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HANDBOOK OF

DEPOSITION TECHNOLOGIES
FOR FILMS AND COATINGS
Science, Technology
and Applications

Second Edition

Edited by

Rointan F. Bunshah

University of California at Los Angeles


Los Angeles, California

NOYES PUBLICATIONS
np Park Ridge, New Jersey, U.S.A.
Copyright © 1994 by Noyes Publications
No part of this book may be reproduced or
utilized in any form or by any means, elec-
tronic or mechanical, including photocopying,
recording or by any information storage and
retrieval system, without permission in writing
from the Publisher.
Library of Congress Catalog Card Number: 93-30751
ISBN: 0-8155-1337-2
Printed in the United States

Published in the United States of America by


Noyes Publications
Mill Road, Park Ridge, New Jersey 07656

10 9 8 7 6 5 4 3 2 1

Library of Congress Cataloging-in-Publication Data

Handbook of deposition technologies for films and coatings /


edited by Rointan F. Bunshah. -- 2nd ed.
p. cm.
Rev. ed of: Deposition technologies for films and coatings.
c1982.
Includes bibliographical references and index.
ISBN 0-8155-1337-2
1. Coating processes. I. Bunshah, R. F. (Rointan
Framroze)
II. Title: Deposition technologies for films and coatings.
TP156.C57H38 1994
667' .9--dc20 9 3 -30751

CIP
DEDICATION

This volume is dedicated to Professor John


Thornton for his many pioneering contributions to thin
film science and technology which have inspired so
many of the scientists and engineers working in this field.

vii
MATERIALS SCIENCE AND PROCESS TECHNOLOGY SERIES

Editors
Rointan F. Bunshah, University of California, Los Angeles (Series Editor)
Gary E. McGuire, Microelectronics Center of North Carolina (Series Editor)
Stephen M. Rossnagel, IBM Thomas J. Watson Research Center
(Consulting Editor)

Electronic Materials and Process Technology


HANDBOOK OF DEPOSITION TECHNOLOGIES FOR FILMS AND COATINGS, Second
Edition: edited by Rointan F. Bunshah
CHEMICAL VAPOR DEPOSITION FOR MICROELECTRONICS: by Arthur Sherman
SEMICONDUCTOR MATERIALS AND PROCESS TECHNOLOGY HANDBOOK: edited by
Gary E. McGuire
HYBRID MICROCIRCUIT TECHNOLOGY HANDBOOK: by James J. Licari and Leonard R.
Enlow
HANDBOOK OF THIN FILM DEPOSITION PROCESSES AND TECHNIQUES: edited by Klaus
K. Schuegraf
IONIZED-CLUSTER BEAM DEPOSITION AND EPITAXY: by Toshinori Takagi
DIFFUSION PHENOMENA IN THIN FILMS AND MICROELECTRONIC MATERIALS: edited by
Devendra Gupta and Paul S. Ho
HANDBOOK OF CONTAMINATION CONTROL IN MICROELECTRONICS: edited by Donald
L. Tolliver
HANDBOOK OF ION BEAM PROCESSING TECHNOLOGY: edited by Jerome J. Cuomo,
Stephen M. Rossnagel, and Harold R. Kaufman
CHARACTERIZATION OF SEMICONDUCTOR MATERIALS, Volume 1: edited by Gary E.
McGuire
HANDBOOK OF PLASMA PROCESSING TECHNOLOGY: edited by Stephen M. Rossnagel,
Jerome J. Cuomo, and William D. Westwood
HANDBOOK OF SEMICONDUCTOR SILICON TECHNOLOGY: edited by William C. O’Mara,
Robert B. Herring, and Lee P. Hunt
HANDBOOK OF POLYMER COATINGS FOR ELECTRONICS, 2nd Edition: by James Licari
and Laura A. Hughes
HANDBOOK OF SPUTTER DEPOSITION TECHNOLOGY: by Kiyotaka Wasa and Shigeru
Hayakawa
HANDBOOK OF VLSI MICROLITHOGRAPHY: edited by William B. Glendinning and John
N. Helbert
CHEMISTRY OF SUPERCONDUCTOR MATERIALS: edited by Terrell A. Vanderah
CHEMICAL VAPOR DEPOSITION OF TUNGSTEN AND TUNGSTEN SILICIDES: by John E.
J. Schmitz
ELECTROCHEMISTRY OF SEMICONDUCTORS AND ELECTRONICS: edited by John McHardy
and Frank Ludwig

v
vi Contents
Series

HANDBOOK OF CHEMICAL VAPOR DEPOSITION: by Hugh O. Pierson


DIAMOND FILMS AND COATINGS: edited by Robert F. Davis
ELECTRODEPOSITION: by Jack W. Dini
HANDBOOK OF SEMICONDUCTOR WAFER CLEANING TECHNOLOGY: edited by Werner
Kern
CONTACTS TO SEMICONDUCTORS: edited by Leonard J. Brillson
HANDBOOK OF MULTILEVEL METALLIZATION FOR INTEGRATED CIRCUITS: edited by
Syd R. Wilson, Clarence J. Tracy, and John L. Freeman, Jr.
HANDBOOK OF CARBON, GRAPHITE, DIAMONDS AND FULLERENES: by Hugh O. Pierson

Ceramic and Other Materials—Processing and Technology


SOL-GEL TECHNOLOGY FOR THIN FILMS, FIBERS, PREFORMS, ELECTRONICS AND
SPECIALTY SHAPES: edited by Lisa C. Klein
FIBER REINFORCED CERAMIC COMPOSITES: edited by K. S. Mazdiyasni
ADVANCED CERAMIC PROCESSING AND TECHNOLOGY, Volume 1: edited by Jon G. P.
Binner
FRICTION AND WEAR TRANSITIONS OF MATERIALS: by Peter J. Blau
SHOCK WAVES FOR INDUSTRIAL APPLICATIONS: edited by Lawrence E. Murr
SPECIAL MELTING AND PROCESSING TECHNOLOGIES: edited by G. K. Bhat
CORROSION OF GLASS, CERAMICS AND CERAMIC SUPERCONDUCTORS: edited by
David E. Clark and Bruce K. Zoitos
HANDBOOK OF INDUSTRIAL REFRACTORIES TECHNOLOGY: by Stephen C. Carniglia
and Gordon L. Barna
CERAMIC FILMS AND COATINGS: edited by John B. Wachtman and Richard A. Haber

Related Titles
ADHESIVES TECHNOLOGY HANDBOOK: by Arthur H. Landrock
HANDBOOK OF THERMOSET PLASTICS: edited by Sidney H. Goodman
SURFACE PREPARATION TECHNIQUES FOR ADHESIVE BONDING: by Raymond F.
Wegman
FORMULATING PLASTICS AND ELASTOMERS BY COMPUTER: by Ralph D. Hermansen
HANDBOOK OF ADHESIVE BONDED STRUCTURAL REPAIR: by Raymond F. Wegman and
Thomas R. Tullos
CARBON–CARBON MATERIALS AND COMPOSITES: edited by John D. Buckley and Dan
D. Edie
CODE COMPLIANCE FOR ADVANCED TECHNOLOGY FACILITIES: by William R. Acorn
Contributors

Rointan F. Bunshah Donald M. Mattox


Department of Materials Science and Society of Vacuum Coaters
Engineering Albuquerque, New Mexico
University of California at Los Angeles
Los Angeles, California Gary E. McGuire
Microelectronics Center of North
Jan-Otto Carlsson Carolina
Department of Chemistry Research Triangle Park, North Carolina
Upsala University
Upsala, Sweden Jerome C. Schmitt
Jet Process Corporation
Joseph E. Greene New Haven, Connecticut
Coordinated Science Laboratory
University of Illinois at Urbana- Morton Schwartz
Champaign Electrochemical/Metal Finishing
Urbana, Illinois Consultant
Los Angeles, California
Bret L. Halpern
Jet Process Corporation Arthur Sherman
New Haven, Connecticut Consultant
Palo Alto, California

xiii
xiv Contents
Contributors

John A. Thornton* Robert C. Tucker, Jr.


Coordinated Science Laboratory Praxair Surface Technologies, Inc.
University of Illinois at Urbana- Indianapolis, Indiana
Champaign
Urbana, Illinois

* Professor Thornton died unexpectedly in


November, 1987.

NOTICE

To the best of our knowledge the information in this publication is


accurate; however the Publisher does not assume any responsibility
or liability for the accuracy or completeness of, or consequences
arising from, such information. This book is intended for informational
purposes only. Mention of trade names or commercial products does
not constitute endorsement or recommendation for use by the Publisher.
Final determination of the suitability of any information or product
for use contemplated by any user, and the manner of that use, is the
sole responsibility of the user. We recommend that anyone intending
to rely on any recommendation of materials or procedures mentioned
in this publication should satisfy himself as to such suitability, and
that he can meet all applicable safety and health standards.
Preface to the Second Edition

A decade after the first edition of this volume was published, a second
edition is being brought out partly due to the excellent response to the first
edition and also to update the many improvements in deposition technologies,
the mechanisms and applications.
The entire volume has been extensively revised and contains 50% or
more new material. Five entirely new chapters have been added. The
organization of the book has also been changed in the following respects:
1. Considerably more material has been added in Plasma
Assisted Vapor Deposition Processes.
2. A new chapter on Metallurgical Coating Applications has
been added.
The chapter in the first edition on Polymeric Coating techniques has
been omitted as it deserves a volume by itself. Large topics such as coatings
technology in microelectronics, diamond films, etc., have been treated in
separate volumes in this series.
Although there are some new competing volumes dealing with selected
topics on the materials science of thin films, this volume remains the only
comprehensive treatment of the entire subject of Deposition Technology.
Applications of films and coatings spans the entire gamut of science and
technology. Generic application areas include electronic, magnetic, optical,
mechanical, chemical and decorative applications. New deposition technolo-
gies such as arc evaporation, unbalanced magnetron sputtering, ion beam
assisted deposition, and metal-organic CVD have come on stream for critical
applications. In this post cold war era, many economic solutions to
engineering problems will necessarily involve coatings, e.g., battery materials
for the emerging electric car industry.

ix
x Preface
Contents

The core subjects are the basic technologies for the deposition of films
and coatings. These are the Physical Vapor Deposition (PVD) Processes
consisting of Evaporation, Sputtering, and Ion Plating; Chemical Vapor
Deposition (CVD) and Plasma-Assisted Chemical Vapor Deposition (PACVD);
Electrodeposition and Electroless Plating; Thermal Spraying, Plasma Spray-
ing and Detonation Gun Technologies. Chapters on other subjects common
to the above technologies are included. These are: Adhesion of Coatings,
Cleaning of Substrates, Role of Plasmas in Deposition Processes, Structure
of PVD Deposits, Growth and Structure of PVD Films, Mechanical and
Tribological Properties of PVD Deposits, Elemental and Structural Character-
ization Techniques, and Metallurgical Coatings. A relatively new develop-
ment, Jet Vapor Deposition Process, was added as the last chapter in the
book during the page proof stage because of its novelty.
We hope that this volume will be useful to the multitude of disciplines
represented by the workers in this field and provide a source for future
developments.

University of California Rointan F. Bunshah


Los Angeles, California
June, 1993
Preface to the First Edition

Almost universally in high technology applications, a composite material


is used where the properties of the surface are intentionally different from those
of the core. Thus, materials with surface coatings are used in the entire cross-
section of applications ranging from microelectronics, display devices, chemi-
cal corrosion, tribology including cutting tools, high temperature oxidation/
corrosion, solar cells, thermal insulation and decorative coatings (including
toys, automobile components, watch cases, etc.).
A large variety of materials is used to produce these coatings. They are
metals, alloys, refractory compounds (e.g., oxides, nitrides, carbides),
intermetallic compounds (e.g., GaAg) and polymers in single or multiple
layers. The thickness of the coatings ranges from a few atom layers to millions
of atom layers. The microstructure and hence the properties of the coatings
can be varied widely and at will, thus permitting one to design new material
systems with unique properties. (A material system is defined as the
combination of the substrate and coating.)
Historically, coating technology evolved and developed in the last 30
years in several industries, i.e., decorative coatings, microelectronics and
metallurgical coatings. They used similar techniques but only with the
passage of time have the various approaches reached a common frontier
resulting in much useful cross-fertilization. That very vital process is
proceeding ever more strongly at this time.
With this background in mind, a short course on Deposition Technolo-
gies and their applications was developed and given on five consecutive
occasions in the last three years. This volume is based on the material used
in the course.

xi
xii

It comprises chapters dealing with the various coating techniques, the


resulting microstructure, properties and applications. The specific techniques
covered are evaporation, ion plating, sputtering, chemical vapor deposition,
electrodeposition from aqueous solution, plasma and detonation gun coating
techniques, and polymeric coatings. In addition several other chapters are
added. Plasmas are used in many of the deposition processes and therefore
a special chapter on this topic has been added. Cleaning of the substrate and
the related topic of adhesion of the coating are common to many processes
and a brief exposé of this topic is presented. Characterization of the films, i.e.,
composition, impurities, crystal structure and microstructure are essential to
the understanding of the various processes. Two chapters dealing with this
area are included. Finally, a chapter on application of deposition techniques
in microelectronics is added to give one example of the use of several of these
techniques in a specific area. This volume represents a unique collection of
our knowledge on Deposition Technologies and their applications up to and
including the state-of-the-art. It is hoped that it will be very useful to students,
practicing engineers and managerial personnel who have to learn about this
essential area of modern technology.

University of California R. F. Bunshah


Los Angeles, California
April 1982
Contents xv

Contents

1 Deposition Technologies: An Overview ....................... 27


Rointan F. Bunshah
1.0 THE MARKET .............................................................................. 27
2.0 INTRODUCTION ........................................................................... 28
3.0 AIM AND SCOPE ......................................................................... 30
4.0 DEFINITIONS AND CONCEPTS ................................................... 31
5.0 PHYSICAL VAPOR DEPOSITION (PVD) PROCESS
TERMINOLOGY ........................................................................... 32
6.0 CLASSIFICATION OF COATING PROCESSES ........................... 34
7.0 GAS JET DEPOSITION WITH NANO-PARTICLES ....................... 36
8.0 MICROSTRUCTURE AND PROPERTIES ..................................... 38
9.0 UNIQUE FEATURES OF DEPOSITED MATERIALS AND GAPS
IN UNDERSTANDING ................................................................... 40
10.0 CURRENT APPLICATIONS .......................................................... 41
10.1 Decorative/Functional Coating ............................................. 41
10.2 High Temperature Corrosion ................................................ 42
10.3 Environmental Corrosion ..................................................... 42
10.4 Friction and Wear ............................................................... 42
10.5 Materials Conservation ........................................................ 43
10.6 Cutting Tools ...................................................................... 43
10.7 Nuclear Fuels ..................................................................... 44
10.8 Biomedical Uses ................................................................. 44

xv
xvi Contents

10.9 Electrical Uses ................................................................... 44


11.0 “FRONTIER AREAS” FOR THE APPLICATION OF
THE PRODUCTS OF DEPOSITION TECHNOLOGY ..................... 44
12.0 SELECTION CRITERIA ................................................................. 46
13.0 SUMMARY ................................................................................... 48
APPENDIX 1: DEPOSITION PROCESS DEFINITIONS........................... 49
Conduction and Diffusion Processes............................................. 49
Chemical processes ..................................................................... 50
Wetting Process........................................................................... 50
Spraying Processes ..................................................................... 51
REFERENCES ...................................................................................... 54

2 Plasmas in Deposition Processes .............................. 55


John A. Thornton and Joseph E. Greene
1.0 INTRODUCTION ........................................................................... 55
2.0 PARTICLE MOTION ..................................................................... 56
2.1 Mean Free Path and Collision Cross Sections .................... 56
2.2 Free Electron Kinetic Energy in a Plasma........................... 58
2.3 Electron Energy Distribution Functions ............................... 59
2.4 Collision Frequencies .......................................................... 61
3.0 COLLECTIVE PHENOMENA ........................................................ 68
3.1 Plasma Sheaths ................................................................. 69
3.2 Ambipolar Diffusion ............................................................. 74
3.3 Plasma Oscillations ............................................................ 75
4.0 PLASMA DISCHARGES .............................................................. 76
4.1 Introduction ......................................................................... 76
4.2 Ionization Balances and the Paschen Relation .................... 77
4.3 Cold Cathode Discharges ................................................... 82
4.4 Magnetron Discharges ........................................................ 84
4.5 RF Discharges .................................................................... 85
5.0 PLASMA VOLUME REACTIONS ................................................. 87
5.1 Introduction ......................................................................... 87
5.2 Electron/Atom Interactions .................................................. 87
5.3 Electron/Molecule Interactions ............................................ 88
5.4 Metastable Species ............................................................ 90
5.5 Applications of Volume Reactions....................................... 92
6.0 SURFACE REACTIONS ............................................................... 93
6.1 Introduction ......................................................................... 93
6.2 Ion Bombardment ................................................................ 93
6.3 Electron Bombardment ..................................................... 100
6.4 Glow Discharge Surface Cleaning and Activation .............. 100
REFERENCES .................................................................................... 103
Contents xvii

3 Surface Preparation for Film and Coating Deposition


Processes ................................................................ 108
Donald M. Mattox
1.0 INTRODUCTION ......................................................................... 108
2.0 CONTAMINATION ...................................................................... 110
2.1 Recontamination ............................................................... 111
3.0 ENVIRONMENT CONTROL ........................................................ 113
4.0 CLEANING PROCESSES .......................................................... 119
4.1 Particulate Removal .......................................................... 120
4.2 Abrasive Cleaning ............................................................. 121
4.3 Etch Cleaning ................................................................... 121
4.4 Fluxing .............................................................................. 122
4.5 Alkaline Cleaners .............................................................. 122
4.6 Detergent Cleaning ........................................................... 122
4.7 Chelating Agents .............................................................. 123
4.8 Solvent Cleaning ............................................................... 123
4.9 Oxidation Cleaning............................................................ 128
4.10 Volatilization Cleaning....................................................... 130
4.11 Hydrogen Reduction Cleaning ........................................... 130
4.12 Electrolytic Cleaning ......................................................... 131
5.0 DRYING AND OUTGASSING ..................................................... 132
6.0 MONITORING OF CLEANING .................................................... 133
7.0 IN SITU CLEANING .................................................................... 134
7.1 Ion Scrubbing .................................................................... 134
8.0 PLASMAS .................................................................................. 134
8.1 Generation of Plasmas ..................................................... 135
8.2 Plasma Chemistry ............................................................ 140
8.3 Bombardment Effects on Surfaces .................................... 141
8.4 Sputter Cleaning and Etching............................................ 143
9.0 STORAGE AND HANDLING ....................................................... 147
10.0 ACTIVATION AND SENSITIZATION ............................................ 148
11.0 SURFACE MODIFICATION ........................................................ 150
12.0 PASSIVATION AND PRESERVATION ....................................... 151
13.0 SAFETY ..................................................................................... 152
REFERENCES .................................................................................... 152

4 Evaporation: Processes, Bulk Microstructures and


Mechanical Properties .............................................. 157
Rointan F. Bunshah
1.0 GENERAL INTRODUCTION ........................................................ 157
2.0 SCOPE ...................................................................................... 159
xviii Contents

3.0 PVD PROCESSES .................................................................... 159


3.1 Preamble .......................................................................... 159
3.2 PVD Processes ................................................................ 160
3.3 Advantages and Limitations .............................................. 165
4.0 THEORY AND MECHANISMS ................................................... 166
4.1 Vacuum Evaporation ......................................................... 166
5.0 EVAPORATION PROCESS AND APPARATUS ......................... 169
5.1 The System ...................................................................... 169
6.0 EVAPORATION SOURCES ....................................................... 172
6.1 General Considerations ..................................................... 172
6.2 Resistance Heated Sources ............................................. 175
6.3 Sublimation Sources ......................................................... 176
6.4 Evaporation Source Materials............................................ 178
6.5 Induction Heated Sources ................................................. 180
6.6 Electron Beam Heated Sources ........................................ 181
6.7 Arc Evaporation ................................................................ 189
7.0 LASER INDUCED EVAPORATION/LASER ABLATION/PULSED
LASER DEPOSITION (PLD) ....................................................... 192
8.0 DEPOSITION RATE MONITORS AND PROCESS CONTROL .... 194
8.1 Monitoring of the Vapor Stream ......................................... 194
8.2 Monitoring of Deposited Mass ........................................... 196
8.3 Monitoring of Specific Film Properties ............................... 196
8.4 Evaporation Process Control ............................................. 199
9.0 DEPOSITION OF VARIOUS MATERIALS .................................. 201
9.1 Deposition of Metals and Elemental Semiconductors ........ 201
9.2 Deposition of Alloys .......................................................... 201
9.3 Deposition of Intermetallic Compounds ............................. 205
9.4 Deposition of Refractory Compounds ................................ 209
9.5 Reactive Evaporation Process ........................................... 213
9.6 Activated Reactive Evaporation (ARE) ............................... 213
9.7 Materials Synthesized by Evaporation-based Processes .. 223
10.0 MICROSTRUCTURE OF PVD CONDENSATES ......................... 224
10.1 Microstructure Evolution .................................................... 224
10.2 Texture ............................................................................. 236
10.3 Residual Stresses ............................................................ 237
10.4 Defects ............................................................................. 237
11.0 PHYSICAL PROPERTIES OF THIN FILMS ................................ 241
12.0 MECHANICAL AND RELATED PROPERTIES ............................ 241
12.1 Mechanical Properties ................................................................ 241
13.0 PURIFICATION OF METALS BY EVAPORATION ...................... 256
APPENDIX ......................................................................................... 258
On Progress in Scientific Investigations in the Field of Vacuum
Evaporation in the Soviet Union................................................... 258
REFERENCES .................................................................................... 261
Contents xix

5 Sputter Deposition Processes .................................. 275


John A. Thornton and Joseph E. Greene
1.0 INTRODUCTION ......................................................................... 275
1.1 Sputter Deposition Systems ............................................. 278
1.2 Sputter-Deposition Applications ........................................ 279
1.3 Process Implementation ................................................... 282
1.4 History of Sputter Deposition and Background Reading .... 283
2.0 SPUTTERING MECHANISMS .................................................... 284
2.1 Sputtering Rate ................................................................. 285
2.2 Momentum Exchange ....................................................... 289
2.3 Alloys and Compounds ..................................................... 292
2.4 Sputtering with Reactive Species ...................................... 295
2.5 The Nature of Sputtered Species ...................................... 296
2.6 Energy Distribution of Sputtered Species .......................... 298
3.0 SPUTTER DEPOSITION TECHNIQUES ..................................... 301
3.1 Planar Diode and the DC Glow Discharge ......................... 301
3.2 Triode Discharge Devices .................................................. 305
3.3 Magnetrons ....................................................................... 306
3.4 RF Sputtering ................................................................... 318
3.5 Ion-Beam Sputtering ......................................................... 327
4.0 SPUTTER DEPOSITION MODES ............................................... 328
4.1 Reactive Sputtering ........................................................... 328
4.2 Bias Sputtering ................................................................. 332
REFERENCES .................................................................................... 337

6 Ion Plating ................................................................. 346


Donald M. Mattox
1.0 INTRODUCTION ......................................................................... 346
2.0 PROCESSING PLASMA ............................................................ 351
3.0 GENERATION OF PLASMAS .................................................... 351
3.1 DC Diode Discharge.......................................................... 351
3.2 RF Discharge .................................................................... 355
3.3 Microwave Discharges ...................................................... 356
3.4 Electron Emitter Discharge ............................................... 356
3.5 Magnetron Discharges ...................................................... 357
3.6 Plasma Enhancement ....................................................... 358
4.0 PLASMA CHEMISTRY ............................................................... 359
5.0 BOMBARDMENT EFFECTS ON SURFACES ............................ 360
5.1 Collisional Effects ............................................................. 363
5.2 Surface Region Effects ..................................................... 368
5.3 Near Surface Region Effects ............................................. 369
5.4 Bulk Effects ...................................................................... 369
xx Contents

6.0 SOURCES OF DEPOSITING ATOMS ........................................ 369


6.1 Thermal Vaporization ........................................................ 370
6.2 Sputtering ......................................................................... 371
6.3 Vacuum Arcs .................................................................... 371
6.4 Chemical Vapor Precursors .............................................. 373
7.0 REACTIVE ION PLATING ........................................................... 373
8.0 BOMBARDMENT EFFECTS ON FILM PROPERTIES ................ 373
8.1 Effects: Adatom Nucleation............................................... 373
8.2 Effects: Interface Formation .............................................. 374
8.3 Effects: Film Growth ......................................................... 374
8.4 Film Adhesion................................................................... 376
8.5 Film Morphology/Density .................................................. 376
8.6 Residual Film Stress ........................................................ 378
8.7 Crystallographic Orientation .............................................. 378
8.8 Gas Incorporation .............................................................. 380
8.9 Surface Coverage .............................................................. 380
8.10 Other Properties ............................................................... 381
9.0 ION PLATING SYSTEM REQUIREMENTS ................................. 381
9.1 Vacuum System ............................................................... 381
9.2 High Voltage Components ................................................ 381
9.3 Gas Handling System ....................................................... 383
9.4 Evaporation/Sublimation Sources ...................................... 383
9.5 Sputtering Sources ........................................................... 383
9.6 Plasma Uniformity ............................................................ 384
9.7 Plasma Generation Near the Substrate Surface ................ 384
9.8 Substrate Fixturing ........................................................... 384
10.0 PROCESS MONITORING AND CONTROL ................................. 385
10.1 Plasma ............................................................................. 385
10.2 Substrate Temperature ..................................................... 385
10.3 Specifications ................................................................... 385
11.0 PROBLEM AREAS .................................................................... 386
12.0 APPLICATIONS.......................................................................... 389
13.0 SUMMARY ................................................................................. 389
REFERENCES .................................................................................... 391

7 Chemical Vapor Deposition ...................................... 400


Jan-Otto Carlsson
1.0 INTRODUCTION ......................................................................... 400
2.0 IMPORTANT REACTION ZONES IN CVD ................................... 401
3.0 DESIGN OF CVD EXPERIMENTS .............................................. 402
3.1 Classification of CVD Reactions........................................ 403
3.2 Thermodynamics .............................................................. 405
3.3 Adhesion .......................................................................... 409
Contents xxi

3.4 Substrate Cleaning Procedures ......................................... 410


3.5 The CVD system .............................................................. 410
3.6 The Gas Dispensing System ............................................ 411
3.7 The Reactor ...................................................................... 413
3.8 The Exhaust System ........................................................ 415
3.9 Analysis of the Vapor in a CVD Reactor............................ 417
4.0 GAS FLOW DYNAMICS ............................................................ 417
4.1 Gas Flow Patterns ............................................................ 420
4.2 Boundary Layers ............................................................... 423
4.3 Mass Transport Processes Across a Boundary Layer ....... 428
5.0 RATE-LIMITING STEPS DURING CVD ....................................... 428
6.0 REACTION MECHANISMS ........................................................ 436
7.0 NUCLEATION ............................................................................. 438
8.0 SURFACE MORPHOLOGY AND MICROSTRUCTURE OF CVD
MATERIALS ............................................................................... 442
9.0 SELECTIVE DEPOSITION .......................................................... 445
9.1 Area-Selective Growth ....................................................... 446
9.2 Phase-Selective Deposition ............................................... 452
10.0 SOME APPLICATIONS OF THE CVD TECHNIQUE ................... 453
11.0 OUTLOOK .................................................................................. 455
REFERENCES .................................................................................... 456

8 Plasma-Enhanced Chemical Vapor Deposition ........ 460


Arthur Sherman
1.0 INTRODUCTION ......................................................................... 460
2.0 REACTOR INFLUENCE ON PLASMA BEHAVIOR ..................... 461
2.1 DC/AC Glow Discharges ................................................... 461
2.2 AC Discharges with Unequal Area Electrodes ................... 464
2.3 Frequency Effects on RF Plasma Reactor Behavior .......... 466
2.4 Adjusting DC Bias for Fixed Electrode Geometry .............. 467
2.5 Plasma-Enhanced CVD (PECVD) Reactors ...................... 467
3.0 FILMS DEPOSITED BY CVD ..................................................... 472
3.1 Silicon Nitride ................................................................... 472
3.2 Silicon Dioxide .................................................................. 478
3.3 Conducting Films .............................................................. 481
REFERENCES .................................................................................... 482

9 Plasma-Assisted Vapor Deposition Processes:


Overview ................................................................... 485
Rointan F. Bunshah
1.0 INTRODUCTION ......................................................................... 485
2.0 PLASMA-ASSISTED DEPOSITION PROCESSES ..................... 488
3.0 MODEL OF A DEPOSITION PROCESS..................................... 488
xxii Contents

4.0 MATERIALS DEPOSITED BY REACTIVE VAPOR DEPOSITION


PROCESSES ............................................................................. 491
5.0 KEY ISSUES IN PLASMA-ASSISTED REACTIVE VAPOR
DEPOSITION PROCESSES....................................................... 492
5.1 Plasma Volume Chemistry ............................................... 492
5.2 Type and Nature of the Bombardment of the Growing Film 493
6.0 PLASMA-ASSISTED DEPOSITION TECHNIQUES IN CURRENT
USAGE ...................................................................................... 495
6.1 Plasma-Assisted Chemical Vapor Deposition ................... 495
6.2 Sputter Deposition ............................................................ 496
6.3 Activated Reactive Evaporation (ARE) ............................... 497
7.0 LIMITATIONS OF CURRENT PLASMA-ASSISTED TECHNIQUES
499
8.0 HYBRID PROCESSES ............................................................... 501
9.0 CONCLUSIONS .......................................................................... 501
REFERENCES .................................................................................... 505

10 Deposition from Aqueous Solutions: An Overview ..... 506


Morton Schwartz
1.0 INTRODUCTION ......................................................................... 506
2.0 GENERAL PRINCIPLES ............................................................ 508
3.0 ELECTRODEPOSITION.............................................................. 520
3.1 Mechanism of Deposition .................................................. 520
3.2 Parameters ....................................................................... 526
4.0 PROCESSING TECHNIQUES .................................................... 536
5.0 SELECTION OF DEPOSIT ......................................................... 539
5.1 Individual Metals ............................................................... 539
5.2 Alloy Deposition ................................................................ 543
6.0 SELECTED SPECIAL PROCESSES ......................................... 550
6.1 Electroless Deposition ...................................................... 550
6.2 Electroforming................................................................... 557
6.3 Anodizing .......................................................................... 560
6.4 Plating on Plastics............................................................ 570
6.5 Plating Printed Circuit Boards ........................................... 571
7.0 STRUCTURES AND PROPERTIES OF DEPOSITS ................... 574
8.0 SUMMARY ................................................................................. 596
APPENDIX A - Preparation of Substrates for Electroplating .................. 597
APPENDIX B - Representative Electroless Plating
Solution Formulation .................................................... 599
APPENDIX C - Comparison of Aluminum Anodizing Processes
(Types I, II and III) ......................................................... 602
REFERENCES .................................................................................... 605
Contents xxiii

11 Advanced Thermal Spray Deposition Techniques ..... 617


Robert C. Tucker, Jr.
1.0 INTRODUCTION ......................................................................... 617
2.0 EQUIPMENT AND PROCESSES ............................................... 618
2.1 Plasma Spray Process ..................................................... 618
2.2 Detonation Gun Deposition Process ................................. 626
2.3 High Velocity Oxy-Fuel Deposition.................................... 628
2.4 Thermal Control ................................................................ 629
2.5 Auxiliary Equipment .......................................................... 630
2.6 Equipment-Related Coating Limitations............................. 631
3.0 TOTAL COATING PROCESS ..................................................... 632
3.1 Powder ............................................................................. 632
3.2 Substrate Preparation ....................................................... 632
3.3 Masking ............................................................................ 633
3.4 Coating ............................................................................. 633
3.5 Finishing ........................................................................... 635
4.0 COATING STRUCTURE AND PROPERTIES .............................. 636
4.1 Surface Macrostructure and Microstructure ....................... 636
4.2 Microstructure................................................................... 637
4.3 Bond Strength ................................................................... 643
4.4 Residual Stress ................................................................ 644
4.5 Density ............................................................................. 645
4.6 Mechanical Properties ...................................................... 647
4.7 Wear and Friction ............................................................. 653
4.8 Corrosion Properties ......................................................... 660
4.9 Thermal Properties ............................................................ 662
4.10 Electrical Characteristics .................................................. 664
5.0 SUMMARY ................................................................................. 665
REFERENCES .................................................................................... 665

12 Non-Elemental Characterization of Films


and Coatings ............................................................ 669
Donald M. Mattox
1.0 INTRODUCTION ......................................................................... 669
2.0 CHARACTERIZATION ................................................................ 671
3.0 FILM FORMATION ..................................................................... 677
4.0 ELEMENTAL AND STRUCTURAL ANALYSIS ............................ 681
5.0 SOME PROPERTY MEASUREMENTS ..................................... 682
5.1 Adhesion .......................................................................... 682
5.2 Film Thickness ................................................................. 689
5.3 Film Stress ....................................................................... 691
5.4 Coefficient of Thermal Expansion ...................................... 695
xxiv Contents

5.5 Mechanical Properties ...................................................... 695


5.6 Electrical Resistivity.......................................................... 696
5.7 Temperature Coefficient of Resistivity (TCR) ...................... 696
5.8 Electromigration ................................................................ 697
5.9 Density ............................................................................. 697
5.10 Porosity ............................................................................ 698
5.11 Chemical Etch Rate (Dissolution) ..................................... 701
6.0 SUMMARY ................................................................................. 701
REFERENCES .................................................................................... 702

13 Nucleation, Film Growth, and Microstructural


Evolution ................................................................... 707
Joseph E. Greene
1.0 INTRODUCTION ......................................................................... 707
2.0 NUCLEATION AND THE EARLY STAGES OF FILM GROWTH.. 708
2.1 Three-Dimensional Nucleation and Growth ........................ 710
2.2 Two-Dimensional Nucleation and Growth .......................... 721
2.3 Stranski-Krastanov Nucleation and Growth ....................... 728
3.0 COMPUTER SIMULATIONS OF MICROSTRUCTURE
EVOLUTION ............................................................................... 730
3.1 Film Growth in the Ballistic Aggregation, Low-Adatom
Mobility, Limit ................................................................... 732
3.2 Effects of Adatom Migration .............................................. 734
4.0 MICROSTRUCTURE EVOLUTION AND STRUCTURE-ZONE...... 736
5.0 EFFECTS OF LOW-ENERGY ION IRRADIATION DURING FILM
GROWTH ................................................................................... 743
5.1 Effects of Low-Energy Ion/Surface Interactions
on Nucleation Kinetics ...................................................... 743
5.2 Effects of Low-Energy Ion/Surface Interactions
on Film Growth Kinetics.................................................... 750
REFERENCES .................................................................................... 760

14 Metallurgical Applications.......................................... 766


Rointan F. Bunshah
1.0 INTRODUCTION ......................................................................... 766
2.0 CORROSION .............................................................................. 766
3.0 GALVANIC CORROSION ........................................................... 767
3.1 Galvanic Cells ................................................................... 768
4.0 EMF AND GALVANIC SERIES .................................................. 770
5.0 COATINGS FOR GALVANIC CORROSION ................................ 770
6.0 METHODS OF DEPOSITION OF METALLIC COATINGS ........... 772
Contents xxv

7.0 EXAMPLES OF CORROSION-RESISTANT COATINGS ............. 773


7.1 Preamble .......................................................................... 773
8.0 HIGH TEMPERATURE OXIDATION/CORROSION ...................... 776
9.0 FRICTION AND WEAR ............................................................... 781
9.1 Adhesive Wear .................................................................. 781
9.2 Fretting Wear .................................................................... 781
9.3 Abrasive Wear .................................................................. 782
9.4 Fatigue Wear .................................................................... 782
9.5 Impact Erosion Wear by Solid Particles and Fluids ........... 782
9.6 Corrosive Wear ................................................................. 783
9.7 Electric Arc Induced Wear ................................................ 783
9.8 Solution Wear (Thermodynamic Wear).............................. 783
10.0 COATINGS TO REDUCE FRICTION AND WEAR ....................... 783
10.1 Friction ............................................................................. 783
10.2 Lubrication ........................................................................ 785
10.3 Wear ................................................................................. 785
REFERENCES .................................................................................... 787

15 Characterization of Thin Films and Coatings ............. 789


Gary E. McGuire
1.0 INTRODUCTION ......................................................................... 789
2.0 SURFACE ANALYSIS TECHNIQUES ........................................ 789
2.1 Auger Electron Spectroscopy ........................................... 789
2.2 Photoelectron Spectroscopy ............................................. 797
2.3 Secondary Ion Mass Spectroscopy .................................. 803
2.4 Rutherford Backscattering Spectroscopy .......................... 812
3.0 IMAGING ANALYSIS TECHNIQUES .......................................... 822
3.1 Scanning Electron Microscopy ......................................... 822
3.2 Transmission Electron Microscopy ................................... 828
4.0 OPTICAL ANALYSIS TECHNIQUES........................................... 834
4.1 Ellipsometry...................................................................... 834
4.2 Fourier Transform Infrared Spectroscopy ........................... 838
4.3 Photoluminescence Spectroscopy .................................... 841
REFERENCES .................................................................................... 845

16 Jet Vapor Deposition ................................................ 848


Bret L. Halpern and Jerome J. Schmitt
1.0 INTRODUCTION ......................................................................... 848
2.0 PRINCIPLES AND APPARATUS OF JVD .................................. 849
3.0 DISCUSSION ............................................................................. 853
3.1 Jet Structure, Behavior, and Vapor Transport .................... 853
3.2 Substrate Motion .............................................................. 856
xxvi Contents

4.0 EXAMPLES OF JVD FILMS AND APPLICATIONS ..................... 857


4.1 Cu, Au Multilayer Electrodes; Al, Al2O3 Microlaminates... 857
4.2 PZT: Ferroelectric FRAM Nonvolatile Memories ................ 858
4.3 Electronic Grade Silicon Nitride ........................................ 859
4.4 Fiber Coating for Composite Materials .............................. 859
4.5 Coating of Thermally Sensitive Membranes ....................... 860
4.6 “Ceramic Host–Organic Guest” Films................................ 860
4.7 Polymer Deposition: Parylene ........................................... 861
5.0 SUMMARY ................................................................................. 861
REFERENCES .................................................................................... 862

Index ......................................................................... 864


1

Deposition Technologies: An
Overview

Rointan F. Bunshah

1.0 THE MARKET

Historically, from the late 1950s onward, decorative coatings or aluminum


provided the initial thrust for surface-engineered products for toys, textiles,
etc. Since then, the uses of deposition techniques in practically all areas of
engineering and many areas of science have produced a dramatic growth in
sales of equipment and products produced, particularly in the last decade.
According to a recent survey (VDI-Technologiezeutrum-FRG), equipment
with an estimated value of $6 billion was produced worldwide in 1989 for their
film surface technology. Components and devices manufactured with such
equipment amounted to $60 billion and the value of the end-products which
contained components made possible by surface engineering is estimated at
$600 billion. Just one industry, semiconductors, has changed entireproduction
lines every 5 to 6 years. It is further estimated that only 10% of all items which
can benefit from surface modifications are being processed today.
Surface engineering will remain a growth industry in the next decade,
because surface-engineered products increase performance, reduce costs,
and control surface properties independently of the substrate, thus offering
enormous potential due to the following:
! Creation of entirely new products
! Solution of previously unsolved engineering problems
! Improved functionality of existing products—engineering or decorative
! Conservation of scarce materials
! Ecological considerations—reduction of effluent output and power
consumption

27
28 Deposition Technologies for Films and Coatings

Research and development expenditures in surface engineering are very


extensive. It is reported that Japan is spending $100 to $150 million for R/D
in diamond and diamond-like carbon coatings. The payoff is estimated at $16
billion by the end of this decade. In advance thermal barrier coatings by PVD
methods for high temperature operation of turbine blades, it is estimated that
more than $10 million have been spent in the United States alone. Wear-
resistant coatings for disc and heads has attracted much more than $10
million in R/D expenditures worldwide. The list continues to expand.

2.0 INTRODUCTION

Most materials used in high technology applications are composites,


i.e., they have a near-surface region with properties differing from those of the
bulk materials. This is caused by the requirement that the material exhibit
a combination of various, and sometimes conflicting, properties. For example,
a particular engineering component may be required to have high hardness and
toughness (i.e., resistance to brittle crack propagation). This combination of
properties can be obtained by having a composite material with high surface
hardness and a tough core. Alternately, the need may be for a high
temperature, corrosion-resistant material with high elevated-temperature
strength as is the case with the hot stage blades and vanes in a gas turbine.
The solution again is to provide the strength requirement from the bulk and the
corrosion requirement from the surface.
In general, coatings are desirable, or even necessary, for a variety of
reasons including economics, materials conservation, unique properties, or
the engineering and design flexibility which can be obtained by separating the
surface properties from the bulk properties.
This near-surface region is produced by depositing a coating onto it (i.e.,
overlay coating) by processes such as physical or chemical vapor deposition,
electrodeposition, and thermal spraying, or by altering the surface material by
the in-diffusion of materials (i.e., diffusion coating or chemical conversion
coating), or by ion implantation of new material so that the surface layer now
consists of both the parent and added materials.
“Coatings” may also be formed by other processes such as melt/
solidification (e.g., laser glazing technique), by mechanical bonding of a
surface layer (e.g., roll bonding), by mechanical deformation (e.g., shot
peening), or other processes which change the properties without changing
the composition.
Deposition Technologies: An Overview 29

As stated above, the coating/substrate combination is a composite


materials system. The behavior of this composite system depends not only
on the properties of the two components (i.e., the coating material and the
substrate material), but also on the interaction between the two (i.e., the
structure and properties of the coating/substrate interface) which is integral to
the very important factor of adhesion of coatings. In some cases, such as for
overlay coatings, this is a distinct region. For others, such as ion implantation
or diffusion coatings, it is not a discrete region.
Historically, most solid metallic and some ceramic materials were
produced by melting/solidification technology. Since the advent of deposition
technologies (i.e., production of solid materials from the vapor), the diversity
of materials that can be produced has more than doubled because the
properties of solid materials produced from the vapor phase can be varied over
a much wider range than the same material produced from the liquid phase.
This is because melt techniques produce solid materials with properties close
to equilibrium properties whereas the deposition conditions may be so chosen
as to produce materials from the vapor phase with properties close to
equilibrium (similar to their melt-produced counterparts), or properties far
removed from equilibrium properties (non-equilibrium properties). Moreover,
a much greater variation in microstructure is possible with vapor source
materials. For example, a copper-nickel alloy produced by solidification from
the melt will always consist of a single phase solid solution, whereas the same
alloy produced by alternate deposition from two sources may consist of
alternate layers of nickel and copper, i.e., a laminate composite or a solid
solution depending on the deposition temperature.
A large number of materials are used for coatings today. These may
range from the naturally occurring oxide layer which protects the surfaces of
many metals such as aluminum, titanium, and stainless steel, to those with
very deliberate and controlled alloying additions to the surface to produce
specific properties, as exemplified by techniques such as molecular beam
epitaxy or ion implantation. Other examples with increasing degree of
criticality range from paint coatings applied to wood and metals, electrostatically
painted golf balls, the print in the daily newspaper, optical coatings on lenses
and other elements, vapor deposited microcircuit elements such as resistors,
diffusion or overlay coatings on superalloys used in gas turbines for high
temperature corrosion protection, hard overlay coatings of engineering
components and machine tools, etc.
30 Deposition Technologies for Films and Coatings

3.0 AIM AND SCOPE

The aim of this volume is to give the reader a perspective on several


coating techniques with emphasis on the techniques which are used in critical
or demanding (i.e., high technology) applications. Consequently, some of the
techniques such as painting, dip coating, or printing will not be emphasized
except as they pertain to some special application like thick film electrical
components. Nevertheless, a wide variety of techniques and their applications
will be covered. The material is intended to present a broad spectrum of
deposition technologies to those who may be familiar with only one or two
techniques. Hopefully, this will help them to select and weigh various
alternatives when the next technological problem involving coatings faces
them.
The specific deposition technologies to be covered are:
1. Physical Vapor Deposition including evaporation, ion plating and
sputtering.
2. Chemical Vapor Deposition and Plasma-Assisted Chemical
Vapor Deposition
3. Electrodeposition and Electroless Deposition.
4. Plasma Spraying as well as a very special variant called
Detonation Gun Technology.
There are some generic areas common to several of the deposition
technologies, the most prominent example being the use of plasmas in many
of the deposition technologies. Therefore, a chapter on plasmas in deposition
processes is included. Another common topic is cleaning of the substrate and
adhesion of the coating. A chapter is included on that topic.
A further common topic is the characterization of the chemical composition
and the microstructure of the coating at various levels of resolution. A chapter
is included to satisfy this need.
New chapters are added dealing with Metallurgical Applications (Corrosion,
Function and Wear), Overview of Plasma-Assisted Deposition Processes,
Plasma-Assisted Chemical Vapor Deposition, and Nucleation/Growth of Thin
Films.
It is realized that all specific applications cannot be satisfied within this
framework. For example, specific applications such as coatings for optical or
magnetic applications are not addressed per se. At the other end of the
spectrum, coatings for the first wall of thermo-nuclear reactors cannot be
discussed since the development of the subject is in an embryonic stage.
Deposition Technologies: An Overview 31

In each of the chapters on deposition technologies, the theory,


methodology, advantages, limitations and applications are discussed.

4.0 DEFINITIONS AND CONCEPTS

In order to avoid potential problems, it is necessary to clarify certain


distinctions which are common and pertinent to deposition technologies.
These are as follows:
1. Diffusion vs.Overlay Coatings—Diffusion coatings are produced
by the complete interdiffusion of material applied to the surface
into the bulk of the substrate material. Examples of this are the
diffusion of oxygen into metals to form various sub-oxide and
oxide layers, the diffusion of aluminum into nickel base alloys to
form various aluminides, etc. A characteristic feature of diffusion
coatings is a concentration gradient from the surface to the
interior, as well as the presence of various layers as dictated by
thermodynamic and kinetic considerations. Ion implantation
may be considered to be a special case where the coating
material is implanted at a relatively shallow depth (a few hundred
angstrom units) from the surface.
An overlay coating is an add-on to the surface of the part, e.g.,
gold-plating on an iron-nickel alloy, or titanium carbide onto a
cutting tool, etc. Depending upon the process parameters, an
interdiffusion layer between the substrate and the overlay coating
may or may not be present.
2. Thin Films vs. Thick Films—Historically, the physical dimension
of thickness was used to make the distinction between thick films
and thin films. Unfortunately, the critical thickness value depended
on the application and discipline. In recent years, a "Confucian"
solution has been advanced. It states that if a coating is used for
surface properties (such as electron emission, catalytic activity),
it is a thin film; whereas, if it is used for bulk properties, corrosion
resistance, etc., it is a thick film. Thus, the same coating material
of identical thickness can be a thin film or a thick film depending
upon the usage. This represents a reasonable way out of the
semantic problem.
32 Deposition Technologies for Films and Coatings

3. Steps in the Formation of a Deposit—There are three steps in the


formation of a deposit:
a. Synthesis or creation of the depositing species
b. Transport from source to substrate
c. Deposition onto the substrate and film growth
These steps can be completely separated from each other or be super-
imposed on each other depending upon the process under consideration. The
important point to note is that if, in a given process, these steps can be
individually varied and controlled, there is much greater flexibility for such a
process as compared to one where they are not separately variable. This is
analogous to the degrees of freedom in Gibbs phase rule. For example,
consider the deposition of tungsten by CVD process. It takes place by the
reaction:

Heated
WF6(vapor) + 3H2(gas) ———" W(deposit) + 6HF(gas)
Substrate

The rate of deposition is controlled by the substrate temperature. At a


high substrate temperature, the deposition rate is high and the structure
consists of large columnar grains. This may not be a desirable structure. On
the other hand, if the same deposit is produced by evaporation of tungsten, the
deposition rate is essentially independent of the substrate temperature so that
one can have a high deposition rate and a more desirable microstructure. On
the other hand, a CVD process may be chosen over evaporation because of
considerations of throwing power, i.e., the ability to coat irregularly shaped
objects, since high vacuum evaporation is basically a line-of-sight technique.

5.0 PHYSICAL VAPOR DEPOSITION (PVD) PROCESS TERMINOLOGY

The basic PVD processes are those currently known as evaporation,


sputtering and ion plating. In recent years, a significant number of specialized
PVD processes based on the above have been developed and extensively
used, e.g., reactive ion plating, activated reactive evaporation, reactive
sputtering, etc. There is now considerable confusion since a particular
process can be legitimately covered by more than one name. As
Deposition Technologies: An Overview 33

an example, if theactivated reactive evaporation (ARE) process is used with


a negative bias on the substrate, it is very often called reactive ion plating.
Simple evaporation using an RF heated crucible has been called gasless ion
plating. An even worse example of the confusion that can arise is found in the
chapter on ion plating in this volume (Ch. 6) where the material is converted
from the condensed phase to the vapor phase using thermal energy (i.e.,
evaporation) or momentum transfer (i.e., sputtering) or supplied as a vapor
(very similar to CVD processes). Carrying this to the logical conclusion, one
might say that all PVD processes are ion plating! On the other hand, the most
important aspect of the ion plating process is the modification of the
microstructure and composition of the deposit caused by the ion bombardment
of the deposit resulting from the bias on the substrate, i.e., what is happening
on the substrate.
To resolve this dilemma, it is proposed that we consider all of these basic
processes and their variants as PVD processes and describe them in terms
of the three steps in the formation of a deposit as described above. This will
hopefully remove the confusion in terminology.
Step 1: Creation of Vapor Phase Specie. There are three ways to put a
material into the vapor phase-evaporation, sputtering or chemical vapors and
gases.
Step 2: Transport from Source to Substrate. The transport of the vapor
species from the source to the substrate can occur under line-of-sight or
molecular flow-conditions (i.e., without collisions between atoms and
molecules); alternately, if the partial pressure of the metal vapor and/or gas
species in the vapor state is high enough or some of these species are ionized
(by creating a plasma), there are many collisions in the vapor phase during
transport to the substrate.
Step 3: Film Growth on the Substrate. This involves the deposition of the
film by nucleation and growth processes. The microstructure and composition
of the film can be modified by bombardment of the growing film by ions from
the vapor phase resulting in sputtering and recondensation of the film atoms
and enhanced surface mobility of the atoms in the near-surface and surface
of the film.
Every PVD process can be usefully described and understood in terms
of these three steps. The reader is referred to Chapter 9 for a more
comprehensive treatment.
34 Deposition Technologies for Films and Coatings

6.0 CLASSIFICATION OF COATING PROCESSES

Numerous schemes can be devised to classify or categorize coating


processes, none of which are very satisfactory since several processes will
overlap different categories. For example, the Appendix contains a list and
definitions of various deposition processes based upon those provided by
Chapman and Anderson with some additions. These authors classify the
processes under the general heading of Conduction and Diffusion Processes,
Chemical Processes, Wetting Processes and Spraying Processes. Here, the
Chemical Vapor Deposition process falls under the Chemical Processes, and
the Physical Vapor Deposition Process (Evaporation, lon Plating and Sputtering)
falls under the spraying processes. The situation can easily get confused as,
for example, when Reactive and Activated Reactive Evaporation, and Reactive
lon Plating are all classified as Chemical Vapor Deposition processes by
Yee[3] who considers them thusly because a chemical reaction is involved and
it does not matter to him whether evaporated metal atoms or stable liquid or
gaseous compounds are the reactants. Another classification of the methods
of deposition of thin films is given by Campbell.[4] He considers the overlap
between physical and chemical methods, e.g., evaporation and ion plating,
sputtering and plasma reactions, reactive sputtering and gaseous
anodization.[5] He classifies the Chemical Methods of Thin Film Preparation
as follows:

Chemical Methods of Thin Film Preparation

Basic Class Method

Formation from the Medium Electroplating


lon Plating
Chemical Reduction
Vapor Phase
Plasma Reaction

Formation from the Substrate Gaseous Anodization


Thermal
Plasma Reduction
Deposition Technologies: An Overview 35

In addition, he considers the following as chemical methods of thick film


preparation: Glazing, Electrophoretic, Flame Spraying and Painting.
In contrast to the chemists’ approach given above, the physicists’
approach to deposition processes is shown in the following classification of
vacuum deposition techniques by Schiller, Heisig and Goedicke[6] and by
Weissmantel.[7]

Figure 1.1. Survey of vacuum deposition techniques (Schiller[6])

A different classification comes from a materials background where the


concern is with structure and properties of the deposits as influenced by
process parameters. Thus, Bunshah and Mattox[8] give a classification based
on deposition methods as influenced by the dimensions of the depositing
specie, e.g., whether it is atoms/molecules, liquid droplets or bulk quantities,
as shown in Table 1.1.
In atomistic deposition processes, the atoms form a film by condensing
on the substrate and migrating to sites, where nucleation and growth occurs.
Further, adatoms do not achieve their lowest energy configurations and the
resulting structure contains high concentrations of structural imperfections.
Often the depositing atoms react with the substrate material to form a complex
interfacial region.
Another aspect of coatings formed by atomistic deposition processes is
as follows. The sources of atoms for these deposition processes can be by
thermal vaporization (vacuum deposition) or sputtering (sputter deposition) in
a vacuum, vaporized chemical species in a carrier gas (chemical vapor
deposition), or ionic species in an electrolyte (electrodeposition). In low
energy atomistic deposition processes, the depositing species impinge on the
surface, migrate over the surface to a nucleation site where they condense and
grow into a coating. The nucleation and growth modes of the condensing
species determine the crystallography and microstructure of
36 Deposition Technologies for Films and Coatings

the coating. For high energy deposition processes, the depositing particles
react with or penetrate into the substrate surface.
Particulate deposition processes involve molten or solid particles and the
resulting microstructure of the deposit depends on the solidification or
sintering of the particles. Bulk coatings involve the application of large
amounts of coating material to the surface at one time such as in painting.
Surface modification involves ion, thermal, mechanical, or chemical treatments,
which alter the surface composition or properties. All of these techniques are
widely used to form coatings for special applications.

