Optics in 111-V Compounds
M.Gershenzon, Radiative Recombination in the 111-V Compounds
Frank Stern, Stimulated Emission in Semiconductors

429
430 I N THISSERIES
OF VOLUMES
CONTENTS

Volume 3 Optical of Properties 111-V Compounds

Marvin Hass, Lattice Reflection
William G. Spifzer,Multiphonon Lattice Absorption
D. L. Stienvalt and R. E Potter, Emittance Studies
H. R. Philipp and H. Ehrenveich, Ultraviolet Optical Properties
Manuel Cardona, Optical Absorption above the Fundamental Edge
Eamesr J. Johnson, Absorption near the Fundamental Edge
John 0. Dimmock, Introduction to the Theory of Exciton States in Semiconductors
B. Lar and J. G. Mavroides, Interband Magnetooptical Effects
H. K Fan, Effects of Free Caniers on Optical Properties
Edward D.Palik and George B. Wright, Free-Canier Magnetooptical Effects
Richard H. Bube, Photoelectronic Analysis
B. 0. Seraphin and H. E. Bennett, Optical Constants

Volume 4 Physics of 111-V Compounds

N. A. Goryunova, A. S.Borschevskii, and D. N. Tretiakov, Hardness
N. N. Sirota, Heats of Formation and Temperatures and Heats of Fusion of Compounds A"'BV
Don L. Kendall, Diffusion
A. G. Chynoweth, Charge Multiplication Phenomena
Robert N! Keyes, The Effects of Hydrostatic Pressure on the Properties of 111-V Semiconductors
L. W Aukerman, Radiation Effects
N. A. Goryunova, F: II Kesamanly, and D. N . Nasledov, Phenomena in Solid Solutions
R. I: Bare, Electrical Properties of Nonuniform Crystals

Volume 5 Infrared Detectors

Henry Levinstein, Characterization of Infrared Detectors
Paul W Kruse, Indium Antinionide Photoconductive and Photoelectromagnetic Detectors
M. B. Prince, Narrowband Self-Filtering Detectors
Ivars Melngalis and Z C. Harman, SingleCrystal Lead-Tin Chalcogenides
Donald Long and Joseph L. Schmidt, Mercury-Cadmium Telluride and Closely Related Alloys
E. H. Putley, The Pyroelectric Detector
Norman B. Srevens, Radiation Thermopiles
R. J. Keyes and I: M. Quist, Low Level Coherent and Incohei-entDetection in the Infrared
M. C. Teich, Coherent Detection in the Infrared
F: R. Arums, E. W Surd, B. J. Peyton, and F: P. Pace, Infrared Heterodyne Detection with Gigahertz IF
Response
H. S. Sommers, J K , Macrowave-Based Photoconductive Detector
Robert Sehr and Ruiner Zuleeg, Imaging and Display

Volume 6 Injection Phenomena

Murray A. Lampert and Ronald B. Schilling, Current Injection in Solids: The Regional Approximation
Method
Richard Williams, Injection by Internal Photoemission
Allen M. Bametf, Current Filament Formation
R. Baron and J. W Mayer, Double Injection in Semiconductors
N! Ruppel, The Photoconductor-Metal Contact
 CONTENTSOF VOLUMESIN THISSERIES 431

Volume 7 Application and Devices

Part A
John A. Copeiand and Stephen Knight, Applications Utilizing Bulk Negative Resistance
E A. Padovani, The Voltage-Current Characteristics of Metal-Semiconductor Contacts
€? L. Hower; W W Hoopec B. R. Cairns, R. D. Fairman, and D. A. Tremere, The GaAs Field-Effect
Transistor
Marvin H. White, MOS Transistors
G. R. Antell, Gallium Arsenide Transistors
T L. Tansley, Heterojunction Properties

Part B
I: Misawa, IMPA'lT Diodes
H . C. Okean, Tunnel Diodes
Robert B. Campbell and Hung-Chi Chang, Silicon Junction Carbide Devices
R. E. Enstrom, H. Kressel, and L. Krassner, High-Temperature Power Rectifiers of GaAsl_,P,

Volume 8 Transport and Optical Phenomena

Richard J. Srirn, Band Structure and Galvanomagnetic Effects in 111-V Compounds with Indirect Band
Gaps
Roland W Ure, J s , Thermoelectric Effects in 111-V Compounds
Herbert Piller, Faraday Rotation
H. Barry Bebb and E. W Williams, Photoluminescence I: Theory
E. W Williams and H. Barry Bebb, Photoluminescence 11: Gallium Arsenide

Volume 9 Modulation Techniques

B. 0. Seraphin, Electroreflectance
R. L. Aggaiwal, Modulated Interband Magnetooptics
Daniel E B l o s s q and Paul Handler, Electroabsorption
Bruno Bafz, Thermal and Wavelength Modulation Spectroscopy
Ivar Balslev, Piezopptical Effects
D. E. Aspnes and N . Bottka, Electric-Field Effects on the Dielectric Function of Semiconductors and
Insulators

Volume 10 Transport Phenomena

R. L. Rhode, Low-Field Electron Transport
J , D. Wiley, Mobility of Holes in 111-V Compounds
C. M. Wolfe and G. E. Stillman, Apparent Mobility Enhancement in Inhomogeneous Crystals
Robert L. Petersen, The Magnetophonon Effect

Volume 11 Solar Cells

Harold J. Hovel, Introduction: Carrier Collection, Spectral Response, and Photocurrent; Solar Cell
Electrical Characteristics; Efficiency: Thickness; Other Solar Cell Devices; Radiation Effects;
Temperature and Intensity; Solar Cell Technology
432 CONTENTS OF VOLUMES IN THISSERIES

Volume 12 Infrared Detectors (11)