Table 1.1. Methods of Fabricating Coatings

7.0 GAS JET DEPOSITION WITH NANO-PARTICLES

One of the chapters in this volume (Ch. 11) deals with Plasma Spraying
and Detonation Gun Techniques where a high velocity stream of macro-
particles (µm dimensions) impinge on a substrate to form a coating. With the
Deposition Technologies: An Overview 37

advent of evaporation[9] and sputtering processes[10] to produce nano-


particles (nm dimensions), the same concept can be used to produce
coatings by carrying nano-particles in a gas stream and impinging them on
a substrate.[11][12] Figure 1.2 shows a schematic of this process where
metallic nano-particles produced by evaporation are carried in a gas stream,
accelerated through a nozzle and impinged on a substrate to produce a
coating. Single nozzles or multiple nozzle configurations can be used, the
latter producing an array of dots, for example. The attributes of this process
are:
1. Direct write maskless processing to produce dots, lines, and
other shapes.
2. High deposition rate, 10 - 20 µm per second over a small area.
3. Low temperature (room temperature) deposition.
4. Metals, alloys, ceramics, and organic materials can be
deposiited.
5. Multiphase films with uniform mixing can be produced.
6. The collection officiency is very high, ~90%, i.e. very little waste
or scatter.
Examples of applications of this technique are:
1. Electrical connecting lines in circuits including the repair aspect.
2. Fabrication of microelectrodes
3. Oxide superconductor contacts.
4. Capacitors
5. Implantation of virus into plants for the bio industry.
6. Cell-gene processing technology.

Figure 1.2. Schematic diagram of gas deposition apparatus.


38 Deposition Technologies for Films and Coatings

8.0 MICROSTRUCTURE AND PROPERTIES

In electrodeposition, typically the growth process involves condensation


of atoms at a kink site on the substrate surface, followed by layered growth
of the deposit. Adatom mobility is increased by the hydrated nature of the ions
and the adatom mobility may vary with crystal orientation. Field ion
microscopy stripping studies of copper electrodeposited on tungsten has
shown that there is surface rearrangement of the tungsten atoms during the
electrodeposition process. Electrodeposited material does not grow in a
uniform manner; rather it becomes faceted, develops dendrites and other
surface discontinuities. Thus the microstructure of electrodeposited coatings
may vary from relatively defect-free single crystals usually grown on single
crystal substrates, to highly columnar and faceted structures. In the
electroplating process, organic additives may be used to modify the nucleation
process and to eliminate undesirable growth modes. This results in a
microstructure more nearly that of bulk material formed by conventional
metallurgical processes. Electrodeposition from a molten salt electrolyte
allows the deposition of many materials not available from aqueous electrolytes.
In vacuum processes, the depositing species may have energies ranging
from thermal (a few tenths of an electron volt) for evaporation to moderate
energies (ten to hundreds of electron volts) for sputtered atoms to high
energies for accelerated species such as those used in ion implantation.
These energies have an important but poorly understood effect on interfacial
interaction, nucleation and growth. Where there is chemical reaction between
the substrate atoms and the depositing atoms, and diffusion is possible, a
diffusion or compound interfacial region is formed composed of compounds
and/or alloys which modify the effective surface upon which the deposit grows.
Low energy electron diffraction studies have shown that this interfacial reaction
is very sensitive to surface condition and process parameters. If the coating
and substrate materials are not chemically reactive and are insoluble, the
interfacial region will be confined to an abrupt discontinuity in composition.
This type of interface may be modified by bombardment with high energy
particles to give high defect concentrations and implantation of ions resulting
in a “pseudodiffusion” type of interface. The type of interface formed will
influence the properties of the deposited coating. In many circumstances,
these interfacial regions are of very limited thickness and pose a challenge to
those interested in compositional, phase, microstructural and property
analysis.
Deposition Technologies: An Overview 39

The microstructure of the depositing coating in the atomic deposition


processes depends on how the adatoms are incorporated into the existing
structure. Surface roughness and geometrical shadowing will lead to
preferential growth of the elevated regions giving a columnar type microstructure
to the deposits.[13] This microstructure will be modified by substrate
temperature, surface diffusion of the atoms, ion bombardment during deposition,
impurity atom incorporation and angle of incidence of the depositing adatom
flux. The structure zone model of Movchan and Demchishin[14] for vacuum
deposited films is discussed in later chapters.
In chemical vapor deposition, the chemical species containing the film
atoms is generally reduced or decomposed on the substrate surface, often at
high temperatures. Care must be taken to control the interface reaction
between coating and substrate and between the substrate and the gaseous
reaction products. The coating microstructure which develops is very similar
to that developed by the vacuum deposition processes, i.e., small-grained
columnar structures to large-grained equiaxed or oriented structures.
Each of the atomistic deposition processes has the potential of depositing
materials which vary significantly from the conventional metallurgically
processed material. The deposited materials may have high intrinsic
stresses, high point defect concentration, extremely fine grain size, oriented
microstructures, metastable phases, incorporated impurities, and macro and
micro porosity. These properties may be reflected in the physical properties
of the materials and by their response to applied stresses such as mechanical
loads, chemical environments, thermal shock or fatigue loading. Metallurgical
properties which may be affected include elastic constants, tensile strength,
fracture toughness, fatigue strength, hardness, diffusion rates, friction/wear
properties, and corrosion resistance. In addition, the unique microstructure
of the deposited material may lead to such effects as anomalously low
annealing and recrystallization temperatures where the internal stresses and
high defect concentration aid in atomic rearrangement.
The high value of grain boundary area to volume ratio found in fine grained
deposited material means that diffusion processes may be dominated by grain
boundary rather than bulk diffusion. The fine grained nature of the materials
also affects the deformation mechanisms such as slip and twinning. For thin
films, the free-surface to volume ratio is high, and the pinning of dislocation by
the free surface leads to the high tensile strengths often measured in thin films
of materials.
40 Deposition Technologies for Films and Coatings

In vapor deposition processes, impurity incorporation during deposition


can give high intrinsic stresses or impurity stabilized phases which are not
seen in the bulk forms of the materials. Reactive species allow the deposition
of compounds such as nitrides, carbides, borides and oxides. Graded
deposits can be formed.
Vapor deposition processes have the capability of producing unique and/
or nonequilibrium microstructures. One example is the fine dispersion of
oxides in metals, where the oxide particle size and spacing is very small (100
- 500 Å). Alternately, metals and alloys deposited at high substrate
temperatures have properties similar to those of conventionally fabricated
(cast, worked and heat treated) metals and alloys. A more recent example
is the nano-scale laminate composites consisting of alternate layers of
refractory compounds with unusually high hardness values.

9.0 UNIQUE FEATURES OF DEPOSITED MATERIALS AND GAPS IN


UNDERSTANDING

It is useful to state at this point some of the unique features of materials


produced by deposition technologies. They are:
1. Extreme versatility of range and variety of deposited materials.
2. Overlay coatings with properties independent of the
thermodynamic compositional constraints.
3. Ability to vary defect concentration over wide limits, thus resulting
in a range of properties comparable to, or far removed from
conventionally fabricated materials.
4. High quench rates available to deposit amorphous materials.
5. Generation of microstructures different from conventionally
processed materials, e.g., a wide range of microstructures—
ultrafine (submicron grain or laminae size) to single crystal films.
6. Fabrication of thin self-standing shapes even from brittle materials.
7. Ecological benefits with certain techniques.
The first edition lists some of the areas where our understanding
of basic processes and phenomena is lacking and which obviously are
the areas where research activities are essential. These are:
Deposition Technologies: An Overview 41

1. Microstructure and properties in the range of 500 to 10,000 Å—


particularly important for submicron microelectronics, reflective
surfaces and corrosion.
2. (a) Effect of the energy of the depositing species on
interfacial interaction, nucleation and growth of deposit.
(b) Effect of “substrate surface condition,” i.e.,
contamination (oxide) layers, adsorbed gases,
surface topography.
3. Residual stresses—influence of process parameters.
Considerable progress and understanding has developed in the last
decade.

10.0 CURRENT APPLICATIONS

The applications of coatings in current technology may be classed into


the following generic areas:
Optically Functional—Laser optics (reflective and transmitting),
architectural glazing, home mirrors, automotive rear view mirrors,
reflective and anti-reflective coatings, optically absorbing coatings,
selective solar absorbers.
Electrically Functional—Electrical conductors, electrical contacts,
active solid state devices, electrical insulators, solar cells.
Mechanically Functional—Lubrication films, wear and erosion
resistant coatings, diffusion barriers, hard coatings for cutting tools.
Chemically Functional—Corrosion resistant coatings, catalytic
coatings, engine blades and vanes, battery strips, marine use
equipment.
Decorative—Watch bezels, bands, eyeglass frames, costume
jewelry.
A few examples are chosen to illustrate them in greater detail.

10.1 Decorative/Functional Coating

Weight reduction is a high priority item to increase gas mileage in


automobiles. Therefore, heavy metallic items such as grills are being
42 Deposition Technologies for Films and Coatings

replaced with lightweight plastic, overcoated with chromium by sputtering for


the appearance to which the consumer is accustomed.
Another extensive application is aluminum-coated polymer films for heat
insulation, decorative and packaging applications.
A rapidly growing application is the use of a gold-colored wear-resistant
coating of titanium nitride on watch bezels, watch bands and similar items.
A new application is black wear-resistant hard carbon films.

10.2 High Temperature Corrosion

Blades and vanes used in the turbine-end of a gas turbine engine are
subject to high stresses in a highly corrosive environment of oxygen-, sulfur-
and chlorine-containing gases. A single or monolithic material such as a high
temperature alloy is incapable of providing both functions. The solution is to
design the bulk alloy for its mechanical properties and provide the corrosion
resistance by means of an overlay coating of an M-Cr-AI-Y alloy where M
stands for Ni, Co, Fe or Ni + Co. The coating is deposited in production by
electron beam evaporation and in the laboratory by sputtering or plasma
spraying. With the potential future use of synthetic fuels, considerable
research will have to be undertaken to modify such coating compositions for
the different corrosive environments as well as against erosion from the
particulate matter in those fuels.

10.3 Environmental Corrosion

Thick ion plated aluminum coatings are used in various irregularly-


shaped parts of aircraft and space-craft as well as on fasteners:(a) to replace
electroplated cadmium coatings which sensitize the high-strength parts to
hydrogen embrittlement or(b) to prevent galvanic corrosion which would occur
when titanium or steel parts contact aluminum or (c) to provide good
brazeability. New alloy coatings in the micron thickness range have been
developed.

10.4 Friction and Wear

Dry-film lubricant coatings of materials such as gold, MoS2 , WSe2 and


other lamellar materials are deposited on bearings and other sliding parts by
sputtering or ion plating to reduce wear. Such dry-film lubricants are
Deposition Technologies: An Overview 43

especially important for critical parts used in long-lifetime applications since


conventional organic fluid lubricants are highly susceptible to irreversible
degradation and creep over a long time.

10.5 Materials Conservation

Aluminum is continuously coated on a steel strip, 2 feet wide and 0.006


inches thick to a 250 micro-inch thickness in an air-to-air electron-beam
evaporator at the rate of 200 feet/minute. The aluminum replaces tin, which
is becoming increasingly scarce and costly. The strip then goes to the lacquer
line and is used for steel can production. With the change in Eastern Europe,
this line has switched to deposition of Cr and Cu on steel.

10.6 Cutting Tools

Cutting tools are made of high-speed steel or cemented carbides. They


are subject to degradation by abrasive wear as well as by adhesive wear. In
the latter mode, the high temperatures and forces at the tool tip promote
microwelding between the steel chip from the workpiece and the steel in the
high-speed steel tool or the cobalt binder phase in the cemented carbide. The
subsequent chip breaks the microweld and causes tool surface cratering and
wear. A thin layer of a refractory compound such as TiC, TiN, Al2 O3 prevents
the microwelding by introducing a diffusion barrier. Improvements in tool life
by factors of 300 to 800% are possible as well as reductions in cutting forces.
The coatings are deposited by chemical vapor deposition or physical vapor
deposition. Some idea of the importance of such coatings can be assessed
from the fact that the yearly value of cutting tools purchased in the U.S. is $1
billion and the cost of machining is approximately $60 billion.
The last decade has seen major advances in this area and some of these
are:
! Ti alloy nitrides, e.g., (Ti, Al) N
! Ti carbonitrides, e.g., Ti (C,N)
! Multilayer coatings of different nitrides
! Diamond coated tools by CVD and PACVD processes for
machining of non-ferrous metals and polymer-matrix
composites. A bond layer such as silicon nitride has to be used
to attach the diamond coating to the carbide cutting tool.
44 Deposition Technologies for Films and Coatings

! Hard diamond-like carbon for heads and discs


! Cubic boron nitride coatings by plasma-assisted PVD and
CVD methods for cutting of hard ferrous materials

10.7 Nuclear Fuels

Pyrolytic carbon is deposited on nuclear fuel particles used in gas-cooled


reactors by chemical vapor deposition in fluidized beds. The coating retains
the fission products and protects the fuel from corrosion.

10.8 Biomedical Uses

Parts for implants such as heart valves are made of pyrolytic carbon by
CVD techniques. Metal parts are coated with carbon by ion plating in order
to obtain biological compatibility.

10.9 Electrical Uses

High temperature cuprate superconductors with transition temperatures


of 85° to 115°K. This permits the operation of liquid nitrogen cooled devices.
Various PVD techniques such as co-evaporation in an oxygen plasma,
sputtering from simple or multiple targets and laser ablation have been used
to fabricate films, ranging from 1 to 50 cm2 . Microwave devices such as delay
lines, quasioptical filters have been fabricated and are being marketed.

11.0 “FRONTIER AREAS” FOR THE APPLICATION OF THE PRODUCTS


OF DEPOSITION TECHNOLOGY

The following were listed in the first edition published in 1982.


1. Reflective surfaces, e.g., for laser mirrors.
2. Thermal barrier coatings for blades and vanes operating at high
temperatures.
3. Corrosion/erosion resistant coatings at high temperatures,
e.g., valves and other critical compounds in coal gasification
plants.
4. Advanced cutting tools.
Deposition Technologies: An Overview 45

5. Wear-resistant surfaces without organic lubricants, particularly


at high temperatures where lamellar solid state lubricants such
as MoS2 are ineffective.
6. First wall of thermonuclear reactor vessels.
7. High-strength/high-toughness ceramics for structural use.
8. Ultrafine powders.
9. Super conducting materials:
High transition temperatures >23.2°K.
Fabricability of these brittle materials into wire or ribbons.
10. CataIytic materials.
11. Thin film photovoltaic devices.
12. Transparent conductive coatings in opto-electronics devices,
photo detectors, liquid crystal and electrochromic displays,
solar photo thermal absorption devices, heat mirrors.
13. Biomedical devices, e.g., neurological electrodes, heart valves,
artificial organs.
14. Materials conservation.
15. Sub-micron microelectronic devices. In this context, a good
question is, How far can dimensions be reduced without running
into some limit imposed by physical phenomena?
In 1992, new additions to the above list are:
16. Diamond and diamond-like carbon for various applications:
! Tribology, particularly cutting tool
! Heat management–heat sinks of diamond sheet currently
several square inches in area are on the market
! Hard protective coatings for infrared applications such as
the protection of germanium and sodium chloride optics
17. Cubic boron nitride for various applications:
! High temperature use (up to 1200°) semiconductor
devices. Very perfect device quality single crystal films
have been grown epitaxially on lattice matched TiC
substrates
! Tribological uses for machining of hard steels
! Optical and opto-electronic devices
46 Deposition Technologies for Films and Coatings

18. Film deposition using a high velocity gas jet. Hayashi and
coworkers[9] have developed a process where ultra-fine powders
(~10 nanometer diameter) are carried on a high velocity gas jet
and impinged on a substrate to “write” lines of deposited
materials, e.g., YBCO superconductors. The usage of material
is very high, almost 97% is collected as a deposit. Various
applications are envisioned.
19. Unbalanced magnetron deposition—very useful new development
where some of the electrons are allowed to escape from the
magnetic trap at the sputtering target and from a plasma near
the substrate from which ions can be extracted to bombard the
growing film.

12.0 SELECTION CRITERIA

The selection of a particular deposition process depends on several


factors. They are:
1. The material to be deposited
2. Rate of deposition
3. Limitations imposed by the substrate, e.g., maximum deposition
temperature
4. Adhesion of deposit to substrate
5. Throwing power
6. Purity of target material since this will influence the impurity
content in the film
7. Apparatus required and availability of same
8. Cost
9. Ecological considerations
10. Abundance of deposition material in the world
In order to aid the reader in the task of selection, Table 1.2 lists several
criteria for each of the processes. It is obvious that there are very few
techniques which can deposit all types of materials. It is also impossible to
detail the advantages and limitations of each of the techniques. However, in
the evaluation of each application, the above factors will lead to a rational
choice of the deposition technique to be used.
Table 1.2. Some Characteristics of Deposition Processes

Deposition Technologies: An Overview


47
48 Deposition Technologies for Films and Coatings

13.0 SUMMARY

In the above discussion, we have noted the following:


1. There are a very large number of deposition techniques.
2. There is no unique way to classify these techniques. Depending
on the viewpoint, the same technique may fall into fall into one or
more classes.
3. Each technique has its advantages and limitations.
4. The choice of the technique to be used depends on various
selection criteria which have been given above.
5. More than one technique can be used to deposit a given film as
shown in Figure 1.3 below from Campbell’s article on preparation
methods in microelectronic fabrication.

Electro- Chemical Vapor Anodization Thermal Evaporation Sputtering


123456789012345678901
plating Reduction Phase
123456789012345678901 12345678
12345678
123456789012345678901 12345678
Conductors, 123456789012345678901
123456789012345678901 12345678
12345678
123456789012345678901
resistiors 123456789012345678901
12345678
123456
123456 12345678
12345678 12345678
12345678
123456
123456 12345678
12345678 12345678
12345678
Insulators, 123456 12345678 12345678
capacitors 123456
123456 12345678
12345678123456789012345678
12345678
1234567890
1234567890
1234567890
Active 1234567890
1234567890
devices 1234567890
1234567890 1234567890
123456789012345678
12345678
1234567890 123456789012345678
Magnetic 1234567890
1234567890 1234567890
123456789012345678
12345678
materials 1234567890
1234567890
1234567 1234567890
123456789012345678
12345678
1234567
1234567
1234567
Super-
1234567
1234567
conductors 1234567

Figure 1.3. Applicability of preparation methods to microelectronics. Light shading


indicates that the component can be prepared by the method; Dark shading
indicates that the method is widely used.
Deposition Technologies: An Overview 49

APPENDIX 1: DEPOSITION PROCESS DEFINITIONS

The definitions of various deposition processes are given below. They


are grouped as proposed by Chapman and Anderson[1] and many of them are
those proposed by these authors.

Conduction and Diffusion Processes

Electrostatic Deposition is the deposition of material in liquid form, the


solvent used then being evaporated to form a solid coating. At the source, the
liquid is atomized and charged, and then it can be directed onto the substrate
using an electrostatic field.
Electrophoretic Coating produces a coating on a conducting substrate
from a dispersion of colloidal particles. The article to be coated is immersed
in an aqueous dispersion which dissociates into negatively charged colloidal
particles and positive cations. An electric field is applied with the article as
anode (positive electrode); the colloidal particles are transported to the anode,
where they are discharged and form a film. In the case of a paint coating, this
requires curing, which further shows that electrophoresis itself is not a very
effective transport process, so that electrodeposition may be a better term for
the coating process.
Electrolytic Depositionis primarily concerned with the deposition of ions
rather than of colloidal particles. Two electrodes are immersed in an
electrolyte of an ionic salt which dissociates in aqueous solution into its
constituent ions; positive ions are deposited onto the cathode (negative
electrode).
Anodizationis a process which occurs at the anode (hence its name) for a few
specific metals. The anode reacts with negative ions from the electrolyte and becomes
oxidized, i.e., it forms a surface coating.
Gaseous Anodization is a process in which the liquid electrolyte of the
conventional wet process is replaced by a glow discharge in a low partial pressure of
a reactive gas. Oxides, carbides and nitrides can be produced this way.
Ion Nitridingis a gaseous anodization to produce nitride diffusion coating on a
metal surface, usually steel.
Ion Carburizingis a gaseous anodization to produce a carbide diffusion coating
on a metal surface, usually steel.
Plasma Oxidationis gaseous anodization to produce an oxide film on the surface
of metal, e.g., SiO2 films on Si.
Diffusion Coating is produced by diffusion of material from the surface into the
bulk of the substrate.
50 Deposition Technologies for Films and Coatings

Metalliding is a method using electrodeposition in molten fluorides.


Spark-hardening is a technique in which an arc is periodically struck
between a vibrating anode and the conducting substrate (cathode); material
is transferred from the anode and diffuses into the substrate.

Chemical processes

Conversion and Conversion/Diffusion Coating is a process in which the


substrate is reacted with other substances (which may be in the form of solids,
liquids or gases) so that its surface is chemically converted into different
compounds having different properties. (Anodization could probably be
described as an electrochemical conversion process). Conversion coating
usually takes place at elevated temperatures and diffusion is often an essential
feature.
Chemical Vapor Deposition (CVD) is a chemical process which takes
place in the vapor phase very near the substrate or on the substrate so that
a reaction product is deposited onto the substrate. The deposition can be a
metal, semiconductor, alloy or refractory compound.
Pyrolysis is a particular type of CVD which involves the thermal
decomposition of volatile materials on the substrate.
Plasma-Assisted CVD is a process where the reaction between the
reactants is stimulated or activated by creating a plasma in the vapor phase
using means such as R F excitation from a coil surrounding the reaction
vessel.
Electroless Deposition is often described as a variety of electrolytic
deposition which does not require a power source or electrodes, hence its
name. It is really a chemical process catalyzed by the growing film, so that
the electroless term is somewhat a misnomer.
Disproportionation is the deposition of a film or crystal in a closed system
by reacting the metal with a carrier gas in the hotter part of the system to form
the compound, followed by dissociation of the compound in the colder part of
the system to deposit the metal. Examples are epitaxial deposits of Si or Ge
on a single crystal substrate and the Van-Arkel-deBoer process for metal
purification and crystal growth.

Wetting Process

Wetting Processes are the coating processes in which material is


applied in liquid form and then becomes solid by solvent evaporation or cooling.
Deposition Technologies: An Overview 51

Conventional Brush Painting and Dip Coating are wetting processes in


which the part to be coated is literally dipped into a liquid (e.g., paint) under
controlled conditions of, for example, withdrawal rate and temperature.
Hydrophilic Method is a surface chemical process known as the
Langmeir Blodgett technique which is used to produce multimonolayers of
long chain fatty acids. A film 25 Å thick can be deposited on a substrate
immersed in water and pulled through a compressed layer of the fatty acid on
the surface of the water. The process can be repeated to build up many layers.
Welding Processesare the range of coating techniques all of which rely
on wetting.

Spraying Processes

Printing Process also relies on wetting and is a process in which the ink,
conventionally pigment in a solvent, is transferred to and is deposited on a
paper or other substrate, usually to form a pattern; the solvent evaporates to
leave the required print.
Spraying Processes can be considered in two categories;(i) macroscopic
in which the sprayed particle consists of many molecules and is usually grater
than 10 µm in diameter; (ii) macroscopic in which the sprayed particles are
predominantly single molecules or atoms.
Air and Airless Spraying are the first of the macroscopic processes.
When a liquid exceeds a certain critical velocity, it breaks up into small
droplets, i.e., it atomizes. The atomized droplets, by virtue of their velocity
(acquired from a high pressure air or airless source) can be sprayed onto a
substrate.
Flame Spraying is a process in which a fine powder (usually of a metal)
is carried in a gas stream and is passed through an intense combustion flame,
where it becomes molten. The gas stream, expanding rapidly because of the
heating, then sprays the molten powder onto the substrate where it solidifies.
Detonation Coating is a process in which a measured amount of powder
is injected into what is essentially a gun, along with a controlled mixture of
oxygen and acetylene. The mixture is ignited, and the powder particles are
heated and accelerated to high velocities with which they impinge on the
substrate. The process is repeated several times a second.
Arc Plasma Sprayingis a process in which the powder is passed through
an electrical plasma produced by a low voltage, high current electrical
discharge. By this means, even refractory materials can be deposited.
52 Deposition Technologies for Films and Coatings

Electric-Arc Spraying is a process in which an electric arc is struck


between two converging wires close to their intersection point. The high
temperature arc melts the wire electrodes which are formed into high velocity
molten particles by an atomizing gas flow; the wires are continuously fed to
balance the loss. The molten particles are then deposited onto a substrate
as with the other spray processes.
Harmonic Electrical Spraying is a process in which the material to be
sprayed must be in liquid form, which will usually require heating. It is placed
in a capillary tube and a large electrical field is applied to the capillary tip. It
is found that by adding an AC perturbation to the DC field, a collimated beam
of uniformly sized and uniformly charged particles is emitted from the tip.
Sense these particles are charged, they could be focused by an electrical field
to produce pattern deposits.
Evaporation is a process in which the boiling is carried out in vacuum
where there is almost no surrounding gas; the escaping vapor atom will travel
in a straight line for some considerable distance before it collides with
something, for example, the vacuum chamber walls or substrate.
Glow Discharge Evaporation and Sputtering are processes in soft
vacuum (10-2 to 10-1 torr) operating in the range 10-1 < pd < 10-2 torr cm where
p is the pressure and d is the cathode fall dimension.
Molecular Beam Epitaxy is an evaporation process for the deposition of
compounds of extreme regularity of layer thickness and composition from well
controlled deposition rates.
Reactive Evaporation is a process in which small traces of an active gas
are added to the vacuum chamber; the evaporating material reacts chemically
with the gas so that the compound is deposited on the substrate.
Activated Reactive Evaporation (ARE) is the Reactive Evaporation
Process carried out in the presence of plasma which converts some of the
neutral atoms into ions or energetic neutrals thus enhancing reaction
probabilities and rates to deposit refractory compounds.
Biased Activated Reactive Evaporation (BARE)is the same process as
Activated Reactive Evaporation with substrate held at a negative bias voltage.
Sputter Depositionis a vacuum process which uses a different physical
phenomenon to produce the microscopic spray effect. When a fast ion strikes
the surface of a material, atoms of that material are ejected by a momentum
transfer process. As with evaporation, the ejected atoms or molecules can be
condensed on a substrate to form a surface coating.
Ion Beam Depositionis a process in which a beam of ions generated from
an ion beam gun, impinge and deposit on the substrate.
Deposition Technologies: An Overview 53

Ion Beam Assisted Deposition—two versions are possible. One, an ion


beam is used to sputter a target and a second beam is used to bombard the
growing film to change structure and properties. This is dual Ion Beam
Assisted Deposition. The other version uses an ion beam to bombard the
growing film to change structure and properties. In this case, conventional
evaporation or sputtering techniques are used to generate a flux of the
depositing species.
Cluster Ion Beam Deposition is an ion beam deposition in which atomic
clusters are formed in the vapor phase and deposited on the substrate.
Ion Plating is a process in which a proportion of the depositing material
from an evaporation, sputtering or chemical vapor source is deliberately
ionized. Once changed this way, the ions can be accelerated with an electric
field so that the impingement energy on the substrate is greatly increased,
producing modifications of the microstructure and residual stresses of the
deposit.
Reactive Ion Plating is ion plating with a reactive gas to deposit a
compound.
Chemical Ion Plating is similar to Reactive Ion Plating but uses stable
gaseous reactants instead of a mixture of evaporated atoms and reactive
gases. In most cases, the reactants are activated before they enter the
plasma zone.
Ion Implantation is very similar to ion plating, except that now all of the
depositing material is ionized, and in addition, the accelerating energies are
much higher. The result is that the depositing ions are able to penetrate the
surface barrier of the substrate and be implanted in the substrate rather than
on it.
Plasma Polymerization is a process in which organic and inorganic
polymers are deposited from monomer vapor by the use of electron beam,
ultraviolet radiation or glow discharge. Excellent insulating films can be
prepared in this way.
54 Deposition Technologies for Films and Coatings

REFERENCES

1. Science and Technology of Surface Coating,(B. N. Chapman and J. C.


Anderson, eds.), Academic Press (1974)
2. Adhesion Measurement of Thin Films, Thick Films and Bulk Coatings,
(K. D. Mittal, ed.), Am. Soc. for Testing Materials (1978)
3. Yee, K. K.,International Metal Reviews,No. 226, The Metals Society and
American Society for Metals (1978)
4. Campbell, D. S.,Handbook of Thin Film Technology,(L. Maissel and R.
Glang, eds.), Ch. 5, McGraw-Hill (1970)
5. Handbook of Thin Film Technology, (L. Maissel and R. Glang eds.),
McGraw-Hill (1970)
6. Schiller, S., Heisig, O., and Geodick, K., Proc. 7th Int’l. Vacuum
Congress, (R. Dobrozemsky, ed.), p. 1545, Vienna (1977)
7. Weissmantel, C., ibid, p. 1533,
8. Bunshah, R. F. and Mattox, D. M., Physics Today (May 1970)
9. Hayashi, C., Paper presented at the International Vacuum Congress,
Hague, Netherlands (Oct. 1992); also: Hayashi, C., J. Vac. Sci. Tech.,
A5(4):1375 (1987)
10. Suc, T. G., Umarjee, D. M., Prakash, S., and Bunshah, R. F., Surface
and Coatings Technology, 13:199 (1991)
11. Hayashi, C., Kashu, S., Oda, M., and Naruse, F., presented at the Int'l
Vac. Cong., The Hague, Netherlands (Nov. 1992) - to be published in Mat.
Sci. Eng., (1993)
12. Oda, M., Katsu, I., Tsuneizumi, M., Fuchita, E., Kashu, S., and Hayashi,
C., presented at Fall Mtg. Mat. Res. Soc., Boston, 1992
13. Thornton, J. A.,Proc. 19th National SAMPLE Symposium, Buena Park,
Ca. (April 23-25, 1974)
14. Movchan, B. A., and Demchishin, A. V., Phys. Met Metallogr., 28:83
(1969)
2

Plasmas in Deposition Processes

John A. Thornton and Joseph E. Greene

1.0 INTRODUCTION

A glow discharge plasma used in deposition processes is a low-pressure


gas which is partially ionized and contains approximately equal numbers of
positive and negative particles. The character of such a plasma is a
consequence of the mass difference between the electrons and the ions.
When an electric field is applied to an ionized gas, energy is transferred more
rapidly to the electrons than to the ions. Furthermore, the transfer of kinetic
energy from an electron to a heavy particle (atom, molecule, or ion) in an elastic
collision is proportional to the mass ratio of electrons and heavy particles and
therefore very small (~10-5). Consequently, at low pressures (low collision
frequencies), the electrons can accumulate sufficient kinetic energy to have
a high probability of producing excitation or ionization during collisions with
heavy particles. The production of these excited species, and their interactions
with surfaces and growing films, is one of the reasons that low pressure glow
discharge plasmas are assuming an ever-increasing role in materials
processing. Examples of application areas include the following.
! Sputter deposition
! Activated reactive evaporation
! Ion plating
! Plasma-assisted chemical vapor deposition
! Plasma-assisted etching
! Plasma polymerization

55
56 Deposition Technologies for Films and Coatings

The purpose of this chapter is to review fundamental aspects of glow-


discharge plasmas which are of importance in understanding the role of
plasma processes in materials processing.

2.0 PARTICLE MOTION

2.1 Mean Free Path and Collision Cross Sections

A glow discharge plasma can be viewed as a medium in which electrical


energy is transmitted, via an electric field, to a gas. The energetic gas particles
are then used to promote chemical reactions or to interact with a surface to
produce desirable effects such as sputtering. Thus, the process of energy
exchange during collisions involving plasma particles is of fundamental
importance.
Gas-phase collision probabilities are often expressed in terms of cross
sections. A related parameter is the mean free path or average distance
traversed by particles between collisions. The mean free pathλ and collision
cross sectionσ are generally defined by a simple relationship which treats the
particles as impenetrable spheres. Thus, the mean free path for electrons
passing through a gas of particle density N is

Eq. (1) λ = 1/(Nσ)

The total collision cross section can be written as

Eq. (2) σt = σel + σex + σion + σ a + σoth

where the subscripts el, ex, ion, a, and oth characterize the particular types
of collisions, namely, elastic or momentum exchange, excitation, ionization,
attachment, and other processes, respectively.
Figure 2.1 shows the cross sections for electrons interacting with Ar
gas. The cross sections are typically a strong function of the energy of the
colliding species. For the case of electrons colliding with gas atoms, the
kinetic energy of the gas atoms is generally much less than that of the
electrons and can be neglected. Consequently, only the electron energy is
shown in Fig. 2.1. The figure shows that at low electron energies the primary
collision process is momentum exchange (σt ≈ σel), while at energies
considerably larger than the ionization potential (15.75 eV for Ar), the primary
process is ionization (σt ≈ σion ).
Plasmas in Deposition Processes 57

Figure 2.1. Collision cross sections for electrons in Ar gas (from Ref. 1).

Cross sections are most easily measured for reactions involving a


species such as an electron or ion which can conveniently be formed as an
energetic beam and passed through a stationary gas. Figure 2.2 shows the
cross section for energetic O+ ions passing through N2 and producing the
reaction O+ + N2 → NO+ + N. Note in comparing Figs. 2.1 and 2.2 that the
collision cross sections are typically a few x 10-15 cm2 in magnitude (i.e., a
few angstroms in diameter). For collision types that cannot be investigated
in beam experiments, the cross sections are often deduced from measurements
of macroscopic parameters such as viscosities, diffusion coefficients, and
chemical reaction rates.[3] Thus one finds reference to viscosity cross
sections, diffusion cross sections, etc. Cross sections are primarily of interest
in making comparisons based on kinetic theory. In most plasma calculations,
the macroscopic rate parameters are used directly if they are available.
58 Deposition Technologies for Films and Coatings

Figure 2.2. Cross section for the reaction of O+ ions with N2 to produce NO+ + N
(from Ref. 2).

2.2 Free Electron Kinetic Energy in a Plasma

r
Consider a plasma electron in an electric fieldE . Between collisions with
the gas particles, the electron will gain an energy Wf from the electric field that
is equal to the force on the electron eE (where e is the electronic charge) times
the distance that it moves in the electric field. This distance can be
approximated by the mean free path so that, on average, Wf = eEλ. In the
steady state case, this energy gain must be balanced against the energy loss
in an average collision. We neglect inelastic collisions for the moment and
consider collisions with heavy particles in which the electrons lose all of their
momentum, i.e., are deflected by 90o . This permits us to use the momentum
exchange cross section, as defined in the preceding section, for estimating
λ. Application of the conservation of energy and momentum shows that loss
of electron energy in such a collision is[4]

Eq. (3) ∆W = (2me /mH) (We - WH)

where me and m H are the electron and heavy-particle masses and We and WH
are the initial electron and heavy particle energies before the collision.
Equating ∆W to the energy Wf gained from the electric field, and using Eq.
1 for λ, yields

Eq. (4) (We - WH) = ½ (mH /me) ( eE/Nσel)


Plasmas in Deposition Processes 59

In making calculations dealing with plasmas it is useful to note that:


! me = 9.11 x 10-31 kg = 9.11 x 10-28 g
! mH = 1.67 x 10-24 x (atomic mass number) g
! N = 3.2 x 1024 particles/m3 = 3.2 x 1016 particles/cm3 at 1 Torr
and 300 K (27oC)
! The electron volt (eV) is the unit of energy generally used in
plasma calculations. One electron volt is the energy gained by
a particle with unit charge which is accelerated in an electric field
produced by a potential difference of one volt (1 eV = 1.602 x 10-
19 joules = 11,600 K).

Consider the case of electrons in an Ar plasma at 1 Torr and 300 K which


is subjected to an electric field of 1 V/cm, thus, N = 3.2 x 1016 cm-3 and eE
is 1 eV/cm. Using Eq. 4 with σel ≈ 10-15 cm2 from Fig. 2.1 yields (We - WH)
≈ 103 eV. Thus, at steady state, the average electron energy will be much
greater than that of the gas atoms (0.03 eV at 300 K). The actual average
electron energy will not reach 103 eV, however, because inelastic collisions
will become important when We exceeds ≈ 10 eV. Nevertheless, the above
analysis shows that even relatively weak electric fields can cause electron
kinetic energies in low-pressure glow discharge plasmas to be elevated above
gas-atom energies until they are finally “clamped” by losses due to inelastic
collisions.
Figure 2.3 shows this elevation of electron energy at low pressures for the
case of plasma arcs. (The energies here are expressed as temperatures.) At
high pressures, electron/gas-atom collisions are so frequent that the gas
temperature increases. Such high-pressure arcs are used for a variety of
applications. However, the discussion in the following sections will be limited
to the low-pressure case where Te > Tg . In this situation, energetic electrons
can produce high temperature chemistry in a gas at low temperatures.[6]

2.3 Electron Energy Distribution Functions

For most purposes, the state of a glow discharge plasma can be


characterized by the densities of heavy particles (N j, where j corresponds
to the jth species), the electron density ne , and the electron energy
distribution function F e(E). [7] Under conditions of local thermodynamic
equilibrium,[8] when the forward and reverse rates for all the electron energy
exchange processes are equal (state of detailed balance), [9] the electrons
will have a Maxwellian velocity distribution and their state can be defined by
60 Deposition Technologies for Films and Coatings

an electron temperature Te. Unfortunately, such a state of equilibrium


seldom exists in a low-discharge plasma.

Figure 2.3. Electron ( Te ) and gas temperatures (Tg ) in an air arc as a function of
pressure (from Ref. 5).

Figure 2.4 schematically illustrates the electron energy distribution


function. The equilibrium energy distribution is also shown for comparison.
The effect of an electric field is to shift electrons to higher energies and
therefore to overpopulate the high-energy region relative to the Maxwellian
distribution. The cross section for a representative inelastic collision is shown
superimposed (see Fig. 2.1). Electrons undergoing inelastic collisions are
transferred from the high-energy to the low-energy end of the distribution.
Electron-electron collisions tend to smooth the distribution and drive it toward
the Maxwellian form. If these collisions dominate such that a state of detailed
balance exists for one dominant process, then Fe(E) can be approximated by
a Maxwellian distribution and an electron temperature can be used to describe
the state of the electrons. However, even this case seldom occurs in practice.
In high-pressure discharges, the electric field perturbation is usually
minimal allowing the distribution function to be approximately Maxwellian,
although it may be somewhat depleted at high energies by inelastic
collisions. In low-pressure discharges, the electric field can generate
relatively large numbers of energetic electrons and, in the extreme, produce
Plasmas in Deposition Processes 61

a bimodal distribution function. This is the case in low-pressure negative


glow discharges of the type used in sputtering.[7]
Electron energy distribution functions are usually measured by
electrostatic analyzer and probe methods. However, interpretation of the
results are complicated by plasma/probe interactions. Therefore electron
temperatures, although not strictly valid, are generally assumed in making
engineering calculations.

Figure 2.4. Schematic illustration of electron energy distribution function and


inelastic collision cross section.

2.4 Collision Frequencies

The collision frequency is an important plasma parameter. It is defined


as the rate at which an average particle undergoes collisions of a specified
type. Thus the total electron-atom collision frequency is the rate at which an
average electron in a plasma undergoes collisions of all types with gas atoms.
The general expression for the collision frequencyν is rather complex and
involves the distribution functions of the colliding species.[10] For the electron/
heavy-particle case, the velocity of the heavy particles can be neglected and
ν is given by

E= ∞
Eq. (5) νk = N (E/2me)1/2 σk(E) Fe (E) dE
E= 0
62 Deposition Technologies for Films and Coatings

where k is the type of collision (e.g., elastic, excitation, ionization, etc). If the
collision cross section σk(E) is assumed to be independent of energy, and the
electrons are assumed to have a Maxwellian velocity distribution at an electron
temperature Te, then Eq. 5 reduces to

Eq. (6) νk = N σk ve

The quantity ve is the average electron speed,

Eq. (7) ve = (8k Te / πme)1/2

where k is Boltzmann’s constant. It is customary to write kTe in units of eV*.


Thus, Eq. 7 becomes

Eq. (8) ve = (6.7 x 107) [kT e (eV)]1/2 cm/sec

For purposes of obtaining rough estimates,σk in Eq. 6 is generally approximated


by its value at the electron energy kTe.
The electron/electron and electron/ion collision frequencies are of
special interest. These are given by[11]

Eq. (9) νee = (3 x 10-6)ne lnΛ /[kTe(eV)]3/2 sec-1

and

Eq. (10) νei = (1.5 x 10-6) ne lnΛ /[kTe(eV)]3/2 sec-1

with

Eq. (11) λee = (4.5 x 1013) [kT (eV)]2 / (ne lnΛ) cm

where lnΛ is a weak function of kT e and ne . The function lnΛ is tabulated


in most books on plasma physics, and has a value of approximately 10 for
the glow discharge plasmas of interest here. [12] The lnΛ term arises

* From kinetic theory, the average particle energy in one dimension is 1/2 kT. The
average energy in three dimensions is 3/2 kT. Since T and E are so closely related,
it is customary in plasma physics to give temperature in units of eV. To avoid
confusion with the number of dimensions involved, it is not the average energy but
the energy corresponding to kT that is used to denote the temperature.[11] By a 2
eV plasma, we mean that kT = 2 eV, although the actual average energy in three
dimensions is 3/2 kT or 3 eV.
Plasmas in Deposition Processes 63

because these collisions involve long-range coulomb forces and the cross
sections do not cut off as in the hard sphere approximation.
The primary use of Eqs. 9 and 10 is in comparing νee and νei with other
relevant collision frequencies. A plasma for which νee > νeA, where νeA is the
elastic electron/atom collision frequency, is said to be coulomb-dominated.
An approximate condition for coulomb domination is easily derived from Eqs.
6 and 9 (see Ref. 13),
ne σeA [kT(eV)]2
Eq. (12) >> αc = (2.23 x 1013)
N lnΛ

The term αc in Eq. 12 is known as the critical degree of ionization. Selecting


kTe ~ 3 eV andσeA ~ 10-15 cm-3 (Fig. 2.1) yields ne/N ≈ 0.02. Thus a moderate-
temperature glow discharge plasma with 2% ionization can be dominated by
coulomb collisions.
A consequence of coulomb domination can be seen by examining Eqs.
9 and 11. As the electron energy is increased, the electron collision frequency
decreases and the mean free path increases. Thus, electrons in an electric
field will find that their energy gain is “unchecked” by collisions. Electron
runaway is an important consideration in highly ionized plasmas (13) but
seldom important in glow discharge plasmas because of inelastic collisions.
For the case of a heavy particle of mass m1 in a gas with density N2 of
heavy particles of mass m2 , the collision frequency can be approximated by
an equation very similar to Eq. 6,[4][14]

1
(
v12 ≈ 2.5 ×105 )σ N
12 12 T 
300
2
Eq. (13)
(m )1
∗ 2  

where the cross section σ12 is assumed to be independent of the velocity of


impact and all the heavy particles are at the common temperature T. In Eq.
13, m* is a reduced mass defined as
m1 m2
Eq. (14 ) m* =
m1 + m2

where the masses are molecular weights expressed in grams.


Reaction Rates: The gas-phase reaction rate R is directly proportional
to the collision frequency. For a process k involving electron collisions,
reactions
Eq. (15) Rk = ne νk
cm3 -sec
64 Deposition Technologies for Films and Coatings

If the electrons are assumed to have a Maxwellian velocity distribution at a


temperature Te, and if the cross section for a given reaction is approximated
by a step function of magnitude σ0 and threshold energy E0 as shown in Fig.
2.5, then the reaction rate is given by

Eq. (16) Rk = ne Nσ0νe [1 + (E0/kTe)] exp(-E0 /kTe )

Figure 2.5. Reaction rate approximation for a Maxwellian velocity distribution.

As a general rule, reaction rate constants rather than actual collision


frequencies are measured and used to describe reactions involving heavy
particle collisions. Thus, for a reaction occurring via a two-body collision
between species A and B in a gas at temperature T, with rate constant κ(T),
one has

Eq. (17) R = κ(T) NA NB

Mobilities: Plasma transport properties are dependent on the frequency


of elastic (momentum exchange) collisions. The mobility µj relates the
electric-field driven drift velocity vd of a given charged particle species j to the
strength of the field E:

Eq. (18) vjd = µj E

When the collision frequency is sufficiently large that the drift velocity is small
compared to the thermal velocity,
1.6 x 10-12 cm2
Eq. (19) µj =
mj ν V-sec

where mj is the particle mass in grams.


Plasmas in Deposition Processes 65

The mobility is generally used to describe the drift of ions through a


plasma that is at a sufficiently high pressure to satisfy the collision frequency
requirement. Mobilities for several gases of interest are given in Table 1.

Table 2.1. Mobilities of Ions in their Own Gas (From Ref. 15)

Ion-Gas Mobility (cm2/V-sec)

He+-He 8,000
Ne+-Ne 3,300
Ar+-Ar 1,200
Kr+-Kr 690
H2+-H2 10,000
N2+-H2 2,000
O2+-O2 1,000
CO2 +-CO2 730

When a positive ion collides with a gas molecule or atom, two processes
can occur. First, the ion and molecule can exchange momentum and energy
in a collision in which the particles preserve their identity. Second, an
exchange of charge can occur. For example, fast ions moving through a gas
can engage in collisions in which the ion extracts an electron from a gas atom
with the result that the fast ion becomes a fast neutral atom while the slow atom
becomes a slow positive ion. Charge exchange is particularly important for
ions of low energy passing through their own gas (resonant charge exchange).
Under these conditions, the charge transfer cross section is about one half of
the total cross section[16] and therefore contributes significantly in determining
the mobility.* Charge transfer is very important in high-pressure sputtering and
ion-plating discharges.
Electrical Conductivity and Diffusion Coefficients: The electrical
conductivity σ is just eNµ, so that

Eq. (20) σj = 1/ρj = 2.6 x 10-31 (Nj /mjν) (Ω-cm)-1

*The charge exchange region surrounding an atom can be considered as a sphere


inside of which the probability of charge transfer is ½ and outside it is zero. As the
ion approaches the atom, it will simply be deflected by the dipole interaction if the
distance of closest approach is greater than the sphere radius. If the ion enters
the charge exchange sphere, half the time it emerges as a neutral and half the time
as an ion.[17]
66 Deposition Technologies for Films and Coatings

where Nj is the particle density in cm-3 and mj is the mass of the current carrier
in grams. The resistivityρ is often used to avoid confusion with σ, which is the
common symbol for both the electrical conductivity and the collision cross
section.
The diffusion coefficient Dj relates the particle flux to the concentration
gradient. Thus, one has

Eq. (21) Nj vjd = Dj (dNj /dx)

where
kT kT (eV) cm2
Eq. (22) Dj = = (1.6 x 10-12)
mj ν mj ν sec

2.5 Particles in Magnetic Fields

Charged particle motion in a magnetic field is summarized in Fig. 2.6.

Figure 2.6. Electron paths in static magnetic and electric fields.


r
A charged particle in a uniform magnetic field B will orbit a field line as
shown in Fig. 2.6a and drift along the field with velocity v|| that is unaffected by
the field, as shown in Fig. 2.6b. The orbiting frequency is called the gyro or
cyclotron frequency and is given by

Eq. (23) ωc = eB/m


Plasmas in Deposition Processes 67

The orbiting radius is called the gyro, cyclotron, or Larmor radius and is given
by

Eq. (24) rg = (m/3) (v⊥/B)

Manipulation and confinement of plasma particles by a magnetic field


requires that rg be small compared to the apparatus size. Note in Eq. 24 that
rg depends directly on the mass of the particle. Thus, very large magnetic
fields are required to influence the motions of the plasma ions. When magnetic
fields are used with glow discharges, they are generally chosen to be just
strong enough to influence the energetic plasma electrons, but not the ions.
However, magnetically-confined electrons in a glow discharge will in turn
provide considerable confinement for the plasma ions since electrostatic
forces prevent the ions from escaping from the electrons. For electrons, Eqs.
23 and 24 become[1]

Eq. (25) ωc = (1.76 x 107 ) B(gauss) rad/sec

and
[W⊥(eV)] 1/2
Eq. (26) rg = 3.37 cm
B(gauss)

Thus, for electrons with an average energy W⊥ of 10 eV and a magnetic field


strength B of 100 G, the gyro radius is ≈ 0.1 cm. Magnetic field strengths
between 50 and 100 G are typically used with glow discharge devices. An
electron that is trapped on a given magnetic field line can advance to an
adjacent field line by making a collision, as indicated schematically in Fig.
2.6c. Collisional diffusion of electrons across magnetic field lines is an
important consideration in manyr glow discharge devices.
When an electric field E is present and directed parallel to the magnetic
field, the electrons are freely accelerated along the field lines.rHowever, if the
electric field has a component E⊥ which is perpendicularrto B , the electrons
undergo a drift in a direction perpendicular torbothrE⊥ andB , asrshown
r in Figs.
2.6d and 2.6e. This motion is known as the E x B drift. The E x B drift has
the cycloidal form shown in Fig. 2.6d if the initial electron energy is
small compared to that gained from the electric field; it has the more
circular form shown in Fig. 2.6e if the initial electron energy is largely
compared to the electric-field-induced variations that occur during the
course of the orbit. In both cases, the electron drift speed is given by
68 Deposition Technologies for Films and Coatings

E⊥ (V/cm)
Eq. (27) ve = 108 cm/sec
B(gauss)

The drift of electrons along a magnetic field line can also be influenced
by gradients in the magnetic field. An example of this behavior is shown in Fig.
2.7.
Electrons moving in such a field tend to conserve the magnetic moment,
µM, defined by[11]

Eq. (28) µM = W⊥ / B

Therefore W⊥ must increase as the electrons move in the direction of


increasing field strength. Conservation of energy requires that W|| + W ⊥ be
constant. Therefore W|| must decrease, and the electron may be reflected as
indicated in the figure. Pinched-field end confinement of this type is frequently
used in glow discharge devices

Figure 2.7. Electron reflection in a magnetic field gradient.

3.0 COLLECTIVE PHENOMENA

Plasmas differ from non-ionized gases by their propensity for undergoing


collective behavior. Three parameters, derived from basic plasma properties,
N, ne, and kTe, provide a useful measure of the tendency toward collective
behavior.
Plasmas in Deposition Processes 69

The Debye length,


kTe (eV) 1/2
Eq. (29) λD = 743 cm
ne (cm3)

corresponds to the distance over which significant departures from charge


neutrality occurs. A plasma cannot exist in a space having a characteristic
size less that λD.
The plasma frequency, ωp , expressed here as

Eq. (30) fp = ωp /2π = 9000[ne (cm -3 )] 1/2 Hz

provides a measure of the tendency for electrostatic waves to develop. Waves


can form if ωp >> νe,el, where νe,el is the electron collision frequency for
momentum exchange.
The critical degree of ionization αc was defined by Eq. 12. When the
degree of ionization α = ne/N >> αc, long range coulomb collisions dominate,
and the charged particles behave as though they were in a fully ionized gas.
Coulomb domination can occur at degrees of ionization of a few percent for
plasmas with low average electron energies (≈1 eV).

3.1 Plasma Sheaths

Given a gas of particle density N (cm-3) and temperature T, the flux of


particles passing to an adjacent wall is given by

Eq. (31) J = Nv/4 = (N/4) (8kT/πm)1/2

For electrons, this becomes (see Eqs. 7 and 8)

Eq. (32) Je = (1.67 x 107 ) ne [kTe (eV)]1/2 particles/cm2 -sec

which, in units of current density, is equal to

Eq. (33) Je = 2.7 x 10-9 ne [kTe (eV)] 1/2 mA/cm 2

Thus, for a typical glow discharge electron density of 109 cm-3 with an average
energy of 1 eV, Je ≈ 3 mA/cm2.
For heavy particles such as ions, Eq. 31 can be written in the following
useful form:
70 Deposition Technologies for Films and Coatings

Eq. (34) Ji = 104 N (40/m)1/2 (T/300)1/2

where T is the gas temperature (K) and m is the species molecular weight. In
units of current density, Eq. 34 becomes

Eq. (35) Ji = 1.6 x 10-9 N (40/m) 1/2 (T/300)1/2 µA/cm2

Thus, for an Ar plasma used in sputtering with an ion density of 109 cm-3 at
300 K, the ion current flux to the wall is 1.6 µA/cm2.
It is clearly seen by comparing Eqs. 33 and 35 that the electrons tend
to flow from a plasma to an adjacent wall at a faster rate than the ions; therefore,
a space charge region in which one species is largely excluded forms adjacent
to such surfaces. The potential variation between the surface and the plasma
is largely confined to this layer, which is called a sheath. Sheaths are typically
several Debye lengths in thickness.
The nature of the sheath will depend upon the current density passing
across it. Except for cases involving very high current densities to anodes, the
space charge region will contain primarily the low-mobility ion species. Such
sheaths are known as positive space charge sheaths. The function of the
sheath is to form a potential barrier, so that the more mobile species, which
is the electrons except in the case of a strong magnetic field, are electrostatically
reflected. Thus, the height of the potential barrier associated with a sheath
adjusts itself so that the flux of electrons to the wall in question just equals the
electron current that is drawn from the wall by the external circuit. If the wall
is electrically isolated, the electron flux is reduced to the point which is equal
to the ion flux.
Figure 2.8 shows that a schematic illustration of a typical glow discharge
plasma which is in contact with wall surfaces that are either cathodes, anodes,
or electrically isolated (floating). The potential Vp is known as the plasma
potential. The potential of a floating surface relative to the plasma potential is
known as the floating potential Vf. For a Maxwellian velocity distribution, the
floating potential is given by[18]

kTe (eV) π me
Eq. (36) Vf = ln
2e 2 m

Typical values are -30 to -40 V. When a floating surface is immersed in a


plasma, the surface will be bombarded with ions having kinetic energies of up
to eVf.
Plasmas in Deposition Processes 71

Figure 2.8. Schematic illustration of sheaths that form between a plasma


discharge and the surrounding apparatus walls for systems having (A) a large
anode and (B) a small anode.

Generally, the anodes used in glow discharges are large enough that the
current density is less than the thermal current given by Eq. 33. In this case,
there is a positive space charge sheath at the anode, as shown in Fig. 2.8a,
and the sheath potential drop is between zero and V f . The potential
72 Deposition Technologies for Films and Coatings

of a plasma locks into the most positive surface, provided that the surface is
large enough.[19] If the anode area is so small that the current density must
exceed the thermal current, then the anode potential will be above the plasma
potential, as shown in Fig. 2.8b. The local electric field surrounding the anode
will draw sufficient electrons to the anode to complete the external circuit.*
A large potential difference Vs, approximately equal to the entire potential
applied by the power supply, occurs in the cathode sheath as shown
schematically in Fig. 2.9. The sheath thickness ds is taken to be the region
corresponding to Vs over which the electron density is negligible. For the low
pressure case where the ion mean free path is larger than ds, the ion current
density Ji is related to ds and Vs by the Child-Langmuir law. [11] It is useful to
write this relationship as

Eq. (37) Ji = 0.273 (40/mi)1/2 (Vs3/2/ds2) mA/cm2

where Vs is in kV, d s is in cm, and mi is the ion molecular weight in grams.


Thus, for an Ar sputtering plasma with Vs = 1 kV and d s = 1 cm, J i = 0.27
mA/cm 2. It is difficult to relate J i to the density N io of ions in the bulk
plasma, because there is a quasi-neutral presheath region where a
potential drop Vx of the order of 1/2(kTe /e) occurs. As an estimate, the
presheath density can be assumed to obey a Boltzmann distribution, [20]
such that Nis /Nio = exp(eV x /kTe ) , and

Eq. (38) Ji ≈ (0.6) eNio (kTe/mi )1/2

where mi is in grams and kTe is in ergs.


For the high pressure case, where collisions are so frequent that the ion
drift velocity is of the order of the thermal velocity, a mobility description is used
for the ion motion.[5] Under this condition,

Eq. (39) Ji = 9.95 x 10-5 µi (Vs2/ds3 ) mA/cm2

where µi is the ion mobility in cm 2/V-sec, Vs is the sheath potential drop in kV,
and ds is the sheath thickness in cm. For an Ar plasma at 1 Torr, µi = 1,200
cm2/V-sec from Table 1. Taking V = 1 kV and ds = 1 cm yields Ji = 0.11 mA/
cm 2.

*The potential rise surrounding a small anode cannot become much larger than
the ionization potential of the gas atoms since this potential causes the sheath
electrons to be accelerated. If these electrons gain sufficient energy to produce
ionization, then the electrons liberated by the ionizing collisions can provide the
anode current flow requirement and no additional rise in potential is required.
Plasmas in Deposition Processes 73

Figure 2.9. Schematic representation of the positive space-charge sheath that


develops over a cathode (from Ref. 1).

In a low pressure plasma, the ions will fall through the entire sheath
potential and bombard the cathode with an energy about equal to eVs. At higher
pressures, where charge exchange is important, the bombarding flux will
consist of both ions and neutrals having energies considerably less than
74 Deposition Technologies for Films and Coatings

eVs as indicated schematically in Fig. 2.10. This is an important consideration


in sputtering, ion plating, and reactive ion etching, as discussed in Ch. 5, Sec.
3.0.

Figure 2.10. Schematic representation of charge exchange reactions in the


cathode fall region of a glow discharge.

3.2 Ambipolar Diffusion

Consider a plasma within a container having electrically isolated or


floating walls. A sheath will develop on these walls to reduce the electron flux
until it is equal to the ion flux as described in Sec. 3.1. Accordingly, an electric
field in the sheath retards the loss of electrons and accelerates the loss of ions.
This coupled particle motion is called ambipolar diffusion. The diffusion flux
J of electrons or ions to a floating wall is given by

Eq. (40) Je = D a (dne/dx) = Ji = D a (dni /dx)

The term Da is called the ambipolar diffusion coefficient. Noting that µe >> µi
(see Eq. 19) permits Da to be approximated as:[11]
Plasmas in Deposition Processes 75

Eq. (41) Da ≈ Di (1 + Te /Ti )

where Di is given by Eq. 22. Thus the effect of the ambipolar field is to enhance
the diffusion of ions by a factor of more than two, but the diffusion rate of the
two species together is primarily controlled by the slower species. In the
presence of a sufficiently strong magnetic field perpendicular to the direction
of diffusion, the electron mobility, and thus the electron diffusion coefficient can
be reduced to the point where it is lower than the ion diffusion coefficient and
therefore rate controlling. Under this condition one can write

Eq. (42) Da ≈ {De/[1 + (ωc2/νe)]} (1 + T i /Te)

where De is the electron diffusion coefficient in the absence of a magnetic field.


The effect of the magnetic field becomes strong when ωc (given by Eq. 25) is
much larger than the electron collision frequency νe , i.e., when the electrons
are trapped on magnetic field lines as shown in Fig. 2.6b, and collisional
hopping to adjacent field lines is infrequent. It should be noted that Eq. 42 is
based on the assumption that electron losses along the lines can be
neglected. Attention to these losses should be given when analyzing the
performance of an actual plasma device.[11][21]

3.3 Plasma Oscillations

The plasma state is rich in wave phenomena when the degree of


ionization is large enough to make long-range forces important, particularly
when a magnetic field is present.[11] Departures from charge neutrality
capable of generating waves can occur in the form of charge bunching and
separation over distances of the order of the Debye length, Eq. 29. A general
discussion of such behavior is beyond the scope of this chapter. However, one
case will be mentioned because of its potential importance in magnetron
sputtering devices.
Consider the case of a plasma in a uniform electricr rand magnetic field,
as illustrated
r inrthe left side of Fig. 2.11. There is an E x B drift perpendicular
to both E and B , but, in the absence of collisions, simple theory predicts no
transport across the magnetic field in the direction of the applied electric field.
If charge bunching occurs, as shownr in the right side of r Fig.r 2.11, the
perturbation produces an electric field r E p that can result inE x B drift across
the magnetic field in the direction ofE . This anomalous collisionless transport
across the magnetic field is believed to be an important mechanism in Penning
discharges as well as in some magnetron sputtering discharges.[22]
76 Deposition Technologies for Films and Coatings

Figure 2.11. Schematic representation of a plasma instability resulting in electron


transport across a magnetic field.

4.0 PLASMA DISCHARGES

4.1 Introduction

A glow discharge plasma is a low temperature, relatively low pressure,


gas in which a degree of ionization is sustained by energetic electrons. Glow
discharge configurations used in materials processing differ in both their
general geometry and in the orientation of the electric field that is used to
provide energy to the electrons.
In sputtering, simple planar diodes of the type shown schematically in
Fig. 2.12a are often used. They may be driven at radio frequencies (RF), as
shown in the figure, or by a DC power supply. RF planar diode discharges are
also used for sputter etching, plasma etching, and reactive ion etching, as
illustrated in Figures 2.13b, 2.13d and 2.13e, respectively. Systems with the
configuration shown in Fig. 2.13d are also used for plasma-assisted chemical
vapor deposition (CVD).
During activated reactive evaporation, a plasma discharge is sustained
in a flux of evaporated material and reactive gas that is directed toward the
substrates, as shown in Fig. 2.14. The discharge may be driven by DC or RF
means, using a variety of electrode configurations. The presence of the
plasma has been shown to influence properties such as the chemical
composition of the resultant films.[53]
Plasmas in Deposition Processes 77

Figure 2.12. Schematic illustration of glow discharge devices commonly used in


plasma-assisted materials processing.

In ion plating, the discharge is generally sustained in a mixture of the


evaporated flux and an inert working gas with the substrate holder biased
negatively relative to the plasma potential. Usually this is done by simply
making the substrate holder the cathode electrode for sustaining the plasma
discharge, as shown in Fig. 2.15. The ion bombardment of the growing coating
has been shown to influence its structure.[53]
In plasma etching, plasma-assisted CVD, and glow discharge
polymerization, discharges are often sustained in glass or quartz reactor
tubes by surrounding electrodes which are driven at high frequencies (from 300
kHz to microwave frequencies)[23] Common electrode configurations are a
pair of ring electrodes along the tube, clam-shell electrodes as shown in Fig.
2.12b, or a solenoidal coil electrode as shown in Fig. 2.12c. It should be noted
that all of these discharges are basically capacitive in nature. Although the
coil electrode will introduce considerable inductance into the load seen by the
matching network, the capacitive fields generated by the coil-to-coil potential
drop dominate over those generated by the time rate-of-change of magnetic
flux and therefore act as the primary source of ionization unless special
precautions are taken to shield them. In the case of microwave discharges,
the reactor tube is generally positioned within the waveguide at a location
which places a strong electric field component within the tube.[6][23]

4.2 Ionization Balances and the Paschen Relation

The degree of ionization in a glow discharge depends on a balance


between the rate at which ionization is produced by energetic electrons and
78 Deposition Technologies for Films and Coatings

the rate at which particles are lost by volume recombination and by passage
to the walls of the apparatus. The rate of ionization depends on a relationship
of the form (see Eqs. 6, 8, and 15)

Eq. (43) R ∝ N ne σion (E)1/2

Figure 2.13. Apparatus configurations commonly used in plasma-assisted


etching.
Plasmas in Deposition Processes 79

SUBSTRATES (S)
ELECTRODE

Figure 2.14. Schematic illustration of the activated reactive evaporation (ARE)


process (see Ref. 49).

Figure 2.15. Schematic illustration of a typical ion plating apparatus.


80 Deposition Technologies for Films and Coatings

Thus, the rate of ionization depends on the type of gas (through the ionization
cross sectionσion), the gas pressure (through the particle density N), and the
electric field strength (through the electron velocity). Wall losses generally
dominate over volume recombination. Accordingly, the occurrence of a
breakdown, and the resulting formation of a sustaining plasma discharge, in
a given apparatus depends on the gas pressure, the electric field strength,
and on the surface-to-volume ratio of the plasma. Figure 2.16 shows the inter-
electrode breakdown voltage as a function of the product of the gas pressure
p and the electrode spacing d for plane parallel electrodes in air[5] and Ar.[24]
Such curves are determined experimentally and are known as Paschen
curves. Relationships of the same general form apply to the conditions under
which a steady-state discharge can be sustained. In such cases d may be
replaced by a characteristic diffusion length for the plasma vessel.[6][17][25]

Figure 2.16. Paschen curves for breakdown between plane-parallel electrodes in


air and argon at 20oC.

The rise in voltage at the low pd side in Fig. 2.16 occurs because the
apparatus is small, or the gas density low, such that electrons are lost to the
walls without colliding with gas atoms and producing ionization. The rise in
the required voltage on the right side happens because the electron energy is
becoming too low to produce ionization. This can occur at high pressures,
because electron collisions with gas atoms become so frequent that the
electrons cannot accumulate sufficient energy to overcome the ionization
potential. It can also occur at a given applied voltage in a very large chamber
where local electric fields in the plasma are too weak to deliver sufficient energy
to the electrons between collisions.
Plasmas in Deposition Processes 81

The functional form of the curves in Fig. 2.16 provides a useful guide for
adjusting the operating conditions within a given device in order to produce a
plasma discharge. Conversely, the relation provides guidance for the
prevention of discharges on surfaces such as the back of cathodes. One
simply places a grounded shield over the surface to be protected ensuring that
the spacing d between the shield and the cathode is small enough that the
breakdown voltage is larger than the voltage required to form and sustain
plasma discharge at the operating pressure of interest.
The above considerations are also important in apparatus scaling. A
discharge sustained in a small apparatus must have a high average electron
energy to counteract wall losses. Such a discharge, with the same electron
density but in a larger apparatus size, will be sustained at a lower average
electron energy. This can in turn change the active species that are produced.
Thus, small-bore discharge tubes are sometimes used in lasers to elevate the
average electron energy to a desired value. Typical glow discharge electron
densities are in the range of 108 to 10 12 cm -3 with average electron energies
of 1 to 30 eV. These conditions are shown in Fig. 2.17 and compared with other
forms of discharges.

Figure 2.17. Regions of average electron density and energy representative of


various types of plasmas (from Ref. 7).
82 Deposition Technologies for Films and Coatings

4.3 Cold Cathode Discharges

A low-pressure cold-cathode discharge is one which is maintained


primarily by secondary electrons emitted from the cathode due to
bombardment by ions from the plasma. These secondary electrons are
accelerated in the cathode dark space and enter the negative glow, as shown
in Fig. 2.18, where they are known as primary electrons. Each primary
electron must produce a sufficient number of ions to result in the ejection of
another secondary electron from the cathode.[15] The secondary electron
emission coefficient is typically about 0.1 for low-energy Ar+ ions (such as are
used in sputtering) incident on clean metal surfaces.[26] The coefficient is
larger, for example, for oxidized surfaces but still small enough that each
primary electron must produce, or lead to the production of, a plurality of
ions.[15]

Figure 2.18. Schematic illustration of a cold-cathode discharge.

The negative glow (NG) region of the plasma is where the primary
electrons expend their energy, and its extent corresponds to the range of their
travel from the cathode.[5][15] The electron energy distribution in the NG is
multimodal. It consists of primary electrons, ultimate electrons (primaries that
have transferred their energy), and much larger numbers of low-energy
ionization products. In the classical glow discharge described in most
Plasmas in Deposition Processes 83

textbooks, a positive column (PC) extends from the NG to the anode.[5][15][17]


The PC is a region in which the electric field is just sufficient to transport the
discharge current from the NG to the anode and to produce sufficient ionization
to make up for wall losses.
In planar-diode material-processing sources of the type shown in Figs.
2.12 and 2.13, the substrate mounting table or anode generally intercepts the
NG and there is no PC. A consequence of this small inter-electrode spacing
is that the operating pressures are relatively high (see discussion of the
Paschen relationship in Sec. 4.2). For example, reasonable operating
conditions for DC planar-diode Ar sputtering discharges are: 75 mTorr
pressure with a substrate-to-cathode spacing of 4.5 cm, a current density of
1 mA/cm2, and a discharge voltage of 3,000 V.
In order for a cold-cathode discharge to operate effectively at low
pressures, it is necessary that the primary electrons be preserved and not lost
from the system until they have had a chance to expend their energy in
ionization. The hollow cathode geometry shown in Fig. 2.19 is effective in this
respect. Electrons which are accelerated in the cathode dark space and enter
the NG cannot escape once they have lost an amount of energy about equal
to their initial ejection energy (which is only a few eV)[26] since they encounter
a sheath with repulsive forces whenever they approach the cathode. The only
losses are out of the ends, and long hollow cathodes with minimized end
losses can be operated effectively at low pressures and voltages. Accordingly,
hollow cathodes are often used as ionization sources.[27]

Figure 2.19. Schematic illustration of a hollow cathode discharge.


84 Deposition Technologies for Films and Coatings

4.4 Magnetron Discharges

Magnetron discharge sources are assuming increasing importance for


sputter deposition. Therefore, these discharges are discussed in some detail
in Ch. 5. It will simply be noted here that magnetrons are cold cathode
discharge devices in which magnetic fields are used in concert
r r with cathode
surfaces to form traps which are so configured that the E x B electron drift
currents can close upon themselves.[1] The cylindrical-post configuration
shown in Fig. 2.20 provides one of the simplest examples of a magnetron.
Primary electrons which leave the cathode barrel and enter the plasma find
themselves trapped in an annular cavity which is closed on three sides by
surfaces at cathode potential (the hollow cathode effect) and on the fourth side
by the magnetic field. The electrons can diffuse across the magnetic field and
reach the anode only by making collisions (the process illustrated in Fig. 2.6c)
and by plasma oscillations (see Sec. 3.3).[22] Because of the effectiveness
of the collisions in producing ionization, these discharges are extremely
efficient and operate at pressures of less than 1 mTorr with high current
densities (10 - 200 mA/cm2 ) and low voltages (700 - 1,000 V). Planar
magnetrons in which plasma rings are magnetically confined on planar
cathodes are very important in sputter-deposition technology.[28][29]

Figure 2.20. Cylindrical-post magnetron sputtering source with electrostatic end


confinement.
Plasmas in Deposition Processes 85

4.5 RF Discharges

RF-driven planar diode discharge devices of the type shown in Figs.


2.12a, 2.13b, 2.13d, and 2.13e are used for sputter deposition, plasma-
assisted etching, and plasma-assisted CVD. Their application to sputtering
is discussed in detail in Ch. 5.
The operating frequency is generally 13.56 MHz, since this is the
frequency in the 10 to 20 MHz range that has been allocated by the FCC for
industrial applications. At this frequency, only the electrons can follow the
temporal variations in applied potential. Thus the plasma can be pictured as
an electron gas that moves back and forth at the applied frequency in a sea
of relatively stationary ions. As the electron cloud approaches one electrode,
it uncovers ions at the other electrode to form a positive ion sheath. This sheath
takes up nearly the entire voltage as in the DC case. The ions are accelerated
by this voltage and bombard the electrodes.
The RF discharge can be further understood by examining the electrode
current flow. These discharges are capacitive in nature, both because of
external capacitance which is placed in the electrical circuits and because one
or both electrode surfaces are generally nonconducting. Consequently, the
total ion and electron charge flow to a given electrode during an RF cycle must
balance to zero and a self bias that is negative with respect to the plasma
potential develops on any surface that is capacitively coupled to a glow
discharge.[51] The basis for this behavior is illustrated in Fig. 2.21, where the
current/voltage characteristics are shown for an electrode immersed in a glow-
discharge plasma. Because of the mobility difference between the electrons
and the ions, much larger currents are drawn when the electrode is positive
relative to the floating potential than when it is negative (upper figure). In order
to achieve zero net current flow, it is necessary for the DC bias to develop such
that the average potential is negative relative to the floating potential, as shown
in the lower figure. Thus both electrodes exceed the floating potential (and
become anodes) only for short portions of each RF cycle. Most of the time
they are cathodes. Because of their inertia, the motion of the ions can be
approximated as if they follow the DC potential and flow to both electrodes
throughout the cycle.
RF discharges in planar diodes can be operated at considerably lower
pressures than DC discharges. Typical operating pressures are 5 to 15
mTorr. This is due to two reasons: a reduction in the loss of primary
electrons and, at high frequencies, by an increase in the volume ionization
efficiency. A fraction of the lower-energy primary electrons are repelled
from the electrode toward which they are accelerated and thus remain in the
86 Deposition Technologies for Films and Coatings

(a)

(b)

Figure 2.21. The formation of a negative bias on a capacitively-coupled surface in


an RF glow discharge (from Ref. 51).

discharge longer to make additional ionizing collisions. In addition, electrons


can gain energy from the RF field by making in-phase collisions with gas
atoms. That is, if an electron, accelerated in one direction during a given half-
cycle, makes an elastic collision in which its direction is reversed near the end
of the half-cycle, it maintains most of its velocity (due to the large mass
mismatch between electrons and ions) and will again be accelerated during
the next half-cycle and thus have gained energy during the complete
Plasmas in Deposition Processes 87

cycle. As the pressure is increased, the volume ionization due to electrons


accelerated by the oscillating electric field becomes increasingly important
Accordingly, when the planar and cylindrical plasma discharge devices shown
in Fig. 2.13 are used for plasma-assisted etching, CVD, and polymerization,
the operating pressures are generally high enough that volume-accelerated
electrons dominate in producing excitation and ionization. The same is true
for high-frequency microwave type discharges.

5.0 PLASMA VOLUME REACTIONS

5.1 Introduction

Electron bombardment of atoms and molecules results in excitation


ionization, and dissociation, thereby producing a variety of active species and
radicals having much different chemical activities than those of the parent
gas.[30][31] Thus, although He and Ar atoms are inert, He+ ions with one
valence electron are hydrogenic. Ar+ ions are similar to Cl and can react with
H2 molecules to form HAr+ ions.[30]
Electron ionization processes are obviously important in the sustaining
of plasma discharges. The excitation and dissociation processes are
important in plasma chemistry and form the basis for plasma-assisted
etching, plasma-assisted CVD, and plasma polymerization.

5.2 Electron/Atom Interactions

An electron with a kinetic energy which exceeds the ionization energy


of an atom has as approximately equal probability of producing either
excitation or ionization as it passes in close proximity to the atom. A semi-
classical picture of such a collision is shown in Fig. 2.22. The Coulomb force
from the electron produces an electric field at the atom. The component of this
field which is perpendicular to the direction of electron motion (E⊥) produces
a time-varying “impulsive” electric field which can act on the atom. The electric
field pulse is equivalent to that which would be produced by a beam of photons
having frequencies corresponding to the Fourier components of the pulse.[32]
The point is that an electron passing close by an atom does not simply knock
an electron out of the atom, but produces a perturbation at the atom which may
be approximated as a beam of white light that induces electronic excitation
and ionization in proportion to the optical oscillator strengths.
88 Deposition Technologies for Films and Coatings

Figure 2.22. Virtual photon model of an electron-atom collision (from Ref. 32).

In making plasma calculations, the average energy Wei spent by an


electron in creating an electron-ion pair in a given gaseous medium is often
used. Values of Wei for various atoms and molecules are shown in Table 2
along with values for the ionization potential I. Note that Wei/I ≈ 2; i.e., there
is an almost equal probability of producing either excitation or ionization,
although excitation is more probable in molecules.

5.3 Electron/Molecule Interactions

Electron interactions with molecules produce excitation and ionization


via mechanisms essentially identical to those for atoms as described above.
The primary difference is in the fate of the excitation energy. In the atomic
case, the excitation energy is lost by radiation unless the transitions are
quantum-mechanically forbidden (see Sec. 5.4 below). In the molecular case,
it may result in dissociation of the molecules. Consider the case of CF4 , a gas
which is commonly used in plasma etching. The threshold for producing
excitation is 12.5 eV.[33] The excitation reaction can be written as

e− + CF4 → CF4* + e−
Plasmas in Deposition Processes 89

where the symbol * refers to an excited species. There is evidence that all
electronic excitation processes in CF4 produce dissociation. [33] Furthermore,
because of the two-step nature of the excitation-dissociation process, one
bond is broken, and the primary radicals produced are CF3 and F rather than
CF2 and F2.[34] The active F atoms produced in this way play a very important
role in many plasma etching processes.

Table 2.2. Approximate Energy Spent to Create Electron-Ion Pairs[32]

Atom or Molecule Wei (eV) I (eV) W ei / I

He 46 24.58 1.87
Ne 37 21.56 1.71
Ar 26 15.76 1.65
Kr 24 14.00 1.71
Xe 22 12.13 1.81
H2 36 15.43 2.33
N2 36 15.59 2.31
NO 29 9.25 3.13
CO 35 14.04 2.49
O2 32 12.15 2.63
CO2 34 13.81 2.46
C2H2 28 11.40 2.45
CH4 29 12.99 2.23
C2H4 28 10.54 2.65
C2H6 27 11.65 2.31
C3H6 27 9.73 2.77
C3H8 26 11.15 2.33
C6H6 27 9.23 2.92

The ionization process can also result in dissociation. Thus, one has
dissociative ionization reactions of the form

e− + CF4 → CF3 + + F + 2e−

as well as simple molecular ionization

e− + O2 → O2 + + 2e −

It has been noted that plasma discharges often contain relatively large
numbers of low energy electrons which have expended their energy in making
inelastic collisions (this is particularly true in regions of low electric field such
as the negative glow). These electrons can attach to electronegative
molecules to form negative ions[23] such as

e− + O2 → O2−
90 Deposition Technologies for Films and Coatings

The ion may then dissociate, for example

O2− → O− + O

Atomic constituents of small molecules such as F2 cannot recombine


in two-body gas-phase collisions because the diatomic molecule formed
cannot conserve both energy and momentum. Thus the gas-phase
recombination reaction requires a third body. Accordingly, the lifetime for such
atoms in a plasma reactor can be long except when the working pressure is
high. However, when two molecular radicals associate, the energy of
dissociation can be distributed within a large number of internal degrees of
freedom. Accordingly, the association efficiency is close to unity for simple
radicals.[23] Thus, for example, one has

CH3 + CH3 → C2 H6

The decay of initial reaction products in cascading reactions, with the


development of high molecular weight species, is a well-known characteristic
of the radiation chemistry of hydrocarbons and halocarbons in both the gas and
solid phases.[31] The general hierarchy for the production of active species in
a molecular gas plasma is shown schematically in Fig. 2.23.

5.4 Metastable Species

An important consideration in using plasmas for materials processing is


the ability of active species to diffuse from the point of production to a point of
reaction. Atoms or molecules that are excited into electronic states which can
decay radiatively have very short lifetimes (~10−9 s). However, some excited
states are forbidden by quantum mechanical considerations from undergoing
radiative transitions. Atoms and molecules in these metastable states have
sufficiently long lifetimes that they can carry their stored electronic energy
from the immediate vicinity of the discharge plasma to other points in a reactor.
Atoms or molecules can be excited directly into metastable states, or
can arrive in these states by radiative decay after having been excited into
states of higher energy. Consequently, a plasma may contain relatively large
numbers of metastable species and they can have an important effect on the
overall discharge chemistry. Metastable states are depopulated when the
atoms undergo collisions. Thus, for example, a metastable atom A* may
subsequently pass its excitation energy to another particle, thereby
Plasmas in Deposition Processes 91

producing ionization or dissociative ionization in atoms or molecules of lower


ionization potential, as indicated below.[35]

A* + Y → Y+ + A + e−

A* + XY → XY+ + A + e−

A* + XY → X + + Y + A + e−

These reactions are known as Penning ionization processes.

Figure 2.23. Schematic illustration of the production of active species in a


molecular plasma.
92 Deposition Technologies for Films and Coatings

5.5 Applications of Volume Reactions

Primary applications of interest here are plasma-assisted CVD,[36]


plasma-assisted etching,[37] and plasma polymerization (38). In each of these
cases, the advantage of using a plasma is that it can effectively produce
reactions at low substrate temperatures. In some cases, the reactions are
unique.
An example is provided by the plasma-assisted deposition of Si3N4 using
a SiH4-NH3 plasma. The plasma chemistry is not understood in detail,
however the overall reaction is

3SiH4 + 4NH3 → Si3N4 + 12H2

The important point is that the substrate temperature is typically 300oC or


lower. When the same reaction is carried out by conventional chemical vapor
deposition, the substrate temperatures are typically between 800 - 1200oC.[39]
The lower substrate temperatures in plasma-assisted CVD are particularly
important in electronic applications where coatings are deposited onto device
structures.
The average electron energies in plasma-assisted CVD are typically low,
≈1 - 10 eV, such that the plasma chemistry is dominated by radicals rather
than ions.[52] Bond energies are therefore an important criteria in the selection
of reactants for a desired process. For example, one of the functions of the
plasma during deposition of nitride films is to provide atomic N in the gas phase
since the partial pressure of atomic N required to obtain stoichiometric nitride
films is much smaller than that of N2. However, 9.83 eV is required to obtain
N atoms by cleaving the N2 molecule,

N2 → NH2 + H (∆H = 9.83 eV)

Alternatively, N atoms can be obtained more efficiently through the following


steps starting with NH3:

NH3 → NH2 + H (∆H = 4.76 eV)

NH2 → NH + H (∆H = 3.90 eV)

NH → N + H (∆H = 3.42 eV)


Plasmas in Deposition Processes 93

in which no reaction step requires more than 4.76 eV. This explains why NH3
is commonly used in Si3 H4 plasma-assisted CVD deposition. Similarly, the
following reactions show why nitrous oxide N2 O, rather than O2, is often used
as a parent donor molecule for O atoms during plasma CVD deposition of
oxides.

N2 O → N2 + O (∆H = 1.73 eV)

O2 → 2O (∆H = 4.13 eV)

Plasma-assisted etching is similar to plasma-assisted CVD, except that


a volatile rather than an involatile compound is produced at the substrate.
Thus, for example, Si etching is accomplished by using a glow discharge to
generate active F atoms from an inert molecular gas such as CF4. The F atoms
cause etching of the Si by forming volatile compounds such as SiF4 on the Si
surface.
Plasma polymerization often proceeds in a series of steps.[38] Thus, for
example, high molecular weight species can be formed in a glow discharge
from low molecular weight starting material by the association processes
discussed in the previous section. These high molecular eight species
condense on the substrates, where they are cross-linked by plasma radiation
and electron bombardment to form a polymer film.

6.0 SURFACE REACTIONS

6.1 Introduction

Surfaces in contact with plasmas are bombarded by electrons, ions, and


photons. The electron and ion bombardment is important and is used in
materials processing, particularly during deposition and etching. Less is
known about the influences of the plasma radiation. The relative number of ions
and electrons which are incident on a surface depends on whether it is biased
as a cathode, an anode, or is electrically isolated. In this section, some of the
effects of ion bombardment and electron bombardment, and of plasma
bombardment of an electrically floating surface, are discussed briefly.

6.2 Ion Bombardment

The momentum exchange associated with ion bombardment can


cause rearrangement and ejection (sputtering) of surface atoms. The
94 Deposition Technologies for Films and Coatings

rearrangement can have dramatic effects on the structure and properties of a


growing film[53] and is of importance in the processes of ion plating and bias
sputtering. The ejection is important in the processes of sputter cleaning and
deposition. Accordingly, these mechanisms are discussed in considerable
detail in Chs. 5 and 13.
At low working pressures (collisionless ion transport), the energy of ions
bombarding a cathode surface will be about equal to the difference between
the cathode potential and the plasma potential (approximately equal to the
applied cathode-to-anode potential). The current density, bias voltage, sheath
thickness, and plasma properties are related by Eqs. 38 and 39.
At higher pressures, where ion collisions become important, the
bombarding flux consists of both ions and energetic neutrals because of
charge exchange collisions (see Fig. 2.10). Thus the average bombardment
energies are considerably less than the potential drop across the cathode dark
space. This is illustrated in Fig. 2.24 with a histogram showing the cathode
arrival energies of 100 Ar+ ions which have crossed a sheath having a voltage
Va in Ar gas at 2.5 mTorr. Approximately half (45%) of the ions arrive at the
cathode with energies corresponding to less than 10% of the sheath voltage.
The sheath parameters for the high pressure case are related by Eq. 39.

Figure 2.24. Calculated ion-energy distribution histogram showing the effect of


charge exchange (from Ref. 50).
Plasmas in Deposition Processes 95

Ion bombardment can greatly influence the processes involved in the


adsorption of molecules onto surfaces and their subsequent reactions. The
process of molecular adsorption[41] and surface compound formation is
illustrated in Fig. 2.25 for the case of gas phase etching. The CVD case with
the formation of a nonvolatile product is similar. Any of the steps shown in the
figure can be rate-limiting. Physical adsorption is due to polarization (van der
Waals) bonding. It is a nonactivated process and occurs with all gas surface
combinations under appropriate conditions of temperature and pressure.
Adsorption energies are typically less than 0.5 eV. Chemisorption involves a
rearrangement of the valence electrons of the adsorbed and surface atoms to
form a chemical bond. It involves an activation energy and has a high degree
of specificity between gas-surface combinations. Adsorption energies are
typically 1 to 10 eV. Molecules may be chemisorbed in their molecular state
or may dissociate into atoms. The latter case is known as dissociative
chemisorption. Dissociative chemisorption is generally a precursor to
compound formation, which is also an activated process. Various types of
chemisorption bond sites can exist on a solid surface. Thus both molecular
and dissociative chemisorption can occur simultaneously on the same
surface. Ion bombardment can influence these processes in the following
ways:
1. Ion bombardment can cause adsorbed molecules to dissociate,
thereby overcoming the activation energy for this process.

2. Ion bombardment can create surface defect sites which have


reduced activation energies for the occurrence of dissociative
chemisorption or for the formation of a solid compound.

3. Ion bombardment can remove (by sputtering) foreign species


from a surface. Such species may interfere with the dissociative
chemisorption of a preferred species.
Low-energy ion irradiation during film deposition can have dramatic
effects on the microstructure and microchemistry, and hence physical
properties, of as-deposited layers as discussed in detail in Chapter 13 and Ref.
53. Applications in which low-energy ion/surface interactions have been used
to modify film microstructure include: densification and increased oxidation
resistance of optical films; minimization or elimination of columnar microstructure
in microelectronic metallization layers; altering the state of stress, average
grain size, and preferred orientation; increased film/substrate adhesion;
enhanced conformal coverage; controlled magnetic anisotropy in recording
layers; and “low-temperature” epitaxy.
96 Deposition Technologies for Films and Coatings

Figure 2.25. Schematic representation of surface chemisorption and volatile


compound formation during dry etching.

While films in most of the above application areas are deposited by bias
sputter deposition or plasma-assisted CVD, experiments to isolate ion
irradiation effects are often carried out using ion beams. One example is
illustrated in Fig. 2.26 showing experimental and calculated (Monte Carlo
simulations) densities of CeO2 films deposited at ambient temperature by
simultaneous evaporation of Ce and O2+ irradiation from an ion-beam source.
The experiments were carried out as a function of ion energy Ei for an ion-to-
vapor flux ratio of Ji /Jv of unity.[54] The film density initially increased with
increasing Ei due primarily to ion implantation, recoil implantation, and, to a
lesser extent, sputtering of weakly bound species. However, an optimum Ei
for densification was reached as an increasing fraction of the ion energy was
lost deeper in the lattice leaving vacancies which could not be filled by arriving
vapor species. The optimum ion energy, which depends upon the masses of
the collision partners, was ≈200 eV in this case.
It should be noted, as discussed in Ch. 13, that while ion irradiation is
useful for increasing the density and modifying the microstructure of films
deposited at low temperatures, other irradiation-induced effects such as
increased defect densities occur simultaneously. This is shown in Fig. 2.27
from the work of Huang et al.[55] who studied the effects of Ar+ ion
bombardment during the growth of Ag films at room temperature using a dual
ion beam apparatus. They found that the grain size decreased while the
dislocation number density increased with increasing average irradiation
energy per deposited Ag atom. At elevated growth temperatures, however,
Plasmas in Deposition Processes 97

low-energy ion irradiation can have the opposite effect and actually reduce
residual defect densities in as-deposited films. This has been demonstrated
by Hultman et al.[56][57] who used electron microscopy to investigate the
dislocation structure in epitaxial TiN films deposited by bias magnetron
sputtering of Ti in pure N2 at growth temperatures between 550 and 850oC.

Figure 2.26. Experimental and theoretical values of the density D of CeO2 films
deposited at ambient temperature by simultaneous evaporation of Ce and ion-
beam acceleration of O2+ as a function of ion energy Ei for an ion-to-vapor flux ratio
Ji /Jv = 1. The bulk density of CeO2 is 8.1 g/cm3 (from Ref. 54).

In addition to modifying film microstructure, low-energy ion irradiation


is often used during thin-film growth to controllably alter the composition of
as-deposited layers. Examples include preferential sputtering from the
growing film during deposition of alloys[58]-[61] enhanced reactive gas
incorporation during deposition of compounds[62]-[65] and increased dopant
incorporation probabilities combined with better control of dopant depth
distributions.[66][67] Again, however, ion bombardment can result in potentially
deleterious effects, depending upon experimental design, such as rare-gas
incorporation in sputter-deposited films.[68]-[71] Mechanisms associated
with accelerated-particle/film interactions leading to changes in incorporation
98 Deposition Technologies for Films and Coatings

probabilities range from purely physical effects such as implantation and recoil
processes to irradiation-assisted chemistry.

Figure 2.27. The average grain size and dislocation number density nd in Ag films
deposited at room temperature as a function of the average energy 〈E〉 per
deposited atom (from Ref. 55).

Reactive ion etching technology also relies heavily on ion-irradiation-


induced effects for both stimulating chemical reaction channels and providing
anisotropy control. An example of the former is shown in Fig. 2.28 illustrating
results for Ar+-ion-assisted F2 /Si chemistry. F2 has a very low probability for
dissociative chemisorption on Si.[34] Consequently the etch rate via the
formation of volatile SiF2 is low. Ar+ irradiation greatly increases the etch rate
by promoting dissociative chemisorption. Fig. 2.28 shows that for the
experimental conditions listed, the Si sputter etch rate using 500 eV Ar+ was
2.5 Å/min. The etch rate increased by a factor of approximately 3.5 in the
presence of F2 gas. However, the Si etch rate due to F2 itself, in the absence
of Ar+ irradiation, was less than 0.1 Å/min.
Plasmas in Deposition Processes 99

Figure 2.28. The results of beam experiments designed to investigate ion-


stimulated interactions between F2 and Si (from Ref. 42).
100 Deposition Technologies for Films and Coatings

6.3 Electron Bombardment

Electron irradiation is a primary source of substrate heating during film


deposition by DC and RF diode sputtering.[72][73] Energetic electron, as well
as photon, irradiation of ionically bonded substrates has also been shown to
strongly affect film nucleation kinetics through the creation of charged surface
vacancies which act as preferential adsorption sites.[74]-[77] Reduced epitaxial
temperatures have been reported for many film/substrate combinations
including Si and Ge on NaCl[78] and PbTe on CaF2 .[76] Electron irradiation can
also give rise to surface chemistry during film growth through, for example,
excitation and ionization of adsorbed molecules into states leading to
dissociation, bond rearrangement, or desorption. Adsorbed organic molecules
can be polymerized by electron irradiation.
An example of electron-stimulated surface chemistry during plasma
etching is shown in Fig. 2.29. XeF2 dissociatively chemisorbs on SiO2 but
etching does not occur due to a high activation barrier for the reaction channel
leading to the formation of SiF4. Electron bombardment alone has been
observed to remove O from the surface of SiO2 and produce elemental
Si,[43][44] but it does not cause etching. However, when SiO2 is subjected to
electron bombardment in the presence of XeF2 , etching occurs at relatively
high rates, ≈ 200 Å/min in the example given in Fig. 2.29.[42]

6.4 Glow Discharge Surface Cleaning and Activation

Glow discharge cleaning, in which electrically isolated parts are immersed


in a low-pressure plasma, has been used for many years,[45] particularly for
glass and other non-conducting materials that cannot be subjected to simple
DC sputter etching. The process, although highly empirical, often provides an
effective final cleaning step prior to vacuum deposition. Working gases are
typically air, O2, or Ar.
Recent work on damage production and sputter cleaning of substrate
surfaces prior to epitaxial growth[79]-[82] suggests that low-energy ion-
irradiation-induced damage can be continuously annealed out at elevated
temperatures. Yu[82] used low-energy electron diffraction (LEED) to show
that the temperature required to maintain a Si(111)7x7 surface
reconstruction during Ne+ ion irradiation decreased from≈ 450 to 150 oC as
the ion energy was decreased from 500 to 80 eV. In sputter cleaning
experiments employing cross sectional transmission electron microscopy,
Gaverick et al.[81] used a low power RF plasma with an acceleration potential of 100
V to etch Si(100) substrates at 750oC immediately prior to Si deposition bylow-
Plasmas in Deposition Processes 101

Figure 2.29. The results of beam experiments designed to investigate electron-


stimulated interactions between XeF2 and SiO2 (from Ref. 42).
102 Deposition Technologies for Films and Coatings

pressure CVD. Rutherford backscattering spectroscopy combined with plan-


view and cross sectional transmission electron microscopy analyses showed
the film and substrate to be defect free.
Corona discharges, operated at atmospheric pressure, have long been
used to prepare polymer surfaces for processing. More recently, low-pressure
glow discharges are being used to modify surface chemistry and promote
adhesion with vacuum-deposited metal overlayers. X-ray photoelectron
spectroscopy (XPS) studies of the effects of O2 plasma treatments on ABS,
polypropylene,[46] and polystyrene[47] surfaces showed the formation of both
single and double C-O bonds. This, in turn, led to stronger metal overlayer
adhesion through the formation of oxygen bridge bonds between C and metal
atoms. Bodo and Sundgren[83] obtained similar increases in metal overlayer
adhesion for Ti on polyethylene using an Ar+ bombardment pretreatment to
remove low molecular weight impurities, promote cross-linking, and allow the
formation of a carbidic Ti-C interfacial layer as observed in XPS. Both Ar+ ion
irradiation and O2 plasma pretreatments also increased the adhesion of T on
polydimethylsiloxane (a silicone rubber) due to the formation of Ti-C and Ti-O
bonds.[84]

ACKNOWLEDGEMENTS

The authors gratefully acknowledge the support of the Joint Services


Electronics Program and the Materials Science Division of the Department of
Energy over the course of several years.
Plasmas in Deposition Processes 103

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104 Deposition Technologies for Films and Coatings

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18. Chen, F. F., in: Plasma Diagnostic Techniques, (R. H. Huddlestone and
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(1953)
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p. 131, Academic Press, New York (1978)
29. Waits, R. K., Ibid, p. 131
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35. Muschlitz, E. E., Jr., Science, 159:599 (1968)
Plasmas in Deposition Processes 105

36. Hollahan, J. R. and Rosler, R. S., in: Thin Film Processes, (J. L. Vossen
and W. Kern, eds.), p. 335, Academic Press, New York (1978)
37. Melliar-Smith, C. M. and Mogab, C. J., Ibid, p. 497
38. Yasuda, H. Ibid, p. 361
39. Kern, W. and Ban, V. S., Ibid, p. 257
40. See Ch. 7
41. Chemisorption and Reactions on Metallic films, (J. R. Anderson, ed.),
Academic Press, New York (1971)
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43. Thomas, S., J. Appl. Phys., 45:161 (1974)
44. Carriere, B. and Lang, B., Surface Science, 64:209 (1977)
45. Holland, L.,Vacuum Deposition of Thin Films, Ch. 3, Chapman and Hall
Ltd., London (1966)
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47. Burkstrand, J. M., Appl. Phys. Lett., 33:387 (1978)
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Greene, J. E, J. Appl. Phys., 61:552 (1987)
106 Deposition Technologies for Films and Coatings

57. Hultman, L., Barnett, S. A., Sundgren, J.-E. and Greene, J. E.,J. Crystal
Growth,92:639 (1988)
58. Winters, H. F., Ramondi, D. L. and Horne, D. E., J. Appl. Phys., 40:2996
(1969)
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Plasmas in Deposition Processes 107

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3

Surface Preparation for Film and


Coating Deposition Processes

Donald M. Mattox

1.0 INTRODUCTION

The termsurface preparation has many interpretations depending on the


application. For instance, atomically clean surfaces are of particular interest
in some studies and these surfaces may be prepared by cleaving a crystal (in
an ultrahigh vacuum), or other very careful surface preparation in ultra-high
vacuum.[1] Deposition techniques that are extremely sensitive to surface
preparation include molecular beam epitaxy (MBE) where great pains are
taken to clean the surface before the deposition of the epitaxial layer, and
surface chemical reaction studies where submonolayer coverages are impor-
tant. Other deposition techniques such as ion plating are less sensitive since
surface preparation is integral to the deposition process.
Substrate preparation for our purposes may be defined as the condition-
ing of the substrate surface prior to film/coating deposition in order to obtain
desirable processing and film/coating properties.[2] Substrate preparation
may involve the reduction of the type and amount of “contaminants” to an
acceptable level (cleaning), modification of the physical or mechanical
properties of the surface,activation of a surface species to enhance reactions,
or the addition of desirable species to the substrate surface to aid in nucleation
and reaction (sensitization). In the extreme case, surface preparation may
mean forming a “new” surface by adding a primer or glue layer.
Substrate preparation determines the surface properties and these are
directly or indirectly related to the film formation stages of adatom nucle–

108
Surface Preparation 109

ation, interface formation, and film growth. These, in turn, affect film
properties such as adhesion, pinhole density, porosity, film microstruc-
ture, morphology and mechanical properties. Often local surface prop-
erties determine film properties such as pinholes which determine the
product yield. Surface treatments that do not influence the product in a
desirable way are unnecessary and expensive.
Surface preparation is an integral part of any film/coating deposition
process. The objective of surface preparation processes is to allow the
fabrication of an acceptable product in the most reproducible and
economical way. In many cases there are allowable trade-offs between
surface preparation and subsequent processing. For example, an
increase in the deposition temperature may decrease the surface clean-
ing requirements. As the technological demands on films and coatings
increase, the need for better and more reproducible surface preparation
techniques also increases.
There is a wide variety of approaches to surface preparation and
each film-substrate couple, deposition process, and function requires
specific techniques and development. Typically, surface preparation
processes are developed empirically and controlled by good processing
specifications.
Process specifications and travelers are the key to obtaining repro-
ducible surface preparation processing, fabrication processes, and thus
product reproducibility. Specifications define the materials, equipment
and procedures that are to be used. Travelers define what has been done
to each individual part or lot. Specifications are the end-product of a
surface preparation development program. Travelers should contain a
response by the operator (e.g., time, meter reading, temperature, etc.).
An important factor in surface preparation is the condition of the
initial surface. A process developed for one surface condition may not
be satisfactory for another surface condition. The initial substrate
material, condition and history (contamination) should be known, and its
condition and properties should be specified where possible.
Monitoring of the surface preparation is often difficult since any
testing of the surface usually contaminates the surface. Generally,
processing relies on following specifications and possibly monitoring and
testing samples from each lot of surfaces.
In addition to the surface preparation process, the handling and
storage of prepared surfaces is an important part of the fabrication process.
If the prepared surfaces are used immediately or if the final step of the
cleaning process is done as part of the deposition process, the problems of
110 Deposition Technologies for Films and Coatings

maintaining the desired surface may be appreciably different than if the


surfaces are exposed to the environment and recontamination, or when
surface changes may occur with time.
Some film deposition processes and material combinations are more
sensitive to surface preparation processes than others. Some deposition
processes may have harmful surface effects such as in CVD where hot
corrosion of the substrate surface by reaction products may give poor
adhesion of the deposited material. In others, the deposition process may aid
in surface preparation; in CVD for example, hydrogen firing can clean the
substrate surface before the film precursor gases are injected.
In many deposition processes the surface preparation is a separate step
from the film deposition, but in some cases the deposition process includes
a surface preparation step (e.g., ion-plating/sputter-cleaning, hot dip galvaniz-
ing/fluxing, electroplating/off-plating). When surface preparation is separate
from the deposition process, the preparation of high quality films in many
cases requires a final in situ surface preparation step in the deposition
system.[3][4] An example of in situ surface preparation is the plasma cleaning
of glass prior to deposition of optical coatings and mirror surfaces.
This chapter covers a broad range of surface preparation techniques and
gives the reader an appreciation of the factors involved in developing a
reproducible surface preparation procedure for a specific application.

2.0 CONTAMINATION

A contaminant is any material on a surface that interferes with the


processing or performance of the surface. Contaminants may be reacted
layers such as oxides, adsorbed layers such as hydrocarbons, segregated
surface layers, or particulates. The contaminant may originate from:(i) natural
reaction with the ambient (oxides, sulfides), (ii) adsorption from the ambient
(hydrocarbons, water), (iii) processing steps (oils, fingerprints), (iv) handling
and storage (polymers, oils), (v) settling from the ambient (particulates), (vi)
electrostatic attraction in the ambient (particulates), (vii) outgassing or out-
diffusion from the bulk (plasticizers, water, solvents -plastics) or (viii) contact
with contaminated surfaces (silicone oils have a very high creep rate). Some
of this recontamination is unavoidable but some is avoidable with proper
fabrication, handling, and storage techniques.
Surface Preparation 111

Many contaminants can be predicted by knowing something about the


material in general and the way that it is normally fabricated and handled.
Examples are: (i) plastics absorb water and solvents easily, (ii) metals are
machined and deformed using oil lubricants, (iii) plastics are molded using
plasticizers to make the material fluid, etc.
The presence of contaminants can be detected without necessarily
identifying the composition of the contaminant. For instance, if a glass surface
is contaminated with a hydrocarbon (hydrophobic), the wetting angle of a fluid
drop will be high (doesn’t wet).[5] However, this type of test must be used with
caution since soap residue (hydrophilic) on the surface will make the surface
wettable like a clean surface. Adsorption of a tracer such as a radioactive
material may also be used to detect the presence of many contaminants.
Particulates originate from a variety of sources including: (i) wear
mechanisms,(ii) vaporization,(iii) vapor phase nucleation,(iv) evaporation of
aerosols, and (v) shedding of particles (skin, paper, cloth etc.). Particulates
adhere to the surface by weak chemical bonds (van der Waals),[6] but for small
particles, the most important adhering mechanism is condensation of water
in the “crack” between the particle and the surface. The evaporation of aerosols
and vapor phase nucleation are the most important sources of ultrafine
particles (10 -100 nm).
Surface adsorption can be very dependent on the surface and the
adsorbing species. For instance, most oxide surfaces do not adsorb O2 while
conducting and semiconducting surfaces do so easily.[7]

2.1 Recontamination

Recontamination of surfaces that have been cleaned is a major concern.


The recontamination rate and amount is a function of time, temperature, and
environment. For example, the oxidation of reactive materials begins
immediately on exposure to oxygen. On materials such as aluminum and
silicon, 10 Å of oxide will re-form within seconds then slowly increase in
thickness. Recontamination can also occur by adsorption of vapors from the
environment. Figure 3.1 shows the recontamination rate of cleaned gold
surfaces in various environments, as determined by coefficient of adhesion
measurements.[8][9] The contaminants are assumed to be condensed
hydrocarbon vapors. Note that recontamination begins immediately. Recon-
tamination can come from a number of other sources such as poor environ-
mental control, poor handling and storage, contamination by subsequent
processing, etc.
112 Deposition Technologies for Films and Coatings

Figure 3.1. Recontamination of clean gold surfaces in various environments as


measured by an Au-Au adhesion tester.[8][9]

Recontamination can also occur in the cleaning process itself. Complete


rinsing is necessary; otherwise residues from the processing chemicals will
recontaminate the surface. For example, in the final rinse, if the part is
submerged in the rinse tank then drawn up through the liquid surface on which
particles have accumulated, the particles will be painted on the surface and
must be removed before they are allowed to dry.
During storage and handling, the type and degree of recontamination is
dependent on: (i) time, (ii) temperature, (iii) environment and, (iv) surface
condition. Many contaminants “harden” with time and become more difficult
to remove, so after exposing the surface to a contaminating process or
environment it is best to clean the surface as soon as possible.
Recontamination can occur in the processing system and during the
processing. Reactive gas contamination (such as oxygen or water vapor) may
come from residual gases, gases desorbed from surfaces, real leaks and
virtual leaks. Heating and plasma-surface interactions enhance gas
Surface Preparation 113

desorption from surfaces. Outgassing from virtual leaks is time/temperature


dependent and processing should be designed to allow for desorption from
these sources. Often, in plasma processes, gas throughput is decreased and
contaminants may build up in the system, and proper gas throughput or clean-
flush-pump cycles should be employed to reduce contaminant levels. Exam-
ples of processing recontamination include: (i) plasma desorption and
activation of contaminants in plasma processing, (ii) outgassing of thermal
vaporization source material, (iii) particulate generation in the deposition
system, (iv) particulate deposition due to turbulence in a vacuum pumping
system, etc.
Vacuum and plasma deposition systems may have their contaminant
gas levels lowered by using the proper construction materials and techniques,
and conditioning their internal surfaces. Conditioning may be done by:
(a) Heating (bake-out, thermal desorption)[10]
(b) Oxidizing techniques (UV/O3), [11][12] (NO at 200°C)[13]
(c) Pump/plasma-discharge/pump to desorb wall species (ion
scrubbing: chamber is a grounded anode of the discharge)
using an inert gas, oxygen[14] or hydrogen plasma
(d) Physical or chemical sputtering of the walls using an inert or
reactive plasma species such as hydrogen[15] or compounds
containing chlorine or fluorine (chamber is cathodic to the
plasma)
Recontamination is controlled by controlling the processing and storage
environments.