W L. Eiseman, J. D. Merriam, and R. F: Potter, Operational Characteristics of Infrared Photodetectors
Peter R. Bratt, Impurity Germanium and Silicon Infrared Detectors
E. H. Putley, InSb Submillimeter Photoconductive Detectors
G. E. Stillman, C. M. Wove, and J. 0.Dimmock, Far-Infrared Photoconductivity in High
Purity GaAs
G. E. Srillman and C. M.Wove, Avalanche Photodiodes
I? L. Richards, The Josephson Junction as a Detector of Microwave and Far-Infrared Radiation
E. H. Putley, The F'yroelectric Detector-An Update

Volume 13 Cadmium Telluride

Kenneth Zanio, Materials Preparations; Physics; Defects; Applications

Volume 14 Lasers, Junctions, Transport

N . Holonyak, Jr and M. H. Lee, Photopumped 111-V Semiconductor Lasers
Henry Kressel and Jerome K. Butler, Heterojunction Laser Diodes
A Van der Ziel, Space-Charge-Limited Solid-state Diodes
Peter J. Price, Monte Carlo Calculation of Electron Transport in Solids

Volume 15 Contacts, Junctions, Emitters

B. L. Sharma, Ohmic Contacts to 111-V Compounds Semiconductors
Allen Nussbaum, The Theory of Semiconducting Junctions
John S. Esclzer, N E A Semiconductor Photoemitters

Volume 16 Defects, (HgCd)Se, (HgCd)Te

Henry Kressel, The Effect of Crystal Defects on Optoelectronic Devices
C. R. Whitsett, J. G. Broerman, and C. J. Summers, Crystal Growth and Properties of
Hgl-,Cd,Se alloys
M. H. Weiler, Magnetooptical Properties of Hgl _*Cd, Te Alloys
Paul W Kruse and John G. Ready, Nonlinear Optical Effects in Hgl -,Cd,Te

Volume 17 CW Processing of Silicon and Other Semiconductors

James E Gibbons, Beam Processing o f Silicon
Arto Lietoila, Richard B. Gold, James F: Gibbons,and Lee A. Christel, Temperature Distributions
and Solid Phase Reaction Rates Produced by Scanning CW Beams
Arlo Leiroila and Jumes E Gibbons, Applications of CW Beam Processing to Ion Implanted
Crystalline Silicon
N . M. Johnson, Electronic Defects in CW Transient Thermal Processed Silicon
K. E Lee, I: J. Stultz, and James R Gibbons, Beam Recrystallized Polycrystalline Silicon: Properties,
Applications, and Techniques
Z Shibara, A. Wakira, Z W Sigrnon, and James E Gibbons, Metal-Silicon Reactions and Silicide
Yves I. Nissim and James E Gibbons, CW Beam Processing of Gallium Arsenide
 CONTENTS OF VOLUMES IN THIS SERIES 433

Volume 18 Mercury Cadmium Telluride

Paul W Kruse, The Emergence of (Hgl -,Cd,)Te as a Modem Infrared Sensitive Material
H. E. Hirsch, S. C. Liang, and A. G. White, Preparation o f High-Purity Cadmium, Mercury, and Tellurium
W E H. Micklerhwaite, The Crystal Growth of Cadmium Mercury Telluride
Paul E. Petersen, Auger Recombination in Mercury Cadmium Telluride
R. M. Broudy and B J. Mazuxzyck, (HgCd)Te Photoconductive Detectors
M . B. Reine, A. K. Soad, and 7: J. Tredwell, Photovoltaic Infrared Detectors
M. A. Kinch. Metal-Insulator-Semiconductor Infrared Detectors

Volume 19 Deep Levels, GaAs, Alloys, Photochemistry

G. E Neumark and K. Kosai, Deep Levels in Wide Band-Gap 111-V Semiconductors
David C. Look, The Electrical and Photoelectronic Properties of Semi-Insulating GaAs
R. E Brebrick, Ching-Hua Su, and Pok-Kai Liao, Associated Solution Model for Ga-In-Sb and Hg-Cd-Te
Yu. Ya. Gurevich and Yu. V Pleskon, Photoelectrochemistry of Semiconductors

Volume 20 Semi-InsulatingGaAs
R. N. Thomas, H. M. Hobgood, G. W Eldridge, D. L. Barrett, Z 7: Braggins, L. B. Ta, and S. K. Wang,
High-Purity LEC Growth and Direct Implantation of GaAs for Monolithic Microwave Circuits
C. A. Sfolfe,Ion Implantation and Materials for GaAs Integrated Circuits
C. G. Kirkpatrick. R. Z Chen, D. E. Holmes, P. M. Asbeck, K. R. Elliott, R. D. Fairman, and J. R. Oliver,
LEC GaAs for Integrated Circuit Applications
J. S. Blakemore and S. Rahimi, Models for Mid-Gap Centers in Gallium Arsenide

Volume 2 1 Hydrogenated Amorphous Silicon

Part A
Jacques I. Pankove, Introduction
Masataka Hirose, Glow Discharge; Chemical Vapor Deposition
Yoshiyuki Uchidu,di Glow Discharge
Z D. Moustakas, Sputtering
Isao Yamaah, Ionized-Cluster Beam Deposition
Bruce A. Scott, Homogeneous Chemical Vapor Deposition
Frank J. Kampus, Chemical Reactions in Plasma Deposition
Paul A. Longeway, Plasma Kinetics
Herbert A. Weakliem, Diagnostics of Silane Glow Discharges Using Probes and Mass Spectroscopy
Lester Gluttman, Relation between the Atomic and the Electronic Structures
A. Chenevas-Paule, Experiment Determination of Structure
S. Minomura, Pressure Effects on the Local Atomic Structure
David Adler, Defects and Density of Localized States

Part B
Jacques I. Pankove, Introduction
G. D. Cody, The Optical Absorption Edge of a-Si: H
Nabil M. Amer and Warren B. Jackson, Optical Properties of Defect States in a-Si: H
I! J. Zanzucchi, The Vibrational Spectra of a-Si: H
YoshihiroHamakawa, Electroreflectance and Electroabsorption
434 CONTENTS OF VOLUMES IN THISSERIES