3.0 ENVIRONMENT CONTROL

A key aspect of surface preparation is the control of the processing


environment to avoid contamination during processing and in subsequent
handling, storage, and processing. Environmental factors include:(i) partic-
ulates,(ii) ambient gases,(iii) processing gases,(iv) condensable vapors, (v)
fluids, and (vi) contacting solids.
Particulates come in all sizes. Metal smokes, aerosols (for example
sneezes and sea spray), viruses and tobacco smoke provide some of the
smallest particle sizes.
114 Deposition Technologies for Films and Coatings

Particulate contamination may be minimized by:


(a) Minimizing dust and particulate generating activities and materials
(e.g., clothing/skin/cosmetics, soldering, aerosols)
(b) Low velocity air currents, little turbulence
(c) Elimination of electrostatic charging of insulator surfaces
(d) Air filtration—“clean” rooms and stations
Particulates on smooth or patterned surfaces (semiconductor) can be
detected by operators using optical microscopes (slow and costly), or by
using a scanning laser microscope which detects scattered light. Ultraviolet
fluorescence can be used to detect some types of particles. Commercial
surface particulate detection systems are available.
Airborne particulate contamination may be effectively controlled by
filtration of air (90 - 100 ft/min), through directional(laminar flow) dry fiber filters
(HEPA—High Efficiency Particle Air). HEPA filters can be made from a variety
of materials, and filters compatible with the environment should be used. For
instance, it has been reported that salt particles on some filter fiber materials
absorb water and degrade the filter to the point that the filter produces
particulates. Filters allow the fabrication of clean rooms, clean benches,
etc.,[16] and must be utilized with care in order to maintain a low particle
count.[17]
It should be noted that air filtration doesnot remove vapor contamination.
In the United States, GSA- Federal Standards 209b utilize the number
of particles per cubic foot of volume with a size greater than 0.5 microns as the
standard (no particles larger than 5 microns). Air filtration with proper flow
patterns can provide a Class 100 or better environment (100 particles per ft3 ).
In 1986, a Class 100 clean room cost an estimated $400 - 500 US per ft2 (some
say $1000) to construct and $30 US per ft2 per day to operate. Continuous
care, maintenance and personnel training are necessary for a properly
functioning clean room!
Airborne particles larger than 0.5 microns are typically counted by light
scattering. Below 0.5 microns the particles are counted by first condensing
a vapor on the surface (like a contrail from a jet) and then using light scattering,
or by electrostatically charging the particle then counting it, or a combination
of the two methods.
Particles may be selectively attracted to charged surfaces. It is
therefore important to prevent electrostatic charging of critical surfaces.
When blowing with an air nozzle, the air should be ionized to prevent
Surface Preparation 115

electrostatic charge buildup. Permanently charged surfaces (electrets)


can be used to preferentially attract particulates. (Note: electret materials have
a permanent surface charge. They are mainly plastics that have been heated
and stretched in a DC electric field. Electret materials may be used in brushes,
filters, or as surfaces.)
Humans, their clothing, and behavior are a major source of contamina-
tion. In clean rooms, particulate generation is minimized by using special
body covering and other techniques. Ultimately robots may be used to
eliminate one of the major sources of particles—man.
In order to attain Class 1 and 10 environments and to control particles
smaller than 0.5 microns, it is proposed that substrate handling and process-
ing will have to be done in small compartmentalized units where the substrates
will not be exposed to the ambient environment. An example of such a system
is the completely-contained processing for metallizing and assembling quartz
crystal oscillators, where vapor and particulate contamination are eliminated
to prevent frequency shift due to contamination of the crystal surface during
use. In the future, more use is expected to be made of containers and
processing equipment that can be mechanically mated so as to only need
small volumes of Class 1 environments. Clean rooms may be less important
in the future!
Particulate contamination from processing gas supplies may be con-
trolled by filtration. Filtration at the point-of-use is often done with 0.2 micron
filters. Teflon filters should be used in oxygen lines. Particulate contamination
in flowing gases may be monitored by the scattering of a laser beam.[18]
Particulates generated in gas piping may be due to:(a) flaking from walls,
oxides, fluxes, polymers, (b) wear particles from mechanical equipment, (c)
contamination from opening system, (d) leaks; and affected by: (i) wear
(valves, pumps),(ii) mechanical vibration, (iii) thermal cycling, and(iv) changes
in flow velocity.
Contamination of gas supplies by unwanted reactive gases can be a
problem. In order to prevent gas contamination, one can: (i) use ultrapure
gases from tanks,(ii) use vapors from liquid gases (LN 2), (iii) purify the gases,
and (iv) be careful to have non-contaminating plumbing. Gas purification can
be used to remove some gaseous contaminants from gas supplies. Purifiers
use hot reactive beds (chips) (Ti, U, Cu) for removal of oxygen, or diffusion—
Pd for H2 , Ag for O2.
Commercial purifiers will purify silane, ammonia, hydrogen and the inert
gases to less than 10 ppb of O2, H2O, CO2 , and chlorinated compounds.
116 Deposition Technologies for Films and Coatings

Particulate contamination from fluids can be avoided by filtration.[19]


Care should be taken that the filter does not contaminate the fluid by extracting
(leaching) material from the filter (use Teflon™ or ceramic filter material).
Particulate contamination in fluids can be measured directly by light scatter-
ing.
Overflow tanks should be used in rinsing operations. Particulates from
the air tend to float on the surface of fluids (like water spiders) and paint on the
substrate surface as it is withdrawn through the fluid surface giving extensive
particulate recontamination of a cleaned substrate surface.
One ambient “contaminant” that should be controlled is electrostatic
charging. This is done by controlling the humidity (typically 40 - 45% relative
humidity) and using ground straps, antistatic coatings, and conductive
clothing on personnel who handle sensitive electronic devices. Electrostatic
charging of insulator surfaces contributes to particulate contamination by
attracting and holding particles. Electrostatic charging of surfaces can result
from blow-off with dry air. The dry air should be ionized before being used for
the blow-off operation.
The humidity in a clean room is normally controlled by dehumidifying
using cold surfaces (air conditioning, or air compression which is more costly)
then re-humidifying using steam or “foggers”. It has been proposed that the
humidifying operation is a major source of fine particulate contamination in the
clean room environment since the evaporation of aerosols is a major source
of fine airborne particulates.
Condensable vapor contamination is generally not controlled in the
processing environment except by venting and segregation of vapor producing
processes (soldering, electroplating, etc.) from “clean” areas. Hydrocarbon
vapors are the most common vapor contaminants and are controlled in the
small volumes used for handling and storage by selective absorption (freshly
oxidized aluminum), or by continuous oxidation in a ultraviolet/ozone atmo-
sphere (UV/O3—see cleaning section), or by condensation on cold surfaces.
Contaminant pick-up from surfaces is controlled by (control of) surface
materials, good housekeeping, smooth surfaces, use of coverings (finger cots,
lint-free cloth), high molecular weight organics (nylon and Teflon™) or metal for
holders and tools, and the use of vacuum tools for handling wherever possible.
Vacuum tooling for holding is preferable to other types of handling tools since
it minimizes abrasive transfer of material.
Special low-contaminant materials have been developed for semicon-
ductor processing applications; unplasticized polyethylene seems to be
Surface Preparation 117

best,and gloves of this material—furnished on paper rolls—is the recommend-


ed handling material. However abrasive transfer of organic materials from soft
plastics can be a problem. Woven nylon gloves prevent direct contact between
skin and surfaces but do allow sweat and body oils to wick through; rubber
finger cots should be worn under the nylon gloves. Alcohol, acetone, and many
other solvents which are used in cleaning processes will leach organics from
vinyl gloves. When using these solvents, unplasticized polyethylene gloves
should be used. Some vinyl (and about all latex) gloves may have powder on
them and, of course, this is a source of particulates.
Processing chemicals may be contaminated when received so ultrapure
chemicals (semiconductor grade) should be used. Improperly rinsed surfaces
which have impure chemicals on them (solvents, etchants) may leave residues
on drying. A chemical may become contaminated by being in contact with a
material which it dissolves or attacks: alcohol in contact with many plastics—
vinyl (use polyethylene - no plasticizers); Tygon™ removes phthalate plasti-
cizers (use Teflon™). Hydroscopic materials such as anhydrous chemicals
(alcohols) will pick up moisture from the atmosphere on exposure. Chlorinated
solvents may react with water vapor and become contaminated with HCl, thus
becoming corrosive.
If impure fluids are allowed to dry on a surface, they leave residues. These
residues are then very difficult to remove. Residue analysis consists of
allowing a volume of the chemical to evaporate and analyzing the residue which
remains (ASTM Method D1353-78), or analyzing the particulate residue from
a sprayed droplet (Wen). Often residue can be detected by the “fogging” of
what should be a clean glass surface on evaporation of some of the solution.
Residues can be minimized by rinsing in copious amounts of ultrapure water
or other appropriate solvent. Wet surfaces should not be allowed to dry without
rinsing with a low residue solution!
Chemicals can be contaminated by “carry-over” from a previous process.
Carry-over can be minimized by good rinsing between cleaning/processing
steps.
Metallic contaminates in electrolytes may result in surface contamina-
tion by displacement plating from solution (Zn and Sn)—don’t use galvanized
parts or soldered plumbing for transferring ultrapure chemicals such as water.
Sodium contamination is of major concern in silicon technology. Sodium
can come from leaching of soft glass, and fingerprints, as well as chemicals,
furnace liners, etc.
118 Deposition Technologies for Films and Coatings

The most common rinsing technique is to use successive rinses


(cascading rinses) in ultrapure water until the rinse water has a high resistivity
(> 15 megohm). This is called “rinse to resistivity”.
Ultrapure water (18 megohm - cm resistivity) is a widely used chemical
for cleaning and rinsing since it leaves a minimum of residues. Water purity
is typically measured using a conductivity cell that measures the ionic
concentration in the water. The semiconductor industry standards call for
detection of ionic impurities to 5 ppb NaCl equivalent. Specific ion content may
be measured using ion chromatography. Conductivity measurements do not
measure the organic or biological contamination and some type of residue
analysis should be used to measure these impurities.
Typical industrial specifications of ultrapure water for endpoint use are:
1. Resistivity—18 megohm continuous at 25°C
2. Particle count—less than 500 particles (0.5 microns or larger)
per liter
3. Bacteria count—less than one colony (cultured) per cc
4. Organics—less than one part per million
5. Total electrolytes—less than 5 parts per billion
6. Quantity requirements
7. Peak-level usage
The ultrapure water is made by:
1. Pretreatments—pH adjustment, coagulation, filtration
2. Reverse osmosis—semipermeable membrane (pore size 10-3
to-4 microns) rejects salts, dissolved solids (90 - 98%) and
organics (99%)—400 to 600 psi feedwater[20]
3. Degasification—remove dissolved CO2
4. Ion exchange resins (anion & cation)—remove ions by ex-
changing H+ for cations and OH- for anions.
5. Absorption materials (activated carbon)—remove organics
6. Filtration—remove particulates and biological matter, 0.2 mi-
crons for bacterial, 1.0 microns general
7. Ultraviolet radiation—kills bacteria on filters
8. Endpoint filtration
PVC plumbing should be used with ultrapure water since the pure water
is rather corrosive to metals (particularly to Cu, Zn). A high volume, ultrapure
water facility can be very large and expensive.
Surface Preparation 119

Bacteriological contamination can penetrate porous filters and has been


correlated to reduced device yields. Ultraviolet radiation or dissolved ozone
may be used to kill the bacteriological contaminate agents (Nebel). End-point
filtration is often used to make sure that bacteriological contamination does
not get on a part and leave a residue.
Activated carbon is an amorphous material with a high surface area (500-
1500 M2/gram). For use in fluids it has a pore size of about 1000 Å. For use
in gases it has a pore size of 12 - 200 Å. Activated carbon has a high affinity
for the absorption of organic molecules (better for non-polar than polar).
Catalytic agents (Cu, Ag, Cr) can be added to improve the absorption of
complex molecules (e.g., gas masks). Activated carbon filters do not remove
biological agents effectively.
An important part of the rinsing operation is the drying of the surface to
prevent particle pickup and adherence—see Sec. 5.0 on drying and outgassing.

4.0 CLEANING PROCESSES

“Cleaning” is the reduction of surface contamination to an acceptable


level. As a practical matter, a “clean” surface is one that contains no significant
amounts of undesirable material; thus what constitutes a clean surface
(degree of cleaning) depends on the requirements. The requirements range
from those concerned with monolayer coverages and atomically clean
surfaces to crude cleaning such as used for fusion welding. The economics
are such that unnecessary cleaning is to be avoided.
Cleaning processes should be as simple and effective as possible in
order to meet the requirements of the processing. Elaborate cleaning
processes are often expensive and self-defeating. Often there is a tradeoff
between the various stages of the cleaning process, handling/storage, and
subsequent processing, such that simple changes in one stage make
complex changes in another step unnecessary.
Effective cleaning generally consists of two or three stages. The first
is removal of gross contamination by fluxes, etchants, or abrasion. In the
second stage, the cleaning steps are designed to remove specific types of
contaminates such as particulates and organics, by solvents, saponifiers,
emulsifiers, oxidation techniques, etc. Cleaning solutions may have several
actions to attack specific contamination, such as detergents, solvents,
wetting agents and mild etchants. Next, the surface is rinsed, dried and
outgassed, (if necessary). Lastly, a final or insitu cleaning step may be used
120 Deposition Technologies for Films and Coatings

in a very controlled environment such as in a vacuum or plasma deposition


chamber or electrochemical solution.

4.1 Particulate Removal

Particulate contamination may be removed by detergent washing, liquid


spray (high pressure), blow-off, brush-off (in liquid or air), flow-off (liquid or
condensing vapor), or spin-off (copious fluids) techniques.
The most effective techniques seem to be detergents (with wetting
agents) and mechanical rubbing in a fluid. High pressure spray, brush-off
under liquid, and flow-off using condensing vapor are less effective. When
using any mechanical rubbing technique, care should be taken to prevent
contamination by abrasive transfer from the rubbing media. Use gentle
pressures.
Blow-off techniques have the advantage that they can be done after the
substrates have been placed in fixtures and even in a deposition system. The
best means of blow-off is to use filtered (0.2 micron) gas from a liquid nitrogen
tank. The gas is filtered in the nozzle and some nozzles allow ionization of
the gas with a radioactive source. Ionized gas should be used when blowing-
off insulator/organic surfaces to prevent electrostatic charge buildup which will
attract particles. When using high velocity gases for blow off one should be
careful not to entrain particles in the gas stream which could impinge on the
surface and stick.
An interesting technique studied at the University of Arizona Center for
Microcontamination Control is the use of high purity carbon dioxide “snow”
formed and blown from a gaseous carbon dioxide cylinder. Apparently the
snow scrubs the particles from the surface without leaving residuals or harming
the surface.
Blow-off of particulates is often done with dusters using canned pressur-
ized gases. One common duster uses dichlorodifluoromethane (DuPont
Freon™ 12—CCl2F2, BP: 30°C) which liquifies under pressure. Residuals from
the blow-off gases should be checked. Also check for residuals with the spray
can in an inverted position (liquid comes out) while spraying. Caution: when
using Freon™ dusters, make sure the gas canister is not intended for
recharging air conditioning systems—these canisters contain oil lubricants
which spray out, particularly when the can is inverted.
In optics, it is common to remove particulates from optical surfaces by
applying a film that is stripped from the surface—leaving hydrocarbon
contamination, no doubt.
Surface Preparation 121

4.2 Abrasive Cleaning

The removal of gross contamination by abrasive cleaning involves the use


of abrasive pads (sandpaper, emery paper, etc.), impacting particles (glass
beads, alumina/silica grit) in air or fluid streams (vapor honing), or mechanical
rubbing of particles in a fluid suspension. Grit blasting uses grit (fractured cast
iron, alumina) of varying sizes and shapes, accelerated in a gas stream, to
deform and gouge the surface. In addition to removing gross contamination,
grit blasting roughens and “activates” the surface, and the surface should be
coated as soon as possible after grit blasting (less than 2 hours). The Society
of Automotive Engineers (SAE) has specifications on grit size and type.
Particle bombardment places the surface in compressive stress and may give
unacceptable distortion of the part.
Glass bead blasting (dry) is a commonly used cleaning technique[21] but
may leave shards of glass embedded in soft surfaces. Particles may be
entrained in a high velocity gas steam by using a siphon system or a pressure
system (sand blasting equipment). Water soluble particles may be used for
abrasive cleaning (example: the Prophy-jet™ dental abrasive unit uses 5
micron baking-soda–magnesium-carbonate particles) and allows easy remov-
al of embedded particles. Bead blasting in a fluid (honing) is also used to clean
surfaces of gross contamination.

4.3 Etch Cleaning

Chemical etching may be used to remove some of the surface material


along with the contaminants. This is a very useful technique for getting the
surface into a “known” condition, removing surface layers (oxides), and
removing difficult-to-remove contaminates. Etchants may change the surface
chemistry! Common etchants for glass are sodium or ammonium bifluoride
and hydrofluoric acid. Note: when using HF extreme care should be taken to
prevent the HF from getting on the skin—bad chemical burns can result. (First
aid: flush with water then use magnesium sulfate to neutralize. A commercial
magnesium-sulfate/glycerin creme is available as Acid-Aid™.)
Acid “pickling” is a common technique for cleaning metal surfac-
es. [22][23] Acid cleaning of metals may have the detrimental effect of
introducing hydrogen into the surface and embrittling the metal. If hydrogen
embrittlement is a problem, either don’t use an acid (best) or give the etched part
a high temperature vacuum fire after etching. When using etchants for
cleaning, care must be taken to prevent selective removal (leaching) of
122 Deposition Technologies for Films and Coatings

surface constituents that are important to further processing (e.g., etching


glass bonded Al2O3 in HF results in selective removal of the glass [Ca-Mg-Al-
Si-O] which can weaken the surface and give problems with adhesion).[24]
Sometimes chemical etching does not remove some constituents from
a surface and leaves a “smut” that must be removed by another etching step.
For example, etching aluminum alloys with NaOH leaves a copper smutand/
or a silicon smut. These may be removed with HNO3 or HNO3/HF respectively.
In some cases an etchant can be devised that will etch all the constituents
uniformly; for instance, in etching aluminum containing silicon (1%) IC
metallization, concentrated nitric acid plus ammonium bifluoride (100 cc:6.8
gr) may be used. The etching mechanism is oxidation of the aluminum and
the silicon, then etching of the resulting oxides—the etchant actually etches
silicon more rapidly than the aluminum.

4.4 Fluxing

Fluxes remove oxides by dissolving them or by undercutting and floating


the surface layers away.[25][26]

4.5 Alkaline Cleaners

Alkaline cleaners are saponifiers which convert organic fats to water-


soluble soaps. Saponifiers are alkaline and are often in the form of hot
solutions. Strong alkaline cleaners have a pH of about 11. When using
alkaline cleaners, the surface should be neutralized by an acid prior to the
water rinse since alkali salts adhere strongly to surfaces. Clean oxide
surfaces strongly adsorb hydrocarbons which detergents and solvents nor-
mally will not completely remove. These hydrocarbons must be removed by
alkaline cleaners or oxidants.

4.6 Detergent Cleaning

In detergent cleaning, the detergent (soap) surrounds the particle


taking it into suspension without actually dissolving the material. This action is
helped by wetting agents which loosen the particles. Many detergents
contain phosphates. Liquid dishwasher soap is an excellent detergent
for many applications (also laboratory green soap). Alconox™ is also a widely used
laboratory cleaning solution though it is somewhat difficult to remove
Surface Preparation 123

from the surface and changes the surface pH. Ajax™ cleaner contains
abrasives and care must be taken to eliminate large chunks which can scratch
surfaces. A major problem with soaps is that metal ions such as the calcium
and magnesium which are found in hard water (high content of ionic material)
make the soaps insoluble and leave a residue. Therefore de-ionized water
should be used for detergent cleaning. There is a tendency for people to use
too much soap in a solution giving problems with rinsing and residues,
particularly if the solution is used cold. About 1 tablespoon of detergent per
gallon of water is generally sufficient.
The author has been told that a slurry of carbon black (from burning
acetylene) in de-ionized water mechanically abraded on a glass surface is very
effective in removing absorbed organic contaminants—I have no first hand
experience with this technique.

4.7 Chelating Agents

Chelating agents keep the normally insoluble phosphates that are


formed in hard water detergent cleaning in solution. Glass cleaning solutions
often use chelating agents such as ethylene diamine tetra-acetic acid (EDTA).

4.8 Solvent Cleaning

Hydrocarbon contaminants may be removed from surfaces by solvents


which dissolve the contaminants. Solvents may vary greatly as to their ability
to dissolve(solvate) contaminants, and their effectiveness needs to be known
by determining the “solubility parameter” for specific contaminants (if contam-
inate is known).[27]
Polar solvents such as water are used to dissolve polar contaminates
(ionic material) while non-polar solvents such as the chlorinated hydrocarbon
solvents, are used to remove non-polar contaminates (grease, rosin solder
flux, etc.). Often a mixture of solvents is used to solvate both polar and non-
polar contaminates.
Chlorinated hydrocarbon solvents are often preferred to hydrocarbon or
petroleum based solvents because of their low flammability (flashpoint),
though there is concern with the toxicity and carcinogenic properties of some
of these materials.
Chlorinated solvents may react with water to form acids. The acids
react with metals causing corrosion. Often stabilizers are added to the
chlorinated solvents to reduce their tendency to react with water (hydrolyze)
124 Deposition Technologies for Films and Coatings

and form acids. Examples of such stabilizers in trichloroethylene (TCE) are:


(i) 1,2 butylene oxide,(ii) cyclohexene oxide,(iii) para-tert-butyl phenol and(iv)
1-propanol. If stabilizers are not used, then the pH of the cleaner should be
monitored to keep a pH of 6 - 7 (IPC Test Method No. 2.2.30; ASTM-D-2989
“Acidity/Alkalinity of Halogenated Organic Solvents”). If there is a possibility
of solvent trapping which prevents complete rinsing, particularly in a stressed
metal joints, chlorinated solvents should not be used since residues will
enhance stress corrosion in those areas. Cleaners containing chlorine-based
oxidants may present the same problem.
Chlorinated halogen solvents are coming under increasing scrutiny as to
their toxicity. Stringent exposure levels are being imposed by OSHA/EPA and
it is anticipated that they will get even more stringent.
Solvent properties to be considered include:
1. Suitability for application technique (spray, vapor degrease,
recycling, etc.).
2. Selective solvency (solubility parameter)—ability to solvate the
contaminants of interest.
3. Wetting characteristics—depends on viscosity and surface ten-
sion. Allows the solvent to wet surfaces and displace soils 17.2
to 21.4 dynes/cm3 for Freon™ solvents.
4. Miscibility with other solvents (to generate solvents for particular
applications)—azeotropes = constant boiling point mixture of two
or more components, i.e., composition of vapor is the same as
the liquid.
5. Safety and environmental concerns—flammability, toxicity
(breathing, contact) carcinogenicity, effect on the ozone layer,
OSHA and EPA regulations present and future.
6. Stability—thermal and chemical, nonreactive with parts to be
cleaned (chlorocarbon and alcohol solvents may react with Al,
Mg, Be, Zn [white metals] to form inorganic salts which give
residues etc). Photochemical stability. Solvents may leach
materials from some container and piping materials.
7. Low energy requirements—low boiling points to give vapors
without high energy requirements (vapor degreasers), parts may
be handled immediately after cleaning.
8. High density—solvents displace soils and float them to the
surface of the cleaning system (e.g., 9.6 to 13 lb/gal for Freon™
solvents)(ASTM-D- 2111 “Specific Gravity of Halogenated Organ-
ic Solvents and their Admixtures”).
Surface Preparation 125

Typical solvent systems are:


1. DuPont Freon™ TF (trichlorotrifluoroethane)
2. Azeotrope mixture of TF with methylene chloride (50%) = Freon™
TMC (metal degreasing)
3. TF with ethanol (4%) and nitromethane (1%) = Freon™ TES (rosin
fluxes and ionic contaminates from solvent sensitive assemblies)
4. TF with ethanol (4%) = Freon™ TE (defluxing)
5. TF with acetone (11%) = Freon™ TA (broad range of solvency)
6. Blends of TF with methanol (6%) and nitromethane (0.25%) =
Freon™ TMS (deflux)
7. TF with anhydrous isopropanol (35%) + stabilizer = Freon™ T-P
35 (cold cleaning )
8. TF with ethanol (35%) = T-E 35 (organic and polar solvents).
This data is taken from DuPont solvent formulation data bulletin no. FST-
5. Other equivalent solvents and solvent blends are available. Caution: Freon™
with water (or alcohol which takes up water) will corrode aluminum, zinc, and
cadmium (white metals) if left in contact for a period of time; aluminum will take
fluorine from the molecule. Aluminum parts should be dried immediately,
preferably by vacuum bake, but at least hot-air-dried to minimize corrosion.
There is also a safety concern: extended breathing of halogenated solvents
can cause liver damage (like glue sniffing). These solvents must be used in
a well ventilated area such as a chemical hood.
Elevated temperatures are often used to increase detergent, solvation,
and etching activities. This is often done using immersion heaters (materials
must be compatible) or externally heated tanks.
Abrasives may also be used in conjunction with solvents to loosen
contaminants from the surface.
Application methods of solvent and fluid type cleaning techniques
include: (i) soaking,(ii) mechanical scrubbing,(iii) mechanical agitation,(iv)
spraying (low and high pressure), (v) vapor condensation (vapor degreasing),
(vi) hydrosonic agitation 2 Hz - 20 kHz),(vii) ultrasonic (20 - 60 kHz) agitation
(cavitation) and(viii) megasonic agitation (850 - 900 kHz) (pressure wave).
In mechanical scrubbing, lint-free, de-sized cloths make good toweling
(sizing can be removed by multiple washings). For brushes, there is a variety
of materials including: camel hair, mohair, polypropylene, Teflon™ and
nylon. In semiconductor technology, mechanical scrubbing combined
126 Deposition Technologies for Films and Coatings

with high pressure fluid jets (2000 - 3000 psi) is a standard cleaning
procedures.
Spraying may be performed at low pressure (50 psi) or at high pressure
(1000 psi). Spray systems often use copious amounts of material so the liquid
is usually recycled. This means that after the fluid becomes contaminated
above a certain level it must be replaced. With increasing concern about
solvent vapors, many of the newer systems are self-contained with condens-
ers to trap the vapors and allow them to be recycled. Some systems allow the
purification of the solvents by distillation.
Vapor degreasers operate by putting a cold part in hot vapor above a vapor
degreaser “sump”. The solvent condenses on the surface and flows off into the
sump. Cleaning action only occurs during the condensation process, and
when the part reaches a temperature where the solvent doesn’t condense,
cleaning stops and the part should be removed. Parts should never be
immersed in the sump fluid. Fluid in the sump should be changed when it
becomes contaminated. Figure 3.2 shows a schematic of a typical old-style
industrial degreaser for cleaning large parts either by spraying or by vapor
degreasing. This type of system allows the escape of vapors and is becoming
increasingly undesirable.

Figure 3.2. Industrial vapor degreaser with spray wand.


Surface Preparation 127

Ultrasonic cleaning[28] relies on the jetting action of collapsing cavitation


bubbles to give a high pressure jet of fluid against a surface. The cavitation
bubbles are formed by the tension wave portion of an ultrasonic wave in a fluid
media. The ultrasonic wave is produced by a transducer typically operating
at 20 - 40 kHz at about 100 watts/gal of fluid. The cavitation nature (size of
bubbles) of the fluid depends on its vapor pressure and temperature (e.g., 3
microns for water at 60°C at 40 kHz). The jet pressure may be as high as 300
psi. The colder the media, the more energetic is the cavitation jetting. The
bubbles nucleate in the fluid or on a surface. With a fixed frequency
transducer, nodes and antinodes are formed (standing waves) which give
variations of cavitation in the fluid. In order to overcome this effect, swept
frequency generation is used with one system at 40 kHz ± 2 kHz. (Frequency
modulation at full amplitude is best for sweeping frequency). If frequency
sweeping is not used, the parts should be moved from one region to another
in the tank.
Variables in ultrasonic cleaning include:
Nature of the transducer fluid (density, vapor pressure)
Temperature of fluid
Gas content of the fluid (function of degassing of fluid and
entrainment with parts)
Energy of cavitation implosion (temperature, pulse height of
ultrasonic wave)
Average cavitation density (volume or surface) with time
Average cavitation density with position in tank
Shape of the ultrasonic pulse
Nature of ultrasonic cycle train (“quiet time”, “degas time”, cycles
per train)
Ultrasonic cleaning has to be used with care since the jetting action
caused by the collapsing gas bubbles on the surface can cause erosion
and introduce fractures in the surface of brittle materials, leading to poor
adhesion. For example: in high power laser applications it has been shown
that improper ultrasonic cleaning increases the light scattering from the
surface, indicating surface damage or possibly surface roughening. Also
ultrasonic agitation has been shown to create particles by erosion of the
container surface, with stainless steel giving 500 times as many particles
as Pyrex™ glass. In all cases studied, particles of the container were
produced. Resonance effects may also damage some parts in an ultrasonic
128 Deposition Technologies for Films and Coatings

cleaner.[29] Surface damage can be controlled by adjusting the energy


density of the jets or controlling the time of application.
The ultrasonic cavitation may be generated by magnetostrictive or
electrostrictive transducers. The power may be from 500 watts for a small
model (5 gallon) on up to very high powers. Ultrasonic erosion of aluminum
foil (or an aluminum metallized glass surface) may be used as an indication
of the cavitation power to which a surface is exposed in the ultrasonic
solution.[30] A general rule is that ultrasonic cavitation will generate 10 holes
in a 1 X 2 inch aluminum foil of 2 mils thickness in 10 sec. The cavitation ability
is dependent on how well the energy is coupled to the fluid.
Fixturing is very important in ultrasonic cleaning to insure that all
surfaces are cleaned. Parts should be held parallel to the stress wave
propagation direction. Energy absorbing containers, such as polyethylene or
TeflonTM beakers and fixtures, should not be used since they absorb the
ultrasonic energy.
Hydrosonic cleaning utilizes hydrodynamic rather than electric genera-
tion of the fluid pressure waves.[31][32] The megasonic agitation system is
applicable to smooth surfaces, particularly for removing particles, but doesn’t
work on configured surfaces since the pressure wave is easily shadowed.

4.9 Oxidation Cleaning

Oxidation cleaning relies on the formation of volatile or soluble oxidation


products. If non-soluble products result from oxidation (e.g., silicone to silica)
then a residue may be left on the surface. Oxidation cleaning may be used
for surfaces that are normally oxides (glass, ceramics, metals that form
coherent oxides) or that don’t oxidize (gold).
High temperature oxygen or air fire is an excellent way to clean surface
that can withstand high temperatures. For instance, to clean Al2O3, air fire
the material to 1000°C then remove it while still warm (to prevent moisture
condensation) and place in container. In thermal oxidation, the type of
contaminate may be determined by monitoring the selective oxidation
products as a function of temperature.
Oxygen (or air) plasmas are very effective in removing hydrocarbons and
absorbed water vapor from surfaces.[33] However the oxygen plasma may
oxidize materials, which may be undesirable. Where oxidation is a problem,
hydrogen plasmas may be used to remove hydrocarbons and adsorbed water
from surfaces.
Surface Preparation 129

The use of oxidation by ultraviolet radiation, which generates ozone and


causes bond scission of the hydrocarbon contaminates (UV/O3 cleaning) has
greatly simplified the production, storage and maintenance of hydrocarbon-
free surfaces.[11][12] UV/O3 exposure also allows the controlled thin-layer
oxidation of surfaces such as silicon and silicon-germanium alloys. In a
typical UV/O3 cleaning/storage chamber, the UV is provided by a mercury
vapor lamp in a quartz envelope so that both the 1849 Å and the 2537 Å
radiation is transmitted. The radiation intensity is 1 - 10 milliwatts/cm2 at the
substrate surface. The chamber is of aluminum with no organic seals, and in
a correctly operating system, ozone can be smelled when the chamber is
opened (10 ppm ozone). The temperature in the chamber is typically 150°F
during the cleaning operation. A heater may be used to decrease the
possibility of moisture condensation when the chamber is open. Typical
exposure times for cleaning are from a few minutes to remove a few
monolayers of hydrocarbon contamination to hours, days, or weeks for
storage of cleaned surfaces. The UV/O3 cleaning technique is also useful for
cleaning holes (vias) in surfaces.[34] Caution: when there are corrosive agents
(or materials that can decompose into corrosive agents, e.g., Freon™) in the
atmosphere, we have found that the UV/O3 greatly enhances the corrosion
rate. For instance, a little chlorine in the atmosphere causes stainless steel
to rapidly corrode.
Hot (115°F) concentrated sulfuric acid plus ammonium persulfate is an
excellent oxidizing cleaner. The addition of the ammonium persulfate (solid)
to the hot sulfuric forms an unstable compound that decomposes releasing
ozone. The ammonium persulfate should be added just prior to the immersion
of the substrate into the solution. This treatment is sometimes followed by a
brief dip in a 10:1 solution of water and HF or immersion for 20 minutes in a
solution of hydrogen peroxide and ammonium hydroxide.

H2 O : H2O2 (30%) : NH4 OH (29%) at 80°C

A hot chromic-sulfuric acid cleaning solution prepared from potassium


dichromate and sulfuric acid provides free oxygen for cleaning but has a
tendency to leave residues unless rinsed very well.

K2 Cr2O7 + 4H2SO4 → K2SO4 + Cr2(SO4)3 + H2O + 3O

Boiling hydrogen peroxide (30%) is a good oxidizing solution. Unstabi-


lized H2 O2 must be used, and it should be stored in a refrigerator to slow
130 Deposition Technologies for Films and Coatings

decomposition. Hydrogen peroxide is sometimes used with ammonia with a


ratio of 8 (H2O2) : 1 (NH3) : 1 (H2O). Caution: 30% H2O2 is extremely reactive
so it must not contact oxidizable materials such as organics.
Oxidation cleaning may be performed using chlorine-containing chemi-
cals. For example, a slurry of sodium dichloroisocyanurate (pool chlorine—
63% available chlorine) in water may be used to scrub an oxide surface to
remove hydrocarbon contamination.

4.10 Volatilization Cleaning

Heating volatilizes some surface contaminates such as water. This


technique can often give problems because it may pyrolyze hydrocarbons into
carbonaceous forms which are then very difficult to dissolve. The temperature
may also cause changes in the surface composition and morphology. The
surface composition may change due to volatilization of a constituent or by
segregation of a bulk constituent to the surface.
Thermally driven surface segregation can be greatly influenced by the
nature of the environment (vacuum or reactive gas). Ga from GaAs surfaces
may be thermally etched to give improved electronic properties at the resulting
film-substrate interface.[35] In the case of some glasses, high temperatures
tend to cause particles of oxidized glass constituents to form on the surface.
Thermal treatment of silicon to >700°C removes the oxide but the surface
begins to vaporize and form surface features.[36]
Thermal cleaning is used to clean porous surfaces by increasing the
surface diffusion of the contaminate from the subsurface regions to the surface
where it can be removed.

4.11 Hydrogen Reduction Cleaning

Hydrogen reduction of oxide layers may be used to clean surfaces in a


furnace environment. Figure 3.3 shows the stability of a number of metal
oxides at various temperatures and varying dew points of the hydrogen. Note
that, depending on the dew point and the temperature, a hydrogen furnace can
be either reducing or oxidizing! In some cases forming gas (90% N2 , 10% H2)
is used instead of hydrogen since it is less explosive. Hydrogen reduction has
been used to clean the oxide from silicon surfaces at 900°C.
Surface Preparation 131

Figure 3.3. Metal-metal oxide equilibria diagram for hydrogen plus water as a
function of temperature.

4.12 Electrolytic Cleaning

Electroetching may be used to anodically remove metal from a surface


(along with contamination) and usually roughens the surface. The higher the
current density, the more roughening occurs. For stainless steel, the surface
is passivated by oxides (hydrated on the surface) at low potentials, while at
higher potentials, the surface is etched.[37]
Carbon fibers often have a weak surface layer and this layer may be
removed by anodically electroetching (oxidizing) the surface followed by
hydrogen firing. This treatment increases the strength of the carbon fiber and
improves the bond when the fiber is used as part of a composite material.
132 Deposition Technologies for Films and Coatings

Electropolishing removes material and smooths the surface.[38][39] The


smoothing action is due to protection of the flat areas by a deposited material
(usually a phosphate) and the preferential erosion of the peaks. Electro-
polishing leaves a surface film (phosphate) which has to be removed (hot water
scrub) to obtain a clean surface.

5.0 DRYING AND OUTGASSING

After fluid cleaning and rinsing it is important to dry the surface quickly
in order to prevent the liquid film from collecting particles. Drying may be done
by blowing the surface with filtered gas (from a liquid nitrogen tank) or by
displacing the water by a high vapor pressure solvent such as anhydrous
alcohol which dries rapidly. The best technique is an “alcohol vapor dry” where
the cold surface is immersed in the vapor above a heated anhydrous alcohol
sump. The cold surface condenses the alcohol vapor which flows off into the
sump taking water and particulates with it. When the surface becomes hot
condensation ceases and the hot part, when withdrawn, will rapidly dry. Spin
drying tends to leave liquid along the outside edges of the substrate which may
result in contamination of this area. If spin drying is used the part should be
flooded with copious amounts of ultrapure water during spinning.
Anhydrous alcohol, which displaces water and dries quickly, is one of the
best materials with which to wipe and flush surfaces—it leaves the least
residue; however it is not a very good solvent. Alcohol should only be used with
polyethylene gloves. Isopropyl alcohol (IPA) is most commonly used since
it requires no denaturant. Ethyl alcohol is generally more pure but requires the
use of denaturants. Alcohol is denatured to avoid tax and accountability.
Denaturants range from ethyl ether to kerosene (over 200 denaturants
allowed). Low residue denaturants include methanol (5% by vol.) and acetone
(10% by vol.). It is best to use pure (undenatured) alcohol if possible.
Anhydrous alcohols can take up water from the atmosphere and lose their
ability to displace water in the drying operation
Drying and outgassing is especially important for polymers and
porous materials which absorb solvents and water. It is often easier to dry
and outgas prior to placing the materials in a deposition chamber. The
usual technique is to heat the material (to some temperature that doesn’t
degrade it) in a vacuum (vacuum bake) or desiccated environment. A
common mistake is to vacuum bake the material for an insufficient time—often many
Surface Preparation 133

hours are necessary. The time-temperature-vacuum conditions necessary


to outgas the material can be determined by weight loss measurements.
Microwave energy may be used to heat polar molecules such as water
(also alcohols, aldehydes, ketones, amides, amines, nitrate, cyanides,
proteins, unsymmetrical halogenated hydrocarbons, and ionic solutions) as
long as there are no electrical conductors present. Microwave heating and
drying of such materials may be more effective than conventional thermal
heating.[40]

6.0 MONITORING OF CLEANING

The best monitoring techniques monitor those elements of the process


which are critical to providing a surface that can be further processed. The
testing of surface preparation such as cleaning will invariably result in
contamination of the surface, so tested surfaces can not be used for
subsequent processing. In some cases, sample surfaces may be tested for
certain properties in order to determine surface conditions. These tests
include(i) contact angle of a water drop (wetting angle),(ii) sheeting behavior
of a fluid draining over a surface, (iii) nucleation of moisture on a surface and
(iv) friction and adhesion tests.
A common check on the cleaning of a glass surface uses the contact
angle of a water drop on the surface of the cleaned glass. If the surface has
no hydrophobic contamination (oil, hydrocarbons, silicones, etc.) the water
will wet and spread over the surface giving a contact angle of <5° as measured
with a contact angle goniometer. This technique must be used with some care
since, if a hydrophilic contaminant such as a soap residue is present, the
contact angle will be low even though the surface is contaminated.
If a glass surface is clean, water will sheet over the surface without
breaking up to avoid areas of contamination (water break test). Observation
of this sheeting during the rinsing operation is a check that an experienced
operator can use in the cleaning process. If the water film breaks up, then the
surface is not clean. This breaking up into “legs” is how a wine taster judges
the viscosity of a wine (i.e., they need a dirty glass).
If you breathe on a clean glass surface, the moisture will condense
uniformly over the surface giving the “black breath figure”.[41] You can see this
effect in your bathroom where condensing moisture shows up the dirt swipes
on the mirror.
A clean glass surface has a high coefficient of friction (“squeakyclean”).
134 Deposition Technologies for Films and Coatings

7.0 IN SITU CLEANING

In situ cleaning is done in the deposition system and is intended to remove


the small amount of contamination that has developed since the primary
cleaning process. Some of the cleaning processes that have already been
described are applicable to in situ processing but others are more desirable.
In situ cleaning in an electrolytic environment may be done by etching or “off-
plating” by making the surface an anode of an electrolytic cell. In situ cleaning
techniques for vacuum or plasma processing include:
! Oxygen plasma cleaning
! Hydrogen plasma cleaning
! UV/O3 cleaning
! Volatilization
! Ion scrubbing
! Sputter cleaning
! Reactive plasma etching (RPE)
! Reactive ion etching (RIE)

7.1 Ion Scrubbing

Ion scrubbing of a surface occurs when the surface is in contact with a


plasma and the plasma sheath potential accelerates low energy ions to the
surface with sufficient energy to desorb absorbed gases. The technique is
often supplemented with a reactive gas to give a version of reactive plasma
cleaning. The technique is widely used in the optical coating business for
substrate preparation in the vacuum deposition system (in situ cleaning) using
an air discharge.[41]

8.0 PLASMAS

Plasmas are gaseous media which contain enough ions and electrons
to be electrically conductive and generally volumetrically neutral. Energy is
introduced into the plasma by the acceleration of electrons in a DC, RF or
microwave field. These electrons then fragment, excite, and ionize particles
by collisions. A processing plasma is one that is used in processing a
material. In a processing plasma, the volume density of the various gaseous
Surface Preparation 135

species and their energies depend on a number of factors including: method


of generating the plasma, processing parameters, and system geometry. In
a processing system, the local plasma densities and properties may vary
significantly due to electrode configurations, presence of surfaces, and other
geometrical factors.
In cleaning processes, the substrate may be in plasma generation
chamber or may be exposed to the plasma in a “downstream” location(remote
plasma processing). In the plasma chamber the substrate may be on a driven
electrode or placed where it is only exposed to the plasma, hence acts like
a wall, though it may be exposed to a variety of plasma-related effects such
as induced bias, electron bombardment, and energetic neutral bombardment.
The downstream location avoids many of these plasma-related effects.
Plasma discharges may also be used as a source of ion beams where ions
are extracted from the plasma chamber and accelerated to a high energy
by using a grid extraction system. Beam intensities are limited by the
extraction grid.

8.1 Generation of Plasmas

In plasmas used for plasma processing, the electron energy is increased


by acceleration in electric field gradients. The most typical configurations for
generation of plasmas are: (i) DC diode discharge, (ii) RF (radio frequency)
discharge,(iii) electron emitter sustained discharge,(iv) magnetron enhanced
discharge,(v) microwave discharge,(vi) vacuum arcs, and (vii) plasma arcs.
Figure 3.4 shows a schematic of some of these plasma generation configu-
rations.
DC Diode Discharge. The DC diode configuration consists of an anode
and a cathode immersed in a low pressure gas. At the cathode, the cathode
potential (-) attracts ions from the edge of the plasma region, and they are
accelerated across the cathode fall region to impinge on the cathode (target).
The cathode fall region, which surrounds the cathode, is where most of the
potential drop in a DC discharge is to be found. The region between the
edge of the cathode fall region and the anode is the plasma region where
there is little potential drop. In the DC discharge, energetic particles (ions
and neutrals) impinging on the cathode (target) cause the ejection of
secondary electrons which are then accelerated across the cathode fall
region and create ions which sustain the discharge process. The
secondary electron emission coefficient of a surface depends on the
chemical nature and morphology of the surface. Oxides typically have
higher electron emission coefficients than do metals. The secondary
136 Deposition Technologies for Films and Coatings

Figure 3.4. Plasma generation configurations: (a) DC diode, (b) DC diode with
permanent magnets giving a planar magnetron (c) RF plasmas with planar
electrodes immersed in the plasma, electrodes external to a dielectric wall and a
coil immersed in the plasma, (e) electron emitter (thermoelectron) with magnetic
confinement and (e) microwave cavity.

electrons can be accelerated to high energies and impinge on the anode or


other surfaces in the system. This can give rise to extensive heating of
surfaces (substrates) in the system. The DC discharge requires a relatively
high gas pressure (> 10 microns argon).
In the cathode fall region, some of the ions may be neutralized by
charge exchange processes which give rise to energetic neutral particles
which are not affected by the applied electric field. The result is fluxes of
Surface Preparation 137

energetic ions and neutrals with a spectrum of energies that bombard the
cathode.
In order to sustain a discharge, the secondary electrons must create
enough ions to compensate for losses. If the anode or ground surface is
brought too close to the cathode, the discharge is extinguished. This effect
can be used to confine the DC discharge to areas of the cathode surface where
bombardment is desired—other areas may have the bombardment prevented
by having a ground shield in closed proximity to the surface. The Paschen
curve gives the relationship between breakdown voltage and the minimum
anode-cathode separation in a gaseous environment. Insulator surfaces
cannot be used as cathodes in a DC diode configuration since charge buildup
on the surface will prevent ion bombardment.
In addition to causing the ejection of secondary electrons, high energy
ions and neutrals which impinge on the target (or other surfaces) cause the
physical ejection of surface atoms (physical sputtering) by momentum
transfer processes. The sputtered particles leave the surface at higher-than-
thermal energies but may be rapidly thermalized by collisions in the gas
phase. The sputtered particles may be scattered back to the target surface;
this effect is more prominent the higher the gas pressure. Some of the
energetic ions that bombard the cathode may be reflected as high energy
neutrals.
The electrical current measured in the DC cathode circuit is the sum of
the charge due to the ion flux to the target and the secondary electron flux away
from the surface. Therefore, the cathode current density and cathode voltage
do not specify the flux and energy of the impinging ions. However these
measurements (along with gas pressure and gas flow) are typically used to
specify the plasma parameters in DC diode plasma processing.
Typically a DC diode discharge plasma is “weakly ionized” with many
more neutral particles than ions (104-107 : 1). It will also have a low electron
temperature and an even lower ion temperature. If molecular gas species are
present in the discharge, many radical species will be formed in the plasma
and they will generally greatly outnumber the ions.
Any surface in contact with the plasma will be subjected to a flux of ions,
neutrals and electrons. A sheath potential will be developed because of the
greater mobility and energy of the electrons as compared to the ions. This wall
potential (typically 3 - 10 volts) will accelerate ions from the plasmas, giving
rise to ion scrubbing of the surface.
In plasma processing, the DC diode configuration has many advantages:
(i) a rather uniform plasma can be generated over large areas; (ii) power
138 Deposition Technologies for Films and Coatings

input (watts/cm2) can be very high;(iii) the power supplies are rather simple,
inexpensive and powerful; (iv) process reproducibility can be attained by
controlling the geometry, gas pressure, and target power (current and
voltage); and(v) sputtering of surfaces may be used as a source of depositing
material. It also has some disadvantages: (i) surface geometries can result
in focusing effects giving non-uniform bombardment; (ii) electron heating of
surfaces can be extensive; and(iii) insulating surfaces cannot be bombarded.
RF Discharge: At high frequencies in a capacitively-coupled discharge,
the electrons oscillate in the changing field thus gaining energy, and by
collision with atoms, create ions and more electrons. Typical RF power
supplies operate at 13.56 MHz (USA industrial frequency) with peak-to-peak
voltages of greater than 1000 volts. The plasma acts as a low density electrical
conductor and the RF field penetrates quite some distance into the plasma.
When the driven RF electrode is a conductor, the surface is bombarded by ions
from the plasma during the half-cycle that the electrode is negative.
If the surface of the RF electrode is an insulator (backed by a conductor),
the metal-insulator-plasma acts as a capacitor and the surface potential that
appears on the insulator surface alternates between a low positive potential
(because the electrons have a high mobility) and a higher negative potential
(because the ions have a relatively low mobility). Ions are extracted from the
RF plasma during the negative portion of the cycle and bombard the insulator
surface. The RF potentials in the plasma can be determined using capacitive
probes. The ion energies bombarding a surface may be determined using a
sampling orifice, a retarding grid and a mass spectrometer.
In capacitively-coupled RF discharges, the plasma potential, hence the
sheath potential at the electrodes, can have a time-varying value of tens to
hundreds of volts. When the electrodes have different effective areas, the
plasma potential can also have a large DC potential with respect to one or more
of the electrodes. These factors affect the distribution of ion energies incident
on the electrode surfaces in an RF discharge. Small area electrodes will attain
higher voltages than large area electrodes and the electrode potentials can be
varied using external capacitance in the circuit.
The amount of energy that is coupled into the RF discharge depends on
the impedance matching (reflected power) and coupling losses to other
surfaces (stray losses). In RF plasma processing, it may be important to
determine just how much energy is actually being coupled into the
plasma.[42] RF power may be coupled to the plasma using metal electrodes
Surface Preparation 139

external to a dielectric wall, or the RF plasma may be excited using immersed


electrodes. Very high plasma densities and ionization can be attained in RF
driven plasmas and the discharge may be established at lower pressures than
the DC diode discharge.
Surfaces immersed in an RF plasma will assume a self-bias. This bias
depends strongly on the surface areas and configurations. Often the value of
the self-bias is not known (or controlled) and can vary within the system, giving
anisotropic bombardment effects.
In plasma cleaning, the RF discharge has the advantage that insulating
surfaces or insulating films can be bombarded by applying an RF potential.
Disadvantages are: (i) high power inputs (heating) to insulating materials
cause cracking; (ii) electrode geometries can cause problems with coupling
to the RF power;(iii) there are many sources of RF power loss in systems;(iv)
plasma uniformity is difficult to obtain over complex surfaces; and (v) the bias
conditions on surfaces in the RF plasma are variable and often difficult to
control.
Microwave Discharges. Plasmas can also be excited at much
higher frequencies, 300 MHz to 10 GHz, where electron cyclotron
resonance coupling gives more efficient ionization.[43] Ionization can be as
high as 20% in a such a microwave discharge. Microwave plasmas are
most often used in the downstream processing configuration since
substrates in the microwave cavity can “detune” the system.
Electron Emitter Discharge. In the DC diode and RF plasma
configurations, the electrons necessary to sustain the plasma are pro-
duced in the plasma. When using electron emitters, the electron source
is independent of the plasma processes. Common electron emitters are
hot thermoelectron emitting cathodic surfaces and hollow cathodes. For
example: LaB6 surfaces can give an electron emission of >20 A/cm 2 at
1700°C. [44] Often the electrons are confined by a magnetic field (50 - 500
gauss) directed along the anode-cathode axis. The magnetic field
increases the electron path length in its movement from the cathode to the
anode by causing the electron to spiral in the magnetic field. This
increases the ionization efficiency of the electron. The ions in the plasma
may be extracted using an electrode at a DC or RF potential to give
bombardment of a surface (triode configuration). The triode configuration
suffers from a nonuniform plasma density along its axis which gives nonuniform
bombardment and a density variation in activated species over a large biased
surface. The thermoelectron emitter system is very amenable to forming dense
plasmas and for application to downstream processing. By applying highmagnetic
140 Deposition Technologies for Films and Coatings

fields, the plasma (ions and electrons) may be confined and steered into a
processing chamber.
In plasma processing, some of the advantages of the electron emitter
configurations are:(i) the flux of electrons is independent of other plasma and
electrode processes; (ii) very high plasma densities can be attained; iii) the
plasma properties can be controlled by controlling the electron emission; and
(iv) the electron beam can be used as a source for thermally vaporizing
material. Disadvantages are:(i) need for well controlled and long life electron
emitting sources, and(ii) plasma non-uniformity over large areas and complex
surfaces.
Low strength (50 - 500 gauss) magnetic fields may be used to confine the
electrons and increase their path length in any plasma system. There are a
number of ways to establish magnetic fields in plasma chambers including:
(i) internal permanent magnets,(ii) external permanent magnets, (iii) external
electromagnets, and (iv) moving magnets. Permanent magnets have the
advantage that they may be placed in such a way as to position the field lines
in a desirable manner; however, getting a uniform magnetic field over a large
or complex surface is difficult.
Magnetron enhanced plasma configurations have many advantages
including: (i) confining the plasma to a small region, (ii) increased ionization
and plasma density, (iii) may be operated at low pressures where gas phase
collisions are reduced. Disadvantages include:(i) non-uniform magnetic fields
give non-uniform plasma generation; (ii) isolation of the plasma to a small
region of the processing chamber requiring auxiliary plasma sources in some
applications; and (iii) low pressure processing can give rise to a flux of high
energy reflected neutral which may affect the processing in an undesirable
manner.