Jefrey S.Lannin, Raman Scattering of Amorphous Si, Ge, and Their Alloys
R. A. Street, Luminescence in a-Si: H
Richard S. Crandall, Photoconductivity
J. Tuuc, Time-Resolved Spectroscopy of Electronic Relaxation Processes
R E. Vanier, IR-Induced Quenching and Enhancement of Photoconductivity and Photoluminescence
H . Schade, Irradiation-Induced Metastable Effects
L. Ley, Photoelectron Emission Studies

Part C
Jacques I. Pankove, Introduction
J. David Cohen, Density of States from lunction Measurements in Hydrogenated Amorphous Silicon
II C. Taylor, Magnetic Resonance Measurements in a-Si: H
K . Morigaki, Optically Detected Magnetic Resonance
J. Dresner, Carrier Mobility in a-Si: H
1: Tiedje, Information about band-Tail States from Time-of-Flight Experiments
Arnold R. Moore, Diffusion Length in Undoped a-Si: H
W Be-yerand J. Overhof, Doping Effects in a-Si: H
H. Frifzche, Electronic Properties of Surfaces in a-Si: H
C. R. Wronski, The Staebler-Wronski Effect
R. J. Nernanich, Schottky Barriers on a-Si: H
B. Abeles and 7: Tiedje, Amorphous Semiconductor Superlattices
Part D
Jacques 1. Pankove, Introduction
D. E. Curlson, Solar Cells
G. A. Swartz, Closed-Form Solution of I-V Characteristic for a a-Si: H Solar Cells
fsamu Shimizu, Electrophotography
Sachio Ishioka, Image Pickup Tubes
F! G. LeComber and W E. Spear, The Development of the a-Si: H Field-Effect Transistor and Its Possible
Applications
D. G. Ast, a-Si: H FET-Addressed LCD Panel
S. Kaneko, Solid-state Image Sensor
Masakiyo Matsumura, Charge-Coupled Devices
M. A. Bosch, Optical Recording
A. D’Amico and G. Fortunato, Ambient Sensors
Hiroshi Kukirnoto, Amorphous Light-Emitting Devices
Roberr J. Phelan, JK,Fast Detectors and Modulators
Jacques I. Pankove, Hybrid Structures
F! G. LeCornber, A. E. Owen, W E. Spew J. Hajto, and W K. Choi, Electronic Switching in Amorphous
Silicon Junction Devices

Volume 22 Lightwave CommunicationsTechnology

Part A
Kazuo Nukajima, The Liquid-Phase Epitaxial Growth of InGaAsP
W 7: Tsang, Molecular Beam Epitaxy for 111-V Compound Semiconductors
G. B. Sfringfellow, Organometallic Vapor-Phase Epitaxial Growth of 111-V Semiconductors
G. Beuchet, Halide and Chloride Transport Vapor-Phase Deposition of InGaAsP and GaAs
 CONTENTS OF VOLUMES IN THISSERIES 435

Manijeh Ruzeghi, Low-Pressure Metallo-Organic Chemical Vapor Deposition of Ga,Inl-,AsP1_, Alloys

F! M. Pefrofl, Defects in 111-V Compound Semiconductors

Part B
J. F! van der Ziel, Mode Locking of Semiconductor Lasers
Kum I.:Lau and Arnmon Yuriv, High-Frequency Current Modulation of Semiconductor Injection Lasers
Charles H. Henry, Special Properties of Semiconductor Lasers
Yasuharu Suemalsu, Katsumi Kishino, Shigehisu Arai, and Fumio Koyama. Dynamic Single-Mode
Semiconductor Lasers with a Distributed Reflector
W I: Tsang, The Cleaved-Coupled-Cavity (C3) Laser

Part C
R. J. Nelson and N. K. Duttu, Review of InGaAsP InP Laser Structures and Comparison of Their
Performance
N . Chinone and M. Nakarnura, Mode-Stabilized Semiconductor Lasers for 0.74.8- and 1.1-1.6-pm
Regions
Yoshiji Horikoshi, Semiconductor Lasers with Wavelengths Exceeding 2 p m
B. A. Dean and M. Dixon, The Functional Reliability of Semiconductor Lasers as Optical Transmitters
R. H. Saul,Z k? Lee, and C. A. Burus, Light-Emitting Device Design
C. L. Zipfel, Light-Emitting Diode-Reliability
Tien Pei Lee and Tingye Li, LED-Based Multimode Lightwave Systems
Kinichiro Ogawa, Semiconductor Noise-Mode Partition Noise

Part D
Federico Capusso, The Physics of Avalanche Photodiodes
7: P. Peursull and M. A. Pollack, Compound Semiconductor Photodiodes
Takuo Kunedu, Silicon and Germanium Avalanche Photodiodes
S. R. Forrest, Sensitivity of Avalanche Photodetector Receivers for High-Bit-Rate Long-Wavelength Optical
Communication Systems
J. C. Campbell, Phototransistors for Lightwave Communications

Part E
Shyh Wang, Principles and Characteristics of Integrable Active and Passive Optical Devices
Shiorno Margalit and Amnon Yariv, Integrated Electronic and Photonic Devices
Tukuoki Mukui, Yoshihisa Yamarnoto, and Tufsuya Kimura, Optical Amplification by Semiconductor Lasers

Volume 23 Pulsed Laser Processing of Semiconductors

R. E Wood, C. W White, and R. Z Young, Laser Processing of Semiconductors: An Overview
C. W White, Segregation, Solute Trapping, and Supersaturated Alloys
G. E. Jellison, J K ,Optical and Electrical Properties of Pulsed Laser-Annealed Silicon
R. E Wood and G. E. Jellison, JK,Melting Model of Pulsed Laser Processing
R. F: Wood and F: W Young, J K ,Nonequilibrium Solidification Following Pulsed Laser Melting
D. H. Lowndes and G. E. Jellison, JK,Time-Resolved Measurement During Pulsed Laser Irradiation of
Silicon
D.M . Zebner. Surface Studies of Pulsed Laser Irradiated Semiconductors
436 CONTENTS OF VOLUMES IN THIS SERIES

D.H. Lowndes, Pulsed Beam Processing of Gallium Arsenide

R. B. James, Pulsed COz Laser Annealing of Semiconductors
R. I: Young and R. F: Wood, Applications of Pulsed Laser Processing

Volume 24 Applications of Multiquantum Wells, Selective Doping,

and Superlattices
C. Weisbuch, Fundamental Properties of 111-V Semiconductor Two-Dimensional Quantized Structures: The
Basis for Optical and Electronic Device Applications
H. Morkoc and H. Unlu, Factors Affecting the Performance of (Al, Ga)As/GaAs and (Al, Ga)AsflnCaAs
Modulation-Doped Field-Effect Transistors: Microwave and Digital Applications
N. L Linh, Two-Dimensional Electron Gas FETs: Microwave Applications
M. Abe el al., Ultra-High-speed HEMT Integrated Circuits
D.S. Chemla, D.A. B. Miller, and fl W Smith, Nonlinear Optical Properties of Multiple Quantum Well
Structures for Optical Signal Processing
E Capasso, Graded-Gap and Superlattice Devices by Band-Gap Engineering
W L Tsang, Quantum Confinement Heterostructure Semiconductor Lasers
G. C. Osbourn et al., Principles and Applications of Semiconductor Strained-Layer Superlattices

Volume 25 Diluted Magnetic Semiconductors

W Giriat and J. K . Furdyna, Crystal Structure, Composition, and Materials Preparation of Diluted
Magnetic Semiconductors
W M . Becker, Band Structure and Optical Properties of Wide-Gap A:l-xMnxBlv Alloys at Zero Magnetic
Field
Saul Oseroff and Piefer H. Keesom, Magnetic Properties: Macroscopic Studies
Giebulrowicz and L M. Holden, Neutron Scattering Studies of the Magnetic Structure and Dynamics of
Diluted Magnetic Semiconductors
J. Kossut, Band Structure and Quantum Transport Phenomena in Narrow-Gap Diluted Magnetic
Semiconductors
C. Riquaux, Magnetooptical Properties of Large-Gap Diluted Magnetic Semiconductors
J. A. Gaj, Magnetooptical Properties of Large-Gap Diluted Magnetic Semiconductors
J. Mycielski, Shallow Acceptors in Diluted Magnetic Semiconductors: Splitting, Boil-off, Giant Negative
Magnetoresistance
A. K. Ramadas and R. Rodriquez, Raman Scattering in Diluted Magnetic Semiconductors
l? A. Wolff, Theory of Bound Magnetic Polarons in Semimagnetic Semiconductors

Volume 26 111-V Compound Semiconductors and Semiconductor Properties of

Superionic Materials
Zou Yuami, 111-V Compounds
H. K Winston, A. L Huntec H. Kimuru, and R. E. Lee, InAs-Alloyed GaAs Substrates for Direct
Implantation
l? K. Bhattacharya and S. Dhar, Deep Levels in 111-V Compound Semiconductors Grown by MBE
Yu. Ya. Gurevich and A. K. Iuanou-Shits, Semiconductor Properties of Supersonic Materials

Volume 27 High Conducting Quasi-One-DimensionalOrganic Crystals

E. M. Conwell, Introduction to Highly Conducting Quasi-One-Dimensiona1 Organic Crystals
I. A. Howard, A Reference Guide to the Conducting Quasi-One-Dimensional Organic Molecular Crystals
J. l? Pouquet, Structural Instabilities
 CONTENTS OF VOLUMES IN THIS SERIES 437

E. M. Conwell, Transport Properties

C. S. Jacobsen, Optical Properties
J. C. Scoff,Magnetic Properties
L. Zuppimli, Irradiation Effects: Perfect Crystals and Real Crystals

Volume 28 Measurement of High-speed Signals in Solid State Devices

J. Frey and D.Ioannou, Materials and Devices for High-speed and Optoelectronic Applications
H. Schumucher and E. Strid, Electronic Wafer Probing Techniques
D. H. Ausron, Picosecond Photoconductivity: High-speed Measurements of Devices and Materials
J. A. Valdmanis, Electro-Optic Measurement Techniques for Picosecond Materials, Devices, and Integrated
Circuits
J. M. Wiesenfeld and R. K. Jain, Direct Optical Probing of Integrated Circuits and High-speed Devices
G. Plows, Electron-Beam Probing
A. M. Weiner and R. B. Marcus, Photoemissive Probing

Volume 29 Very High Speed Integrated Circuits: Gallium Arsenide LSI

M.Kuzuharu and 7: Nazuki, Active Layer Formation by Ion Implantation
H. Husimoto, Focused Ion Beam Implantation Technology
L Nozuki and A. Higashisuku. Device Fabrication Process Technology
M. In0 and L Tukada, GaAs LSI Circuit Design
M. Hirayumu, M. Ohmori, and K. Yamusuki, GaAs LSI Fabrication and Performance

Volume 30 Very High Speed Integrated Circuits: Heterostructure

H. Wafanabe, L Mizutuni, and A. Usui, Fundamentals of Epitaxial Growth and Atomic Layer Epitaxy
S. Hiyumizu, Characteristics of Two-Dimensional Electron Gas in 111-V Compound Heterostructures
Grown by MBE
L Nakanisi, Metalorganic Vapor Phase Epitaxy for High-Quality Active Layers
I: Nimuru, High Electron Mobility Transistor and LSI Applications
Z Sugefu and I: Ishibashi, Hetero-Bipolar Transistor and LSI Application
H. Matsuedu, L Tanaka, and M. Nukamuru, Optoelectronic Integrated Circuits