8.2 Plasma Chemistry

Plasma is a very energetic environment and many chemical processes


can occur.[45]-[47] The principal chemical processes are: (i) electron impact
ionization, (ii) dissociation (fragmentation) of molecules (formation of radi-
cals), (iii) Penning ionization (metastable collision),(iv) dissociative electron
attachment, (v) electron attachment, (vi) excitation,(vii) momentum transfer
collisions, (viii) de-excitation of excited species, and (ix) recombination
(neutralization). As an example of the complexity of plasma chemical
processes, consider that there can be 24 reactions and 16 species formed by
the decomposition and reaction of CF4 in a plasma.[48]
Surface Preparation 141

As an example of Penning ionization, consider argon which has


metastable excited states of 11.55 and 11.75 eV and copper which has an
ionization energy of 7.86 eV. Thus a copper atom colliding with a metastable
argon atom is easily ionized. Metastable atoms may be very effective in
ionizing other species by collision.
Many of these processes are characterized by “cross sections” for
collision processes and threshold energies for attachment processes. For
example, CF3Cl has a high cross section and low threshold energy (2 - 3 eV)
for electron dissociative attachment. CF4 has a low cross section and high
threshold energy (5 - 6 eV) for electron dissociative attachment and CCl4 is not
activated at all by electron attachment. Therefore CF3Cl is much more easily
fragmented and ionized in a plasma than is CF4 or CCl4 . The degree of
ionization, dissociation and excitation of the species depends strongly on the
gaseous species, electron energy, and density in the plasma. Generally
there is much more dissociation than there is ionization of molecular species.
Many of these plasma processes serve to activate gas species, i.e., to
make them more chemically active by dissociation, ionization, or excitation
(plasma activation).
Plasma discharges are very effective in desorbing contaminates (e.g.,
H2 O) from surfaces in a plasma processing chamber. These impurities are
activated in the plasma and may contaminate the depositing material.
A number of techniques may be used to determine plasma properties.[49]
Optical emission is the most common. Actinometry compares the emission
interactions of the excited states of reference and subject species to obtain
the relative concentrations of the ground states. Optical absorption tech-
niques may also be used to characterize the gaseous species and tempera-
ture in a gas discharge. Electron and ion densities in a plasma may be
measured by the use of small area Langmuir probes.

8.3 Bombardment Effects on Surfaces

The physical effects of energetic particle bombardment on surfaces and


depositing films is very dependent on the mass, flux, and energy of the
bombarding particles, the flux of non-energetic particles (i.e., depositing or
absorbing species), and the atomic mass and chemical nature of the
bombarded surface. In many cases the fluxes of impinging particles are not
determined or controlled except by the processing parameters.
Figure 3.5 depicts the effects of bombardment by energetic species
(not electrons) on the surface and the subsurface region. Surface effects
142 Deposition Technologies for Films and Coatings

include: (i) desorption of weakly bonded surface species, (ii) ejection of


secondary electrons, (iii) reflection of the energetic species as high energy
neutrals, (iv) sputter ejection (physical sputtering) of surface atoms by
momentum transfer through collision cascades, (v) sputtering and redeposi-
tion of sputtered species by collisions in the gas phase, ionization and
acceleration back to the surface and byforward sputter deposition due to the
ejection angle on a rough surface, (vi) enhanced surface mobilities of atoms
on the surface, and (vii) enhanced chemical reaction of impinging and
adsorbed species to produce condensed species (“reactive deposition”) or
volatile species (etching). In the subsurface region:(i) the impinging particles
may be physically implanted (ii) the collision cascades cause displacement
of lattice atoms and the creation of lattice defects, (iii) surface species may
be recoil-implanted into the subsurface lattice, (iv) mobile species may be
trapped at lattice defects, and (v) much of the particle kinetic energy is
converted into heat. Lattice channeling processes can carry these effects
deeply into the surface.

Figure 3.5. Schematic depiction of the energetic particle bombardment effects on


surfaces and growing films.

The desorption of weakly bound surface species is important to plasma


cleaning and may be used to reduce the incorporated contaminants in
deposited films. The desorption may also be useful in desorbing unreacted
species in reactive deposition processes giving rise to more stoichiometric
and chemically stable deposits.
Surface Preparation 143

The physical sputtering of a surface may lead to surface texturing to give


a roughened surface (e.g., Ref. 50, 51). Preferential crystallographic
sputtering will result in some crystalline orientations being etched at faster rate
than others (sputter etching). Preferential atomic sputtering can cause
changes in the chemical composition of alloy and compound surfaces.[52][53]
If a reactive species is used for bombardment, the surface may be etched if
the resulting chemical species is volatile (reactive ion etching, chemical
sputtering), or the surface may be converted to a compound if the chemical
species is not volatile.
Most of the bombarding energy goes into heating the bombarded
surface.[54]
The incorporation of bombarding species into the surface gives rise togas
charging which increases the chemical potential between this region and the
interior and thus the diffusion of the gas into the material. In hydrogen-
bombardment cleaning of a hydrogen-sensitive metal, the hydrogen must be
desorbed while the surface is hot.

8.4 Sputter Cleaning and Etching

Sputter cleaning uses physical sputtering to remove some of the surface


layer which includes contaminates. Sputter cleaning has been called the
universal etch since everything can be removed by the sputtering process at
approximately the same rate.
Sputtering from a plasma environment has disadvantages:
! Contaminates in the plasma become activated and can react
with the surface being cleaned.
! Sputtered species can be returned to the surface by scattering
(redeposition).
! Surface species can be recoil implanted into the surface.
! Sputtering may develop undesirable surface features.
! High voltages are used in the process.
! Bombardment from the plasma may electronically damage
semiconductor materials.
! Special equipment and fixturing may be required.
Low energy ion bombardment can be used to clean surfaces without
electronic damage.[3][4][55][56] The low energy ion bombardment can be
obtained from high pressure plasmas, downstream processing with low
biases, and with low energy ion beams.
144 Deposition Technologies for Films and Coatings

Ion beam sputter cleaning may be done in a vacuum environment where


the sputtered species are not redeposited on the substrate surface.
Reactive plasma cleaning/etching (RPE) uses a reactive species in the
plasma which reacts with the surface to form a volatile species which will leave
the surface (no concurrent ion bombardment of the surface).[57] Plasmas
containing reactive species are used in plasma etching (dry etching) and
“reactive plasma cleaning”.[58] Fluorine (from CF4, CHF3, C2F6 , C3F8 and SF6)
and chlorine (from Cl2 , CCl4 and BCl3 ) are the most widely used reactive
gases. Oxygen is often added to the fluorine system to promote the formation
of atomic fluorine and thus increase the etch rate. One of the most common
gas mixtures is 96% CF4 with 4% O2. Helium is often added as a diluent and
to increase the thermal conductivity of the plasma hence reducing the
temperature rise of the surface. The reactive plasma technique is typically
specific and may be selectively used to take the oxide from the substrate
materials and then etch the substrate material at a low rate. Numerous gases
and gas mixtures are available for RPE.[59]-[61]
Examples of plasma etching (cleaning) of aluminum with various gases
are: Al etched with Cl2, BCl3, CCl4 and SiCl4.[62] The BCl3 removes the oxides,
others don’t do very well on oxides. (BCl3 is a good scavenger of H2O and O2
in the plasma system; it produces condensible material—B2O3). If Cu is
present in the aluminum there will be a CuCl2 residue which may be volatilized
by heating above 200°C. Most metals are most easily cleaned using fluorine
gas (because the products are more volatile) rather than chlorine. Caution:
etching and cleaning with compound gases should be done with caution since
the decomposition products (B,C,Si) may react with or deposit on the surface,
thereby changing the chemical composition or contaminating the surface.
When using a carbon containing chemical (e.g., CCl4, CF3) in the
plasma, a residual carbon contaminate remains—using of HCl or SF6 avoids
this problem. Exposure to reactive plasmas may leave a reacted/chemisorbed
layer of halogen species. This layer may be very important to the sensitization
of the surface to atomic nucleation, or the wettability of organic species to a
surface. For instance, the NH4 plasma treatment of Ti gives good adhesion
when coated with an amine epoxy. Reactive plasma etching of silicon in CCl4
plasmas has been reported to give a very thin fluoride layer that passivates
semiconductor surfaces to oxidation.
Oxygen plasmas can be used to reactively remove materials that have
volatile oxidation products (e.g., C, hydrocarbons). Hydrogen plasmas can
be used to remove materials with volatile hydrides (e.g., C, Si, hydrocarbons).
Surface Preparation 145

In reactive ion etching (RIE), ion bombardment of the surface is used


to add energy and secondary electrons to the depositing/etching surface
environment. It has been shown with RIE of silicon that carbon residue limits
the rate of etching; when etching oxides, the oxygen prevents the formation
of the carbon layer and higher etch rates result.[63] In RIE of silicon, the residue
that remains on the surface must be removed by a postdeposition treatment
of low temperature oxygen annealing.[64] Carbon residuals, when using
carbon-containing etchant gases, have also been found in the reactive plasma
cleaning of metals where the problem was avoided by using HCl as the etching
gas.[58] Typically RIE introduces less surface damage in semiconductor
materials than does sputter etching[65] but more than does RPE.
The use of ion bombardment with a molecular beam of the etchant gas
in vacuum (bombardment enhanced chemical etching) allows reactive clean-
ing to be used in a vacuum environment.[66] It has been shown that
bombardment does increase chemical reactivity at a surface although the
mechanism is not well defined.[67] For instance the role of absorbed reactive
species, which are subjected to the bombardment, has not been determined
and this effect will be different in a plasma environment than in a vacuum
environment. Secondary electron emission may play an important role in
chemical reactions on a bombarded surface.
Plasma etching is used for pattern delineation in semiconductor wafer
fabrication, particularly VLSI fabrication. In RIE, electric fields direct ions
normal to the surface and etch anisotropy can be obtained. This anisotropy
can be used to etch steep-walled features but can be a problem on non-
planar surfaces where off-normal surfaces are etched slowly. A major concern
in plasma etching is the etch selectivity which determines the ability to stop
or significantly slow down the etching process when materials change (SiO2
on Si).
Plasma etching was introduced into the semiconductor industry in the
mid-70s in the form of batch reactors, namely barrel reactors (or volume-
loading or tubular reactors)[68] and parallel-plate reactors (diode, Reinberg
reactors, surface-loading reactors), and more recently, the “HEX” reac-
tors.[69] These reactors hold a number of wafers and are available in a large
number of configurations and plasma generation techniques, ranging from
planar diodes to triodes to magnetrons. In barrel reactors the etching is
due to the activated species, and electric fields (with their associated bias)
are often eliminated by the addition of a conducting etch tunnel around the
wafers which confines the plasma generation to the region between the
146 Deposition Technologies for Films and Coatings

tunnel and the reactor walls. The etching in a barrel reactor with an etch tunnel
depends on long-lived activated species and the etching is isotropic.
To achieve high reaction rates, one needs high plasma densities and a
large number of reactive species at reasonable power densities. These
characteristics can be increased by increasing the electron-atom collision
probability by:
! Short mean free paths (diode)—“high” pressures (<1 torr)
! Auxiliary electron source (triode)—low pressures (0.01- 0.2
torr)
! Increased path length (magnetron)—very low pressures(<0.01
torr)(Hill)
! Microwave plasma excitation
Flow uniformity is extremely important to etch/cleaning uniformity. Gas
is typically introduced through a series of orifices or in some cases porous
diffusers (though these may clog up easily). Large orifices allow high pressure
regions and electron trapping that give local high density plasma that affect
uniformity.
In high pressure reactors, the electrode spacing is small and plasma
uniformity is difficult to obtain. Various techniques are used to hold the plasma
over the driven electrode. The use of guard rings on the edge of the driven
electrode is the most common technique.
In low pressure plasma reactors, an auxiliary electron (or plasma) source
is used to sustain the plasma and allow the decoupling of the plasma source
and the driven electrode. This allows more process variation to be used.
Electrode spacing is larger but the non-symmetry of the plasma may make
plasma uniformity difficult to achieve, particularly when varying process
parameters. The higher plasma densities may also increase the plasma
sheath potential giving rise to increased radiation damage of the wafer, but it
provides more directional ion bombardment therefore better directional etch-
ing.
In very low pressure reactors, the use of the magnetic fields at high
plasma densities results in a lowered plasma sheath potential so a biased
electrode may be useful.
The reactive etching/cleaning process gives volatile species which may
be deposited in other parts of the system under different conditions and may
have a detrimental effect on the gas handling/pumping system, and may be
a source of particulates in the etching system.[70]
Surface Preparation 147

9.0 STORAGE AND HANDLING

An integral, and often neglected aspect of surface preparation is that of


handling and storage before the next processing step or usage. Handling and
storage during processing and after cleaning is a major source of recontam-
ination. It is not unusual to see someone put a carefully cleaned substrate into
a plastic bag where it is contaminated by the polymer.
Storage should be in a non-recontaminating (particles, vapors) environ-
ment. Non-contaminating environments may be passive or active. Passive
environments are those such as carefully cleaned glass containers—possibly
evacuated and desiccated. Active environments are ones where the contam-
inants are continually removed by adsorption or oxidation. Adsorption can be
on freshly oxidized aluminum or activated carbon (particulate problem).
Oxidation may be done using the UV/O3 cleaning cabinet described in Sec.
4.9. This is by far the best technique for storing surfaces where surface
oxidation is not a problem.
The materials used for storage are very important. Storage should
generally not be done in a plastic container since recontamination can occur
from vapors, physical contact, abrasive transfer or the diffusion of moisture
through the polymer. If polymer bags are to be used, and moisturepermeation
is a problem or potential problem, the best ones have a metal foil laminated
between two layers of polymer. Most paper products are acidic and can be
corrosive. Paper products may have also absorbed corrosive gases from the
environment. Many polymer sheet products have antistatic coatings on the
surface; these antistatic coatings are often hydrophilic electrolyte materials
which may be corrosive. Polymers may have plasticizers in them that will
volatilize and contaminate surfaces. Polyvinyl chloride (PVC) can breakdown
and form hydrochloric acid. Most adhesives have corrosive components.
Cloth has “sizing” on the surface of the fibers to aid in weaving and this may
be transferred to parts wrapped or handled with the cloth. Aluminum foil
generally has a layer of oil on the surface.
Materials that may be suitable for storage of surfaces that are extremely
sensitive to corrosion are:
! Cleaned glass containers
! Cleaned metal containers
! Cleaned aluminum foil
! Desized cloth (desize by multiple washing)
! Acid-free paper products—buffered or non-buffered
148 Deposition Technologies for Films and Coatings

! Polyester polymers (e.g., Mylar™) (no plasticizers, no antistat-


ic coating), Polyester laminate (aluminum foil between plastic
sheets - reduces moisture permeation)
! Polypropylene (no plasticizers, no antistatic coating)
! Polyethylene (no plasticizers, no antistatic coating)
! Methyl cellulose glue (neutral pH, high water content)

10.0 ACTIVATION AND SENSITIZATION

Activation of a surface means making the surface more reactive without


the addition of material to the surface. For example, activation in electroplating
may be the removal of oxide layers by chemical or electrolytic treatments just
prior to insertion into the electroplating bath. Such activation is used for
plating: nickel-on-nickel, chrome-on-chrome, gold-on-nickel, silver-on-nickel,
nickel-on-Kovar™. For example: the acid cleaning of nickel by immersion into
an acid bath (20% by volume sulfuric acid) then transferring through the rinse
into the deposition tank, keeping the part wet at all times and minimizing the
transfer time.
Methods for activating polymer surfaces include:[71] corona discharges
(air), glow discharges (radiation, ion bombardment) (oxygen, fluorine, ar-
gon),[72] x-ray irradiation,[73] electron irradiation,[73] low energy electron
bombardment, ion bombardment,[74][75] ultraviolet radiation, and mechanical
abrasion
Plasma activation of a polymer involves taking an existing member of a
polymeric chain (atom, molecule etc.) and making it more reactive by breaking
bonds and leaving dangling bonds which are capable of reacting with
depositing species. The resulting chemical bonding contributes to the
adhesion of the deposited film to the polymeric substrate. The number of
active sites generated by the plasma treatment determines the nucleation
density and the strength of the chemical bond contributes to the adhesion
strength. The plasma treatment of polymers is sometimes called CASING
(Crosslinking by Activated Species of Inert Gas).[76]-[78] Sometimes plasma
activation is followed by exposure to ammonia before the surface is used for
bonding.
The following are some bond strengths between fluorine (the most
electronegative element) and common depositing atomic species.
Surface Preparation 149

Bond Dissociation energy

Ag-F 135.5 Kcal/mole


Al-F 163.8
Fe-F 135.0
C-F 116.8
Ni-F 148.1
Ti-F 145.5
Au-F Unstable

The more electronegative the element, the higher the chemical bond strength
one would expect. Active bonding sites may become saturated (“poisoned”)
by reacting with molecules in the ambient atmosphere (oxygen, OH, etc.) so
activation of a surface will degrade with time. The activation process may also
permanently change the polymer surface by increasing crosslinking.
Plasma treatment of polymer surfaces with inert gas species may give
surface texturing, and the improved bond strengths are then attributed to
mechanical interlocking.
Mechanical activation of metal surfaces by mechanical brushing just
prior to film deposition is a technique that gives improved adhesion of vacuum
deposited coatings on steel.[79][80]
Plasma deposited polymer films (plasma polymerization) have high
concentrations of dangling bonds and are adherent to many surfaces and may
act as good coupling layers (primer) for subsequent metal deposition if used
before the unsaturated bonds become saturated.
Activation of ionically bonded solids may be by exposure to radiation
which creates point defects which may act as bonding sites. Electrons and
photon radiation of insulator and semiconductor surfaces prior to film deposi-
tion have been used to enhance the adhesion of the film,[81] probably by
changing the nucleation behavior.
Sensitization of a surface means adding a small amount of material to
the surface to act as nucleation sites for adatom nucleation. This may be less
than a monolayer of material. In electroplating, the addition of nucleating
agents (Sn - stannate, Zn - zincate) to the surface of difficult-to-plate metals
such as Ti, Al, Zr, and U[82] allows the deposition of adherent metal coatings
(example, zincate process for Al, ASTM -B-253). In electroplating, the
sensitization process often involves simultaneous etching and displacement
plating.
150 Deposition Technologies for Films and Coatings

Various materials are used to sensitize polymer surfaces for bonding and
electroplating (Teflon™—napthelenides or alkali metals, Nylon™— iodine). In
plasma processing, polymer sensitization is the addition (chemisorption) of a
surface species which acts as a coupling agent to react with the depositing
atoms. One sensitization technique is plasma activation with the addition of
a coupling agent (usually oxygen) to the active site; this coupling agent in turn
reacts with other organics (amine epoxy treated with oxygen plasma then
coated with urethane) or with depositing metal atoms.
Oxygen plasma treatment of polymer surfaces has been shown to form
an oxygen complex with the carbon in the plastic.[83]-[85] The deposition of
copper allows the copper to react with the oxygen giving improved adhe-
sion.[86]

11.0 SURFACE MODIFICATION

Surface modification may involve changing the surface chemical compo-


sition by: (i) conversion to a chemical compound (nitride, carbide, oxide); (ii)
changing the chemical composition by selective loss, e.g., hydrogen ion
bombardment of carbide surfaces results in carbon depletion to a depth
corresponding to the physical penetration of the hydrogen into the surface,[87]
hydrogen firing of a carbide surface results in the decarburization of the
surface;[88] (iii) the addition of a surface layer which is compatible with the
substrate material and forms a new surface on which to deposit the film. In
thin film metallization this layer is sometimes called the “glue” layer (e.g., Ti
on oxides under Au, Ni on metals, Cr on polymers,[89]).
Surface modification may be done by changing the physical properties
of the surface such as roughness or hardness. Surface roughening may be
used to give more mechanical bonding. Roughening may be accomplished by
grit blasting, mechanical abrasion, chemical etching (grain boundaries,
crystal orientation, phase), oxidation then reduction or etching, electrochem-
ical etching, or sputter texturing[51]
Examples of surface roughening are:
! AlN ceramics with NaOH[90]
! Al2O3 ceramics with molten NaOH[91]
! ABS copolymer: etch to remove one phase and give porous
surface
! Chemical etching of Kovar™ by ferric chloride
Surface Preparation 151

! Sputter texturing of copper[92]


! Oxidation and reduction of a molybdenum surface to make it
porous for gold deposition
! Sputter texturing of medical implants
! Sputter texturing of polymers
! Anisotropic chemical etching of silicon[93]

12.0 PASSIVATION AND PRESERVATION

Clean surfaces (or those freshly prepared) may be passivated or


protected by the addition of a layer of a material that is easily removed.
Examples are:
! Au flash on metallization surface to prevent oxidation and make
the surface solderable
! Strippable organic films on metal surfaces to prevent corrosion
! Strippable coating on optical surfaces to prevent particulate
contamination
! Water-wetted surface after activation (oxide strip) in electro-
plating to prevent re-oxidation
! I on HF-cleaned Si to prevent oxidation—desorbed at 500°C in
vacuum[94]
Cleaned parts may also be stored under liquids to exclude reactive
gaseous agents. Metals may be stored in anhydrous liquids such as alcohol
or acetone until needed. Storage of material in deoxidized water (boiled) will
decrease the oxidation of the surface compared to air or oxidated (cold) water.
Nitridation of UHV cleaned surfaces minimizes recontamination and
makes subsequent cleaning easier.[13] Coating of UHV surface with gold
makes them less likely to adsorb contamination.
The UV/O3 oxidation of GaAs [95][96] has been used to form a passivating
(sacrificial) layer that can subsequently be vaporized as an in situ cleaning
technique that leaves no residue and doesn’t damage the crystal surface. This
has been reported to be better than thermal or air oxidation since thermal
oxidation selectively oxidizes one constituent and when removed, leaves a poor
surface composition.
152 Deposition Technologies for Films and Coatings

Some silicon surfaces have been preserved by coating with a metal such
as Ga,[97] In[98] or I[99] onto the clean surface and then evaporating the species
from the surface as an in situ technique.

13.0 SAFETY

Chemical manufacturers and distributors are required to provide “Material


Safety Data Sheets” (MSDS’s) for hazardous materials with or before
shipment of the materials. OSHA has mandated that employees must be
given information and training as to the hazards of the materials that they are
using (Hazard Communication Standard 29 CFR 1910.1200)
It should be recognized that chemicals in combination can generate a
safety hazard where the separate chemicals may not. Examples are:
! Organics with oxidants = fire, explosion
! Cyanide compounds with acids = poison (hydrogen cyanide)
Various industry organizations have formulated guidelines for using of
industrial chemicals safely. For instance the Institute for Interconnecting and
Packaging Electronic Circuits has issued a guideline entitled “Guidelines for
Chemical Handling Safety in Printed Board Manufacture” (IPC-CS-70).

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4

Evaporation: Processes, Bulk


Microstructures and Mechanical
Properties

Rointan F. Bunshah

1.0 GENERAL INTRODUCTION

Physical Vapor Deposition (PVD) technology consists of the techniques


of evaporation, ion plating and sputtering. It is used to deposit films and
coatings or self-supported shapes such as sheet, foil, tubing, etc. The
thickness of the deposits can vary from angstroms to millimeters. The wide
variety of applications of these techniques ranges from decorative to
utilitarian over significant segments of the engineering, chemical, nuclear,
microelectronics and related industries. Their use has been increasing at a
very rapid rate since modern technology demands multiple, and often
conflicting, sets of properties from engineering materials, e.g., combinations
of two or more of the following: high temperature strength, impact strength,
specific optical, electrical or magnetic properties, wear resistance, ability to
be fabricated into complex shapes, biocompatibility, cost, etc. A single or
monolithic material cannot meet such demands in high technology
applications. The solution is, therefore, a composite material, i.e., a core
material and a coating each having the requisite properties to fulfill the
specifications.
PVD technology is very versatile, enabling one to deposit virtually
every type of inorganic materials—metals, alloys, compounds and mixtures
thereof, as well as some organic materials. The deposition rates can be
varied from 10 to 750,000 Å (10 -3 to 75 µm) per minute, the higher
rates having come about in the last twenty years with the advent of

157
158 Deposition Technologies for Films and Coatings

electron beam heated sources. For zinc and aluminum, deposition rates
as high as 25 µm per second have been reported using electron beam
evaporation sources.
The thickness limits for thin and thick films are somewhat arbitrary. A
thickness of 10,000 Å (1 µm) is often accepted as the boundary between thin
and thick films. A recent viewpoint is that a film can be considered thin or thick
depending on whether it exhibits surface-like or bulk-like properties.
Historically the first evaporated thin films were probably prepared by
Faraday[1] in 1857 when he exploded metal wires in a vacuum. The
deposition of thin metal films in vacuum by Joule heating was discovered in
1887 by Nahrwold[2] and was used by Kundt[3] in 1888 to measure refractive
indices of such films. In the ensuing period, the work was primarily of
academic interest concerned with optical phenomena associated with thin
layers of metals, researches into kinetics and diffusion of gases, and gas-
metal reactions.[4][5] The application of these technologies on an industrial
scale had to await the development of vacuum techniques and therefore
dates to the post World War II era, i.e., 1946 and onwards. This proceeded
at an exponential pace in thin films and is covered in an excellent review by
Glang[6] on evaporated films and in other chapters of the Handbook of Thin
Film Technology[7] as well as in the classic text by Holland.[8] A more recent
reference on the Science and Technology of Surface Coatings[9] includes
material on PVD techniques as well as the other techniques for surface
coatings. The work on mechanical properties of thin films has been reported
in several review articles.[10]-[15]
The work on the production of full-density coatings or self-supported
shapes by high deposition rate PVD processes started around 1961
independently at two places in the U.S.A. Bunshah and Juntz at the
Lawrence Livermore Laboratories of the University of California produced
very high purity beryllium foil,[16]-[21] titanium sheets,[22] and studied the
variation of impurity content, microstructure and mechanical properties with
deposition conditions, thus demonstrating that the microstructure and
properties of PVD deposits can be varied and controlled. At about the same
time, Smith and Hunt were working at Temescal Metallurgical Corporation in
Berkeley on the deposition of a number of metals, alloys and compounds and
reported their findings in 1964.[23][24] The development of evaporation
processes in the U.S.S.R is described in the Appendix kindly supplied to the
author by Dr. A. V. Demchishin of the Paton Electric Welding Institute, Kiev.
In the years between 1962 and 1969, there was considerable effort on
the part of various steel companies to produce Al and Zn coatings on steel
using HRPVD techniques on a production scale.[25][26] In 1969, Airco
Evaporation 159

Temescal Corp. decided to manufacture Ti-6Al-4V alloy foil in pilot production


quantities for use in honeycomb structures on the SST aircraft. The project
was eminently successful but the patient, the supersonic transport aircraft
“SST,” died. The results of this work were published in 1970.[122a] To give
some idea of the production capability, 1,200 ft/run of Ti-6Al-4V foil, 12" wide,
0.002" thick was produced at the rate of 2 to 3 ft/min. The stated cost at that
time was about one-fifth of the cost for similar material produced by rolling
(i.e., $60/lb for HRPVD vs. $300/lb for rolled material). It is very difficult to roll
this alloy because it work-hardens very rapidly and therefore needs many
annealing cycles to be reduced to thin gauge (A. B. Sauvegot, TMCA Tech.
Report AFML-TR-67-386, Dec. 1967).
The work on thick films and bulk deposits has matured later than the
work on thin films and reviews on it have been given by Bunshah[114][116] and
by Paton, Movchan and Demchishin[122] who summarized the work done at
the Paton Electric Welding Institute up to 1973. In addition, the Soviet
literature in the 1960s has numerous references to the extensive work on thin
and thick films by Palatnick and coworkers of the Kharkov Polytechnic
Institute (see Appendix). Note should also be made of a recent book in
German on electron beam technology by Schiller, Heisig, and Panzer in
which many of the PVD aspects are treated.[27]

2.0 SCOPE

The scope of this chapter will be to review the evaporation technologies,


theory and mechanisms, processes, deposition of various types of materials,
the evolution of the microstructure and its relationship to the properties of the
deposits, preparation of high purity metals, current and future applications,
and finally cost analysis as far as possible.

3.0 PVD PROCESSES

3.1 Preamble

In general, deposition processes may principally be divided into two


types: (i) those involving droplet transfer such as plasma spraying, arc
spraying, wire-explosion spraying, detonation gun coating, and (ii) those
involving an atom by atom transfer mode such as the physical vapor
160 Deposition Technologies for Films and Coatings

deposition processes of evaporation, ion plating and sputtering, chemical


vapor deposition, and electrodeposition. The chief disadvantage of the
droplet transfer process is the porosity in the final deposit which effects the
properties.
There are three steps in the formation of any deposit:
1. Synthesis of the material to be deposited:
a. Transition from a condensed phase (solid or liquid) to
the vapor phase.
b. For deposition of compounds, a reaction between the
components of the compound, some of which may be
introduced into the chamber as a gas or vapor.
2. Transport of the vapors between the source and substrate.
3. Condensation of vapors (and gases) followed by film nucleation
and growth.
There are significant differences between the various atom transfer
processes. In chemical vapor deposition and electrodeposition processes,
all of the three steps mentioned above take place simultaneously at the
substrate and cannot be independently controlled. Thus, if a choice is made
for a process parameter such as substrate temperature (which governs
deposition rate in CVD), one is stuck with the resultant microstructure and
properties. On the other hand, in the PVD processes, these steps (particularly
steps 1 and 3 can be independently controlled and one can therefore have
a much greater degree of flexibility in controlling the structure and properties,
and deposition rate. This is a very important consideration.

3.2 PVD Processes

There are three physical vapor deposition processes, namely


evaporation, ion plating, and sputtering. Ion plating is a hybrid process.
In the evaporation process, vapors are produced from a material
located in a source which is heated by direct resistance, radiation, eddy
currents, electron beam, laser beam or an arc discharge. The process is
usually carried out in vacuum (typically 10-5 to 10-6 torr) so that the
evaporated atoms undergo an essentially collisionless line-of-sight transport
prior to condensation on the substrate. The substrate is usually at ground
potential (i.e., not biased).
Figure 4.1 is a schematic of a vacuum evaporation system illustrating
electron beam heating. It may be noticed that the deposit thickness is greatest
directly above the center-line of the source and decreases away from
Evaporation 161

it.[28] This problem is overcome by imparting a complex motion to substrates


(e.g., in a planetary or rotating substrate holder) so as to even out the vapor
flux on all parts of the substrate; or by introducing a gas at a pressure of 5
to 200 µm into the chamber so that the vapor species undergo multiple
collisions during transport from the source to substrate, thus producing a
reasonably uniform (±10%) thickness of coating on the substrate. The latter
technique is called gas-scattering evaporation or pressure plating. [29][30]

Figure 4.1. Vacuum-evaporation process using electron beam heating.


162 Deposition Technologies for Films and Coatings

In the ion-plating process, the material is vaporized in a manner similar


to that in the evaporation process but passes through a gaseous glow
discharge on its way to the substrate, thus ionizing some of the vaporized
atoms (see Fig. 4.2). The glow discharge is produced by biasing the
substrate to a high negative potential (-2 to -5 kV) and admitting a gas,
usually argon, at a pressure of 5 to 200 mTorr into the chamber. In this
simple mode, which is known as diode ion-plating, the substrate is

Figure 4.2. Ion-plating process.


Evaporation 163

bombarded by high-energy gas ions which sputter off the material present
on the surface. This results in a constant cleaning of the substrate (i.e., a
removal of surface impurities by sputtering) which is desirable for producing
better adhesion and lower impurity content. This ion bombardment also
causes a modification in the microstructure and residual stresses in the
deposit. On the other hand, it produces the undesirable effects of decreasing
the deposition rates since some of the deposit is sputtered off, as well as
causing a considerable (and often undesired for microelectronic applications)
heating of the substrate by the intense gas ion bombardment. The latter
problem can be alleviated by using the supported discharge ion-plating
process[31a,b] where the substrate is no longer at the high negative potential;
the electrons necessary for supporting the discharge come from an auxiliary
heating tungsten filament. The high gas pressure during deposition causes
a reasonably uniform deposition of all surfaces due to gas-scattering as
discussed above.
In the sputtering process, illustrated schematically in Fig. 4.3, positive
gas ions (usually argon ions) produced in a glow discharge (gas pressure:
20 to 150 mTorr) bombard the target material (also called the cathode)
dislodging groups of atoms which then pass into the vapor phase and deposit
onto the substrate. Alternate geometries of importance in various processing
applications are shown in Fig. 4.4. For example, hollow cathode sputtering
would be the ideal geometry for coating the outer surface of a wire.
Sputtering is an inefficient way to induce a solid-to-vapor transition. Typical
yields (atoms sputtered per incident ion) for a 50 eV argon ion incident on a
metal surface are unity. Thus the phase change energy cost is from 3 to 10
times larger than evaporation.[32] Thornton[32] has provided an excellent
review on sputtering as applied to deposition technology. The reader is also
referred to the proceedings of a special conference on "Sputtering and Ion-
Plating."[33]
The deposition rates for the various processes are indicated in Table
4.1. The deposition rates of the evaporation and ion-plating processes are
much higher than those of the sputtering process. Recently, Schiller and
Jasch,[228] reported on large scale industrial applications of deposition of Al
on strip steel continuously at a deposition rate of 20 µ/min. It should be noted
that sputter deposition rates at the high side (approximately 10,000 Å/min)
with diode sputtering can only be obtained for target materials of high thermal
conductivity like copper, since heat extraction from the target is the limiting
parameter. For most materials, it is much lower, i.e., 50 to 1,000 Å/min. With
magnetron sputtering, much higher deposition rates are obtained (see Ch.
5 in this volume).
164 Deposition Technologies for Films and Coatings

Figure 4.3. Basic sputtering process.

Figure 4.4. Cylindrically symmetric sputter-coating systems.


Evaporation 165

Table 4.1. Deposition Rates for Various PVD Processes

Evaporation, Å/min 100 - 250,000*


Ion Plating, Å/min 100 - 250,000
Sputtering, Å/min 25 - 10,000

*In special cases to 500,000 Å/sec

3.3 Advantages and Limitations

There are several advantages of PVD processes over competitive


processes such as electrodeposition, CVD, and plasma spraying. They are:
1. Extreme versatility in composition of deposit. Virtually any
metal, alloy, refractory or intermetallic compound, some
polymeric type materials and their mixtures can be easily
deposited. In this regard, they are superior to any other
deposition process.
2. The ability to produce unusual microstructures and new
crystallographic modifications, e.g., amorphous deposits.
3. The substrate temperature can be varied within very wide
limits from subzero to high temperatures.
4. Ability to produce coatings or self-supported shapes at high
deposition rates.
5. Deposits can have very high purity.
6. Excellent bonding to the substrate.
7. Excellent surface finish which can be equal to that of the
substrate.
8. Elimination of pollutants and effluents from the process which
is a very important ecological factor.
The present limitations of PVD processes are:
1. Inability to deposit polymeric materials with certain exceptions.
2. Higher degree of sophistication of the processing equipment
and hence a higher initial cost.
166 Deposition Technologies for Films and Coatings

4.0 THEORY AND MECHANISMS

4.1 Vacuum Evaporation

Reference to the various steps in the formation of a deposit enumerated


in the previous section shows that the theory of vacuum evaporation involves
thermodynamic considerations, i.e., phase transitions from which the
equilibrium vapor phase pressure of materials can be derived, as well as the
kinetic aspects of nucleation and growth. Both of these are of obvious
importance in the evolution of the microstructure of the deposit.
The transition of solids or liquids into the gaseous state can be
considered to be a macroscopic or an atomistic phenomenon. The former
is based on thermodynamics and results in an understanding of evaporation
rates, source-container reactions and the accompanying effect of impurity
introduction into the vapor state, changes in composition during alloy
evaporation, and stability of compounds. An excellent detailed treatment of
the thermodynamic and kinetic bases of evaporation processes is given by
Glang.[6] He points out that the application of kinetic gas theory to interpret
evaporation phenomena resulted in a specialized evaporation theory. Such
well known scientists as Hertz, Knudsen and Langnuir were the early
workers in evaporation theory. They observed deviations from ideal behavior
which led to refinements in the theory to include concepts of reaction kinetics,
thermodynamics, and solid state theory. From the kinetic theory of gases,
the relationship between the impingement rate of gas molecules and their
partial pressure, p, is given by

dNi
Eq. (1) = (2πmkT )−½ p
A e dt

where Ni is the number of molecules striking a unit area of surface, and Ae


is the area of the surface.
Hertz,[34] in 1882, first measured the evaporation rate of mercury in
high vacuum and found that the evaporation rate was proportional to the
difference between the equilibrium vapor pressure of mercury, p*, at the
evaporant surface and the hydrostatic pressure, p, acting on the surface,
resulting from the evaporant atoms or molecules in the gas phase. Thus, the
evaporation rate based on the concept of the equilibrium vapor pressure,
(i.e., the number of atoms leaving the evaporant surface is equal to the
number returning to the surface) is given by:
Evaporation 167

dN e
Eq. (1a) = ( 2 πmkT ) −½(p* − p ) cm2 sec −1
A e dt

such that dN e, the number of molecules evaporating from a surface area


A e in time dt, is equal to the impingement rate of gas molecules based on
the kinetic theory of gases with the value of p* inserted therein, minus the
return flux corresponding to the hydrostatic pressure p of the evaporant
in the gas phase. In the above equations, m is the molecular weight, k
is Boltzmann’s constant, and T is the temperature in °K. The maximum
possible evaporation rate corresponds to the condition p = 0. Hertz
measured evaporation rates only about one-tenth as high as the theoretical
maximum rates. The latter were subsequently measured by Knudsen[35]
in 1915. Knudsen postulated that some of the molecules impinging on
the surface were reflecting back into the gas phase rather than becoming
incorporated into the liquid. As a result, there is a certain fraction (1 - αν)
of vapor molecules which contribute to the evaporant pressure but not to
the net molecular flux from the condensed phase into the vapor phase.
To this end, he postulated the evaporation coefficient, αν, which is
defined as the ratio of the real evaporation rate in vacuum to the
theoretically possible value defined by Eq. (1a). This then results in the
well-known Hertz-Knudsen equation

dN e
Eq. (2) = α ν ( 2 πmkT ) −½(p* − p )
A e dt

The value of αν is very dependent on the cleanliness of the evaporant


surface and can range from very low values for dirty surfaces to unity for
clean surfaces. In very high rate evaporation with a clean evaporant
surface, it has been found that the maximum evaporation given by Eq. (2)
has been exceeded by a factor of 2 to 3 for the evaporation of a light metal
such as beryllium[21] using electron beam heating. The reason for this is
that the high power input results in considerable agitation of the liquid
evaporant pool resulting in a real surface area much larger than the
apparent surface area.
The directionality of evaporating molecules from an evaporation
source is given by the well-known cosine law. Figure 4.5 shows a small
surface element dAr receiving deposit from a small area source Ar. The mass
deposited per unit area
168 Deposition Technologies for Films and Coatings

dMr ( σ, θ) Me
Eq. (3) = cos φ cos θ
dA r πr 2

where Me is total mass evaporated.

Figure 4.5. Surface element dA r receiving deposit from a small-area source dAe.
(From Handbook of Thin Film Technology. © 1970, McGraw-Hill. Used with
permission of McGraw-Hill Book Company.)

For a point source, Eq. (3) reduces to:

dMr M
Eq. (4) = e cos φ
dAr πr 2

For a uniform deposit thickness, the point source must be located at the center
of the spherical receiving surface such that r is a constant and cosθ = 1.
In high rate evaporation conditions, e.g., using a high power electron
beam heated source, the thickness distribution is steeper than with a point
or small area source discussed above. This has been attributed by some
Evaporation 169

authors[28][36] to the existence of a virtual source of vapor located above the


molten pool. On the other hand, at high power, the electron beam impact
area on the surface of the molten pool is not flat but pushed down into an
approximate concave spherical segment which as Riley shows[37] can
equally well account for the steeper thickness distribution.
The above discussion points out one of the problems with evaporation
technology, i.e., the variation in thickness of the deposit on a flat substrate.
Numerous solutions are possible which involve either moving the substrate
in a manner so as to randomly sample the vapor flux, the use of multiple
sources, or sources of special shapes. These have been discussed in some
detail by Holland[8] as well as by Bunshah and Juntz.[38]
Models have also been presented for calculating the deposit
temperature[39] and thickness distribution[40] during high-rate evaporation
and verified against experimental data. In a more recent paper, Szekely and
Poveromo[41] have given a more general formulation describing the net rate
of vapor deposition from a molten source onto an initial cold surface, making
allowance for both molecular transport and diffusion effects.

5.0 EVAPORATION PROCESS AND APPARATUS

5.1 The System

A schematic of the evaporation apparatus has been illustrated in Fig.


4.1. It consists of the following: chamber, vacuum pumps, vacuum gages,
including total and partial pressure gages on sophisticated systems,
evaporation sources, substrate holders, rate monitors, process controller,
etc.
Vacuum Chamber: This ranges from a simple bell jar or rectangular
box for experimental or batch type production to more complex gear for
production applications. The latter may consist of a deposition chamber with
loading and unloading chambers attached to the deposition chambers by
manifolds with isolation high vacuum valves. These are called fast cycle
coaters. Alternate approaches are semi-continuous in-line systems where
a strip substrate stored in the vacuum chamber can be fed continuously over
the source (Fig. 4.6) or a continuous system where the strip or sheet
substrate is inserted and removed from the deposition chamber through air-
to-air seals[4][42] as shown in Figs. 4.7 and 4.8.
170 Deposition Technologies for Films and Coatings

Figure 4.6. A schematic representation of a 24 inch continuous high vacuum strip


processing line.

Figure 4.7. A three-high roll seal arrangement for stripline.


Evaporation 171

Figure 4.8. Vacuum seal using steam jet or curtain.

Vacuum Pumping System: The gas loads in evaporation processes


are fairly high due to outgassing from chamber walls promoted by the heat
load from the evaporation source and substrate heaters, particularly for high
deposition rate conditions. Therefore the pumping system is usually based
on a diffusion pump with a liquid nitrogen cooled anti-creep type baffle-
backed with a mechanical pump or a Roots blower/mechanical pump
combination for large systems. For very high purity, low deposition rate, low
heat flux conditions, ion pumped systems backed with cryosorption rough
pumping are used, since a base pressure of 10-9 to 10-10 torr is needed. More
recently, turbomolecular and cryogenic pumps are used instead of diffusion
pumps where desired (e.g., oil-free systems). This is particularly true for
molecular beam epitaxy where extreme control over composition and layer
thickness are essential and deposition rates can be quite low. In such cases,
the chamber and pumps are to be baked as with any other ultra-high vacuum
operation.
Pressure Measurement: The vacuum gages used depend again on
specific applications. A combination of high pressure gages (such as the
Pirani or Thermocouple Gage) for monitoring the roughing of the system in
172 Deposition Technologies for Films and Coatings

combination with high vacuum gages (such as the hot cathode ionization
gage and/or capacitance manometer). A partial pressure gage is highly
desirable particularly for ultra-clean applications as well as for leak hunting.
Evaporation Sources: These are discussed separately in Sec. 6).
Substrate Holders and Heaters: Substrate holders may be very
simple for stationary flat substrates or can incorporate quite complex motions
as illustrated by planetary or rotating devices. The reason for this is to ensure
deposition thickness uniformity and control over a large number of small
parts such as lenses or silicon wafers. Substrate heating can be accomplished
by radiant heaters with refractory wires or quartz lamps acting as the heat
source. Occasionally, substrates are directly heated by a scanning or diffuse
electron beam.
Deposition Rate Monitors: These are discussed in Sec. 8.

6.0 EVAPORATION SOURCES

6.1 General Considerations

Evaporation sources are classified by the mode of heating used to


convert the solid or liquid evaporant to the vapor phase. Thus one talks of
resistance, arc, induction, electron beam, arc imaging, lasers, and exploding
wire types of sources. A very important fact to be noted is that we cannot
evaporate every material fromany of the types of sources listed above for the
following reasons.
1. Chemical interaction between the source material and the
evaporant which would lead to impurities in the deposit. For
example, evaporation of titanium from a MgO source would
cause oxygen and magnesium contamination of the deposit;
the titanium would reduce the MgO. Therefore, for the
evaporation of reactive metals like titanium, zirconium, etc.,
we use water cooled copper crucibles.
2. Reaction between metallic source (such as a W or Ta boat)
and evaporant (Ti) could occur. In many cases at high
temperatures two metals can mutually dissolve in each other
leading to a destruction of the source.
3. The power density (i.e., watts per sq. cm) varies greatly
between the various heat sources.
Table 4.2 from Ref. 6 from the article by Glang lists the temperature
and support materials to be used in the evaporation of elements. Similar
tables are found in the literature of many of the manufacturers.
Evaporation of alloys and compounds pose additional problems and
they are considered in Sec. 9.
Evaporation 173

Table 4.2. Temperatures and Support Materials Used in the Evaporation of


the Elements
174 Deposition Technologies for Films and Coatings

Table 4.2. (Cont'd)


Evaporation 175

6.2 Resistance Heated Sources

The simplest vapor sources are resistance heated wires and metal
foilsof various types shown in Fig. 4.9.

Figure 4.9. Wire and metal-foil sources. (A) Hairpin source. (B) Wire helix. (C) Wire
basket. (D) Dimpled foil. (E) Dimpled foil with alumina coating (F) Canoe type.
(From Handbook of Thin Film Technology. © 1970, McGraw-Hill. Used with
permission of McGraw-Hill Book Co.)

They are available in a variety of sizes and shapes and at sufficiently


low prices so that they can be discarded after one experiment if necessary.
They are usually made from the refractory metals, tungsten, molybdenum,
and tantalum which have high melting points and low vapor pressure so as
not to contaminate the deposit. Their properties are given in Table 4.3.
Platinum, iron or nickel are sometimes used for materials which
evaporate below 1000°C. The capacity (total amount of evaporant) of such
sources is small. The hairpin and wire helix sources are used by attaching
the evaporant to the source in the form of small wire segments. Upon
melting, the evaporant must wet the filament and be held there by
176 Deposition Technologies for Films and Coatings

surface tension. This is desirable to increase the evaporation surface area


and thermal contact. Multistrand filament wire is preferred because it
increases the surface area. Maximum amount held is about 1 gram. Dimpled
sources and basket boats may hold up to a few grams.

Table 4.3. Properties of Refractory Metals

Since the electrical resistance of the source is small, low voltage power
supplies, 1 to 3 kW, are recommended. The current in the source may range
from 20 to 500 amps. In some cases, the evaporant is electroplated onto the
wire source.
The principal use of wire baskets is for the evaporation of pellets or
chips of dielectric materials which either sublime or do not wet the wire on
melting. In such cases, if wetting occurs, the turns of the baskets are shorted
and the temperature of the source drops.
The rate of evaporation from such sources may vary considerably due
to localized conditions of temperature variation, wetting, hot spots, etc.
Therefore, for a given thickness of film, the procedure is to load the source
with a fixed weight of evaporant and evaporate to completion or use a rate
monitor and/or thickness monitor to obtain the desired evaporation rate and
thickness.

6.3 Sublimation Sources

For materials evaporating above 1000°C, the problem of non-reactive


supports may be circumvented for materials such as Cr, Mo, Pd, V, Fe and
Evaporation 177

Si which reach a vapor pressure of 10-2 torr before melting. Hence, they can
sublime and produce a sufficiently high vapor density. The contact area
between the evaporant and the source crucible is held to a minimum. Figure
4.10 shows such a source designed by Roberts and Via.

Figure 4.10. Chromium sublimation source after Roberts and Via. The electric
current flows through the tantalum cylinder (heavy lines). (From Handbook of Thin
Film Technology. © 1970, McGraw-Hill. Used with permission of McGraw-Hill Book
Co.)

A different type of sublimation source is used for the vaporization of


thermally stable compounds such as SiO which are commonly obtained as
powders or loose chunks. Such source material would release large
quantities of gases upon heating thus causing ejection of particles of the
evaporant which may get incorporated into the film. Figure 4.11 shows two
sources which solve this problem by reflection of the vaporized material.
178 Deposition Technologies for Films and Coatings

Figure 4.11. Optically dense SiO sources. (A) The Drumheller source. (B)
Compartmentalized source. (After Vergara, Greenhouse and Nicholas.) (From
Handbook of Thin film Technology. © 1970, McGraw-Hill. Used with permission of
McGraw-Hill Book Co.)

6.4 Evaporation Source Materials

We have already discussed the potential problems concerned with the


reaction between metal sources and evaporants. Oxides and other
compounds are more stable than metals. Table 4.4 gives the thermal stability
of refractory oxides in contact with metals. There are many metals not listed
in Table 4.4 which can be evaporated from refractory oxide sources. Note
that there is no such thing as an absolutely stable oxide, nitride or other
compound. Reaction is controlled by kinetics, i.e., temperature and time.
Oxide crucibles have to be heated by radiation from metal filaments or
their contents can be heated by induction heating. This is illustrated in Fig.
4.12 and 4.13 for resistance heated sources.
Other source materials are nitrides such as boron nitride. A 50% BN-
50% TiB2 is also well established as a crucible material. This material (HDA
composite, Union Carbide) is a fairly good electrical conductor and hence
can be directly heated to evaporate materials. It can be readily machined to
shape.
Pyrolytic BN and carbon are also used.
Evaporation 179

Table 4.4. Thermal Stability of Refractory Oxides in Contact with Metals*

Figure 4.12. Oxide crucible with wire-coil heater. (From Handbook of Thin Film
Technology. C 1970, McGraw-Hill. Used with permissionof McGraw-HillBookCo.)
180 Deposition Technologies for Films and Coatings

Figure 4.13. DaSilva crucible source. (From Handbook of Thin Film Technology.
© 1970, McGraw-Hill. Used with permission of McGraw-Hill Book Co.)

6.5 Induction Heated Sources

Figure 4.14 shows the induction heated sources using a BN-TiB2


crucible. Figure 4.15 shows an induction heated evaporation sublimation
source using a water cooled copper crucible.[19] This is suited to the
evaporation of reactive metals such as Ti, Be, etc., which will react with all
the refractory oxides, nitrides, etc.

Figure 4.14. RF heated aluminum source with boron-nitride/titanium-diboride


crucible. (After Ames, Kaplan and Roland). (From Handbook of Thin Film
Technology. © 1970, McGraw-Hill. Used with permission of McGraw-Hill Book Co.)
Evaporation 181

Figure 4.15. Schematic representation of the distillation setup.

6.6 Electron Beam Heated Sources

Electron beam heated sources have two major benefits. One is a very
high power density and hence a wide range of control over evaporation rates
from very low to very high. Two, the evaporant is contained in a water-cooled
copper hearth thus eliminating the problem of crucible contamination.
The evaporation rate for pure metals like Al, Au, Ag, which are good
thermal conductors, from water-cooled copper crucibles decreases due to
heat loss to the crucible walls. In such cases, crucible liners of carbon and
other refractory materials are used.
Any gun system must consist of at least two elements—a cathode and
anode. In addition, it is necessary to contain these in a vacuum chamber in
order to produce and control the flow of electrons, since they are easily
182 Deposition Technologies for Films and Coatings

scattered by gas molecules. A potential difference is maintained between


the cathode and the anode. This varies from as little as a few kilovolts to
hundreds of kilovolts. In melting systems, a normal operational range is of
the order of 10 - 40 kV. In the simple diode system, the cathode emits
electrons, which are then accelerated to the anode across the potential drop.
Where the anode is the workpiece to be heated, this is termed a work-
accelerated gun. It is shown schematically in Fig. 4.16a. In a self-
accelerated gun structure, an anode is located fairly close to the cathode,
electrons leave the cathode surface, are accelerated by the potential
difference between the cathode and anode, pass through the hole in the
anode and continue onward to strike the workpiece. Self-accelerated guns
have become the more common type in use and offer more flexibility than the
work-accelerated gun.

Figure 4.16. Simple electron beam guns. (a) Work-accelerated gun. (b) Self-
accelerated gun.
Evaporation 183

Electron beam guns may be further subdivided into two types depending
on the source of electrons: (i) thermionic gun and (ii) plasma gun.
Thermionic Gun: In thermionic guns, the source of electrons is a
heated wire or disc of a high temperature metal or alloy, usually tungsten or
tantalum. Such guns have the limitation of a minimum operating gas
pressure of about 1 x 10-3 torr. Higher pressures cause scattering of the
electron beam as well as a pronounced shortening of the cathode life (if it is
a wire or filament) due to erosion by ion bombardment. Figure 4.17 shows
examples of thermionic electron beam heated work-accelerated sources.
The close cathode gun shown in Fig. 4.17A is not a desirable configuration
since molten droplet ejection from the pool impinging on the cathode will
terminate the life of the cathode due to low melting alloy formation. Thus
cathodes are hidden from direct line-of-sight of the molten pool and the
electron beam is bent by electrostatic fields (Figs. 4.17B and 4.17C) or
magnetic field (Figs. 4.18 and 4.19) generated by electromagnets. The latter
is a preferred arrangement since variation of the X and Y components of the
magnetic field can be used to scan the position of the beam on the molten
pool surface.

Figure 4.17. Work-accelerated electron-bombardment sources. (A) Pendant-drop


method. (B) Shielded filament (Unvala). (C) Shielded filament (Chopra and
Randlett). (From Handbook of Thin Film Technology. © 1970, McGraw-Hill. Used
with permission of McGraw-Hill Book Co.)
184 Deposition Technologies for Films and Coatings

Figure 4.18. Bent-beam electron gun with water-cooled evaporant support. (With
permission of Temescal Metallurgical Co., Berkeley, CA). (From Handbook of Thin
Film Technology. © 1970, McGraw-Hill. Used with permission of McGraw-Hill Book
Co.)

Figure 4.19. Transverse electron beam gun.


Evaporation 185

Figures 4.17, 4.18 and 4.19 show linear cathodes (i.e., wires or rods)
and are referred to as transverse linear cathode guns. Figure 4.20 shows a
disc cathode which is characteristic of a high power Pierce type electron
beam gun. Low power Pierce type guns may have a hair pin filament or awire
loop as the cathode. In either case the beam geometry of the Pierce gun is
different than that of the transverse linear cathode guns. In some instances,
the electron emitter assembly is located at a distance from the crucible in a
separately pumped chamber to keep the pressure below 1 x 10 -3 torr, with
a small orifice between the emitter chamber and the crucible chamber for the
passage of electrons.