Volume 3 1 Indium Phosphide: Crystal Growth and Characterization

J. P. Farges, Growth of Discoloration-free InP
M. J. McCollum and G. E. Stillman, High Purity InP Grown by Hydride Vapor Phase Epitaxy
I: Inadu and 7: Fukuda, Direct Synthesis and Growth of Indium Phosphide by the Liquid Phosphorous
Encapsulated Czochralski Method
0. Oda, K. Kutugiri, K. Shinohara, S. Katsuru, Y Tukahashi, K. Kainosho, K. Kohiro, and R. Hirano, InP
Crystal Growth, Substrate Preparation and Evaluation
K. Tuda, M. Tatsurni, M. Morioku, I: Araki, and L Kawase, InP Substrates: Production and Quality Control
M. Razeghi, LP-MOCVD Growth, Characterization, and Application of InP Material
7: A. Kennedy and P. J. Lin-Chung, Stoichiometric Defects in InP

Volume 32 Strained-Layer Superlattices: Physics

T. P. Pearsall, Strained-Layer Superlattices
Fred H. Pollack, Effects of Homogeneous Strain on the Electronic and Vibrational Levels in
Semiconductors
438 CONTENTS OF VOLUMES I N THISSERlES

J. Y. Marzin, J. M. Gerrird, I? Voisin,and J.A. Brum, Optical Studies of Strained 111-V Heterolayers
R. People and S. A. Jackson, Structurally Induced States from Strain and Confinement
M. Jarus, Microscopic Phenomena in Ordered Superlattices

Volume 33 Strained-Layer Superlattices: Materials Science and Technology

R. Hull and J. C. Bean, Principles and Concepts of Strained-Layer Epitaxy
William J. Schafi Paul J. Tuskel; Marc C. Fuisy, and Lester E Eastmun, Device Applications of
Strained-Layer Epitaxy
S. T. Picraux, B. L. Doyle, and J. Y. Tsao, Structure and Characterization of Strained-Layer Superlattices
E. Kasper and I? Schaffer, Group IV Compounds
Dale L. Martin, Molecular Beam Epitaxy of IV-VI Compounds Heterojunction
Robert L. Gunshoc Leslie A. Kolodziejski, Arto V Nurmikko, and Nobuo Otsuka, Molecular Beam Epitaxy
of 11-VI Semiconductor Microstructures

Volume 34 Hydrogen in Semiconductors

J. I. Pankove and N. M. Johnson, Introduction to Hydrogen in Semiconductors
C. H . Seager, Hydrogenation Methods
J. I. Pankove, Hydrogenation of Defects in Crystalline Silicon
J. W Corbett, I? Dea'k, U. V Desnica, and S. J. Pearton, Hydrogen Passivation of Damage Centers in
Semiconductors
S.J. Pearfon, Neutralization of Deep Levels in Silicon
J. I. Pankove, Neutralization of Shallow Acceptors in Silicon
N. M . Johnson, Neutralization of Donor Dopants and Formation of Hydrogen-Induced Defects in n-Type
Silicon
M. Stavola and S. J. Peartun, Vibrational Spectroscopy of Hydrogen-Related Defects in Silicon
A. D. Marwick, Hydrogen in Semiconductors: Ion Beam Techniques
C. Herring and N. M. Johnson, Hydrogen Migration and Solubility in Silicon
E. E. Haller, Hydrogen-Related Phenomena in Crystalline Germanium
J. Kakalios, Hydrogen Diffusion in Amorphous Silicon
J. Chevaliel; 8.Clerjaud, and B. Pajot, Neutralization of Defects and Dopants in Ill-V Semiconductors
G. G. DeLeo and W B. Fowler, Computational Studies of Hydrogen-Containing Complexes in
Semiconductors
R. F Kiefl and T. L. Estle, Muonium in Semiconductors
C. C. Van de Walle, Theory of Isolated Interstitial Hydrogen and Muonium in Crystalline Semiconductors

Volume 35 Nanostructured Systems

Mark Reed, Introduction
H. van Huuten, C. W J. Beenakkel; and B. J. van Wees, Quantum Point Contacts
G. Timp, When Does a Wire Become an Electron Waveguide?
M. Buttiker, The Quantum Hall Effects in Open Conductors
W Hansen, J. I? Kotthaus, and U. Merkt, Electrons in Laterally Periodic Nanostructures

Volume 36 The Spectroscopy of Semiconductors

D. Heiman, Spectroscopy of Semiconductors at Low Temperatures and High Magnetic Fields
Arto V Nurmikko, Transient Spectroscopy by Ultrashort Laser Pulse Techniques
 CONTENTS OF VOLUMES IN THISSERIES 439

A. K. Ramdas and S. Rodriguez, Piezospectroscopy of Semiconductors

Orest J. Glembocki and Benjamin K Shanabrook, Photoreflectance Spectroscopy of Microstructures
David G. Seiler; Christopher L. Littler, and Margaret H. Wiler, One- and Two-Photon Magneto-Optical
Spectroscopy of InSb and Hgl-,Cd,Te

Volume 37 The Mechanical Properties of Semiconductors

A.-B. Chen, Arden Sher and W 1: Yost, Elastic Constants and Related Properties of Semiconductor
Compounds and Their Alloys
David R. Clarke, Fracture of Silicon and Other Semiconductors
Hans Siefhoff, The Plasticity of Elemental and Compound Semiconductors
Sivaraman Guruswamy, Katherine T Faber and John P: Hirth, Mechanical Behavior of Compound
Semiconductors
Subhanh Mahajan, Deformation Behavior of Compound Semiconductors
John P. Hirrh, Injection of Dislocations into Strained Multilayer Structures
Don KendaJJ, Charles B. Fleddermann, and Kevin J. Malloy, Critical Technologies for the Micromachining
of Silicon
Ikuo Matsuba and Kinji Mokuya, Processing and Semiconductor Thermoelastic Behavior

Volume 38 Imperfections in I I W Materials

Lido Scherz and Matthias Schefler, Density-Functional Theory of sp-Bonded Defects in IIW
Semiconductors
Maria Kaminska and Eicke R. Weber, El2 Defect in GaAs
David C. Look, Defects Relevant for Compensation in Semi-Insulating GaAs
R. C. Newman, Local Vibrational Mode Spectroscopy of Defects in IIW Compounds
Andrzej M. Hennel, Transition Metals in I I W Compounds
Kevin J. Malloy and Ken Khachaturyan, DX and Related Defects in Semiconductors
R Swaminuthan and Andrew S. Jordan, Dislocations in IIW Compounds
Krzysztof W Nauka, Deep Level Defects in the Epitaxial IIW Materials

Volume 39 Minority Carriers in Ill-V Semiconductors: Physics and

Applications
Niloy K . Dutra, Radiative Transitions in GaAs and Other 111-V Compounds
Richard K . Ahrenkiel, Minority-Carrier Lifetime in 111-V Semiconductors
Tomofumi Furura, High Field Minority Electron Transport in p-GaAs
Mark S. Lundstrom, Minority-Carrier Transport in 111-V Semiconductors
Richard A. Abram, Effects of Heavy Doping and High Excitation on the Band Structure of GaAs
David Yevick and Witold Bardyszewski, An Introduction to Non-Equilibrium Many-Body Analyses of
Optical Processes in 111-V Semiconductors

Volume 40 Epitaxial Microstructures

E. F: Schubert, Delta-Doping of Semiconductors: Electronic, Optical, and Structural Properties of Materials
and Devices
A. Gossard, M. Sundaram, and f? Hupkins, Wide Graded Potential Wells
P: Petroff, Direct Growth of Nanometer-Size Quantum Wire Superlattices
E. Kapon, Lateral Patterning of Quantum Well Heterostructures by Growth of Nonplanar Substrates
H. Temkin, D.Gershoni, and M. Panish, Optical Properties of Gal-,In,As/InP Quantum Wells
440 CONTENTS OF VOLUMES I N THSS SERIES

Volume 41 High Speed HeterostructureDevices

E Capasso, E Beltram, S. Sen, A. Pahlevi, and A. K Cho, Quantum Electron Devices: Physics and
Applications
k? Solomon, D.J. Frank, S. L. Wright, and E Canora, GaAs-Gate Semiconductor-Insulator-Semiconductor
FET
M. H. Hashemi and U. K. Mishra, Unipolar InP-Based Transistors
R. Kiehl, Complementary Heterostmcture FET Integrated Circuits
I: Ishibashi, GaAs-Based and InP-Based Heterostructure Bipolar Transistors
H. C. Liu and T. C. L. G. Sollner, High-Frequency-Tunneling Devices
H . Ohnishi, I: More, M. Takatsu, K. Imamura, and N. Yokoyama, Resonant-Tunneling Hot-Electron
Transistors and Circuits

Volume 42 Oxygen in Silicon

F: Shimura, Introduction to Oxygen in Silicon
W Lin, The Incorporation of Oxygen into Silicon Crystals
7: J. Schafier and D.K . Schroder, Characterization Techniques for Oxygen in Silicon
W M. Bullis, Oxygen Concentration Measurement
S. M. Hu, Intrinsic Point Defects in Silicon
B. Pajot, Some Atomic Configurations of Oxygen
J. Michel and L. C. Kimerling, Electical Properties o f Oxygen in Silicon
R. C. Newman and R. Jones, Diffusion of Oxygen in Silicon
?: E Tan and W J. Taylor, Mechanisms of Oxygen Precipitation: Some Quantitative Aspects
M. Schrems, Simulation o f Oxygen Precipitation
K. Simino and I. Yonenaga, Oxygen Effect on Mechanical Properties
W Bergholz, Grown-in and Process-Induced Effects
F: Shimura, Intrinsic/lntemal Gettering
H. Tsuyu, Oxygen Effect on Electronic Device Performance

Volume 43 Semiconductors for Room Temperature Nuclear

Detector Applications
R. B. James and 7: E. Schlesinger, Introduction and Overview
L. S. Darken and C. E. Cox, High-Purity Germanium Detectors
A. Burger: D. Nason, L. Van den Berg, and M . Schieber, Growth of Mercuric Iodide
X . J. Bao, I: E. Schlesinger, and R. B. James, Electrical Properties o f Mercuric Iodide
X . J. Bao, R. B. James, and T. E. Schlesinger, Optical Properties of Red Mercuric Iodide
M. Huge-Ali and F? Siffert, Growth Methods of CdTe Nuclear Detector Materials
M. Hage-Ali and P Sigert, Characterization of CdTe Nuclear Detector Materials
M. Huge-Ali and k? Sifert, CdTe Nuclear Detectors and Applications
R. B. James, I: E. Schlesingeq J. Lund, and M. Schieber, C ~ I _ ~ Z spectrometers
~ , T ~ for Gamma and
X-Ray Applications
D. S. McGregor, J. E. Kammeraad, Gallium Arsenide Radiation Detectors and Spectrometers
J. C. Lund, E Olschner, and A. Burger, Lead Iodide
M . R. Squillante, and K. S. Shah, Other Materials: Status and Prospects
I.: M. Gerrish, Characterization and Quantification of Detector Performance
J. S. Iwanczyk and B. E. Patt, Electronics for X-ray and Gamma Ray Spectrometers
M. Schieber: R. B. James, and I: E. Schlesinger, Summary and Remaining Issues for Room Temperature
Radiation Spectrometers
 CONTENTS OF VOLUMES IN THISSERIES 441

Volume 44 11-IV Blue/Green Light Emitters: Device Physics and

Epitaxial Growth
J. Han and R. L. Gunshor, MBE Growth and Electrical Properties of Wide Bandgap ZnSe-based 11-VI
Semiconductors
Shizuo Fujita and Shigeo Fujita, Growth and Characterization of ZnSe-based 11-VI Semiconductors by
MOVPE
Easen Ho and Leslie A. Kolodziejski, Gaseous Source UHV Epitaxy Technologies for Wide Bandgap 11-VI
Semiconductors
Chris G. Van de Walk, Doping of Wide-Band-Gap 11-VI Compounds-Theory
Roberto Cingolani, Optical Properties of Excitons in ZnSe-Based Quantum Well Heterostructures
A. Ishibashi and A. K Nurmikko, 11-VI Diode Lasers: A Current View of Device Performance and Issues
Supratik Guha and John Petruzello, Defects and Degradation in Wide-Gap 11-VI-based Structures and
Light Emitting Devices