Figure 4.20. Schematic representation of a Pierce gun.


186 Deposition Technologies for Films and Coatings

Plasma Electron Beam Gun:A plasma is defined as a region of high-


temperature gas containing large numbers of free electrons and ions. By a
proper application of electrical potential, electrons can be extracted from the
plasma to provide a useful energy beam similar to that obtained from
thermionic guns. There are two types of plasma e-beam guns:
(a) The Cold Cathode Plasma Electron Beam—The plasma
electron beam gun has a cylindrical cathode cavity made from
a metal mesh or sheet (Fig. 4.21) containing the ionized
plasma from which electrons are extracted through a small
aperture in one end. The cathode is maintained at a negative
potential, e.g., -5 to -20 kV, relative to the workpiece and
remainder of the system, which are at ground potential. After
evacuation of the system, a low pressure of ionizable gas
in the range of 10 -3 to 10 -1 torr is introduced. Depending
upon the high voltage level, a long path discharge between the
cathode and other parts of the system will occur in the gas at
a particular pressure. Ionizing collisions in the gas then
produce positive ions which are accelerated to the cathode,
causing electrons to be released from the cathode surface.
Although the cathode may heat up slightly due to ion
bombardment, no heating is required for electron emission.
Upon proper adjustment of cathode voltage and gas pressure,
a beam mode of operation is established, since interaction
between the plasma inside and outside of the cathode and the
electric fields between cathode surface and plasma boundary
will largely confine electron emission to the end of the cathode
and its interior. In argon, a beam mode is supported at about
10 -2 torr with 5 - 10 kV. Beam currents range up to 3 A for a
3 inch diameter cathode in argon at 20 kV. With lighter gases,
e.g., helium, higher pressure to about 10 -1 torr will yield a
beam mode in this same voltage range. Beam current will
vary with voltage and pressure control, also. More specific
information is given by Cocca and Stauffer.[44] The beam
is self-collimating because of the focusing effect of positive
ions in the beam path and the electrostatic lensing action of
the aperture since it separates regions of different potential
gradient. The beam is well collimated, having a cross section
equal to that of the cathode aperture. Adjustment of focus
can be achieved to some extent by varying pressure and voltage,
Evaporation 187

but external focusing may also be used if desired, with


magnetic or electrostatic lenses, as with conventional election
beams.

Figure 4.21. Cold cathode plasma electron beam gun.

(b) The Hot Hollow Cathode Discharge Beam—The hollow cathode


discharge beam applied to vacuum processing has been reported
by Morley[45] and differs in a number of respects from the plasma
beam. A schematic of the hollow cathode discharge beam is
shown in Fig. 4.22. Here the cathode must be constructed of a
refractory metal since it operates at elevated temperature. An
ionizable gas, usually argon, is introduced into the system
through the tubular-shaped cathode. A pressure drop across the
orifice in the cathode provides a sufficient amount of gas inside
the cathode to sustain the plasma, which generates the beam.
188 Deposition Technologies for Films and Coatings

A low voltage, high amperage DC power source is utilized.


When RF power from a commercial welding starter is coupled
to the gas, it becomes ionized and the plasma is formed.
Continued ion bombardment of the cathode results in heating
of the cathode and increased electron emission. Ultimately, a
high current “glow discharge” will occur, analogous to that
experienced in vacuum arc melting at higher pressures. At this
point, the discharge appears as a low power density beam
“flowing” from the cathode aperture and fanning out in conical
shape into the chamber. However, a parallel axial magnetic
field is imposed on the beam (as seen in Fig. 4.22) which then
forms a high power density, well-collimated beam. The hollow
cathode discharge beam is operationally stable and efficient
over the pressure range from 10-4 to 10-1 torr. A more detailed
description of physical aspects, operational characteristics,
and cathode design has been given by Morley.[45]

Figure 4.22. Schematic of the hot hollow cathode electron beam gun.
Evaporation 189

Comparisons:Thermionic as well as the plasma e-beam guns can be


used equally well for evaporation. Focusing of the beam spot is easier for the
thermionic guns. The plasma guns have the advantage of being able to
operate at higher pressures which can be important for gas scattering
evaporation, reactive evaporation, and ion plating.

6.7 Arc Evaporation

The definitions of arcs are:


Karl T. Compton, Princeton University: “A discharge in a gas or vapor
that has a voltage drop at the cathode of the order of the minimum ionizing
or exciting potential of the gas or vapor.” Lafferty: “The arc is a self sustained
discharge capable of supporting large currents by providing its own mechanism
of electron emission from the cathode.”
Berghaus[46] describes the use of arcs to form refractory compounds
by reactive evaporation. Since 1940, consumable and nonconsumable
vacuum arc melting processes have been developed to melt and refine
various reactive metals such as Ti, Hf, Zr, etc. More recently, arc techniques
have been used to deposit metals[47][48] and refractory compounds, and
even for extraction of ions from the vacuum arc plasma for the deposition of
metal films.[49]
Wroe[50] in 1958 and Gilmour et al.[51] suggested vacuum arcs as a
source for metallic coatings. The US patents to Snaper[52][53] in 1971 and the
Russian patents to Sablev[54][55] in 1974 set the stage for the commercial
production of arc coatings which were achieved in the USSR around 1977
- 1978. The first commercial use of the arc evaporation-deposition method
was for TiN coatings deposited at low temperatures, particularly for high
speed steel cutting tools by arc evaporation of titanium in a nitrogen plasma.
This follows on the heels of the Activated Reactive Evaporation (ARE)
process developed in 1971 for deposition of refractory compounds such as
TiN using electron beam evaporation techniques and discussed in Sec. 9.6.
There is very extensive Russian literature on vacuum arc coating technology
and the reader can find a convenient source in recent reviews by Sanders[56]
and by Martin.[57]
There are two types of cathodic arc systems—pulsed and continuous.
In the pulsed devices, the arc is repeatedly ignited and extinguished using
a capacitor blank to supply the arc power.[51] Pulsed arcs have the
advantage of letting the target cool between the pulses. The disadvantage
is the decrease in steady state coating rates.
190 Deposition Technologies for Films and Coatings

The continuous cathodic arc can be random in nature or controlled. By


the use of an insulating ring, a random arc source can be constrained at the
edge of the target, but allowed random motion within that constraint. Random
arc sources have the advantage of simplicity and excellent target utilization
because the entire target (except near the very edge) is utilized in the arc of
very large parts. The main disadvantage of random arcs is the formation of
macroparticles which may cause the resulting coating to be unsuitable in
some applications. Figure 4.23 shows that macroparticles are ejected at
small angles with respect to the target surface, and can therefore be
minimized using appropriate shielding. Such a strategy has made possible
arc-produced decorative coatings where surface finish and optical specularity
are of concern.

Figure 4.23. Phenomena occurring at a discrete cathodic arc spot.


Evaporation 191

Magnetic fields can be used to control the trajectories of the arcs.


These fields can be used to discourage the arc from leaving the desired
portion of the target surface or can actually be used to define a well controlled
path for the arc to follow in the so called “steered arc” devices. While the
mechanism is still the subject of some debate, it is clear, at least in the case
of ceramic coatings based on refractory metals, that steered arcs can
produce coatings having extremely low or no measurable macroparticle
component.
Macroparticles can also be removed by the use of suitable filters as
discussed by Sanders[56] and by Martin.[58] This is the so-called “filtered arc
evaporation process.“ Other strategies for macroparticles involve the
production of diffuse arcs. In one case, the cathode is contained in a crucible
which is allowed to heat up to a temperature where the target material has
a substantial vapor pressure.[59] This causes a decrease in the arc voltage
and current density, the discharge becomes diffuse and macroparticles no
longer form. The other approach is the so-called "anodic arc,“[60]-[62] (see
Fig. 4.24). In this process the cathode initially supplies electrons as well as
ions until the anode heats up. At this point, with sufficient electron emission,
a diffuse arc forms on the hot anode target material which supplies the ions
necessary to sustain the discharge. The cathode material is not evaporated
and the coating material now emanates from the anode. There are no
macroparticles formed. High deposition rates (several µm per minute) are
obtained for a variety of metals including Al, Ti, V, Ca, Mn, Fe, Ni, Cu, Pd, Ag,
Au and Pt.[60] Since the substrate is left relatively cool, the process makes
it possible to produce adherent coatings on plastics at temperatures less
than 70°C which makes this relatively new process a competitor for sputter
deposition. Alloy coatings such as stainless steel can be readily deposited
with good stoichiometric transfer. For example, Ni, Al, and stainless steel
coatings less than 1 µm thickness impart excellent corrosion protection to
iron.[63]
One of the main advantages of arc deposition processes is the
relatively high level of ionizing atoms in the plasma. This makes it convenient
to extract ion beams from the plasma and deposit macroparticle free coatings
entirely from the ion beam.[56][58]
192 Deposition Technologies for Films and Coatings

Figure 4.24. Schematic of the anodic arc evaporation process.

7.0 LASER INDUCED EVAPORATION/LASER ABLATION/PULSED


LASER DEPOSITION (PLD)

This technique with many names was first used by Smith and Turner[64]
in 1965 to deposit thin films in a vacuum chamber using a pulsed ruby laser.
Systematic studies in the 1970’s were performed to provide a better
understanding of the physics of laser-solid interactions and the related
issues of deposition mechanisms and film quality. More recently the process
has been extensively used for growing highly crystalline dielectric films,[65]
compound semiconductor epitaxial layers, layers for band-gap
engineering,[66][67] and very extensively for high T c superconducting
films.[68][69] The reader is referred to an excellent review by Cheung and
Sankur.[70]
Evaporation 193

In this technique, material is vaporized and ejected from the surface


of a target as it irradiated by a laser beam. Films are formed by condensing
the material ablated from the target onto a solid substrate. Absorption
characteristics of the material to be evaporated determine the laser wavelength
to be used. To obtain the high power density required in many cases, pulsed
laser beams are generally employed. Pulse width, repetition rate, and pulse
intensity are selected for specific applications.
In some studies on YBCO film deposition, the laser version of a
plasma-assisted reactive evaporation process was used. Oxygen was bled
into the system and a plasma was created in the target-substrate space by
the use of a positively biased electrode placed some distance above the
target. This is the ARE process geometry developed earlier and described
in Sec. 9.6
Although laser evaporation is an attractive approach for synthesis of
high purity metal alloys and compound films, it suffers from the following
limitations:
1. Complex transmitting and focusing systems need to be
employed to direct the beam from the laser located outside the
vacuum system onto the evaporant placed inside the system.
This involves special optical path designs and increases the
cost of the set-up. Also, a window material which efficiently
transmits the wavelength band of the laser must be found and
mounted in such a way that it is not rapidly covered up by the
evaporant flux.
2. It is not always possible to find a laser with wavelength
compatible with the absorption characteristics of the material
to be evaporated.
3. Energy conversion efficiency is very low—usually around 1 to
2%.
4. The size of the deposited film is small (10 to 20 mm, or 0.4 to
0.8 in., diameter), resulting from the small size of the laser
impact spot.
5. The “splashing effect,”[69] which involves the production of
microparticles between 0.1 and 10 µm in size, diminishes film
quality.
The main advantages of this technique are:
1. the production of high-energy species which enhances film
quality.
194 Deposition Technologies for Films and Coatings

2. Excellent transfer of stoichiometry between the target and the


film, e.g., the deposition of hydroxyl apatite thin films for
biomedical applications such as implants.
The macroparticle density can be decreased by lowering the power
level at the expense of deposition rate. The latter may not be important for
many thin film applications.
The question of large area deposition has been recently addressed by
Greer.[71] He has constructed a vacuum deposition system in which the laser
beam is scanned on a rotating YBCO target and the substrate is itself rotated.
This rather complex apparatus is capable of depositing YBCO films onto two
or three inch diameter substrates.

8.0 DEPOSITION RATE MONITORS AND PROCESS CONTROL

The properties of deposits are dependent on the control exercised


during the process. The thinner the deposit, the more critical is the control
of the operation.

8.1 Monitoring of the Vapor Stream

Ionization Gauge Rate Monitor: This device is very similar to a hot


cathode ionization gauge and monitors the atom density in the vapor phase
by ionizing the vapors, collecting and measuring the ion current. Several
arrangements are shown in Fig. 4.25.
Particle Impingement Rate Monitors: The gauge which is a cylinder
suspended by a wire or riding on a bearing is imparted a momentum by the
impinging particles which can be measured by the torsional forces. They are
illustrated in Fig. 4.26.
Ion Current Monitor for Electron Beam Heated Source:An electron
beam heated molten pool has a plasma sheath above it. Positive ions from
the plasma follow a very similar trajectory as the electrons with a slightly
larger radius of curvature, due to their higher mass, and are beamed away
from the molten pool by the same magnetic field which bends the electrons
towards the pool. Therefore an ion collector can be placed so as to intercept
this ion beam and the resultant ion current can be used in a feed-back loop
to control the evaporation rate. Two manufacturers of electron beam guns
have offered this option.
Evaporation 195

Figure 4.25. Ionization rate monitor designs and arrangements. (A) After Schwarz.
(B) After Giedd and Perkins. (C) After Perkins. (D) After Dufour and Zega. (From
Handbook of Thin Film Technology. © 1970, McGraw-Hill, Used with permission
of McGraw-Hill Book Co.)

Spectroscopic Methods: Monitoring and control of the deposition


rate can be done on the basis of mass spectrometry, atomic absorption
spectrometry and electron emission impact spectrometry. Each of them
involves the choice of an appropriate materials-selective sensor. The
principles, advantages and limitations of each of these are presented in a
good review paper by Lu in Thin Solid Films 45:487 (1977). The reader is
referred to this paper and the references cited therein.
196 Deposition Technologies for Films and Coatings

Figure 4.26. Particle-impingement-rate monitors. (A) Torsion-wire device. (After


Neugebaur.) (B) Pivot-supported device. (After Beavitt.) (From Handbook of Thin
Film Technology. © 1970, McGraw-Hill. Used with permission of McGraw-Hill Book
Co.)

8.2 Monitoring of Deposited Mass

Microbalances: There are various types of devices which measure a


change in mass due to condensed atoms based on elongation of a thin
quartz-fiber helix, the tension of a wire or the deflection of a pivot-mounted
beam. Examples are shown in Figs. 4.27 and 4.28.
Crystal Oscillators: The crystal oscillator monitor utilizes the
piezoelectric properties of quartz. The resonance frequency induced by an
AC field is inversely proportional to crystal thickness. In practice, the change
in frequency of a crystal exposed to the vapor beam is compared to that of
reference crystal. An example is shown in Fig. 4.29.

8.3 Monitoring of Specific Film Properties

In preparing thin films, often only one property is of interest, e.g.,


optical or electrical.
Optical Monitors: They measure phenomena such as light
absorbence, transmittance, reflectance or related interference effects during
film deposition. An example is shown in Fig. 4.30.
Resistance Monitors: The film thickness can be continuously
monitored using in situ resistance measurements as shown in Fig. 4.31.
Evaporation 197

Figure 4.27. (A) Schematic drawing and (B) circuit diagram of a microbalance
constructed from a micro-ammeter movement. (Hayes and Roberts.) (From
Handbook of Thin Film Technology. © 1970, McGraw-Hill. Used with permission
of McGraw-Hill Book Co.)

Figure 4.28. Microbalance with torsion-fiber suspension and electromagnetic


force compensation at beam end (Mayer et al.) (From Handbook of Thin Film
Technology. © 1970, McGraw-Hill. Used with permission of McGraw-Hill Book Co.)
198 Deposition Technologies for Films and Coatings

Figure 4.29. Oscillator crystal holders for deposition monitoring. (A) After Behrndt
and Love. (B) After Pulker. (From Handbook of Thin Film Technology. © 1970,
McGraw-Hill. Used with permission of McGraw-Hill Book Co.)

Figure 4.30. Schematic of an RF sputtering system (after Davidse and Maissel) with
optical-thickness monitor. (From Handbook of Thin Film Technology. © 1970,
McGraw-Hill. Used with permission of McGraw-Hill Book Co.)
Evaporation 199

Figure 4.31. Wheatstone-bridge circuit for resistance monitoring. (From Handbook


of Thin Film Technology. © 1970, McGraw-Hill. Used with permission of McGraw-
Hill Book Co.)

8.4 Evaporation Process Control

Thickness Control: Usually monitoring of an evaporation process is


combined with means to control film deposition. Frequently, the only
requirement is to terminate the process when the thickness or a thickness-
related property has reached a certain value. The simplest way is to
evaporate a weighed amount of source material to completion. Knowing the
emission characteristics of the source will allow the film thickness to be
calculated. Alternately, monitoring devices discussed earlier can be calibrated
to measure thickness directly.
Rate Control: Rate control is a more complex task and involves
measuring the signal from a rate monitor and using it in a feedback loop to
control the power to the source and hence its temperature and evaporation
rate. Table 4.5 illustrates the pros and cons of various evaporation process
control methods.
200
Table 4.5. Evaporation Process Control

Deposition Technologies for Films and Coatings


From Handbook of Thin Film Technology. Copyright © 1970, McGraw-Hill. Used with permission of McGraw-Hill Book Company.
Evaporation 201

9.0 DEPOSITION OF VARIOUS MATERIALS

The family of materials which are deposited by evaporation include


metals, semiconductors, alloys, intermetallic compounds, refractory
compounds (i.e., oxides, carbides, nitrides, borides, etc.) and mixtures
thereof. An important point is that the source material should be pure and free
of gases and/or inclusions to forestall the problem of molten droplet ejection
from the pool commonly called spitting.
Let us consider each of the materials.

9.1 Deposition of Metals and Elemental Semiconductors

Evaporation of single elements can be carried out from a variety of


evaporation sources subject to the restrictions discussed above dealing with
melting point, reactions with container, deposition rate, etc. A typical
arrangement is shown in Fig. 4.1 for electron beam heating. As discussed
above, either heating method can also be used. These are the simplest
materials to evaporate. Fortunately, at this time, it is estimated that 90% of
all the material evaporated is aluminum!

9.2 Deposition of Alloys

Alloys consist of two or more components, which have different vapor


pressures and hence different evaporation rates. As a result, the composition
of the vapor phase, and therefore the deposit, has a constantly varying
composition. There are two solutions to this problem—multiple sources and
single rod-fed or wire-fed electron beam sources.
Multiple Sources: This is the more versatile system. The number of
sources evaporating simultaneously is equal to or less than the number of
constituents in the alloy. The material evaporated from each source can be
a metal, alloy or compound. Thus, it is possible to synthesize a dispersion-
strengthened alloy, e.g., Ni-ThO2. On the other hand, the process is complex
because the evaporation rate from each source has to be monitored and
controlled separately. The source-to-substrate distance has to be sufficiently
large (15 inches for 2 inch diameter sources) to have complete blending of
the vapor streams prior to deposition, which decreases the deposition rate
(See Fig. 4.32). Moreover, with gross difference in density of two vapors, it
may be difficult to obtain a uniform composition across the width of the
substrate due to scattering of the lighter vapor atoms. Some examples are
given in Table 4.6.
202 Deposition Technologies for Films and Coatings

Figure 4.32. Two-source evaporation arrangement yielding variable film composition.


(From Handbook of Thin Film Technology. © 1970, McGraw-Hill. Used with
permission of McGraw-Hill Book Co.)

It is possible to evaporate each component sequentially, thus producing


a multi-layered deposit which is then homogenized by annealing after
deposition. This procedure makes it even more difficult to get high
deposition rates. A multiple source arrangement for production of alloy
deposits at high rates is not known.
Single Rod-Fed Electron Beam Source: The disadvantages of
multiple sources for alloy deposition can be avoided by using a single
source.[72][73] It can be a wire-fed or rod-fed source; the latter is shown in
Fig. 4.33. There is a molten pool of limited depth above the solid rod. If the
components of an alloy, A1 B10, have different equilibrium vapor pressures,
then the steady-state composition of the molten pool will differ from the feed
rod, e.g., A1 B10. Under steady-state conditions, the composition of the
vapor is the same as that of the solid being fed into the molten pool. One
has the choice of starting with a button of appropriate composition A1B10 on
top of a rod A1 B1 to form the molten pool initially or one can start with a rod
of alloy A1B1 and evaporate until the molten pool reaches compositions
A1 B10. Precautions to be observed are that the temperature and volume of
the molten pool have to be constant to obtain a constant vapor composition.
A theoretical model has been developed and confirmed by experiment. Ni-
20Cr, Ti-6Al, Ag-5Cu, Ag-10Cu, Ag-20Cu, Ag-30Cu, Ni-xCr-yAl-xY alloy
deposits have been successfully prepared. To date, experimental results
indicate that this method can be used with vapor pressure differences of a
factor of 5,000 between the components. This method cannot be used
where one of the alloy constituents is a compound, e.g., Ni-ThO2 .
Table 4.6. Two-Source Evaporation, Experimental Conditions, and Types of Films Obtained

Evaporation
203
204 Deposition Technologies for Films and Coatings
Table 4.6. (Cont'd)
Evaporation 205

Figure 4.33. Schematic of direct evaporation of an alloy from a single rod-fed


source.

In a recent paper, Shevakin et al.[74] investigated the relationship


between the composition of the evaporant material and the condensates for
alloy evaporation using electron beam evaporation techniques. They used
this method to determine thermodynamic activities of the components of
binary alloys at temperatures above the melting point of the alloy.

9.3 Deposition of Intermetallic Compounds

Intermetallic compounds which are generally deposited such as


GaAs, PbTe, InSb, etc. have as their constituents elements with low melting
points and high vapor pressures. These compound semiconductors need to
have a carefully controlled stoichiometry, i.e., cation:anion ratio. Therefore,
they can best be prepared by flash evaporation or sputtering.
206 Deposition Technologies for Films and Coatings

In flash evaporation, powder or chips of the two components are


sprinkled onto a superheated sheet to produce complete evaporation of both
components. Various possible arrangements are shown in Fig. 4.34. Table
4.7 gives examples of the use of this technique.

Figure 4.34. Flash-evaporation mechanisms. (A) Belt feeder. (Harris and Siegel.)
(B) Worm-drive feeder with mechanical vibrator. (Himes, Stout, and Thun, Braun
and Lood.) (C) Disk feeder (Beam and Takahashi.) (D) Disk magazine feeder.
(Marshall, Atlas, and Putner.) (E) Mechanically vibrated trough and cylinder source.
(Richards.) (F) Electromagnetically vibrated powder dispenser. (Campbell and
Hendry.) (From Handbook of Thin Film Technology. © 1970, McGraw-Hill. Used
with permission of McGraw-Hill Book Co.)
Table 4.7. Flash Evaporation of Materials

Evaporation
207
208 Deposition Technologies for Films and Coatings
Table 4.7. (Cont'd)
Evaporation 209

9.4 Deposition of Refractory Compounds

Refractory compounds are substances like oxides, carbides, nitrides,


borides, and sulfides which characteristically have a very high melting point
(with some exceptions). In some cases, they form extensive defect structure,
i.e., exist over a wide stoichiometric range. For example, in TiC, the C:Ti ratio
can vary from 0.5 to 1.0, demonstrating vacant carbon lattice sites. In other
compounds, the stoichiometric range is not so wide.
Evaporation processes for the deposition of refractory compounds are
further subdivided into two types: (i) Direction Evaporation [75] where the
evaporant is the refractory compound itself; and(ii) Reactive Evaporation[76]
or Activated Reactive Evaporation (ARE)[77] where the evaporant is a metal
or a low-valence compound, e.g., where Ti is evaporated in the presence of
N2 to form TiN or where Si or SiO is evaporated in the presence of O2 to form
SiO2.
Direct Evaporation: Table 4.8 gives the experimental conditions for
the direct evaporation of refractory compounds. Evaporation can occur with
or without dissociation of the compound into fragments. As seen from Table
4.8, the observed vapor specie show that very few compounds evaporate
without dissociation. Examples are SiO, MgF2, B2 O3 , CaF2 and other Group
IV divalent oxides (SiO homologs like GeO and SnO).
In the more general case, when a compound is evaporated or
sputtered, the material is not transformed to the vapor state as compound
molecules but as fragments thereof. Subsequently, the fragments have to
recombine, most probably on the substrate, to reconstitute the compound.
Therefore, the stoichiometry (anion:cation ratio) of the deposit depends on
several factors including the deposition rate and the ratios of the various
molecular fragments, the impingement of other gases present in the
environment, the surface mobility of the fragments (which in turn depends on
their kinetic energy and substrate temperature), the mean residence time of
the fragments of the substrate, the reaction rate of the fragments on the
substrate to reconstitute the compound, and the impurities present on the
substrate. For example, it was found that direct evaporation of Al2O3 resulted
in a deposit which was deficient in oxygen, i.e., which had the composition[78]
Al2O3-x. This O2 deficiency could be made up by introducing O2 at a low
partial pressure into the environment. In other cases, for example the direct
evaporation of TiB2 and ZrB2 , the deposit contains both the monoboride and
diboride phases.[79]
210 Deposition Technologies for Films and Coatings

Table 4.8. Direct Evaporation of Inorganic Compounds


Evaporation 211

Table 4.8. (Cont'd)


212 Deposition Technologies for Films and Coatings

Table 4.8. (Cont'd)


Evaporation 213

9.5 Reactive Evaporation Process

The difficulties involved in direct evaporation processes due to


fragmentation of the vaporized compounds are overcome in reactive
evaporation where a metal is evaporated in the presence of the reactive gas;
the compound is formed by reaction of the evaporated metal species with the
molecules of the reactive gas. Though this technique has been extensively
used to deposit a variety of oxide films for optical applications, it is generally
observed that the films are deficient in oxygen. It is also observed in some
cases, especially in the synthesis of carbide films, that the deposition rate
becomes a limiting factor governing the growth of the films. In such cases,
stoichiometric TiC films could only be deposited at very low rates (~1.5 Å/sec
max).[80] This limitation of deposition rate in the case of the reactive
evaporation process is due to the reaction kinetics of the compound
formation by this process. The presence of a “plasma” in the ARE process
influences the reaction kinetics by providing activation energy to the reactive
species, thereby making it possible to synthesize compound films at
considerably higher rates[82]-[84] and lower temperatures.

9.6 Activated Reactive Evaporation (ARE)

The ARE process generally involves evaporation of a metal or an alloy


in the presence of the plasma of a reactive gas.[81][82] For example, TiC and
TiN coatings are deposited by this process by evaporating Ti in the presence
of C2H2 and N2 plasma respectively. The two basic variants of the ARE
process are shown in Figs. 4.35, 4.36. For more information on the ARE
process, please refer to a review by Bunshah and Deshpandey.[83] The role
of the plasma in this process is two-fold:
1. To enhance the reactions that are necessary for deposition of
compound films.
2. To modify the growth kinetics and hence the structure/
morphology of the deposits.
In the following section we discuss the above two aspects.
Thermodynamic and Kinetic Considerations In Plasma Assisted
Deposition Processes. For the formation of a compound by any chemical
reaction, the corresponding thermodynamic and kinetic constraints must be
satisfied which also apply to the deposition of refractory compound films by
reactive evaporation. In order to understand the role of plasma in enhancing
the chemical reactions essential for the formation of a particular compound,
one has therefore to consider the kinetics of these reactions.
214 Deposition Technologies for Films and Coatings

Figure 4.35. Schematic of the Activated Reactive Evaporation Process.

Let us consider the reactions involved in the synthesis of some oxides,


carbides, and nitrides by reactive evaporation. Given below are the reactions
for forming Al2O3, TiC, and TiN.

2Al + 3 /2 O2 → Al2O3 ∆G° = -250 kcal (mol O2)-1 at 298 K


2Ti + C2H2 → 2TiC + H2 ∆G° = -7.65 kcal (mol C 2H2 )-1 at 298 K
2Ti + N2 → 2TiN ∆G° = -73.5 kcal (mol N2 )-1 at 298 K
Evaporation 215

Figure 4.36. The Activated Reactive Evaporation (ARE) Process[182] using


resistance-heated evaporation source.

As can be seen from the above reactions, the thermodynamic criterion


of free energy of formation is satisfied for the respective compounds.
The reaction kinetics in reactive evaporation process can be treated
in exactly the same manner as for reactions occurring in heterogeneous
systems of condensed phases. The model for heterogeneous metallurgical
kinetics involves: (i) transport of reactant to the reaction interface; (ii)
transport of reaction products away from the reaction interface; (iii) the
chemical reaction at the chemical interface;(iv) the nucleation of new phase;
and (v) heat transfer to or away from the reaction interface.
For reactive evaporation, this model may be depicted as follows (e.g.,
for TiC formation):
216 Deposition Technologies for Films and Coatings

Reactants Products
Ti (metal atoms) TiC (deposit)
C2 H2 (gas) H2 (gas)
Reaction
Interface

On the basis of the above model, the rate-controlling steps in the


reactive evaporation process are: (i) adequate supply of reactants; (ii)
adequate collision frequency; (iii) the rate of chemical reactions at the
interface; and (iv) the rate of removal of the reaction products from the
interface.
It is easy to satisfy (i), (ii), and (iv) above for a reactive evaporation
process. However, condition (iii), i.e., the rate of reaction, becomes the rate
governing step. The “plasma” in the ARE process influences this step, i.e.,
the rate of reaction, by providing the necessary activation energy to the
reactive species. The effect of plasma on rate of reaction can be clearly
demonstrated by considering the results of Abe et al.[80] and Bunshah and
Raghuram[84] on deposition of TiC coatings. Abe et al. found that titanium
carbide with a carbon-to-titanium ratio of 1 could be formed by a reaction
between Ti and C2H2 or C2 H4 molecules on a substrate at 300 - 500°C only
if the deposition rate is 1 to 1.5 Å/sec. At higher deposition rates, no TiC was
formed. Clearly the activation barrier could not be overcome at the higher
deposition rates. Bunshah and Raghuram[84][85] have similarly reported that
the deposition of TiC by reactive evaporation at higher deposition rates (150
- 200 Å/sec) required a very high substrate temperature, exceeding 1000°C.
However, in the presence of plasma, these authors reported that it was
possible to deposit TiC at a high rate at a relatively low substrate temperature.
The plasma imparts sufficient energy to the reacting species to overcome the
activation energy barrier, and hence condition (iii), i.e., the rate of reaction,
no longer remains the rate-governing step.
Basic Variants of the ARE Process. The two basic variants of the
ARE process are activated reactive evaporation with an electron-beam
evaporation source[82] and the ARE processes with a resistance-heated
source.[86]
1. ARE processes with an electron-beam-heated evaporation
source are illustrated in Fig. 4.35. In this process, the metal is
heated and melted by a high-acceleration-voltage electron
beam that produces a thin plasma sheath on top of the melt.
The low energy secondary electrons from the plasma sheath
Evaporation 217

are pulled upwards into the reaction zone by an electrode


placed above the pool biased to a low positive DC or AC
potential (20 to 100 V), thus creating a plasma-filled region
between the electrode and the electron-beam gun. The low-
energy electrons have a high ionization cross section, thus
ionizing or activating the metal and gas atoms and increasing
the reaction probability on collision. Charge-exchange
processes between positive ions and neutral atoms take place
in the plasma. In addition, as suggested by Yee, [87] transient
highly excited compound species are formed. The formation
of the compound is completed most probably on the substrate
from these energetic and excited transient species. The
synthesis of TiC by reaction of Ti metal vapor and C2H2 gas
atoms with a carbon-to-metal ratio approaching unity was
achieved with this process.[82][84] Moreover, by varying the
partial pressure of either reactant, the carbon-to-metal ratio of
carbides could be varied[84] at will. The ARE process has also
been applied to the synthesis of all five different Ti-O oxides.[88]
These authors noted that in the ARE process (i.e., with a
plasma) as compared to the RE process (i.e., without a
plasma), a higher oxide is formed for the same partial pressure
of O2 , thus demonstrating a better utilization of the gas in the
presence of a plasma. The same observation was noted by
Bunshah and Raghuram,[84] as well as by Granier and
Besson,[89] for the deposition of nitrides.
2. A variation of the ARE process uses a resistance-heated
evaporation source. The basic ARE process uses electron-
beam-heated sources, which are expensive and inconvenient
for the evaporation of low-melting-point high-vapor-pressure
materials. Nath and Bunshah[86] modified the ARE process for
resistance-heated sources, as shown in Fig. 4.36. The metal
vapors are generated from the chamber; the reaction is
enhanced by a plasma generated by injecting low energy
electrons from a heated thoriated tungsten emitter towards a
low-voltage anode assembly. A transverse magnetic field is
applied to cause the electrons to go into a spiral path, thus
increasing the probability of electron/atom collision and
subsequent ionization.
218 Deposition Technologies for Films and Coatings

Modifications of the Basic ARE Process. The ARE process has


substantial versatility since the substrate can be grounded, positively or
negatively biased, or it can be allowed to float electrically. There are several
modifications of the basic ARE process, as illustrated in Fig. 4.37.
1. The Enhanced ARE Process.[90] This is the conventional ARE
process using electron-beam heating with the addition of a
thermionic electron emitter (e.g., a tungsten filament) for the
deposition of refractory compounds at lower deposition rates
as compared to the basic ARE process. The low-energy
electrons from the emitter sustain the discharge, which would
otherwise be extinguished since the primary electron beam
(used to melt the metal) is so weak that it does not generate an
adequate plasma sheath above the molten pool from which low
energy electrons can be extracted by positively biased
interspace electrode. The substrate may be biased, grounded
or floating.
2. Low-Pressure Plasma Deposition (LPPD) Process. Using
electron-beam evaporation sources, the electric field may be
generated by biasing the substrate positively instead of using
a positively biased interspace electrode. In this case, it is called
low-pressure plasma deposition (LPPD) by Nakamura et al.[91]
However, this version has a disadvantage over the basic ARE
process since one does not have the freedom of choice to
ground the substrate, let it float, or bias it negatively (the BARE
process—see #4 below).
3. ARE Using Plasma Electron-Beam Guns. The plasma electron-
beam gun, instead of the thermionic electron-beam gun, can
be used to carry out the ARE process. The hot hollow cathode
gun has been used by Komiya et al.[92] to deposit TiC films,
whereas Zega et al.[93] used a cold cathode discharge electron-
beam gun to deposit titanium nitride films. The plasma e-beam
sources produce an abundant supply of low-energy electrons
for the ARE-type process.
4. Reactive Ion Plating (RIP) Processes. If the substrate is biased
in the ARE process, it is called biased activated reactive
evaporation (BARE). This bias is usually negative to attract the
positive ions in the plasma. The BARE process has been
reinvented and called reactive ion plating by Kobayashi
Evaporation 219

Figure 4.37. Basic “ARE” process and later variations.

and Doi.[94] Reactive ion plating (RIP) is very similar to the


reactive evaporation process in that metal atoms and reactive
gases react to form a compound aided by the presence of a
plasma. Since the partial pressure of the gases in reactive ion
plating are much higher (> 10-2 torr) than in the ARE process
(> 10-4 torr), the deposits can become porous or sooty. The
plasma cannot be supported by lower pressure in the simple
diode ion plating process; therefore, Kobayashi and Doi[94]
introduced an auxiliary electrode biased to a positive low
220 Deposition Technologies for Films and Coatings

voltage (as originally conceived for the ARE process) to


initiate and sustain the plasma at low pressure (~10-3 torr).
This is no different than the ARE process with a negative bias
on the substrate reported[81] much earlier by Bunshah, which
was designated by him as the biased ARE (or BARE) process.
5. Another variation of reactive ion plating using a triode
configuration[95] involves injection of electrons into the reaction
zone between the electron-beam-heated evaporation source
and the negatively biased substrate from a heated tungsten
filament transversely to the metal vapor path. These low-
energy electrons are pulled across the reaction zone by a
positively biased anode located opposite to the cathode. The
arrangement is very similar to that shown in Fig. 4.27 except for
the use of an electron-beam-heated evaporation source, and
is also very similar to the triode sputtering. This adds versatility
as well as complexity to the process through the addition of
another process variable.
6. Murayama[96] uses an electron-beam-heated source with a
negatively biased substrate and RF activation of the reactants
by means of a coil electrode of aluminum wire in the reaction
zone to deposit oxide and nitride films.
7. ARE Process Using an Arc Evaporation Source. Evaporation
of metals using a low-voltage arc in the presence of a plasma
and a negatively biased substrate is used by Snaper[52][53] and
Dorodnov[97] to deposit nitride and carbide films, with N2 and
hydrocarbon reactive gases, respectively.
Recent Developments in the ARE Process. In the last few years,
new techniques based on ARE are being developed for synthesis of novel
and unique materials. The emphasis of such developments is generally on
two aspects: i) new approaches to produce the vapor species, and ii) new
plasma excitation and confinement techniques and development of modified
plasma excitation geometries.
New Approaches to Produce the Various Species. The basic
process involves evaporation of the constituent metal alloy or compound
using e-beam or resistance/induction heated sources. However, it is
difficult to use this approach with certain materials such as boron and
carbon. Two possible solutions can be used to overcome these difficulties:
i) use a low melting point compound of the respective element, and ii) use
Evaporation 221

a pulsed laser beamwherethe pulse rate and pulse width can be appropriately
adjusted to control the rate of material generation and fragmentation.
Moreover, in many cases, the energy of the laser beam can also be used as
source for plasma excitation.
Both of these approaches have been explored. A process developed
by Bunshah et. al.[98] for the synthesis of cubic boron nitride involves boric
acid as an reactant, which can be easily evaporated from a resistance-
heated tungsten boat. In addition to the ease of evaporation, this process
also excludes the toxicity problems associated with fine boron particles
which can be produced during e-beam evaporation of boron. A similar
approach can be extended to evaporation of carbon using a low melting point
carbon compound such as adamantine. It is likely that many new materials
hitherto difficult to synthesize may possibly be deposited using this routine.
Moreover, this novel approach may contribute to further development in
reactive MBE processes and other vapor deposition processes involving
organometallic compound reactants.
The use of pulsed laser beams in an ARE type of process has been
demonstrated in recent literature on high Tc superconducting films. Films
with high Tc (90 K) and high critical current density (0.7 x l06 A·cm-2 at 77 K)
have been produced.[99] It is claimed that pulsing of the laser beam avoids
fractionation of the compound and hence good control of film stoichiometry
is achieved. It is also suggested that the photon energy is sufficient to
activate the reactive gas/metal species thereby increasing their reactivity,
leading to increase in oxygen concentration in the deposited films.
New Plasma Excitation Modes and Geometries. As discussed
earlier, the attributes of the ARE processes are due to the possibility of
controlling the plasma parameters independently of the deposition process.
However, improvement in excitation and confinement of the plasma, as well
as control and optimization of plasma parameters in the ARE processes, are
likely to enhance the process capabilities. Recent developments include (i)
the use of inductively coupled RF with parallel plate RF geometries, and (ii)
the use of multiple filaments and anodes with magnetic confinement. These
enhancements have led to substantial improvements in film properties as
well as process control. Examples are high rate deposition of a-Si-H
films,[100] transparent conducting films on polymeric substrates(101) and TiSx
and MoSx[102][103] films with variable x values.
Two additional modes of ionization are being explored. Currently an
auxiliary RF excitation source similar to that reported by Oeschner[104] is
being developed for use in ARE. It is believed that the high electron density
222 Deposition Technologies for Films and Coatings

and energy selectivity offered by this source is likely to enhance advantages


of the ARE processes for compound synthesis. Also, work is underway to
integrate Electron Cyclotron Resonance (ECR) excitation at microwave
frequencies with the ARE process. ECR plasmas are characterized by a
very high level of ionization and excitation, and may greatly enhance the use
of ARE for the deposition and synthesis of films.
Mechanism of the ARE Process. A reactive evaporation process
can be simply written as a reaction between the reactants giving rise to the
products. Illustrating this for the deposition of TiC films, one may write

xTi (vapor) + CxHy (gas) → xTiC (solid) + yH (gas)

In a plasma-assisted deposition process, the reactants dissociate into


fractions/radicals and ionic species are produced. Therefore a multiplicity of
reaction paths are possible and the overall reaction becomes more complex.
Deshpandey, O’Brien, Doerr, and Bunshah[105][106] studied the
synthesis of TiC and TiN films, evaporating Ti in a plasma of CxHy gases for
the synthesis of TiC films and N2 or NH3 with Ti for the synthesis of TiN films.
Several spectroscopies were used to carry out diagnostics on the plasma in
the source-substrate volume to determine the species present and the
potential reaction paths leading to film formation. Neutral mass spectrometry
(MS), plasma mass spectrometry (PMS), and optical emission spectroscopy
(OES) were used to examine the nature and relative concentrations of
neutral, excited and ionized species present in the process.
The main results of these investigations are as follows:
1. Polymerizing reactions producing higher molecular weight
hydrocarbon species are dominant in the case of methane.
Polymerization increases with increasing flow rate of CH4 for
a given electron beam current. The above reactions lead to the
formation of relatively soft films containing TiC and graphitic
phases.
2. Hard, single-phase TiC films are formed at flow rates of about
50 standard cm3 min-1 C2 H2 for beam currents in the range of
0.2 - 0.3 A. Polymerization reactions do not take place when
C2 H2 is used as a reactive gas. Species such as carbon, CH,
and CH2 formed in the plasma from the dissociation of C2H2
react with titanium to form TiC. The PMS and MS data indicate
the following possible routes for formation of TiC:
Evaporation 223

a. formation of TiC in the plasma volume through reactions


such as:

Ti + C → TiC Ti + CH → TiC + H
Ti + CH2 → TiC + 2H Ti + CH3 → TiC + 3H

followed by condensation of TiC molecules on the substrate;


or
b. formation of TixCy or Ti2 Cy or Ti2CyHz complexes in the
plasma volume followed by condensation on the substrate
to form TiC according to:

TixCy → TiC + C TixCyHz → TiC + CyHz

Present data are not sufficient to determine which of these two


schemes is dominant in the formation of TiC. PMS and MS
sampling of the arriving flux on the substrate as well as studies
with a biased substrate are necessary to resolve this issue.
Similar studies on the deposition of TiN films revealed the following:
1. Evaporation of Ti in a N2 plasma showed that the predominant
species leading to hard stoichiometric TiN films is 2Ti+ + N2+ →
2TiN. The ratio of Ti+/N2+ in the plasma was 1.05, i.e., close to
unity. When this ratio was increased to 1.5, soft films with
excess Ti in the deposit were produced. Yee[87] also proposed
the same reaction path based on his optical emission
spectrographic studies.
2. Evaporation of Ti in an NH3 plasma showed similar results.
Under conditions where the Ti+/N2+ ratio was high, the films
were soft and titanium rich. With a higher flow rate of NH 3, the
N2+ concentration in the plasma was higher and the films were
hard.

9.7 Materials Synthesized by Evaporation-based Processes

A variety of metals, alloys, and compounds (oxides, nitrides, carbides,


sulfides) have been deposited using evaporation and related processes. In
particular, the plasma-assisted variant of the evaporation process, such as
activated reactive evaporation, has been successfully used for deposition of
a variety of compounds for tribological as well as opto-electronic applications.
Recently, a modified process basedon the ARE technique has also proved
224 Deposition Technologies for Films and Coatings

to be successful in synthesizing c-BN.[98][107] A representative list of the


compounds synthesized by the ARE process is given below. In a very recent
development, the ARE process has been able to deposit Al2O3 films at very
high deposition rates (8 to 12 µm/hr); these rates are 10 to 30 times higher
than those by sputter deposition.[108]
The compounds synthesized by the ARE process include:
Carbides: TiC, HfC, ZrC, VC, W2C, TaC
Carbonitride: Ti (C,N)
Nitrides: TiN, HfN, ZrN
Oxides: TiO2, ZrO2, Al2O3, SiO2
Sulfides: TiS2, MoS2, MoS3
Superconductors: Low Tc: Nb3Ge, CuMo6 S8
High Tc: YBa2CU3O7-8
Photovoltaic Materials: a-SiH, CuInS2
Opto-electric Materials: In(Sn)O2, ZnO
Novel Materials: c-BN, Diamond, i-C, a-C

10.0 MICROSTRUCTURE OF PVD CONDENSATES

10.1 Microstructure Evolution

PVD condensates deposit as single crystal films on certain crystal


planes of single crystal substrates, i.e., by epitaxial growth,[109] or in the more
general case, the deposits are polycrystalline. In the case of films deposited
by evaporation techniques, the main variables are: (i) the nature of the
substrate;(ii) the temperature of the substrate during deposition; (iii) the rate
of deposition; (iv) the deposit thickness; (v) the angle of incidence of the
vapor stream; and (vi) the pressure and nature of the ambient gas phase.
Contrary to what might be intuitively expected, the deposit does not start out
as a continuous film one monolayer thick and grow. Instead, three-
dimensional nuclei are formed on favored sites on the substrates, e.g.,
cleavage steps on a single crystal substrate; these nuclei grow laterally and
in thickness (the so-called island growth stage) ultimately impinging on each
other to form a continuous film. Figure 4.38 shows the growth of gold film on
rock-salt. The average thickness at which a continuous film forms
depends on the deposition temperature and the deposition rate (both
of which influence the surface mobility of the adatom) and varies from
10 Å for Ni condensed at 15°K to 1000 Å for Au condensed at 600°K.
Evaporation 225

This familiar model of island growth of a polycrystalline film during the


initial stages of deposition illustrates the case where there is limited interaction
between depositing atoms and the substrate. This is not always the case.

Figure 4.38. Sequence of micrographs illustrating the effect of increasing deposit


thickness of gold on rock salt (x 8000). (After Pashley,[101] with permission.)

Important differences have been observed. Namba and Mori[237]


found that by converting a significant fraction (~ 10%) of the vapor flux of
Ag to positive ions, epitaxial growth of a single crystal Ag film on a single
226 Deposition Technologies for Films and Coatings

crystal Ag film on a single crystal NaCl substrate biased to -3,000 V was


observed, whereas with vacuum evaporation, the Ag film was polycrystalline.
No clear explanation is possible except to note that the mobility of the
deposited species is much greater when partially ionized than for neutral
vapor specie. The effective surface temperature of the growing film is much
higher due to ion bombardment, thus permitting greater surface mobility and
resulting in epitaxial growth. Taylor(238) used low energy electron diffraction
(LEED) techniques to study the epitaxial deposition of Cu onto a single
crystal[196] face of tungsten under ultra-high vacuum conditions. This
represents the case where there is appreciable bonding between depositing
atoms and the substrate. The deposit on a clean tungsten surface was a
uniformly thin[166] Cu film, i.e., no island growth prior to the formation of a
continuous film even at thicknesses of 1½ atomic layers. He further
observed that chemisorption of even a half monolayer of oxygen severely
inhibited epitaxial growth.
Sherman, Bunshah, and Beale[119] studied the deposition of thick Mo
films onto a rolled Mo sheet substrate as a function of deposition temperature.
They observed polycrystalline deposits at all temperatures except in the
range of 973° to 1188°K, where the surface oxide MoO3 is unstable and
evaporates rapidly, thereby leaving behind a “clean” Mo surface on which
epitaxial growth can readily occur aided by the high surface mobility at the
elevated deposition temperature.
Once a continuous film has formed, the subsequent evolution to the
final structure of the thin film is poorly understood at present. It undoubtedly
depends on the factors mentioned above which in turn influence the primary
variables of nucleation rate, growth rate, and surface mobility of the adatom.
The problem has been tackled by Van der Drift[110] and is also the subject of
a paper by Thornton.[111]
The microstructure and morphology of thick single phase films have
been extensively studied for a wide variety of metals, alloys and refractory
compounds. The structural model was first proposed by Movchan and
Demchishin,[75] Fig. 4.39, and was subsequently modified by Thornton as
shown in Fig. 4.40. Movchan and Demchishin’s diagram was arrived at from
their studies on deposits of pure metals and did not include the transition zone
of Thornton’s model, Zone T, which is not prominent in pure metals or single
phase alloy deposits, but becomes quite pronounced in deposits of refractory
compounds or complex alloys produced by evaporation, and in all types of
deposits produced in the presence of a partial pressure of inert or reactive
gas, as in sputtering or ion plating processes.
Evaporation 227

Figure 4.39. Structural zones in condensates. (Movchan and Demchishan.)

Figure 4.40. Structural zones in condensates. (Thornton.)

The evolution of the structural morphology is as follows:


At low temperatures, the surface mobility of the adatoms is reduced
and the structure grows as tapered crystallites from a limited number of
nuclei. It is not a full density structure but contains longitudinal porosity of
228 Deposition Technologies for Films and Coatings

the order ofa few hundred angstroms width between the tapered crystallites.
It also contains a high dislocation density and has a high level of residual
stress. Such a structure has also been called “Botryoidal” and corresponds
to Zone 1 in Figs. 4.39 and 4.40.
As the substrate temperature increases, the surface mobility increases
and the structural morphology first transforms to that of Zone T, i.e., tightly
packed fibrous grains with weak grain boundaries, and then to a full density
columnar morphology corresponding to Zone 2 (Fig. 4.40).
The size of the columnar grains increases as the condensation
temperature increases. Finally, at still higher temperatures, the structure
shows an equiaxed grain morphology, Zone 3. For pure metals and single
phase alloys, T1 is the transition temperature between Zone 1 and Zone 2
and T2 is the transition temperature between Zone 2 and Zone 3. According
to Movchan and Demchishin’s original model,[75] T1 is 0.3 Tm for metals, and
0.22 - 0.26 Tm for oxides, whereas T2 is 0.45 - 0.4 (Tm is the melting point in
°K).
Thornton’s modification shows that the transition temperatures may
vary significantly from those stated above and, in general, shift to higher
temperatures as the gas pressure in the synthesis process increases.
It should be emphasized that:
1. The transition from one zone to the next is not abrupt but
smooth. Hence the transition temperatures should not be
considered as absolute, but as guidelines.
2. All zones are not found in all deposits. For example, Zone T is
not prominent in pure metals, but becomes more pronounced
in complex alloys, compounds, or in deposits produced at
higher gas pressures. Zone 3 is not seen very often in
materials with high melting points.
The reader is referred to a more extensive description given by Greene
in this book in Ch. 13, which includes a discussion of the effects of substrate
surface roughness and pressures.
Most thick deposits exhibit a strong preferred orientation (fiber texture)
at low deposition temperatures and tend towards a more random orientation
with increasing deposition temperature. Figure 4.41 shows the evolution of
a large-grained columnar morphology in a Be deposit from a much larger
number of fine grains which were originally nucleated on the substrate. As
growth proceeds, only those grains with a preferred growth direction survive,
presumably due to considerations of the minimization of surface energy.
Evaporation 229

Figure 4.41. Photomicrograph of a Be deposit showing the evolution of large


columnar grains.