Volume 45 Effect of Disorder and Defects in Ion-Implanted Semiconductors:

Electrical and Physiochemical Characterization
Heiner Ryssel, Ion Implantation into Semiconductors: Historical Perspectives
You-Nian Wang and Teng-Cai Ma, Electronic Stopping Power for Energetic Ions in Solids
Sachiko 7: Nakagawa, Solid Effect on the Electronic Stopping of Crystalline Target and Application to
Range Estimation
G. Miiller; S. Kalbitzer and G. N. Greaves, Ion Beams in Amorphous Semiconductor Research
Jumuna Boussey-Said, Sheet and Spreading Resistance Analysis of Ion Implanted and Annealed
Semiconductors
M. L. Polignano and G. Queirolo, Studies of the Stripping Hall Effect in Ion-Implanted Silicon
J. Stoernenos, Transmission Electron Microscopy Analyses
Roberta Nipoti and Marc0 Servidori, Rutherford Backscattering Studies of Ion Implanted Semi-conductors
P Zuurnseil, X-ray Diffraction Techniques

Volume 46 Effect of Disorder and Defects in Ion-Implanted Semiconductors:

Optical and Photothermal Characterization
M. Fried, 7: Lohner and J. Gyulai, Ellipsometric Analysis
Antonio3 Seas and Constantinos Christojdes, Transmission and Reflection Spectroscopy on Ion Implanted
Semiconductors
Andreas Othonos and Constantinos Christojides, Photoluminescence and Raman Scattering of Ion
Implanted Semiconductors. Influence of Annealing
Constantinos Christojdes, Photomodulated Thermoreflectance Investigation of Implanted Wafers.
Annealing Kinetics of Defects
U.Zarnrnit, Photothermal Deflection Spectroscopy Characterization of Ion-Implanted and Annealed Silicon
Films
Andreas Mandelis, Arief Budiman and Miguel Vargas, Photothermal Deep-Level Transient Spectroscopy of
Impurities and Defects in Semiconductors
R. Kalish and S. Charbonneau,Ion Implantation into Quantum-Well Structures
Alexandre M. Myasnikov and Nikolay N. Gerasimenko, Ion Implantation and Thermal Annealing of 111-V
Compound Semiconducting Systems: Some Problems of 111-V Narrow Gap Semiconductors
442 C O N T E N T S OF VOLUMES IN THISS E R I E S

Volume 47 Uncooled Infrared Imaging Arrays and Systems

R. G. Buser and M. l? Tompsett, Historical Overview
f? W. Kruse, Principles of Uncooled Infrared Focal Plane Arrays
R. A. Wood, Monolithic Silicon Microbolometer Arrays
C. M. Hanson, Hybrid Pyroelectric-FerroelectricBolometer Arrays
D. L. Polla and J. R. Choi, Monolithic Pyroelectric Bolometer Arrays
N. Teranishi, Thermoelectric Uncooled Infrared Focal Plane Arrays
M. E Tompsetf, Pyroelectric Vidicon
?: W. Kenny, Tunneling Infrared Sensors
J. R. Vig, R. L. Filler and E: Kim, Application of Quartz Microresonators to Uncooled Infrared Imaging
Arrays
l? W. Kruse, Application of Uncooled Monolithic Thermoelectric Linear Arrays to Imaging Radiometers

Volume 48 High Brightness Light Emitting Diodes

G. B. Stringfellow, Materials Issues in High-Brightness Light-Emitting Diodes
M. G. Craford, Overview of Device Issues in High-Brightness Light-Emitting Diodes
E M. Steranka, AlGaAs Red Light-Emitting Diodes
C. H. Chen, S. A. Stockman, M. J. Peanasb, and C. l? Kuo, OMVPE Growth of AlGaInP for High
Efficiency Visible Light-Emitting Diodes
E A. Kish and R. M. Fletcher, AlGaInP Light-Emitting Diodes
M. W. Hodapp, Applications for High Brightness Light-Emitting Diodes
I. Akasaki and H. Amano, Organometallic Vapor Epitaxy of GaN for High Brightness Blue Light-Emitting
Diodes
S. Nakamura, Group 111-V Nitride Based Ultraviolet-Blue-Green-Yellow Light-Emitting Diodes and Laser
Diodes

Volume 49 Light Emission in Silicon: from Physics to Devices

David J. Lockwood, Light Emission in Silicon
Gerhard Absfreifer,Band Gaps and Light Emission in Si/SiGe Atomic Layer Structures
Thomas G. Brown and Dennis G. Hall, Radiative Isoelectronic Impurities in Silicon and
Silicon-Germanium Alloys and Superlattices
1. Michel, L. V C. Assali, M. 7: Morse, and L. C. Kimerling, Erbium in Silicon
Yoshihiko Kanemifsu, Silicon and Germanium Nanoparticles
Philippe M. Fauchet, Porous Silicon: Photoluminescence and Electroluminescent Devices
C. Delerue, G. Allan, and M. Lannoo, Theory of Radiative and Nonradiative Processes in Silicon
Nanocrystallites
Louis Brus, Silicon Polymers and Nanocrystals

Volume 50 Gallium Nitride (GaN)

J. I. Pankove and 7: D. Moustakas, Introduction
S. I? DenBaars and S. Keller, Metalorganic Chemical Vapor Deposition (MOCVD) of Group 111Nitrides
W. A. Bryden and 7: J. Kistenmacher, Growth of Group 111-A Nitrides by Reactive Sputtering
N. Newman, Thermochemistry of 111-N Semiconductors
S.J. Pearton and R. J. Shul, Etching of 111Nitrides
S. M. Bedair, Indium-based Nitride Compounds
A. Trampert, 0.Brandt, and K. H. Ploog, Crystal Structure of Group 111Nitrides
 CONTENTS OF VOLUMES IN THISSERIES 443

H. Morkoc, E Hamdani, and A. Salvador, Electronic and Optical Properties of 111-V Nitride based
Quantum Wells and Superlattices
K. Doverspike and J. I. Pankove, Doping in the 111-Nitrides
I: Suski and P. Perlin, High Pressure Studies of Defects and Impurities in Gallium Nitride
B. Monemar, Optical Properties of GaN
W R. L.Lambrecht, Band Structure of the Group 111 Nitrides
N. E. Christensen and P. Perlin, Phonons and Phase Transitions in GaN
S. Nakamura, Applications of LEDs and LDs
I. Akasaki and H. A m n o , Lasers
J. A. Cooper;JK,Nonvolatile Random Access Memories in Wide Bandgap Semiconductors

Volume 5 1A Identification of Defects in Semiconductors

George D.Warkins, EPR and ENDOR Studies of Defects in Semiconductors
J.-M. Spaeth, Magneto-Optical and Electrical Detection of Paramagnetic Resonance in Semiconductors
I: A. Kennedy and E. R. Glaser, Magnetic Resonance of Epitaxial Layers Detected by Photoluminescence
K. H. Chow, B. Hitri, and R. E Kiefi, fiSR on Muonium in Semiconductors and Its Relation to Hydrogen
Kimmo Saarinen, Pekka Hautojarvi, and Catherine Corbel, Positron Annihilation Spectroscopy of Defects
in Semiconductors
R. Jones and P. R. Briddon, The A b Initio Cluster Method and the Dynamics of Defects in Semiconductors

Volume 5 1B Identification of Defects in Semiconductors

Gordon Davies, Optical Measurements of Point Defects
P. M. Mooney, Defect Identification Using Capacitance Spectroscopy
Michael Stavola, Vibrational Spectroscopy of Light Element Impurities in Semiconductors
P. Schwande,: W D. Rau, C. Kisielowski, M. Gribelyuk, and A. Ourmazd, Defect Processes in
Semiconductors Studied at the Atomic Level by Transmission Electron Microscopy
Nikos D. Jager and Eicke R. Weber, Scanning Tunneling Microscopy of Defects in Semiconductors

Volume 52 S i c Materials and Devices

K. Jarrendahl and R. E Davis, Materials Properties and Characterization of SIC
V A. Dmitriev and M . G. Spencer, S i c Fabrication Technology: Growth and Doping
1.: Saxena and A. J. Steckl, Building Blocks for SIC Devices: Ohmic Contacts, Schottky Contacts, and p n
Junctions
M. S. Shur, S i c Transistors
C. D. Brandt, R. C. Clarke, R. R. Siergiej, J. B. Casady, A. W Morse, S. Sriram, and A. K. Aganval, S i c for
Applications in High-Power Electronics
R. J. Trew, Sic Microwave Devices
J. Edmond, H. Kong, G. Negley, M. Leonard, K. Doverspike, W Weeks, A. Suvorov, D. Waltz, and C. Carte6
Jr., Sic-Based UV Photodiodes and Light-Emitting Diodes
H. Morkoc, Beyond Silicon Carbide! 111-V Nitride-Based Heterostructures and Devices

Volume 53 Cumulative Index

444 CONTENTS OF VOLUMES I N THISSERIES

Volume 54 High Pressure in Semiconductor Physics I

William Paul, High Pressure in Semiconductor Physics: A Historical Overview
N. E. Christensen, Electronic Structure Calculations for Semiconductors under Pressure
R. J. Nelmes and M. I. McMahon, Structural Transitions in the 111-V and 11-VI and Group-IV
Semiconductors under Pressure
A. R. Goni and K. Syassen, Optical Properties of Semiconductors under Pressure
R Trautman, M. Baj, and J. M. Earanowski, Hydrostatic Pressure and Uniaxial Stress in Investigations of
the EL2 Defect in GaAs
M. Li and R !I Yu, High Pressure Study of DX Centers Using Capacitance Techniques
7: Suski, Spatial Correlations of Impurity Charges in Doped Semiconductors
N. Kuroda, Pressure Effects on the Electronic Properties of Diluted Magnetic Semiconductors

Volume 55 High Pressure in Semiconductor Physics I1

D.K. Maude and J. C. Portal, Parallel Transport in Low-Dimensional Semiconductor Structures
R C. Klipstein, Tunneling Under Pressure: High-pressure Studies of Vertical Transport in Semiconductor
Heterostructures
Evangelos Anastassakis and Manuel Cardona, Phonons, Strains, and Pressure in Semiconductors
Fred H. Pollak, Effects of External Uniaxial Stress on the Optical Properties of Semiconductors and
Semiconductor Microstructures
A. R. Adams, M. Silvec and J. Allam, Semiconductor Optoelectronic Devices
S.Porowski and I. Grzegory, The Application o f High Nitrogen Pressure in the Physics and Technology of
111-N Compounds
Mohammad Yousuf,Diamond Anvil Cells in High Pressure Studies of Semiconductors

Volume 56 Germanium Silicon: Physics and Materials

John C. Bean, Growth Techniques and Procedures
Donald E. Savage, Feng Liu, Volkmar Zielasek, and Max G. Lagally, Fundamental Mechanisms of Film
Growth
R. Hull, Misfit Strain and Accommodation in SiGe Heterostructures
M. J. Shaw and M. Jaros, Fundamental Physics of Strained Layer GeSi: Quo Vadis?
Fernando Cerdeirn, Optical Properties
Steven A. Ringel and Patrick N. Grillot, Electronic Properties and Deep Levels in Germanium-Silicon
Joe C. Campbell, Optoelectronics in Silicon and Germanium Silicon
Karl Eberl, Karl Brunner and Oliver G. Schmidt, Sil-,C, and Sil-,_,Ge,C, Alloy Layers
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