Elegant proof of the importance of surface mobility was also provided


by Movchan and Demchishin.[75] Plots of the log of the grain diameter versus
the inverse of deposition temperature in Zones 2 and 3 yield straight lines
from which activation energies can be computed. It was found that the
activation energy for Zone 2 growth corresponded to that for surface self-
diffusion and for Zone 3 growth to volume self-diffusion.
The morphological results reported by Movchan and Demchishin for
nickel, titanium, tungsten, Al2O3 and ZrO2 have been confirmed for several
metals and compounds. The data are given in Table 4.9.[114][124][115][116]
Bunshah and Juntz [117] studied the influence of condensation
temperature on the deposition of titanium. Their microstructures, shown in
Fig. 4.42, agree substantially with those of Movchan and Demchishin for
Zones 1 and 2 and T1, the transition temperature between Zones 1 and 2.
However, they failed to observe Zone 3 at the temperatures above 700°C
found by Movchan and Demchishin.[75] The structure was columnar up to
833°C, which is the α:β phase transformation temperature for titanium. At
deposition temperatures above 833°C, the deposit crystallizes as the β
phase and on cooling to room temperature, should transform to theα phase,
resulting in the typical “transformed-beta” microstructure shown in Fig. 4.42
(900°C deposit), which could be mistaken for an equiaxed microstructure.
Hence, the claim of such a transition in structure from Zone 2 to 3 by Movchan
and Demchishin for titanium deposits is confusing.
230 Deposition Technologies for Films and Coatings

Table 4.9. Transition Temperatures between Various Structural Zones

Kane and Bunshah[118] observed the change in morphology in deposited


nickel sheet. At 425°C deposition temperature, the deposit showed a Zone
2 morphology, whereas, at 554°C, the deposit showed a Zone 3 morphology.
Chambers and Bower[123] studied the deposition of magnesium,
copper, gold, iridium, tungsten, and stainless steel. Of the photomicrographs
presented, gold and magnesium showed Zone 2 columnar morphology at the
appropriate substrate temperatures.
Figure 4.43 shows surface and cross section photomicrographs of a
Ni-20Cr sheet deposited by Agarwal, Kane and Bunshah.[124] At 950°C,
760°C, 650°C, and 427°C deposition temperatures, the surface and cross
section showed an equiaxed Zone 3 morphology.
Mah and Nordin[121] found that the Movchan-Demchishin model was
obeyed by beryllium also. They observed structures corresponding to all
three zones with transition temperatures as predicted by the model.
Evaporation
231
Figure 4.42. Structure of titanium deposits at various substrate temperatures (Bunshah and Juntz).
232 Deposition Technologies for Films and Coatings

Figure 4.43. Photomicrographs of typical Ni-20Cr deposits at various substrate


temperatures. (Agarwal, Kane, and Bunshah.)[124]
Evaporation 233

Neirynck, Samaey and Van Poucke[125] studied the influence of


deposition rate and substrate temperature on the microstructure, adhesion,
texture, and condensation mechanism of aluminum and zirconium coatings
on steel substrates and wires in batch and continuous-coating methods.
Kennedy[120] showed a change in morphology from columnar to
equiaxed in Fe and Fe-10Ni alloy with higher deposition temperature.
Deposits of Fe-1%Y which is a two phase alloy, showed columnar morphology
only, the structure becoming coarser at higher deposition temperature. The
second phase appears to nucleate new grains so that the grain size in Fe-
1%Y alloys is much finer than that of iron.
The microstructure of copper-nickel alloys[122] produced by co-
deposition from two sources showed a single phase, as might be expected
for this system, which shows a complete solid solubility. On the other hand,
sequential deposition of Cu and Ni from two sources shielded from each
other onto a rotating substrate produced a microlaminate structure in the
deposit where the laminate size can be varied from 0.01 to 40 µm by adjusting
the deposition parameters.[239] Similar structures were also developed in the
Fe-Cu[239] and in the Ti-B4C system.[239]
ln alloy systems showing the presence of several phases, e.g., Ni-B
and Cr-Si, the deposits showed the phases present corresponded to those
expected from the diagram.[122]
Smith, Kennedy, and Boericke[122a] studied the deposition of the two
phase (α+β) type Ti-6Al-4V alloy deposited from a single rod-fed source. The
microstructure was very similar to wrought material with the same
characteristic α+β morphology present on a finer scale in the deposited
material.
Dispersion-strengthened alloys produced by co-deposition from multiple
sources have also been produced. Paton et al.[122] produced Ni-TiC, Ni-NbC
and Ni-ZrO2 alloys. The particle size increases from 100 to 1000 Å by
changing the deposition temperature from 350° to 1000°C. The size of the
dispersed carbide phase particles increased on annealing at 1000° to
1100°C due to their slight solubility in nickel. On the other hand, the size and
distribution of ZrO2 dispersion remained constant even after exposure at
1300°C for 5 hours as shown in Fig. 4.44.
Movchan, Demchishin, and Kooluck[126] produced Fe-NbC and Fe-Ni-
NbC dispersion strengthened alloys by co-evaporation. The microstructure
exhibited columnar morphology, with the inclusion of a fine dispersion of NbC
particles.
234 Deposition Technologies for Films and Coatings

Figure 4.44. Microstructure of dispersion strengthened Ni-ZrO2 alloy before and


after exposure at 1300°C for 5 hours (Paton, Movchan, and Demchishin).[122]
Evaporation 235

Raghuram and Bunshah[127] studied the microstructure of TiC deposits


from 500° to 1450°C shown in Fig. 4.45. They observed the transition from
the tapered crystallite (Zone 1) to columnar structure at 973°K, or 700°C (0.3
Tm). The highest deposition temperature (1450°C) used by these investigators
was not sufficient to produce an equiaxed structure although this temperature
corresponds to 0.51 Tm.

Figure 4.45. Structure of TiC deposits at various substrate temperatures (Raghuram


and Bunshah).[127]
236 Deposition Technologies for Films and Coatings

The energy of the depositing beam of atoms can be increased if some


of them are ionized. It has been shown by Smith[23] that a small fraction of
the vaporized species from an electron beam heated source is ionized due
to collisions with electrons in the plasma sheath above the molten pool.
Bunshah and Juntz[128] biased the substrate to -5,000 V during the deposition
of beryllium at 570°C and found that the columnar grain size was markedly
refined by the ion bombardment as compared to the grain size produced
without biasing the substrate at the same deposition temperature. It may be
postulated that the ion bombardment causes a localized increase in
temperature at the surface where deposition is occurring, thus causing a
higher nucleation rate and a finer grain size. Similar results have been
reported for tantalum.[129] The use of hollow cathode gun intensifies the
degree of ionization of the vapor species, resulting in a marked increase in
kinetic energy of the vaporized atoms.[130] The effects of substrate bias are,
therefore, easier to observe. Increasing the substrate bias results in a
change in morphology from columnar to fine, equiaxed grains for silver
deposited on beryllium and stainless steel,[131] and for silver and copper
deposited on stainless steel.[132]
On the other hand, the presence of a gas at high pressures (5 to 20 µm)
results in a net decrease in kinetic energy of the vaporized atoms due to
multiple collisions during the transverse from source to substrate. This
degrades the microstructure to loose columnar grains[132] and eventually to
an agglomerate of particles. (This, in fact, is a way to produce fine powders
by evaporation and subsequent gas-phase nucleation and condensation.)
The negative effects of the presence of a high gas density on the kinetic
energy and the mobility of adatoms on the deposit surface can be overcome
by either biasing the substrate[132][133] and/or heating the substrate to a
higher temperature.[134]

10.2 Texture

The texture of evaporated deposits is, in general, dependent on


deposition temperature. At low deposition temperatures, a strong preferred
orientation is generally observed: {211} in iron,[120] {220} in TiC,[127] and
{0002} in Ti.[135] As deposition temperature increases, the texture tends to
become more random. In the case of beryllium,[114] the texture changed to
a {110} orientation at high deposition temperatures. The presence of a gas
tends to shift the preferred orientation to higher index planes.[136] For silver,
increasing the substrate bias changes the preferred orientation from {111} to
{200} and back to {111}.[121]
Evaporation 237

10.3 Residual Stresses

Residual stresses in deposits are of two types. The first kind arises
from the imperfections built in during growth (the so-called growth stresses).
An increase in deposition temperature produces a marked decrease in the
magnitude of this stress.[127][137] The other source of residual stress is due
to the mismatch in the coefficient of thermal expansion between the substrate
and the deposit. Its magnitude and size depend on the values of the thermal
expansion coefficients as well as the thickness and size of the substrate and
deposit. The influence of a negative bias on the substrate produces a
compressive stress in the deposit, which reaches a maximum value at -200
to -300 V DC bias and then decreases.[133]
High residual stresses can cause plastic deformation (buckling or
bending), cracking in the deposit or the substrate, or cracking at the
substrate-deposit interface. The latter can be minimized by grading the
interface, i.e., producing the change in material over a finite distance instead
of producing it abruptly at a sharp interface. A graded interface can be
produced by gradually changing the deposition conditions or by interdiffusion,
which is enhanced by higher substrate temperature or increased kinetic
energy of the vapor species.

10.4 Defects

Let us next consider the “defects” found in vapor-deposited materials.


The first one is classified as a spit, or small droplet ejected from the molten
pool, which lands on the substrate and is incorporated into the coating.[138]
An example is shown in Fig. 4.46. The composition of the droplet is different
from that of the coating in the case of an alloy and can therefore be the site
of corrosion initiation. The bond between the droplet and the surrounding
material is usually poor. Hence, corrosion attack can proceed down the
boundary to the substrate or undermine the coating. The spit may also fall
out, leaving a pinhole behind which can act as a stress concentrator and limit
the ductility or the uniform elongation of a sheet material. Spits or pinholes
do not affect the yield strength or reduction of area in a ductile material, but
they can be stress raisers and sites for fatigue-crack initiation. Both spits and
foreign particles on the substrate surface induce preferential growth of the
deposit in that area because of higher exposure to the vapor flux than the
general growing interface. This region of preferential growth is termed a
flake; typical flakes are shown in Fig. 4.47. There is marginal bonding
between the flake and the deposit, which can lead to formation of a pit or
crack, or to nucleation of corrosive attack.
238
Deposition Technologies for Films and Coatings
Figure 4.46. Vapor source droplet (spit) defect in M-Cr-Al-Y coatings. (a) and (b) show defects overcoated with additional material.
(c) fatigue crack initiated at spit (Boone et al.). (Courtesy of Amer. Inst. of Physics.)
Evaporation 239

Figure 4.47. Flake defects in (a) and (b) produced by accelerated coating
deposition on foreign particles. Glass bead peening incorporates flake into the
coating (c) or knocks it out and forms a pit (d) (Boone et al.). (Courtesy of Amer. Inst.
of Physics.)

Spits can be suppressed by eliminating porosity, oxide inclusions and


compositional inhomogeneities in the evaporant source material, since
spitting can be caused by included-gas release or by the release of bound
gas through thermal decomposition. In electron-beam evaporation, the
beam of electrons dissipates energy over a path extending as much as a mil
(25 µm) or more into the melt. If this energy is delivered at a rate faster than
the coating material can accommodate by evaporation, conduction, or
radiation, a pocket of vapor forms and spitting occurs. Spits are also caused
by gas pockets included in the evaporant rod that suddenly expand when
rapidly heated by the beam. Nonmetallic inclusions also can trap
pockets of superheated vapor below them, which can erupt in a
shower of molten droplets. Spits can be avoided by using a high
purity vacuum melted rod as the evaporant. Flake formation can be
avoided by avoiding the presence or impingement of foreign particles on the
240 Deposition Technologies for Films and Coatings

substrate (primarily by substrate surface cleaning and good housekeeping


of the deposition apparatus). Deep grooves or ridges on the substrate can
also produce flake-type defects by shadowing adjacent regions of the
specimen surface.
Another type of defect occurs in complex alloys[138] such as M-Cr-Al-
Y (where M can be nickel, cobalt or iron), where even at deposition
temperatures of 955°C, the deposit morphology corresponds to the fibrous
transition zone between Zone 1 and Zone 2. The grain boundaries in this
morphology are weak, causing intergranular corrosive attack (see Fig. 4.48).
The problem can be obviated by increasing the adatom mobility through the
use of a higher substrate temperature or specimen bias of about -200 V, or
by using a post-coating process that consists of a room temperature high
intensity glass bead peening followed by a high-temperature anneal in
hydrogen. Compound rotation of the specimen, which exposes higher
surface irregularities to varying angles of impingement of incoming vapor
atoms, produces a significant decrease in the number and size of open,
columnar defects.

Figure 4.48. SEM photomicrograph of impact fracture surface of as-deposited


overlay coating. Fracture is intercolumnar indicating weak boundaries (Boone et
al.). (Courtesy of Amer. Inst. of Physics.)

Another problem in deposits of complex alloys is due to the variation


in deposit chemistry attributable to segregation in the ingot and large pool
temperature variations caused by the finite size of the electron beam.[138][139]
Improved ingot quality, development of improved electron beam sources,
Evaporation 241

and decrease in the temperature gradient at the crucible walls by using


crucible liners or coolant of lower heat capacity, such as NaK, instead of
water would minimize this problem.
In a more recent investigation on the origin of defects and continuing
on the above,[140] it was found that spits in M-Cr-Al-Y type alloys consist of
ejected pool material exhibiting enrichment in impurity elements of low vapor
pressure as a result of superheating of non-metallic particles (carbides or
oxides) in the melt initiating the ejection of pool material. Flakes, generally
cone shaped, were found to originate at non-metallic particles loosely
attached to the surface. Leader formation was found to be weakly dependent
on the angle of incidence of the arriving vapor flux. Both flakes and leaders
seem to be enhanced by preferential growth and shadowing phenomena.

11.0 PHYSICAL PROPERTIES OF THIN FILMS

The Handbook of Thin Film Technology[7] contains an extensive


section on the electrical and electronic conduction, piezoelectric and
piezoresistive, dielectric and ferromagnetic properties of thin films. The
reader is referred to it.

12.0 MECHANICAL AND RELATED PROPERTIES

12.1 Mechanical Properties

Mechanical Property Determination:A number of testing techniques


have been used to determine the strength properties of thin films. They
include the high speed rotor test,[141] the bulge test,[142]-[146] microtensile
testing machines of the soft[147]-[150] and the hard categories[142]-[146] and
even fixtures which can be operated in the electron microscope.[155][156]
Hoffman[157][158] has reviewed the test techniques and the reader could do
no better than to read Hoffman’s article or the original references. The basic
handling problem encountered with the preparation and mechanical property
testing of thin film specimens is much less severe with thick films for which
many of the standard test specimens, machines, and techniques can be
readily used. Therefore, the spectrum of mechanical properties measured
on thick films is much broader than with thin films.
242 Deposition Technologies for Films and Coatings

Tensile Properties of Thin Films:The tensile properties of thin films


have been reviewed.[154][157]-[159] As Hoffman concludes,[157] the data
reported are not very consistent even on the same material. The reader is
advised to consult the references for details.
In general, the observed strength of vapor-deposited metal films
consists of three parts:

σOBS = σBulk + σImperfections + σThickness

whereσBulk is the inherent strength level of bulk polycrystalline material in the


annealed state,σImperfections is the contribution due to point defects in excess
of those normally found in the bulk annealed state and σThickness is the
contribution arising from the smallest dimension of the film and its limiting
effect on grain size such that dislocation multiplication and migration are
impeded.[149]
Table 4.10 gives the strength properties of thin films of some metals
and compares them to bulk values.[158] In many cases, the strengths are
about 200 times those of annealed bulk samples and 3 to 10 times those of
hard drawn samples. The tensile strength values are given numerically as
well as by fractions of the shear modulus. The ductility of the high strength
films is very limited, which is similar to the behavior of high strength fibers or
whiskers. A principal point of contention is whether the ultimate tensile
strength is a function of the film thickness or not. The discrepancy also
appears to be dependent on the test method used, i.e., between the bulge
test and tensile test. In many cases, it appears that the strength decreases
as the film thickness increases from approximately the 200 - 300 Å range to
about 2000 - 4000 Å range. At the greater thickness, the strength is about
the same as that of heavily worked bulk material. There are several papers
relating the strength properties of thin films to the “crystallite size” and “block
structure” as influenced by the deposition temperature, stress, recovery, and
recrystallization process.[160]-[169] One manifestation of this is the phenomenon
of creep or plasticity in room temperature tensile tests as exhibited by an
irreversible initial loading curve but almost reversible unloading and reloading
curves as long as the previous stress level is not exceeded. An example of
this is shown in Fig. 4.49 from Neugebauer[148] as the change in slope of the
stress-strain curve. The possibility that this change in slope is related to an
elastically soft measurement or to creep in the cementation of the grips
cannot altogether be discarded.
Evaporation 243

Table 4.10. Strength of Properties of Thin Films

Figure 4.49. Typical stress-strain curve for thin film.


244 Deposition Technologies for Films and Coatings

Long term creep rates have been measured and for gold they vary
from 10-7 to 10-4 min-1 depending on load, dimensions and the amount of
prestrain.[148] The estimates of the relative elastic and plastic extension at
fracture vary from completely elastic to an almost even mixture of elastic and
plastic deformation.
Fracture in ductile gold single crystal films[154] results from a localized
plastic deformation with resultant thinning of the film and a rise in stress level.
Eventually the smaller cracks formed in this manner join to cause fracture.
The dislocations—necessary for the deformation—are not the grown-in
dislocations but those which nucleate and multiply in discontinuous regions.
Most observations show no necking prior to fracture. The maximum stress
appears to correspond to that needed to propagate cracks from flaws
existing in the specimen. In polycrystalline nickel, the fracture is the “clean-
cleavage” type.[149]
Mechanical Properties of Thick Condensates and Bulk Deposits:
Table 4.11 lists the mechanical properties of thick deposits of metals, alloys,
refractory compounds, and laminated structures. In many cases, the
mechanical test data are quite extensive showing yield strength, ultimate
tensile strength, hardness, and ductility as a function of grain size, deposition
temperature, and test temperature. One of the features of the data is that the
properties of thick deposits of metals and alloys are very similar to those of
wrought materials which are produced by the conventional processes of
melting, casting, mechanical working, and heat treatment.
We consider each type of material separately since the behavior of
metals and alloys is vastly different from that of refractory compounds.
The early work in this area was that of Bunshah,[17][18] Bunshah and
Juntz, and Smith[23] who deposited thick films of Be, Ti, and Cu, respectively,
[22]

and measured mechanical properties. In 1965, Palatnik and coworkers


published a paper on mechanical properties of Al condensates.[160] It is
impossible to review in detail all the papers. The pertinent data are shown
in Table 4.11 and the discussion below concentrates on the highlights.
Tensile Properties and Hardness of Metal and Alloy Deposits.
Movchan and Demchishin studied the tensile properties and microhardness
of Ni, Ti, and W condensates produced at various deposition temperatures.
No tensile tests were performed on specimens deposited in Zone 1 (Fig.
4.49). Tests on specimens deposited in Zone 2 showed high strength and
low ductility at low deposition temperature. The strength decreased and the
ductility increased with deposition temperature. The strength and ductility
values of specimens deposited in Zone 3 showed approximately the same
Table 4.11. Mechanical Properties of Thick Films or Bulk Condensates

Evaporation
245
246 Deposition Technologies for Films and Coatings
Table 4.11. (Cont'd)
Table 4.11. (Cont'd)

Evaporation
247
248 Deposition Technologies for Films and Coatings
Table 4.11. (Cont'd)
Evaporation 249

values as for recrystallized specimens produced from wrought material. The


microhardness variation with deposition temperature for Ni, Ti, and W is
shown in Fig. 4.50. The tapered crystallite morphology in Zone 1 showed a
high hardness much greater than that of annealed metal. The hardness
decreased rapidly with increasing deposition temperature to a fairly constant
value for Zone 3 morphology which corresponds to the hardness of
recrystallized metals.

Figure 4.50. Variation of microhardness with deposition temperature of metals.

Bunshah and coworkers studied the effect of deposition temperature


on the grain size, tensile properties, and hardness of Ti,[22][117] Ni,[118] Nb, V,
Mo,[119] and Ni-20Cr[124] alloys for deposits made in Zones 2 and 3. They
found that increasing deposition temperature produced larger grain size,
lower strength, higher ductility, and lower hardness. Even at the lowest
deposition temperature in Zone 2, the ductility was good (>20% RA for 1 µm
grain diameter Ti at a yield strength of 56,000 psi). Moreover, they found that
both the yield strength and hardness varied as the inverse square root of
grain diameter, i.e., followed the Hall-Petch relationship[192][193] which is

σys = σo + kd-½

where σys is the yield strength, d is the grain diameter, and σo and k are
constants. Figure 4.51 shows an example of this relationship for Ni-20Cr
alloy.
250 Deposition Technologies for Films and Coatings

Figure 4.51. Yield stress vs. inverse square root of average diameter for Ni-20Cr
alloy at 25°C. ∆ - wrought; O - deposited; # - Wilcox et al.; $ - Webster. (J. Vac.
Sci. Technol., Vol. 12, No. 2:662 (1975), Refs. 12 and 13).

For all these metals and alloys, the yield strength, ductility and
hardness values correspond to those of the same materials produced by
casting, mechanical working, and recrystallization. The variation of yield-
strength and hardness with grain size, i.e., Hall-Petch type relationships,
were also very similar between the deposited and wrought materials, small
variations being ascribable to differences in grain morphology and preferred
orientations. The Ni-20Cr alloy showed good strength at 1000°C and also
obeyed the Hall-Petch relationship.
The Hall-Petch relationship is also obeyed by thick films of Cu and Ag
to grain-sizes as small as 0.05 µm as shown by Nenioto, Jumbou and
Suto.[194] Thus, these thick deposits behave as true engineering materials.
Chambers and Bower[195] studied the mechanical properties of 18-8
stainless steel, gold, and magnesium, and showed that their tensile properties
were very similar to their wrought counterparts.
Smith, Kennedy, and Boericke[122a] studied the (α + β) type Ti-6Al-4V
alloy. They showed that the tensile properties are very similar to the wrought
material except for a much smaller value in percent elongation due to
Evaporation 251

premature onset of plastic instability in a tensile test at pinholes in the


deposited samples. The bend ductility was, however, superior to the wrought
material.
Shevakin et al.[74] studied the strength and hardness of aluminum and
copper condensates as a function of the deposition parameters. They found
that the mechanical properties varied widely with changes in process
parameters. The deposited materials also showed higher strength and
plasticity than the same materials conventionally fabricated, i.e., casting
followed by the neo-mechanical treatments. They also found that the
hardness values obeyed the Hall-Petch relationships.
Paton, Movchan, and Demchishin[122] showed that it is possible to
produce thick deposits of all the alloys across the Cu-Ni system and that the
mechanical properties vary systematically with composition as would be
expected.
Dispersion-Strengthened Alloy Deposits. The first data on
dispersion-strengthened alloys produced by evaporation methods was
reported by Paton, Movchan, and Demchishin[122] who showed that Ni-ZrO2
alloys produced by co-evaporation from two sources contained ZrO2 particles
in the size range of 150 - 3000 Å by changing the deposition temperature from
650° to 1100°C. They also showed that the creep strength at 1000°C
increased with volume fraction of zirconia. These alloys showed remarkable
stability in the microstructure and mechanical properties even after creep
exposures of 5 hours at 1300°C. Subsequently, Movchan and coworkers
studied the structure and properties of Ni-ZrO2 alloys,[196] and Fe with Al2 O3,
ZrO2, ZrB2, TiB2, NbC, or TiC second phases.[197] The alloys were produced
by co-evaporation of the constituents from electron-beam heated evaporation
sources.
One of the very striking effects of the incorporation of a dispersed
phase in an evaporated metallic coating is a very pronounced refinement in
grain size, often by a factor of 10 to 100 or more, and the inhibition of grain
growth at elevated temperatures. This was first reported by Kennedy[120] for
the incorporation of Y2O3 dispersions in Fe condensates. It was also
observed by Majumder[204] for Cu-Al2O3 deposits and by Jacobson et al.[224]
in Ni-Al2 O3 deposits. In a very recent paper, Movchan et al.[75] show the grain
size reduction in the Ni-Al2O3, Fe-ZrO2, Fe-ZrB2, and Fe-NbC deposits. The
most intense grain refining effect is observed at low volume fractions (0.5
vol.%) of the second phase.
Of particular interest to this topic is a subsequent paper by Majumder[205]
showing the strong effect of alumina content in increasing creep strength,
252 Deposition Technologies for Films and Coatings

which confirms the model proposed by Mott[225] who suggested that the ideal
creep-resistant material is one with a fine grain size in which the grain
boundaries are filled with some substance, say a refractory oxide, to inhibit
the motion of grain boundaries.
Perhaps the most interesting result from Movchan’s work[196][197][226]
is that the dispersed phase alloys show a maximum in room temperature
ductility in the W-ZrO2 system at 1 vol.% ZrO2, in the Fe-Al2 O3 system at 0
3 vol.% Al2O3, and in the Fe-NbC system at 0.1 vol.% NbC. The yield
strength and tensile strength do not show such a maximum but monotonically
increase with volume fraction of the oxide phase. The significance of this
observation lies in the possibility of increasing the ductility of MCrAlY
coatings which, in turn, would result in increased resistance to spalling,
thermal shock and fracture, thus improving the performance of the coating.
One might speculate on reasons for this effect including strain-relaxation
sites at particle matrix interface, or at grain boundaries due to the greatly
increased grain boundary area, favorable changes in residual stress
distribution in the coating possibly due to changes in elastic modulus or
strength, increased toughness or crack propagation resistance conferred by
the dispersed phase particles, change in crystallographic texture, etc.
Movchan, Badilenko, and Demchishin[227] have recently presented a
very detailed treatment on the regulation of microstructure and mechanical
properties of thick vacuum condensates with the help of dispersed phases.
They give a detailed theoretical model of(i) the influence of dispersed phases
on grain size; (ii) the size and shape of dispersed particles as affected by
deposition parameters; (iii) strength and ductility of two phase condensates
as influenced by the grain size, particle size, mean free path, nature of the
particle (deformable vs. nondeformable) and particle-matrix adhesion
energies; (iv) steady-state creep behavior. The model is then confirmed
by the experimental results. As a good illustration of one of these points,
Fig. 4.5 shows the difference in strength and ductility vs. volume fraction
of second phase when the latter is deformable or nondeformable. For
both types of particles, there is a ductility maximum at a particular Dg / l
ratio, but the strength behavior is diametrically opposite showing a monotonic
increase for a nondeformable particle and a minimum for the deformable
particle. Dg is the grain size in the plane perpendicular to the vapor flux
direction and λ is the interparticle spacing. This model forms an excellent
basis for design of experiments to study the effect of dispersed phases on
the structure and properties of MCrAlY alloys.
Evaporation 253

Another fascinating observation by Movchan et al.[227] applies to two


phase alloys with deformable particles having a high adhesion to the matrix.
The ductility of the alloys exceeds that of the pure matrix material at room
temperature by a factor of 1.5 to 2 at a strain rate of 1.67 x 10-3 sec -1 (0.1 min-
1). At high temperatures, the elongation at fracture exceeds 100%, i.e.,

superplasticity is developed.
Laminate Composites. Laminate composites are attractive and
preferable over fibrous composites because of their uniform properties in the
plane of the sheet. In comparison to mechanical methods of producing
laminate composites, e.g., bonding of sheets or foil, physical vapor deposition
techniques are very suited to the production of such composites, particularly
if each lamellae is to be very thin (0.01 to 1 µm thickness) in order to improve
the strength and toughness of the composite.
From theoretical considerations, it may be expected that the mechanical
properties of microlaminate composites would follow an adaptation of the
well known Hall-Petch relationship.[192][193] (Yield strength or hardness =αd-
½ where d is a characteristic microstructural parameter such as grain

diameter, sub-grain diameter, laminae thickness, etc.). This correlation will


be explored later.
In another approach, Koehler[241] proposed that a laminate structure
which is formed of thin layers of two metals, A and B, where one metal,A, has
a high dislocation-line energy and the other metal, B, has a low dislocation-
line energy, should exhibit a resistance to plastic deformation and brittle
fracture well in excess of that for homogeneous alloys. If the dislocation-line
energies are so mismatched, the termination of the motion of dislocations in
metal B is energetically favored over dislocation propagation across the
layer interface into metal A. In the case of thick layers, the dislocations
generated in either of the layers will pile-up in B at the A-B interface and
thereby provide the stress concentrations needed for premature yield.
Therefore, to suppress the generation of new dislocations in the layers, the
thicknesses ofA and B must be small. Thus, there is a critical minimum layer
thickness required for the generation of dislocations.
This model does not take into account a high imperfection content in
the laminate layers but assumes that their mechanical properties are similar
to bulk annealed materials.
Most of the prior work on microlayer condensates was investigated in
condensates produced at low deposition temperatures[240][242]-[249] (T <0.3
Tm) thus resulting in a high imperfection content. Moreover, the deposits
were very thin (<25 µm in thickness), which makes it very difficult to measure
the mechanical properties (particularly ductility) and draw good
254 Deposition Technologies for Films and Coatings

correlations with theory. The systems investigated were Ge/GaAg, Al/Mg,


Be/Al, Al/Cu, Al/Ag, Ni/Cu, Mg/Cu, Al/Al2 O3 .
Recently Lehoczky[249] studied the layer thickness dependence of the
yield strength of Al-Cu and Al-Ag laminates of thin specimens prepared by
alternate vapor-deposition. Below the critical layer-thicknesses required for
dislocation generation in the layers, the experimental results are in good
agreement with Koehler’s predictions. For layer thicknesses greater than
those required for dislocation generation, he has extended the theoretical
model to include dislocation pile-up groups.
A very recent investigation, on the other hand, by Bunshah et al.[239]
used high deposition temperatures (T ≅ 0.4 - 0.45 Tm) where equilibrium
structures are formed, and thick specimens (200 to 1,000 µm thickness)
containing a very large number of microlayers were produced such that
mechanical properties can be easily measured on standard test specimens.
Fe-Cu and Ni-Cu microlaminate composites were prepared by sequential
deposition from two evaporation sources. Very marked increases in strength
were observed, by as much as a factor of 10 as compared to the pure metals
and a factor of 5 as compared to the solid solution Cu-Ni alloy of the same
composition. The ductility decreased somewhat but was still appreciable
(5% elongation) for the highest strength alloys. The strength and hardness
values followed the Hall-Petch relationship. Superplastic behavior was
observed in Fe-Cu microlaminates when the average grain size of the metal
equals the interlammellar spacing (approximately 0.45 - 0.50 µm) at a test
temperature of 600°C at a strain rate of 0.005 min-1 .
High temperature creep properties of thick Fe/Cu and Ni/Cu
microlaminate condensates were studied at 600°C as a function of layer
thickness. Steady state creep rate has been found to increase with a
decrease in microlayer thickness. Microstructural study of the specimens
after creep tests revealed the disintegration of iron and nickel layers in Fe/
Cu and Ni/Cu condensates respectively with the formation of separate
inclusions of an oval shape. The creep rate variation in the microlayer
condensates is explained with the help of a structural model of high
temperature creep.
Refractory Compounds. Deposits of refractory compounds, oxides,
nitrides, and carbides are very important for wear resistant applications in
industry. Their structure and properties are strongly dependent on the
deposition process. Their behavior is very different from metals and
alloys. It is also very hard to measure the mechanical properties of
ceramics by tensile tests similar to those used for metals and alloys
because of their brittle nature. A very good test to measure the fracture
Evaporation 255

stress of such brittle coatings is the Hertzian fracture test which measures
the fracture stress and the surface energy at the fracture surface.[198] Colen
and Bunshah[182] used this test to measure the fracture behavior of Y 2O3
deposits of various grain sizes.
Figure 4.52 shows the variation in microhardness with deposition
temperature for Al2O3 and ZrO2 from the work of Movchan and Demchishin,(75)
showing that the behavior of these oxide deposits is quite different in one
respect from that of metals (Fig. 4.47). The hardness falls when the structure
changes from tapered crystallites (Zone 1) to columnar grains (Zone 2) as
with metals. However, unlike metals, the hardness increases markedly as
the deposition temperature rises from 0.3 Tm to 0.5 Tm. The authors attribute
this to a more “perfect” material produced at the higher deposition temperature
due tovolume processes of sintering. A similar hardness curve was obtained
for Y2 O3 deposits. [182]

Figure 4.52. Variation of microhardness with deposition temperature for Al 2O3


and ZrO 2.

Figure 4.53 from the work of Raghuram and Bunshah[127] also shows
a very marked increase in microhardness of TiC deposits on going from 0.15
Tm (500°C) to 0.3 Tm (1000°C). The hardness increases for the oxides and
TiC with increasing deposition temperature. Both sets of results may be
explained by the following concept. Since the strength of ceramics is very
adversely effected by growth defects and at the higher deposition temperature,
the occurrence of these defects is markedly reduced, the hardness (or
strength) increased very significantly. However, it should be noted that
the absolute value of the hardness of the oxides is much lower than that of
the carbides. Thus thepossibility of a different explanation for the “similar”
256 Deposition Technologies for Films and Coatings

behavior of these materials, i.e., the hardness increase with the deposition
temperature needs to be investigated.
The hardness data on sputtered TiC and TiN coatings are quite similar
to those produced by evaporation techniques.[186]

Figure 4.53. Variation of microhardness with deposition temperature for TiC.

13.0 PURIFICATION OF METALS BY EVAPORATION

Impurities in the deposit can be classified into two types, metallic and
nonmetallic. Knowing the composition of the evaporant, the experimental
conditions (temperature and time), certain thermodynamic data (vapor
pressure and activities in solution), the composition of the vacuum environment
during the experiment, and the types of melt-crucible reactions, if any, it is
possible to estimate the impurity content of the distillate. The amount of
impurity transfer to the vapor phase and hence in the deposit (assuming a
sticking coefficient of unity) depends directly on the partial pressures of the
impurity and the basis metal. For metallic impurities, one assumes that each
impurity behaves independently of the other and, using Rayleigh’s equation,
the metallic impurity content of the distillate may be estimated. Experimental
verification has been demonstrated by Bunshah for beryllium.[20]
The amount of nonmetallic impurity (C, O2, N 2, and H2) is estimated
as follows: for example, for oxygen,
Evaporation 257

∑ υG
ppm (atomic) O2 =
υM

where ∑υG = sum of the impingement frequencies (number of atoms/cm2/


s) of the various gases and vapors present in the vacuum environment
containing oxygen, such as H2, CO, CO2 and MO (metal suboxide), on the
substrate, andυM = impingement frequency of metal atoms on the substrate,
an experimentally determined parameter.
Implicit in this treatment is the assumption that the sticking coefficient
for all the species is unity. This assumption is good for reactive gases such
as CO, CO2 and H2O but poor for gases such as H2, as has been shown by
Bunshah and Juntz[21] for beryllium; they also demonstrated a satisfactory
agreement between computed and experimentally observed values for the
nonmetallic impurities. Table 4.12 shows the production of very high purity
beryllium in sheet form by vacuum melting followed by vacuum distillation.
The oxygen content of the distillate is due to suboxide vaporization (Be2 O)
from the melt and consequent contamination of the substrate, since the
suboxide has a higher vapor pressure than the evaporating species. The
oxygen content of refractory metal deposits produced by vacuum evaporation
can also be substantially increased by suboxide vaporization from the melt.
The suboxide can be that of the deposit itself, e.g., MoO in the case of
molybdenum deposition; or that associated with an impurity in the evaporant,
e.g., MoO in the evaporation of vanadium.

Table 4.12. Purification of Beryllium by Vacuum Melting and Distillation (in


parts per million atomic)
258 Deposition Technologies for Films and Coatings

APPENDIX

On Progress in Scientific Investigations in the Field of Vacuum


Evaporation in the Soviet Union

A. V. Demchishin
E. O. Paton Electric Welding Institute
Kiev, Ukraine, U.S.S.R

The first investigations dealing with the problems of evaporation and


condensation were carried out by Soviet scientists as early as the twenties.
Y. I. Frenkel[A1] found theoretically that there exists a critical temperature of
reflection of metal atoms from a substrate.[A1] Y. B. Kharitonov and N. N.
Semenov have shown experimentally that this phenomenon actually took
place.[A2] The problem of formation of chemical compound with a simulta-
neous condensation of molecular beams of cadmium and sulfur was studied
by A. I. Shal’nikov and N. N. Semenov.[A3] Structural studies of condensates
of gold-copper alloys by electron and x-ray diffraction were carried out by M.
M. Umanskii and V. A. Krylov.[A4]
At the beginning of the forties, S. A. Vekshinskii and his colleagues
performed a lot of work on a development of methods for production of
specimens of condensates, on experimental verification of condensate
distribution law, on studying physical and chemical properties of condensed
metal films of pure metals and binary alloys.[A5] S. A. Vekshinskii suggested
the use of a method of co-condensation of vapor mixtures of several
components for producing the films of variable composition thus enabling the
structure and properties of an entire n-component system or its part to be
studied at once without recourse to production of a great number of separate
samples of constant composition alloys.
In the middle of the fifties, investigation of condensates was conducted
by L. S. Palatnik and his collaborators at the Kharkov Polytechnic Institute
towards the following trends:
• structure and substructure of thin and massive condensed films;
• mechanism of formation and kinetics of growth of continuous and
island films;
• physical properties of films (mechanical, electrical, semiconductive,
magnetic, thermal and other properties);
Evaporation 259

• studying the correlation between structure (substructure) and


physical properties of films;
• the effect of physical and technological variables of evaporation
processes and vacuum condensation on structure (substructure)
and physical properties of continuous (thin and massive) and island
films.
The main results of these investigations are published in Refs. A6, A7,
and A8.
In addition to the said studies, in the sixties and seventies, the
characteristics of macro-, micro- and submicroporosity of condensed films
depending on substrate temperature, angle of incidence of molecular flow,
condensation rate, film thickness, pressure and composition of residual gas
atmosphere were investigated. Mechanisms of porosity formation processes
were established and relationships between the porosity characteristics and
physical-mechanical properties of films have been studied.[A9][A10]
In the middle of the sixties, B. A. Movchan and his collaborators
developed an electron-beam technology for production of preparations of
condensed systems and commenced the study of thick (up to 1 mm)
condensates. In the sixties-seventies the effect of condensation conditions
on structure and physical-mechanical properties of thick condensates of
pure metals, refractory oxides, carbides, borides and their mixtures, ceramic-
metallic materials and dispersion strengthened compositions were
investigated. Their main results were published in Refs. A11 to A15.

REFERENCES (for Appendix)

A1. Frenkel, J. I., Zeitschr. f. Physik, 26:117 (1924)


A2. Chariton, J. B. and Semenoff, N. N.,Zeitschr. f. Physik, 25:287 (1924)
A3. Shal’nikov, A. I., Semenov, N. N.,The Journal of Russian Physical and
Chemical Society, 60:33 (1928)
A4. Umanskii, M. M., Krylov, V. A.,The Journal of Exp. and Theor. Physics,
6:691 (1936)
A5. Vekshinskii, S. A., A New Method of Metallographic Studies of Alloys,
Bostechizdat, Moscow-Leningrad (1944)
A6. Palatnik, L. S., Papirov, I. I., Epitaxial Films, Nauka, Moscow (1971)
A7. Palatnik, L. S., Fux, M. Y., Kosevich, V. M., Mechanism of Formation
and Substructure of Condensed Films, Nauka, Moscow (1972)
260 Deposition Technologies for Films and Coatings

A8. Palatnik, L. S., Sorokin, V. K., Fundamentals of Film Semiconductive


Materials Technology, Energia, Moscow (1973)
A9. Palatnik, L. S., Fux, M. Y., Cheremskoi, P. G., Transactions of the
Academy of Sciences of the U.S.S.R., 203(5):1058 (1972)
A10. Fux, M. Y., Palatnik, L. S., Cheremskoi, P. G. Toptygin, A. L., Physics
of Metals and Physical Metallurgy, 46(1):114 (1978)
A11. Movchan, B. A., Demchishin, A. V., Physics of Metals and Physical
Metallurgy, 28, No. 4:653 (1969)
A12. Paton, B. E., Movchan, B. A., Demchishin, A. V., Proceedings of the
Fourth Int'l. Conf. on Vac. Metallurgy, p. 251, Tokyo, (June 4-8, 1973).
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No. 2:61 (1978)
A15. Movchan, B. A., Malashenko, I. S., Pap, P. A., Problems of Special
Electro Metallurgy, Naukova Dumka, Kiev, No. 8:78 (1978)
Evaporation 261

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Evaporation 269

160. Palatnik, L. S., Ill’inski, A. I., Federov, G. V., and D’yachenko, V. S.,
Izvestra VUZ, Fizika (Soviet Physica Journal) 1:122 (1966)
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162. Ya Fuks, M., Belozerov, V. V., and Boyko, Y. F., Fizika Metall.,33:571
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164. Ya Fuks, M., Velozero V. V., and Boyko, Y. F., Fizika Metall., 33:571
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165. Doljack, F. A. and Hoffman, R. W., Thin Solid Films, 12:71 (1972)
166. Ya Fuks, M., Palatnik, L. S., Belozerov, V. V., Zolotnitsky, Y. V., and
Roschchenko, S. T., Fizika Metall., 36:316 (1973)
167. Pines, B. Y. and Tan, N. S., Fizika Metall., 19:899 (1965)
168. Aleksanyan, I. T., Fizika Metall., 25:947 (1968)
169. Hoffman, R. W., Thin Solid Films, 34:185 (1976)
170. Palatnik, L. S., Federov, G. V., Prokhavulov, A. I., and Federenko, A.
I., Fizika Metall., 20:574 (1965)
171. Palatnik, L. S., Ya Fuks, M., Boiko, B. T., and Pugacheu, A. T., Soviet
Phys. Dokl., English Translation, 8:713 (1964)
172. Oding, A. and Aleksanyass, I. T., Soviet Phys. Dokl., 8:818 (1964)
173. Bunshah, R. F., Vacuum, 27(4):353 (1977)
174. Yamamoto, H. and Kamoshita, G., Trans. Jpn. Inst. Metals, 12:12
(1971)
175. Palatnik, L. S., Ya Fuks, M., Ill’inski A. I., and Alaverdova, O. G., Fizika
Metall., 22:744 (1966)
176. Henning, C. A. O., Boswell F. W., and Corbett, J. M., Acta Met.,23:177
(1975)
177. Ziling, K. K., Pkrovskiy, L. D., and Pohelkin, V. Y., Fizika Metall.,
29:1112 (1970)
178. Palatnik, L. S., Ill’inski A. I., and Ravlik, A. G., Fizika Metall., 19:310
(1965)
179. Henning, C. A. O., Boswell, F. W., and Corbett, J. M.,Acta Met.,23:187
(1975)
270 Deposition Technologies for Films and Coatings

180. Palatnik, L. S., Ill’inski, A. I., Ravhk, A. G., Nechitayls, A. A., and Lyakh,
G. Y., Fizika Metall., 27:1114 (1969)
181. Bunshah, R. F. and Schramm, R. J., Thin Solid Films, 41 (1977) in
press
182. Colen, M. and Bunshah, R. F., J. Vac. Sci. Tech., 13:536 (1976)
183. Furuuchi, S., Sakata, H., and Aiwaka, K., Japan J. Appl. Phys.,
13:1905 (1974)
184. Grossklaus, W. and Bunshah, R. F., J. Vac. Sci. Technol., 12:811
(1975)
185. Wasa, K., Nagai, T., and Hayakowa, S., Thin Solid Films, 31:235
(1976)
186. Mah, G., Norden, C. W., and Fuller, J. F.,J. Vac. Sci. Technol., 11:371
(1974)
187. Henning, C. A. O., Boswell, F. W., and Corbett, J. M.,Acta Met.,23:193
(1975)
188. Palatnik, L. S., Ill’inski, A. I., and Sapelkin, N. P.,Soviet Phys. Solid St.,
8:2016 (1967)
189. Solonovich, I. I. and Startsev, V. I., Problemy Prochn., 1:28 (1973)
190. Palatnik, L. S., Ill’inski, A. I., Biletchanko, N. M., and Sinel’nikova, R.
I., Fiz. Metall., 32:199 (1971)
191. Bunshah, R. F., Gupta, Y. D., and Raghuram, A. C., unpublished data
192. Hall, E. O., Proc. Phys. Soc, Lond., B64:747 (1951)
193. Petch, N. J., J. Iron Steel Inst., 174:25 (1951)
194. Nenioto, M., Jumbou, R., and Suto, H.,Trans. Jpn. Inst. Metals,12:113
(1971)
195. Chambers, D. L. and Bower, W. K.,J. Vac. Sci. Technol.,7:S62 (1970)
196. Movchan, B. A., Demchishin, A. V., and Badilienko, G. F., Thin Solid
Films, 40:237 (1977)
197. Movchan, B. A., Demchishin, A. V., and Kooluck, L. D., Thin Solid
Films, 44:285 (1977)
198. Frank, F. C. and Lawn, B. R., Proc. R. Soc. Lond., 229A:291 (1967)
199. Boone, D. H. and Sullivan, C. P., STP, 520:401, Am. Soc. for Testing
and Materials (1973)
Evaporation 271

200. Goward, G. W., J. Metals, 22:31 (1970)


201. Clough, P. J., New Types of Metal Powders, (H. H. Hausner, ed.), p.
9, Gordon and Breach (1964)
202. Hayashi, C., Jpn. J. Appl. Phys., 12:1675 (1973)
203. Bunshah, R. F., unpublished research
204. Majumder, K. S., Thin Solid Films, 42:327 (1977)
205. Majumder, K. S., Thin Solid Films, 42:343 (1977)
206. Chi, K. C., Dillon, R. O., Bunshah, R. F., Alterovitz, S., Martin, D. C.,
and Vollam, J. A., Thin Solid Films (1978)
207. Zubeck, R. F., King, C. N., Moore, D. F., Barbee, T .W., Hallak, A. B.,
Salem, J., and Hammond, R. H., Thin Solid Films, 40:249 (1977)
208. Martin, P. L., Bunshah, R. F., and Dymond, A. M., J. Vac. Sci Tech.,
12:754 (1975)
209. Agarwal, P. L., Bunshah, R. F., and Crandall, P. H., unpublished
research, UCLA (1978)
210. Sinha, A. K., Giessen, B. C., and Polk, D. E., Treatise on Solid State
Chemistry, (N. V. Hannay, ed.), 3:1, Plenum Press, New York (1976)
211. Keung, P. K. and Wright, J. G., Phil. Mag., 30:995 (1974)
212. Hughes, J. L., Metals Eng. Quart. 14, No, 1:1 (1974)
213. Hill, R. J., Hughes, J. L., and Harker, H. R., Proc. of the 4th Int'l. Conf.
on Vacuum Metallurgy, p. 248, Iron and Steel Institute of Japan,
Tokyo, Japan (June 1973)
214. Harker, H. R., and Hill, R. J., J. Vac. Sci. Technol., 9:1395 (1972)
215. Bunshah, R. F., U.S. Patent No. 3,971,582 (Feb. 12, 1974)
216. Nakamura, K., Inagawa, K., Tsuruoka, K., and Komiya, S., Thin Solid
Films, 40:155 (1977)
217. Kodama, M., Bunshah, R. F., and Shabaik, A. H., Thin Solids Films,
(1978)
218. Bunshah, R. F., and Shabaik, A. H., Res./Dev., 26:46 (1975)
219. Bunshah, R. F., Shabaik, A. H., Nimmagadda, R., and Covey, J., Thin
Solid Films, 45:1 (1977)
220. Hewig, G. H. and Bloss, W. H., Thin Solid Films, 45:1 (1977)
221. Boer, K. W., Annual Progress Report, NSF/RANN/SE/G134872.,
University of Delaware (Jan. 1974)
272 Deposition Technologies for Films and Coatings

222. Brody, T. P. and Shirland, F. A.,Proc. of NSF Workshop on Photovoltaic


Conversion of Solar Energy for Terrestrial Applications, p. 63, Cherry
Hill, NJ (Oct. 1973)
223. Laegreid, N., in ibid, p. 63
224. Jacobson, B. E., Springarn, J. R., and Nux, W. D., Thin Solid Films,
45:517 (1977)
225. Mott, N. F., Phil. Mag., 44:742 (1953)
226. Movchan, B. A., Soviet Physics Doklady, 20(7):575 (1975)
227. Movchan, B. A., Badilenko G. F. and Demchishin, A. V., Thin Solid
Films, 63:67 (1979)
228. Schiller, S. and Jasch, G., Thin Solid Films, 54:9 (1978)
229. Kobayashi, M. and Doi, Y., Thin Solid Films, 54:57 (1978)
230. Komiya, S., Umezu, N., and Narusawa, T., Thin Solid Films, 54:51
(1978)
231. Zega, B., Kornmann, M., and Amiguet, J., Thin Solid Films, 45:577
(1977)
232. Berghaus, B., German Patent No. 683,414 (1939)
233. Sabalev, L. P., et al., U.S. Patent 3,783,231 (Jan. 1, 1974); 3,793,179
(Feb. 19, 1974)
234. Dorodnov, A. M., Soviet Phys. Tech. Phys., 23:1058 (1978)
235. Osipov, V. A., et al., Soviet Rev. Sci. Inst., 21:1651 (1978)
236. Nath, P. and Bunshah, R. F., Thin Solid Films, 69:63 (1980)
237. Namba, Y. and Mori, J., J. Vac. Sci. Technol., 13:693 (1976)
238. Taylor, N. J., Surface Science, 4:161 (1966)
239. Bunshah, R. F., Nimmagadda, R., Doerr, H. J., Movchan, B. A.,
Grechanuk, N. I., and Dabizha, E. V., Thin Solid Films, 72:261 (1980)
240. Hordon, M. J., Titanium Science and Technology, (R. I. Jaffee and H.
M. Burte, eds.), 4:2347-57, Plenum Press (1973)
241. Koehler, J. S., Phys. Rev., B 2:547 (1970)
242. Henning, C. A. O., Boswell, F. W., and Corbett, J. M. Acta. Met.,
23:193.
243. Palatnik, L. S. and Ill’inski, A. I., Soviet Phys. Dokl., 9(1):93 (1961)
Evaporation 273

244. Palatnik, L. S., Ill’inski, A. I., and Sapelin, N. P., Soviet Physics Solid
State, 8(8):2016 (1967)
245. Palatnik, L. S., Ill’inski, A. I., Biletchenko, N. M., and Sinel’nikova, R.
I., Fiz. Met. Metalloved., 32(6):1312 (1971)
246. Solonovich, I. I. and Startsev, V. I., Problemy Prochnosti, 1:28-30
(1973)
247. Hordon, M. J. and Wright M. A., in Metal-Matrix Composites, Symp. of
the Metallurgical Soc. AIME,DMIC Memorandum 243, pp.10-12 (May
1969)
248. Springer, R. W. and Catlett, D. S., Thin Solid Films, 54:197 (1978)
249. Lehoczky, S. L., J. App. Phys., 49:5479 (1978)

SUGGESTIONS FOR FURTHER READING

Books

Berry, R. W., Hall, P. M., Harris, M. T., Thin Film Technology, D. Van
Nostrand Co. (1968)
Bhushan, B. and Gupta, B. K., Handbook of Tribology, McGraw-Hill (1992)
Chopra, K. L., Thin Film Phenomena, McGraw Hill Book Co., (1969)
Handbook of Thin Film Technology, (L. I. Maissel, and R. Glang, eds.)
McGraw Hill Book Co. (1970)
Holland, L., Chapman and Hall, Vacuum Deposition of Thin Films, (1968);
The Bible
Ohring, M., Materials Science of Thin Films, Academic Press, (1992)
Physics of Thin Films, Vols. 1-6, Academic Press (1963-1971)
Science and Technology of Surface Coatings, (B. N. Chapman and J. C.
Anderson, eds.) Academic Press (1974)
Techniques of Metals Research, Vol. 1, part 3, (R. F. Bunshah, ed.) John
Wiley & Sons (1968)
Thin Films, Am. Soc. for Metals (1964)
The Use of Thin Films in Physical Investigation, (J. C. Andrews, ed.)
Academic Press (1966)
274 Deposition Technologies for Films and Coatings

Journals

Applied Surface Science


Japanese Journal of Applied Physics, Japan
Journal of Applied Physics, USA
Journal of Electrochemical Society, USA
Journal of Materials Research
Journal of Materials Science, England
Journal of Materials Synthesis and Processing
Journal of Vacuum Science and Technology, Am. Phys. Society
Materials and Manufacturing Processes
Processing of Advanced Materials
Review of Scientific Instruments, USA
Surface and Coatings Technology, Elsevier, S. A.
Thin Solid Films, Elsevier, S. A., Switzerland
Vacuum, England
5

Sputter Deposition Processes

John A. Thornton and Joseph E. Greene

1.0 INTRODUCTION

The process of sputtering may be defined as the ejection of particles from


a condensed-matter target due to the impingement of energetic projectile
particles. The use of sputtered species as source material to deposit thin films
was first reported in the literature in 1852[1] and has since enjoyed several
periods of scientific and commercial interest interspersed with periods of
disrepute. However, it is only relatively recently that sufficient understanding
of the complex processes occurring during ion bombardment of solid surfaces
has been developed to allow the reproducible and controllable use of sputter
deposition for growing high-quality single crystals, complex alloys,
superlattices, and materials with tailored microstructures. The evolution of the
branch of science concerned with ion/surface interactions has been facilitated
by the parallel development of ultra-high vacuum technology and highly
sensitive microanalytic techniques for identifying the state of scattered
particles, sputtered species, and implanted material.
Sputter-ejected species have kinetic energies considerably greater
than thermal. In addition, depending on the experimental configuration, the
substrate and growing film may also be subjected to low-energy particle
bombardment from accelerated host lattice species, dopants, inert-gas
ions, and energetic particles backscattered from the target. Thus, ion/
surface interactions are not only important at the target, but they can also

275
276 Deposition Technologies for Films and Coatings

play a decisive role, as discussed in Ch. 13, in determining film nucleation and
growth kinetics, microstructure evolution, dopant incorporation probabilities,
and hence the physical properties of as-deposited layers. The controlled use
of ion bombardment effects allows a considerable enhancement in the ability
to tailor film properties.
Sputter deposition is inherently a vacuum coating process. In operation,
the source of coating material, termed the “target,” is mounted opposite the
substrates in a vacuum chamber which is then evacuated to a base pressure
which typically ranges from 10-6 to 10-10 Torr*, depending upon the process.
The most common method of providing the ion bombardment necessary for
sputtering is to backfill the evacuated chamber, using a continuous flow of a
gas such as Ar, to a pressure of from 1 to 100 mTorr, and establish a glow
discharge. A negative potential, typically between 0.5 and 5 kV, is applied to
the target in order to initiate positive-ion bombardment while the counterelectrode
(the substrate) is grounded. A sputtering apparatus in which the target and
substrate are opposing parallel plates, shown schematically in Fig. 5.1, is
termed a diode system. The discharge in such a device is commonly operated
in the abnormal negative-glow mode.[2]
The most striking characteristic of the sputtering process is its universal-
ity. Since the coating material is passed into the vapor phase by a physical
momentum-exchange process, rather than a chemical or thermal process,
virtually any material is a coating candidate. DC discharge methods are
generally used for sputtering metals, while an RF potential must be applied to
the target when sputtering nonconducting materials. In some applications,
rather than immersing the target in a plasma, it is more convenient to use a
separate ion-beam source consisting of a self-contained discharge with ion-
acceleration optics.
Sputter-deposition technology includes many variations of the basic
process described above. For example, coatings may be formed by:
1. Employing a target which is a mosaic of several materials.
2. Employing several different targets simultaneously to obtain an
alloy film.
3. Employing several targets sequentially to create a composi-
tionally layered coating.

*The pressure unit of Torr (1 Torr = 1 mm Hg) is a carryover from the time when pressure was
measured with a Hg manometer. Most commercial pressure gauges are still calibrated in Torr
or microns (1 µm Hg = 1 mTorr). Therefore, Torr will be used in this chapter although both
Torr and Pa (SI units) are given in some of the figures. 1 Torr = 133 Pa = 1.33 mbar = 1.316
x 10-3 atm.
Sputter Deposition Processes 277

Figure 5.1. Schematic representation of a parallel-plate diode sputtering system.

4. Electrically biasing the substrate to provide ion bombardment


of the growing film during deposition in order to modify the film
microstructure and/or microchemistry.
5. Employing a gas (e.g., O2, N2 , H2 S, etc.) to introduce one of
the coating materials into the chamber. This process is known
as reactive sputtering.
278 Deposition Technologies for Films and Coatings

1.1 Sputter Deposition Systems

Sputtering systems can assume an almost unlimited variety of configura-


tions, depending on the application. The simplest is the parallel-plate diode
shown schematically in Fig. 5.1. Such systems have played a major role in the
development of sputtering technology over the past twenty years and are still
widely used. Figure 5.2 shows a planar-diode sputtering installation of a type
commonly used in research and for small production runs.

Figure 5.2. Planar-diode sputtering system of the type used for research end small
production runs. The system can be used for both DC and RF sputtering. (Photo
courtesy of CVD Products, Inc., Rochester, NY)

The substrates in a planar-diode system are in contact with the plasma.


This makes it relatively easy to carry out the processes of substrate sputter
cleaning and bias sputtering. It is partly due to the effects of these processes
that sputtering has long enjoyed a reputation for providing coatings with
superior adhesion. However, the heating associated with plasma and electron
bombardment often prohibits the use of planar diodes for coating thermally-
sensitive substrates.
It is difficult to sustain an intense plasma discharge in the planar-diode
electrode geometry. Thus, working pressures are necessarily relatively high
at 20 to 75 mTorr and current densities are low, ≈1 mA/cm2 . The high
Sputter Deposition Processes 279

pressure causes the transport of coating material from the target to the
substrate to be primarily diffusive rather than ballistic and sputtered material
is lost to the walls of the container by scattering. This, coupled with the low
current density, leads to deposition rates which are generally less than 75 nm/
min (4.5 µm/h).
Triode devices, in which additional electrons are injected into the
discharge by thermionic emission from a third electrode, can be used to
produce intense sputtering discharges at low pressures. The deposition rates
that can be achieved with triode devices are also higher than with planar
diodes. For example, high-rate triode sputtering has been used to fabricate
a free-standing 1.3 kg deposit of a Cu-alloy in the form of a cylinder 15 cm in
diameter.[3] However, the complexity of triode designs for obtaining uniform
deposition has, in general, limited their use to special applications.
The recent development of a class of sputtering sources with magnetic
plasma confinement, called magnetrons, has greatly enhanced the capabili-
ties of the sputtering process. There are many forms of magnetrons. They vary
from small ring sources—often referred to as Sputter-gunsTM (Sloan Technol-
ogy, Santa Barbara, CA) and S-gunsTM (Varian Associates, Palo Alto, CA)—
to long rectangular planar magnetrons and cylindrical magnetrons with post
or hollow cathodes. Magnetrons can be used for both DC and RF sputtering
but are particularly effective for DC sputtering, where deposition rates can be
more than an order of magnitude larger than those obtained with planar diodes.
Planar and cylindrical magnetrons can be scaled to large sizes to provide
uniform deposition over very large areas (many m2). In addition, well-designed
magnetrons virtually eliminate substrate heating caused by electron bombard-
ment.

1.2 Sputter-Deposition Applications

The enormous range of sputtering applications reflects the universal-


ity of the process. Films containing essentially every element in the
periodic table have been prepared by sputtering. Alloys and compounds
can generally be sputter-deposited while preserving their compositions.
For example, PTFE (Teflon ) has been sputtered to produce lubricous
films having many of the properties of the starting material. The ability to
control composition has caused sputtering to become widely used in the
electronics industry. Typical applications are aluminum alloy and refrac-
tory metal microcircuit metallization layers, microcircuit insulation layers,
transparent conducting electrodes, amorphous optical films for integrated
optics devices, piezo-electric transducers, photoconductors and luminescent films
280 Deposition Technologies for Films and Coatings

for display devices, optically addressed memory devices, amorphous bubble


memory devices, thin film resistors and capacitors, video-discs, solid electro-
lytes, thin film lasers, and microcircuit photolithographic mask blanks.
Figure 5.3 shows a multisource sputtering system designed for wafer
processing. Sputter deposition is also beginning to replace evaporation for
depositing high performance optical components and is commonly used for
depositing magnetic alloys with strong preferred orientation in magnetic
recording devices. In addition, one finds applications ranging from coating
razor blades to depositing wear-resistant coatings for machine tools.

Figure 5.3. Multi-source sputtering system designed for wafer processing. Wafer
batches are passed into and out of the coating chamber through vacuum interlocks.
(Photo courtesy GCA Corporation, Vacuum Industries Division, Somerville, MA)
Sputter Deposition Processes 281

Planar diodes are still widely used, particularly for depositing materials
requiring RF power. However, recent trends find magnetrons replacing planar
diodes for many DC, and some RF, applications. In addition, the magnetrons
have opened up new applications because of their large-area capability and
reduced substrate heating. For example, large in-line systems with vacuum
interlocks use planar magnetron sources to coat 2 m x 3.5 m architectural
glass plates at three-shift production volumes of about 106 m2/yr.[4] Sputtering
is being investigated as a means for depositing selective absorber coatings for
solar heating and for manufacturing photovoltaic cells for direct solar-to-
electrical energy conversion. Because of the reduced substrate heating,
magnetrons are used on a production basis to deposit chromium decorative
coatings on automobile grilles and other exterior trim. Figure 5.4 shows an
automated load-lock sputtering system designed for metallizing plastic
automotive parts.

Figure 5.4. Automated load-lock magnetron-sputtering system designed for


metallizing plastic automotive parts. System throughput is 46.5 m2/h of platen
surface on which substrates may be mounted. (Photo courtesy of Varian Associ-
ates, Inc., Palo Alto, CA)
282 Deposition Technologies for Films and Coatings

The selection of a sputtering apparatus for a given application depends


on the substrate size, shape, and sensitivity to heat and plasma irradiation.
It also depends on the nature of the coating—e.g., single layer or multilayer,
thickness, types of materials involved, and critical parameters such as
hardness, porosity, resistivity, semiconductor charge-carrier lifetimes, and
magnetic anisotropy—as well as the production volume. Planar targets of an
almost unlimited range of materials, including the new high temperature
superconducting oxides, are available from many suppliers. Thus planar
diodes are attractive for depositing thin coatings of complex materials onto
planar substrates for research studies or for small production volumes.
However, the substrates must be capable of withstanding the plasma
environment, particularly electron bombardment.
Triode devices are attractive when thicker coatings are required. How-
ever, for large production volumes, thick coatings, complex substrate shapes,
or thermally sensitive substrates, magnetron type sources should be consid-
ered. The selection of a particular type of magnetron will depend on the nature
of the coating and substrate and the availability of sputtering targets of the
required material in the desired geometry. The procurement of high-quality
targets is an important consideration for all sputtering systems.
Sputtering, like other vacuum coating processes, suffers from the
disadvantage that the equipment is expensive. In addition, high-rate sputtering
equipment generally incorporates large, nonstandard, power supplies and
automatic control systems. As a general rule, sputtering is most effective
when production volumes are sufficient to permit the equipment cost to be
amortized over a large number of parts. An advantage of sputtering is that it
is reliable and lends itself to automatic control.

1.3 Process Implementation

Almost any vacuum chamber capable of evacuation into the 10-6 Torr
range can be used for sputtering. Provisions are usually required for throttling
the pumping system so that the desired working gas pressure can be
sustained with the pumps in operation. Small planar and gun-type magnetrons
are particularly easy to install. Some forms of cylindrical magnetrons require
special chamber geometries. Chambers used in large production runs
generally include substrate-loading interlocks so that the target surface is not
exposed to the atmosphere between deposition cycles. Examples are shown
in Figs. 5.3 and 5.4.
Sputter Deposition Processes 283

Pre-deposition pumping and the importance of achieving low base


pressures will depend on the application. It is important to remember that
sputtered coatings are deposited in an atmosphere which contains outgassing
flux from the substrates and chamber walls. This flux can have a significant
influence on the growth and properties of the coatings. Special problems may
be encountered if the substrates themselves undergo severe outgassing.[5]
Generally, pre-deposition pumping is continued until the total outgassing flux
from the chamber walls and substrates has decreased to a value that is
significantly less than the total sputtering flux that will be used. The working
gas is then injected into the chamber with the pumps throttled and sputtering
is initiated. New, or air-exposed, targets should be “pre-sputtered,” with the
substrates shielded, prior to deposition in order to clean and condition the
target and chamber surfaces.
The selection of deposition conditions is generally determined empiri-
cally. The primary control parameters are the deposition rate, target voltage,
working gas species and pressure, and the substrate temperature and plasma
bombardment conditions. The available selection range for the deposition
parameters is determined largely by the apparatus. In planar diodes, many
of the parameters are interrelated and unavailable for independent control.
Much greater control is possible with magnetrons. However, other variables
become important. For example, in many magnetron geometries, along with
operation at low pressures where the sputtered atoms can pass to the
substrates while making few collisions, coating-flux angle-of-incidence con-
siderations become important in determining coating properties.[6] Thus, in
all applications where large production volumes are anticipated, it is wise to
perform development work using an apparatus of the same type and geometry
anticipated for the production facility. Scale-up increments should generally
not exceed a factor of three in apparatus size.

1.4 History of Sputter Deposition and Background Reading

Several review papers written over the last twenty years permit the
interested reader to follow the developments in sputtering technology. An
extensive review of the basic process was published by G. K. Wehner, one of
the most prominent of the early workers, in 1955.[7] Film properties obtained
in early experiments were discussed by E. Kay in a 1962 review.[8] Sputter
deposition processes were reviewed by L. Maissel[9] and Kay[10] in 1966. The
Handbook of Thin Films , published in 1970, contains reviews by Wehner
and Anderson [11] and by Maissel. [12] A review article by Thornton
284 Deposition Technologies for Films and Coatings

in 1973 discusses sputtering equipment.[13] Process considerations in glow


discharge sputtering were reviewed by Westwood in 1976.[14] A book edited
by J. L. Vossen and W. Kern contains several chapters reviewing magnetron
sputtering[15] and B. Chapman’s book[2] provides an introduction to glow
discharges used in sputtering and plasma etching. The growth and properties
of semiconductors deposited by sputtering have been reviewed by J. E.
Greene.[16]-[18] Harper and co-workers [19]-[21] have written review articles on
ion-beam sputter deposition. Finally, the role of low-energy ion/surface
interactions in controlling the microstructure and microchemistry of vapor-
phase deposited films has been discussed in detail in a number of review
articles by Greene and co-workers.[22]-[25]
Developments in the science and technology of sputtering are most
commonly reported in the following journals: Journal of Vacuum Science and
Technology, Thin Solid Films, Journal of Applied Physics, Vacuum, Surface
Science, Applied Surface Science, and the Journal of the Electrochemical
Society.

2.0 SPUTTERING MECHANISMS

Sputtering is a statistical process which occurs as a result of a


momentum-exchange collisional cascade process initiated near the target
surface by an incident energetic projectile. Figure 5.5 shows a computer
simulation of such a process resulting from a single bombardment event. It
is immediately clear that sputtering cannot result from a single binary
collision since the momentum vector of the struck target atom must be
altered by more than 90o . In the simulated collision sequence of Fig. 5.5,
the incoming projectile (depicted as a solid circle) strikes target atom 1
driving it deeper into the lattice. The collision is elastic and the subsequent
path of the initial projectile towards atom 2 can be calculated from conser-
vation of energy and momentum considerations. The glancing collision with
atom 2 causes the projectile to hit atom 3 which is displaced and collides with
surface atom 4 imparting sufficient momentum to allow atom 4 to overcome
the surface energy barrier and be ejected. The initial projectile as well as
atoms 1 and 2 displace other lattice atoms in subsequent “knock-on”
collisions but, in this simulation, fail to lead to any further sputtering events.
The statistical nature of the sputtering process is evident from the
above example. Computer simulations of Cu bombardment by 600 eV Ar+
ions [26] have shown that the radius of a collision cascade under such
Sputter Deposition Processes 285

conditions is of the order of 10 nm and that the fraction of collision sequences


which actually intersect the surface and transfer sufficient momentum to
result in sputtering is quite low. Statistical analyses show that sputter ejection
very rarely occurs due to collision cascades initiated more than five atomic
layers below the surface. Most of the energy transferred to the lattice during
ion bombardment is lost as heat. The time associated with a particular
collision event is short with respect to the projectile time of flight between
collisions. Thus, under normal sputter deposition conditions, the probability
that overlapping lattice regions will be excited simultaneously by individual
bombardment events is small.

Figure 5.5. Computer simulation of a portion of a collision sequence initiated by


a single ion-bombardment event in a solid lattice.

2.1 Sputtering Rate

The sputtering process is quantified in terms of the sputtering yield,


defined as the number of target atoms ejected per incident particle. The
yield depends on the target species and the nature, energy, and angle of
incidence of the bombarding species. It is relatively insensitive to the
target temperature. [11] (At sufficiently high temperatures, of course, the
evaporation rate becomes of the order of, or larger than, the sputtering
rate). The yield is also independent of whether or not the bombarding species
is ionized. In fact, incident ions have a high probability of being neutralized by
286 Deposition Technologies for Films and Coatings

a field-emitted electron prior to impact.[11][26]-[29] Molecular bombarding


species behave as if the atoms of the molecule arrived separately with the
same velocity as the molecule and initiated their own sputtering events.[11]
The sputtering yield tends to be greatest when the mass of the
bombarding particle is of the same order of magnitude or larger than that of the
target atoms. The use of inert-gas ions avoids chemical reactions at the target
and substrate. Accordingly, Ar is often used because of its mass compatibility
with materials of engineering interest and its low cost.
Sputtering yields are determined experimentally. Figure 5.6 shows yield
versus ion-energy data for several materials under normal ion incidence.
Additional data are given in Table 5.1. The dependence of the yield on the
bombarding-ion energy exhibits a threshold of 20 - 40 eV,[11] followed by a
nearly linear region which may extend to several hundred eV. At higher
energies, the yield vs ion-energy dependence becomes sublinear. The
sputtering process is most efficient from the standpoint of energy consumption
when the ion energies are within the linear range.

Figure 5.6. Variation of the sputtering yield of several materials as a function of Ar+
ion energy at normal angle of incidence. Data from R. V. Stuart and G. K. Wehner,
J. Appl. Phys. 33, 2351 (1962); D. Rosenberg and G. K. Wehner, J. Appl. Phys. 33,
1842 (1962); and R. Behrisch, Ergeb. Exakt. Naturw. 35, 295 (1964).
Sputter Deposition Processes 287

Table 5.1. Sputtering Yields for Various Materials under Argon Ion
Bombardment. Ion energy in eV. Data from Ref. 36.

Ion Energy (eV) Heat of


Target 200 600 1,000 2,000 5,000 10,000 Sublimation
Metal Sputtering Yields (Atoms/Ion) (eV/atom***)
Ag 1.6 3.4 - - - 8.8 2.94
Al 0.35 1.2 - - 2.0 - 3.33
Au 1.1 2.8 3.6 5.6 7.9 - 3.92
C 0.05* 0.2* - - - - 7.39
Co 0.6 1.4 - - - - 4.40
Cr 0.7 1.3 - - - - 4.11
Cu 1.1 2.3 3.2 4.3 5.5 6.6 3.50
Fe 0.5 1.3 1.4 2.0** 2.5** - 4.13
Ge 0.5 1.2 1.5 2.0 3.0 - 3.98
Mo 0.4 0.9 1.1 - 1.5 2.2 6.88
Nb 0.25 0.65 - - - - -
Ni 0.7 1.5 2.1 - - - 4.45
Os 0.4 0.95 - - - - 8.19
Pd 1.0 2.4 - - - - 3.90
Pt 0.6 1.6 - - - - 5.95
Re 0.4 0.9 - - - - 8.06
Rh 0.55 1.5 - - - - 5.76
Si 0.2 0.5 0.6 0.9 1.4 - 4.68
Ta 0.3 0.6 - - 1.05 - 8.10
Th 0.3 0.7 - - - - 5.97
Ti 0.2 0.6 - 1.1 1.7 2.1 4.86
U 0.35 1.0 - - - - 5.00
W 0.3 0.6 - - 1.1 - 8.80
Zr 0.3 0.75 - - - - 6.34
Compound Sputtering Yields (Molecules/Ion)
CdS(1010) 0.5 1.2 - - - -
GaAs(110) 0.4 0.9 - - - -
GaP(111) 0.4 1.0 - - - -
GaSb(111) 0.4 0.9 1.2 - - -
InSb(110) 0.25 0.55 - - - -
PbTe(110) 0.6 1.40 - - - -
SiC(0001) - 0.45 - - - -
SiO2 - - 0.13 0.4 - -
Al2O3 - - 0.04 0.11 - -
*Kr+ ions **Type 304 stainless steel ***From Ref. 240

Note that for typical ion acceleration energies, the sputtering yields of
most metals are near unity and within an order of magnitude of one another.
This is in contrast to evaporation where the rates for different materials at a
given temperature can differ by several orders of magnitude. In addition, the
evaporation rate for a given material varies exponentially with temperature
while the sputtering yield is essentially independent of temperature.
The general dependence of the sputtering yield on the ion angle of
incidence is indicated in Fig. 5.7.[30] In glow-discharge sputtering devices,
the ions generally approach the target in a direction normal to the target
288 Deposition Technologies for Films and Coatings

surface. Thus, the relationship shown in Fig. 5.7 is of particular significance


when the target surface is highly irregular or for ion-beam sputtering where the
ion-incidence angle can be controlled.

Figure 5.7. Schematic diagram showing variation of the sputtering yield with ion
angle of incidence for a constant ion energy.

Sputtering systems are generally calibrated to determine the deposition


rate under a given set of operating conditions. However, yield data of the type
described above are often used in estimating rate changes when changing
coating materials and in estimating the amount of material removed during
sputter cleaning and bias sputtering. The erosion rate is given by

JSMA
Eq. (1) R = 6.23 (nm/min)
δ
Sputter Deposition Processes 289

where J is the ion current density in mA/cm2, S is the sputtering yield in atoms/
ion, MA is the atomic weight in grams, andδ is the density of the target material
in g/cm3.
The reader should be cautious about using Eq. 1 in attempting to predict
absolute sputtering rates, especially in planar diode systems where the
average energy of ions striking the target may be considerably less than Ei =
eVT (VT is the applied target potential), due primarily to inelastic charge
exchange collisions[31] between accelerated ions and neutral sputtering gas
species. S(Ei ) data, on the other hand, are usually obtained from ion beam
experiments carried out in low pressure (long mean-free path) environments
where the ion energy is given by the accelerating energy. The apparent lower
yield in the glow discharge sputtering case (due to the lower average ion
energy) is, however, partially offset by the flux of energetic charge-exchanged
neutrals which are incident at the target.

2.2 Momentum Exchange

Consider a particle of mass Mi and velocity v i which impacts on a line of


centers with a target particle of mass Mt that is initially at rest, as shown in
Fig. 5.8a. Three simple observations can be made. First, as noted above, the
momentum imparted to the target particle drives it into the lattice. Secondly,
from a simple line-of-centers atomic collision calculation, a fraction

4 Mi Mt
Eq. (2) ε =
(Mi + Mt)2

of the kinetic energy of the incident particle is transferred to the target particle.
An expression for the yield, which can be written in the form shown in Eq.
3 below, has been derived by assuming perpendicular ion incidence onto a
target consisting of a random array of atoms (a good approximation for a small-
grain polycrystalline material) with a planar surface.[32]-[34]

E
Eq. (3) S = (constant) ε α(Mt/M i)
U

The relationship is useful for illustrating the functional dependences of the


important parameters and provides reasonably good agreement with
measurements for medium mass (Ar, Kr) bombardment of a wide variety of
290 Deposition Technologies for Films and Coatings

materials. The yield is seen to depend directly on the energy transfer


coefficient ε. The term α(M t/Mi ) is a near-linear function of Mt/Mi, E is the
kinetic energy of the incident ion, and U is the heat of sublimation for the target
material. The mass dependence ofεα does not vary greatly from one material
to another. The primary material-sensitive factor is the heat of sublimation, and
this is only a first power dependence. This is in contrast to chemical and
thermal processes that depend exponentially on an activation energy. It is this
relative insensitivity to the properties of the target material that gives sputtering
the universality referred to previously.

Figure 5.8. Schematic diagram showing momentum exchange processes that


occur during sputtering; Mi and vi are the ion mass and velocity, Mt and vt are the
target-atom mass and velocity, and the prime superscript denotes velocities after
collision.

When the ion mass is lower than that of the target atom, it may be
reflected backward in a single collision with a kinetic energy that is still a
significant fraction of its initial energy. For a 180o reflection, this fraction is

(Mi - M t)2
Eq. (4) f =
(Mi + Mt)
Sputter Deposition Processes 291

If Mi > Mt, reflection requires more than one collision and the reflection
coefficient is low.[35]
Since the ions have a high probability of being neutralized prior to impact,
they are reflected as energetic neutrals which are therefore not influenced by
the electric field over the target surface.[36] The flux of reflected species
contributes to substrate heating,[37] particularly in devices operating at low
pressures where the reflected neutralized ions may reach the substrates with
little loss of kinetic energy by gas-phase collisions. Consequently, the
reflected species bombard, and can become entrapped in, the growing
film.[38]-[41]
The energy flux which leaves the cathode via backscattering can be
estimated using the sputtering efficiency[42]-[44] which is defined as the
fraction γ of the bombarding ion energy incident on the target surface, Ein,
which leaves the surface in the backward direction, Eout, in the form of
sputtered atoms or backscattered ions.

Eout Esputtered + Ebackscattered


Eq. (5) γ = =
Ein Ein

The energy of the sputtered atoms is discussed in a subsequent section.


Theoretical calculations[42] for a target consisting of a random array of atoms
in which the surface binding energy was neglected indicates that the
sputtering efficiency is independent of the energy of the incident ion and is
simply a monotonically increasing function of the target-atom/ion mass ratio.
This dependence, which has been confirmed for both low and high ion
energies, is shown in Fig. 5.9.
Momentum exchange processes also provide an explanation for the
angular dependence of the sputtering yield shown in Fig. 5.7. An ion which
is incident on the target surface at an angle θ will, to first order, have its path
length increased by a factor secθ before it passes through depth d. At larger
angles of incidence, ion reflection dominates and the yield decreases.
Another question of interest is the ultimate fate of the inert gas ions that
bombard the target. The probability of their becoming trapped in the target
increases with ion energy above a threshold of ~ 50 - 100 eV.[45] Thus, a
concentration of inert gas, which depends on a balance between the rates of
implantation and release, will develop in the near-surface region of the target.
The amount of gas entrapped in the target can be large enough to influence the
sputtering yield.[46]
292 Deposition Technologies for Films and Coatings

Figure 5.9. Sputtering efficiency versus target-to-ion mass ratio. The solid curve
is from the theoretical work of Sigmund (Ref. 42). The experimental data is from
substrate heating experiments with cylindrical-post magnetrons (Ref. 37).

2.3 Alloys and Compounds

An important advantage of the sputtering process is that the composition


of a sputter-deposited film tends to be the same as that of the target, provided
that: (i) the target is maintained sufficiently cool to avoid bulk diffusion of the
constituents, (ii) the target does not decompose, (iii) reactive contaminants
are not present,(iv) the gas-phase transport of the components is the same,
and (v) the sticking coefficients for the components on the substrate are the
same. Targets can be formed by casting or by hot pressing powders. In
addition, composite targets can be formed by placing wires, strips, or discs
of one material over a target of another material.
The details of ion/surface interactions with multicomponent materials
are complex[47]-[49] and poorly understood. Consider the case of a homoge-
neous starting material composed of species having different individual
sputtering yields or masses. When sputtering is first initiated from such a
Sputter Deposition Processes 293

target, the sputtered flux will, in general, be rich in one of the constituents. The
composition of this altered surface layer continues to change until the product
of the partial sputtering yield times the surface concentration for each species
is proportional to its concentration in the target. The process is indicated
schematically in Fig. 5.10. Once a steady-state altered layer is formed, the
composition of the sputtered flux is equal to the bulk target composition.

Figure 5.10. Schematic illustration of the surface composition modification which


occurs during sputtering of a single-phase alloy.

The thickness and composition of the altered layer will depend on the
target material and sputtering conditions. Typical altered-layer thicknesses
are 3 - 10 nm for single-phase alloys[49][51] and up to several µm for multiphase
alloys.[52] A change in sputtering conditions will in general require an
adjustment of the altered layer. It is important to note that the partial sputtering
yield of a constituent in an alloy or compound will not be the same as for that
constituent by itself because of the difference in binding energies and the
different atomic masses involved in the collision sequence within the alloy or
compound. In an alloy for which the constituent species have similar binding
energies, the low mass species can be expected to have higher partial
sputtering yields. If the masses are similar, the weakly-bound species will
have higher partial sputtering yields.[34][47]-[48] Thus, in the sputtering of most
oxides, the altered layer becomes deficient in the flow-mass oxygen compo-
nent.[47]
294 Deposition Technologies for Films and Coatings

Sputtering of two-phase alloys in which the phases have significantly


different sputtering yields results in the development of an irregular surface
topography.[30][53]-[55] The sloping surfaces that survive tend to be those that
make an angle with the sputtered flux such that the sputtering yield is
maximized. If the second phase, or any included impurity particles, have very
low sputtering yields, the surface may develop into a forest of cones with side
walls at the maximum sputtering angle[52][56]-[59] as shown in Fig. 5.11. The
cones will eventually be sputtered away; however, the receding target surface
will expose new second-phase regions and impurity particles (if they are
distributed throughout the bulk) and new cones will form. Thus a steady-state
surface topography will develop. Surface diffusion on the target will, in general,
make this situation more complex than the picture described above. The
important point is that, following an incubation period, the composition of the
sputtered flux leaving the target will become identical to that of the target.
Nevertheless, the irregular surface topography may cause the overall yield to
be considerably lower than what might be expected on the basis of the yields
of the primary target constituents.

Figure 5.11. Schematic representation showing stages of cone formation during


ion irradiation of a contaminated or two-phase target.

Topographical evolution such as cone formation can also influence the


performance of composite sputtering targets.[60][61] When such targets are
used in sputtering systems that operate at high pressures (greater than about
20 mTorr), some of the sputtered material will be backscattered by the working
gas. Thus mixing of low and high yield materials can occur on the target
segments. When atoms of a low-yield material are deposited on a high-
yield target surface, the low-yield material can agglomerate into islands
capable of protecting the material underneath and cones will form. [58]
Sputter Deposition Processes 295

Relative sputtering yields as well as the target temperature appear to be


important in predicting this behavior. An example is the formation of Mo-
protected cones on Cu surfaces.[58] The resultant sputtering rate from the
cone-covered surface has been found to be very close to that for the low-yield
material, Mo. Thus the composition of films deposited from composite targets
can be much different than that estimated using the individual sputtering yields
and the relative areas of the target segments.
Special care should be exercised when using hot-pressed targets. Hot-
pressed Au-Ni and Au-Co targets composed of powders in the 50 to 130 µm
range were found to yield deposits with compositions that matched those of
the target after a transition period during which a layer≈20 µm thick had been
sputtered from their surfaces.[62] However, the overall yield dropped to a value
equal to that of the low-yield constituents (Ni or Co), even when the volume
fraction of that constituent was only ≈30%.
Contamination can present a particular problem with hot-pressed targets
because of the large surface area contained in the starting powder. Such
contamination may be present throughout the target and will provide a
continuous virtual leak as the target is used.[63][64]
Particular caution must also be exercised when using targets composed
of compounds having poor electrical and thermal conductivities. Cracking
often limits allowable current densities. The problem is especially egregious
in planar magnetron systems where concentrated heating occurs under the
plasma ring.[65] Poor thermal conductivity leads to high surface temperatures
and may also result in the loss of volatile constituents by evaporation or
sublimation. The high electric field in a poorly conducting target can act in
concert with the high temperature and promote diffusion within the target. Thus
the requirements listed at the beginning of this section for obtaining films with
the same composition as the target are violated. It is not uncommon for films
sputter deposited from such targets to be deficient in the more volatile
constituents.[66][67]

2.4 Sputtering with Reactive Species

The most complete data on the dependence of the sputtering yield on the
ion species are those collected by Almen and Bruce, shown in Fig. 5.12.[68]
Although the ion energies were considerably above those generally used for
sputter coating technology, they do illustrate trends. Sputtering yields
increase with the mass of the ions and, for a given row in the periodic table,
the rare-gas ions have the highest yields. Of particular interest is the fact
that yields vary much more with ion species (factor of 100 or more) than
296 Deposition Technologies for Films and Coatings

they do with target atom species (factor of 10).[11] This is believed to result
from the bombarding ions forming alloys or compounds with high binding
energies on the surface of the target. Note that the yields for the three target
materials examined in Fig. 5.12 are particularly low for reactive species such
as Be, C, Mg, Si, Ti, and Zr.

Figure 5.12. Sputtering yields for various ions impacting at normal incidence on
Ag, Cu, and Ta surfaces at high energies (45 keV). Data from Ref. 68.

Reduced yields are commonly observed in reactive sputtering (see Sec.


4.1 in this chapter) and attributed to compound formation on the target surface.
Such surface interactions can also significantly influence the surface topog-
raphy that develops on the target. Thus, 20 keV O2+ bombardment of an Fe
target yielded a considerably smoother surface than 20 keV Ar+ bombard-
ment.[69]

2.5 The Nature of Sputtered Species

Under typical metal or semiconductor thin-film deposition conditions,


most sputtered material is ejected in the neutral atomic state. The fraction of
charged particles sputtered from clean metal and semiconductor surfaces
is on the order of 10-4, becoming larger for surfaces contaminated with
Sputter Deposition Processes 297

strongly electropositive or electronegative species.[70]-[73] In glow discharge


sputtering, the target is biased negatively and hence ejected positive ionswill
be recaptured. The fraction of negative ion emission from pure semiconduct-
ing targets such as Si, GaAs, or GaP is typically less than 10-4 .[74] However,
the negative ion yield can be quite large for targets composed of elements,
one of which has a low ionization potential, while another has a high electron
affinity. Examples are TbF3 ,[75] SmAu,[76] and YBa2 Cu3Ox.[77] Glow
discharge sputtering of such materials results in acceleration of the negative
ions, via the cathode fall potential, to the substrate.
Relatively little experimental data is available on the probability of
material being sputtered as molecules or clusters. Investigation by Oechsner
and Gerhard[78][79] and Gerhard[80] using mass spectrometric analyses of
post-ionized sputtered neutral particles has shown that with 1 keV Ar+
bombardment, the maximum fraction of sputtered dimers is 0.1 for Ag, Au, and
Cu and about 0.03 for other metals. The fraction of trimers is about 0.001.
Molecular-dynamic computer simulations by Winograd et al.[81] indicate that
the fraction of sputtered Cu multimers varies strongly with crystal orientation,
being largest for the (111) face. While such simulations are useful for
predicting trends, the number of individual events sampled is too small to
expect reliable statistics. Nevertheless, the predicted yield fractions of
sputtered dimers and trimers agree reasonably well with the measured results
of Gerhard and co-workers.
The mechanism for the sputtering of molecular species is not well
established. So-called “statistical models” have been proposed in which
sputtered neutral atoms resulting from nearly-simultaneous ejection events
agglomerate above the surface if their ejection is properly correlated in
space and time and their relative kinetic energy is less than the dissociation
energy of the molecule formed.[79][82]-[84] Können et al.[82] used such a
model to describe the energy distribution of sputtered K2 and KI molecules.
Winograd et al.[81][84] invoked a similar mechanism to obtain sputtered
clusters in their computer simulations. However, Prigge and Bauer[85]
reported experimental results which may indicate that, at least for the case
of dimer and trimer ions, species comprising sputtered molecules were
originally vertically displaced nearest neighbors in the lattice. In their
experiments, they used 1 keV Ar+ ions to sputter thin Cu or Pd layers which
had been deposited onto (110) W. The metal layers ranged in thickness
from less than a monolayer to greater than three monolayers and sputtered
species were detected by secondary-ion mass spectrometry. No sputtered
Cu2+ or Pd2 + ions were observed emanating from targets with less than one
298 Deposition Technologies for Films and Coatings

monolayer coverage and no trimer ions from samples with less than two
monolayers. The sputtering yield of monomer, dimer, and trimer ions all
saturated at a coverage of ≈3 monolayers.
In the case of compounds, most of the information available on molecular
sputtering is for alkali halides and oxides where clusters can account for a
significant percent of the total sputtered flux. Coburn et al.[86] showed that the
relative fraction MO/(M + O) of sputtered species from MxOy metal oxide
targets increased with increasing M-O bond energy. Rare gas matrix isolation
spectroscopy was used by Gruen et al.[87][88] to identify Al2 O and AlO
molecular species sputtered from Al2 O3 targets under Ar + bombardment and
TiO and ZrO species from metal targets sputtered with 2 keV O2 + ions.[89]
The only published work on compound semiconductors is for GaAs.
Using 140 eV Ar+ bombardment, comparable to the average impact energy in
many glow discharge deposition experiments, Comas and Cooper[90] found
from post-ionized mass spectroscopy measurements that molecular species
(GaAs, Ga2, As2) amounted to less than 1% of the total sputtered flux.
However, for 6 keV Ar+ ion sputtering, Szymonski and Bhattacharya[91]
observed that at room temperature, sputtered GaAs and As2 molecules
accounted for ~14% and 11% (data uncorrected for the variation in the detector
efficiency as a function of mass), respectively, of the flux. The fraction of
sputtered GaAs molecules was found to increase rapidly for target tempera-
tures above 250oC. This latter effect was explained as being due to enhanced
sputtering from collisional spikes.

2.6 Energy Distribution of Sputtered Species

An important distinction between sputtering and other vapor-phase


deposition techniques is that sputtered atoms can have quite high kinetic
energies. For example, the average ejection energy of Ge atoms under 1.2
keV Ar+ bombardment is ≈15 eV[92] compared to only≈0.1 eV for evaporated
Ge. In sputter deposition systems for which the target-substrate separation
is less than a few mean free paths, the energy distribution of sputtered species
impinging on the substrate will be approximately the same as the ejected
species energy distribution.
The most probable ejection energy is typically of the order of one half the
surface binding energy, but because of the extended high-energy tail the
average ejection energy is considerably higher (see Fig. 5.13)[92] and, in
general, is found to increase with the atomic number of the target.[93]-[95]
Sputter Deposition Processes 299

From collision cascade theory,[96] the energy distribution of sputtered species


is expected to be

E
Eq. (6) ∆N/∆E ∝
(E + U)3

where ∆N/∆E is the differential flux of sputtered particles with energy E and
U is the surface binding energy. In practice, the high-energy tails of
experimentally determined sputtered-atom energy distributions for rare-gas
bombardment energies from≈1 to 10 keV generally follow a E-2 dependence
in agreement with Eq. (6).

Figure 5.13. (Top) Energy distribution of sputtered Cu atoms ejected by Kr + ions


at various bombarding energies. (Bottom) Comparision of velocity distributions of
sputtered and evaporated Cu atoms. Data from Ref. 92.
300 Deposition Technologies for Films and Coatings

Sputter-ejected atoms from metals with atomic number Zt > 20 have


ejection velocities which lie in a relatively narrow range (see Fig. 5.14b).
Average ejection energies therefore increase with increasing Zt as shown in
Fig. 5.14a for neutral metal atoms sputtered from polycrystalline targets with
1.2 keV Kr+ ions.[11]

Figure 5.14. Average energies (top) and velocities (bottom) of sputtered atoms
ejected by 1.2 keV Kr+ ion bombardment. Data from Ref. 11.

Atoms sputtered from polycrystalline or amorphous targets under


perpendicular-incidence bombardment by medium-mass ions with energies
of 1 - 3 keV are ejected in nearly random directions, as a consequence of
multiple collisions within the target, and therefore have near cosine distribu-
tions.[11] At low ion energies (≈1 keV), the distribution may be slightly under
Sputter Deposition Processes 301

cosine (more emission at large angles) while at higher energies (≈3 keV) it is
over cosine.[10] Under oblique-incidence bombardment, the target atoms are
sputtered in the forward direction from smooth surfaces. However, the
roughness of most practical targets causes the emission to be random. This
is particularly true for polycrystalline targets, where the difference in yield for
different crystallographic directions can lead to an increase in surface
roughness as sputtering proceeds. Thus, a cosine distribution is often a
reasonable approximation for estimating deposition profiles.[11]

3.0 SPUTTER DEPOSITION TECHNIQUES

The fundamental problem in implementing the sputtering process is to


provide a uniform and copious supply of ions over the surface of the target. The
low-pressure glow discharge has proven to be the most cost-effective source
of ions. A wide range of glow discharge apparatus geometries have been used
in attempts to: (i) increase the ion supply and thus the sputtering rate, (ii)
increase the target area and thus the available deposition area, (iii) reduce
plasma heating of the substrates, (iv) permit operation at lower working-gas
pressures, and(v) facilitate the coating of particular substrate shapes. In the
following discussion, the essential features of the glow discharge and several
of the more commonly used apparatus types are reviewed.

3.1 Planar Diode and the DC Glow Discharge

The planar diode shown schematically in Fig. 5.15 is the simplest and
probably the most widely used sputtering configuration. Cathode diameters
are typically 10 to 30 cm and the cathode-to-anode spacing≈5 to 10 cm. Such
systems are operated with both DC and RF power supplies. In DC diodes, the
cathode serves a dual capacity. It is the target or source of coating material
as well as the cathode electrode for sustaining the glow discharge and is
generally water-cooled. Often the target consists of a disc of the material to
be sputtered which is attached with solder or conducting epoxy to a backing
plate which serves as part of the cathode-cooling channel. A low-pressure
glow discharge of a type known as an abnormal negative glow[97] is maintained
between the cathode and an adjacent anode which may also serve as the
substrate mounting table, as shown in Fig. 5.15.
302 Deposition Technologies for Films and Coatings

Figure 5.15. Schematic representation of the plasma in a planar diode sputtering


source.

A grounded shield is used to promote a uniform erosion rate over the


target surface and to prevent sputtering from the sides and the rear surface of
the target. The discharge current is carried, in the vicinity of the negatively
biased cathode, primarily by positive ions passing out of the plasma volume,
and, in the vicinity of the anode, by electrons passing from the plasma volume
to the anode. Thus, a necessary condition for sustaining the discharge is that
the plasma volume be a suitable source of electrons and ions.
Because of the relatively low mobility of the ions compared to the
electrons, most of the electrical potential that is applied between the anode
and cathode by the power supply is consumed in a cathode dark space, or
sheath region.[97] Dark-space thicknesses are typically 1 to 4 cm, depending
on the pressure and current density.[99] Accordingly, strong electric fields are
formed, and ions passing from the plasma volume to the cathode are
accelerated by these fields to impact the cathode. However, these ions also
cause a small number of secondary electrons to be emitted from the surface
(approximately one for every ten ions in the case of Ar+ ions impacting on a
metal cathode).[100][101] These electrons are accelerated in the cathode dark
space to energies approaching the applied potential and enter the plasma
volume (negative glow) where, known asprimary electrons, they collide with
gas atoms and produce the volume ionization necessary to sustain the
discharge.[97][102]
The requirement for sustaining such a discharge is that each primary
electron must produce sufficient ions to release one further electron from the
Sputter Deposition Processes 303

cathode. Therefore, the interelectrode spacing must be large compared to the


electron mean free path. The cross section, σ, for Ar ionization by the impact
of 500 eV electrons is about 10-16 cm2.[103] Thus, for example, at an Ar
pressure of 1 mTorr (gas density N = 3.2 x 1013 atoms/cm3) the electron mean
free path (1/Nσ) for the production of ionization is 300 cm; i.e., much larger than
the cathode-to-anode spacing. Consequently, discharges of the form shown
in Fig. 5.15 can be sustained only at relatively high working pressures (50 - 100
mTorr), where a high density of Ar collision partners is provided for the primary
electrons. (The grounded shields shown in Fig. 5.15 prevent the discharge
from forming on the sides of the cathode because the electrode separation is
too small to support the ionization mechanisms described above at the
operating pressures of interest.).
Attempts to increase the discharge current in a planar diode by
increasing the applied voltage are thwarted to a large degree by the fact that
the ionization cross-section decreases with increasing electron energy for
energies greater than about 100 eV.[103] The current, and thus the sputtering
rate, can be effectively increased at a given voltage by increasing the Ar
pressure. However, if the pressure is too high, the deposition rate starts to
decrease since the motion of both ions and sputtered atoms is impeded by the
working gas atmosphere, as discussed below. These conflicting require-
ments result in an optimum operating pressure for producing the maximum
deposition rate in a given apparatus. Typical operating conditions for metal
deposition in a DC planar diode sputtering source are listed below.
Cathode current density - 1 mA/cm2
Discharge voltage - 3,000 V
Ar pressure - 75 mTorr (10 Pa)
Deposition rate - 40 nm/min (2.4 µm/h)
At typical planar diode operating pressures, the motion of the ions
across the dark space is disrupted by collisions with gas atoms. In such
collisions, there is a high probability of charge exchange, particularly when
noble gas ions are passing through an atomic gas of their own species
(resonance charge exchange).[97] A fast ion extracts an electron from a slow
gas atom. The fast ion then becomes a “fast” neutral atom, while the “slow”
atom becomes a positive ion, as indicated schematically in Fig. 5.16. Thus,
instead of being bombarded by a current of ions having an energy equal to the
potential drop across the cathode dark space, the target is bombarded with
a much larger number of ions and fast neutrals having an average energy that
is often less than 10 - 20% of the applied potential.[31][104]
304 Deposition Technologies for Films and Coatings

Figure 5.16. Schematic illustration of the charge-exchange process that affects ion
transport across the cathode dark space.

The deposition rate in planar diodes is further reduced by gas-scattering


of sputtered atoms during transport between the target and the substrate.
Optical emission measurements have confirmed that at typical sputtering
pressures, sputtered-atom transport within the negative glow region is largely
by diffusion.[105][106] The combination of charge transfer processes and
diffusion transport make it necessary to determine deposition rates experi-
mentally for each set of operating conditions. Another consequence of the
collision-dominated transport of the sputtered atoms is a reduction in their
kinetic energy at the substrate.[14][107][108] Figure 5.17 shows the results of
an approximate calculation of the maximum distance required for sputtered
atoms with various initial energies to have their kinetic energy reduced to the
thermal energy of the gas atoms (≈0.025 eV).[109] At typical planar diode
operating pressures, the equilibration distances are short compared to target-
to-substrate spacings.
Even under the relatively high-pressure conditions that yield the maxi-
mum deposition rates, the planar-diode discharge is inefficient. Many of the
high-energy primary electrons fail to transfer their energy in the plasma volume
and are incident at the anode and substrates while still possessing consider-
able energy. Ions and electrons are also lost from the edges of the discharge.
Note also that the substrates are in contact with the plasma and are therefore
also subjected to bombardment by plasma electrons and ions. This irradiation
precludes the coating of many heat-sensitive materials such as plastics.[110]
Sputter Deposition Processes 305

Figure 5.17. Maximum distance from the target at which sputtered Al and Ta
atoms of different initial energies are thermalized in Ar at various pressures.
Data from Ref. 109.

Planar diodes are widely used despite substrate heating and low
deposition rates. The reason is their simplicity and the relative ease with which
planar targets can be fabricated from a wide range of materials. Sputter
cleaning of the substrate and bias sputtering are easily accomplished by
adding an auxiliary anode and applying a negative bias to the substrate holder.

3.2 Triode Discharge Devices

Triode discharge devices utilize an additional electrode, independent of


the target, to sustain the glow discharge.[13] The most common configuration
is the hot-cathode triode shown schematically in Fig. 5.18. Electrons are
emitted from the cathode surface thermionically rather than by ion bombard-
ment. This relaxes the volume ionization requirement for sustaining the
discharge. Consequently, hot-cathode triodes can be operated at low
pressures (0.5 to 1 mTorr). The driving voltage is only 50 - 100 V, although
the current may be several amperes. Radial plasma losses are often
minimized through the confining effect of an axial magnetic field as shown in
the figure. However, such a field produces a distortion of the current
distribution over the target.
306 Deposition Technologies for Films and Coatings

Figure 5.18. Schematic drawing of hot-cathode assisted discharge device (triode)


From Ref. 13.

Triodes permit high deposition rates (several hundred nm/min) to be


achieved, even at low pressures (mTorr range).[3] Although thick coatings have
been deposited,[111] use of triodes has been limited by difficulties in scaling
and the vulnerability of the thermionic emitter to reactive gases. Conse-
quently, magnetron sources (next section) are assuming primary importance
as high-rate sputtering devices.

3.3 Magnetrons

The development of high performance magnetron sputtering sources that


provide (i) relatively high deposition rates,(ii) large deposition areas, and(iii)
low substrate heating, revolutionized the sputtering process by greatly
expanding the range of feasible applications.[112]
Magnetron sputtering sources can be defined as diode devices in which
magnetic fields are used in concert with the cathode surface to form electron
traps which are so configured that the ĒxB̄ electron drift currents close upon
themselves.[113][114] Magnetrons can be configured in a variety of forms.
Examples include the planar magnetrons shown in Fig. 5.19a, the S-gun type
shown in Fig. 5.19b, and the cylindrical type shown in Fig. 5.20.
Sputter Deposition Processes 307

Figure 5.19. Magnetrons with magnetic end-confinement: (a) planar magnetron,


(b) gun type. From Ref. 110.

Figure 5.20. Cylindrical-post magnetron sputtering source with electrostatic end-


confinement. From Ref. 110.

The magnetron configuration shown in Fig. 5.20 has been termed the
“cylindrical-post magnetron.”[113]-[115] It provides the simplest geometry for
explaining the principles of magnetron operation.[113]-[118] The cathode
consists of a cylindrical barrel with end plates, all composed of the material
to be sputtered. It is mounted in a chamber with a uniform magnetic field B̄
directed parallel to the cathode axis. The magnetic field is of such strength
308 Deposition Technologies for Films and Coatings

(a few hundred gauss or less) that it affects the plasma electrons but not the
ions. Figure 5.21 shows a typical chamber configuration for cylindrical
magnetrons. A set of solenoidal field coils is positioned surrounding the
cylindrical vacuum wall, which is constructed of a nonmagnetic material. A
magnetic steel shell surrounds the coils and makes contact with the chamber
top and bottom plates which are also fabricated from a magnetic material such
as low-carbon steel. Thus, a low reluctance return path is provided for the
solenoidal flux, as indicated in the figure, with the consequence that the coil
system efficiently provides a uniform magnetic field within the chamber.

Figure 5.21. Chamber and magnetic field coil configuration used for cylindrical-
post magnetron sputtering sources.

Secondary electrons which are emitted from the cylindrical-magne-


tron cathode barrel due to ion bombardment find themselves trapped in an
annular cavity which is closed on three sides by surfaces at cathode
Sputter Deposition Processes 309

potential and on the fourth side by the magnetic field. Anode rings are
located adjacent to the end plates on one or both ends of the cathode.
Therefore, electrons emitted from the cathode must migrate radially across
the cavity in order to reach the anode. Electron collisions of the type required
to sustain a plasma discharge play an essential role in allowing this migration
to occur. Thus, in contrast to the conventional discharge, the electrons are
forced to make the required collisions, and an effective sputtering discharge
is maintained in the cavity.
The electron motion can be understood as follows.[119][120] When an
electron is in a uniform magnetic field, its motion perpendicular to the field
lines can be pictured as an orbit around a field line, as shown in Fig. 5.22a.
Its motion along the field is unimpeded, so that if it has a component of
velocity along the field line its net motion is a spiral as shown in Fig. 5.22b.
Such electrons can be considered to be trapped on magnetic field lines and
can advance to adjacent field lines by making a collision, as indicated
schematically in Fig. 5.22c. An electron will also undergo a drift motion
across the magnetic field if an electric field E is present. However, this
motion, known as ĒxB̄ drift, is not in the direction of the electric field but in
a direction perpendicular to both the electric and the magnetic fields. ĒxB̄
drift has the cycloidal form shown in Fig. 5.22d if the initial electron energy
is small compared to that gained from the electric field, and the more circular
motion shown in Fig. 5.22e if the initial electron energy is large compared
to the electric-field-induced variations during the course of an orbit.
Referring back to Fig. 5.20, a radial electric field also exists in the
annular cavity. The field will be strong in the sheath region adjacent to the
cathode but relatively weak at larger radii. Electrons emitted from the
cathode will therefore undergo motions of the type shown in Fig. 5.22d and
will become trapped in orbits revolving around the cathode. They will be
able to advance radially only by making collisions or by the action of plasma
oscillations which produce azimuthal electric fields and radial drifts.[113][114]
Since the electrons leave the cathode sheath with energies of several
hundred eV, electron collisions with gas atoms have a high probability of
resulting in ionization. The ĒxB̄ drift motions of the primary electrons and
the products of ionization collisions produce an intense azimuthal current
sheet of trapped electrons adjacent to the cathode. Because of the free axial
movement of the electrons along the field lines, the sheet tends to be uniform
along the cathode length. Large numbers of ions are produced which give
rise to uniform sputter-erosion and high sputtering rates along the cathode
barrel.
310 Deposition Technologies for Films and Coatings

Figure 5.22. Electron motion in static magnetic and electric fields.

As the electrons give up energy by collisions and become ultimate


electrons,[102] they move into regions of weak electric field at larger radii,
and their motion becomes more like that shown in Fig. 5.22e. The ĒxB̄ drift
velocity is relatively small, and the electrons move primarily up and down the
field lines, reflecting off the end plates as indicated in Fig. 5.20.[121] When
they reach the anode radius R, they immediately pass into the anode.
Therefore, the high mobility of the electrons along the magnetic field lines
causes the anode ring to be projected as a virtual anode sheet which
surrounds and terminates the plasma discharge but is transparent to the
sputtered flux.[113][114] Thus the electrons are trapped within the annular
cavity throughout their lifetimes. The ions are constrained electrostatically
to stay with the electrons and are therefore largely confined to this region as
well. Consequently, there is virtually no plasma bombardment of substrates
located beyond the anode radius.[37] Low-energy ion irradiation of the
growing film (in order to controllably alter microstructure and/or microchem-
istry)can be induced, however, by "unbalancing" the magnetic confinement
as discussed at the end of this chapter in Sec. 4.2.
Sputter Deposition Processes 311

Because of the efficiency of the ionization mechanisms in the magne-


tron cavity, intense plasma discharges capable of providing high sputtering
rates can be maintained at moderate and near-constant voltages, even at low
pressures. Deposition rates will depend on the radial position of the
substrates. Typical operating conditions for cylindrical magnetrons of the type
shown in Fig. 5.20 are:[114]
Cathode current density - 20 mA/cm2
Discharge current - 1 to 50 A
Discharge Voltage - 800 V
Argon Pressure - 1 mTorr (0.13 Pa)
Cathode erosion rate - 1.2 µm/min
Substrate position - radius equal to 6 cathode radii
Deposition rate - 200 nm/min (12 µm/h)
While these deposition rates are approximately 10x lower than those of planar
magnetrons, the deposition areas are proportionally larger since the substrates
surround the cylindrical source.
An important attribute of cylindrical magnetrons is their capability of
being scaled through a range of sizes while retaining common operating
characteristics.[114] Cathodes which range in length from 0.1 m to 2.1 m have
been used. Figure 5.23 shows a 2.1 m cylindrical magnetron designed for
depositing decorative coatings.[122] Such long cathodes provide a large
substrate placement area around the circumference. Substrates can also be
passed on each side of a cylindrical post magnetron in systems that operate
continuously or semi-continuously. However, the most common application
is batch processing in which the substrates are arranged around the cathode
as shown in Fig. 5.24. Post cathodes have been used to coat the insides of
tubes up to 1.8 m long.[123]
Cylindrical magnetrons can also be configured in the inverted or hollow
cathode form shown in Fig. 5.25.[114][116][124] Long hollow cathodes have the
property that the coating flux at all points within the cathode is approximately
equal to the erosion flux at the wall. This makes hollow cathodes particularly
effective for coating objects with complex shapes.[125]
Cylindrical magnetrons can also be designed in an arrangement
whereby the magnetic field lines are bent such that they intersect the cathode
barrel as shown in Fig. 5.26. The annular cross section of the electron trap
is now closed on three sides by the magnetic field and on the fourth side by
the surface at cathode potential. The plasma has the form of a ring rather than
a sheet. Therefore such systems are generally configured with several such
electron traps along the cathode cylinder.[116][117][126] Magnetrons of this
312 Deposition Technologies for Films and Coatings

type are often referred to as having magnetic end-confinement, as opposed


to those shown in Figs. 5.20 and 5.25 which are referred to as having
electrostatic end-confinement.[112][113] Magnetic end-confinement devices
have also been operated in the inverted or hollow cathode form.[126]

Figure 5.23. Large cylindrical-post magnetron sputtering source with a length =


2.1 m. See Ref. 122.

Cylindrical magnetrons with electrostatic end-confinement can be con-


figured with large-diameter cathodes which provide a large inventory of coating
material. Furthermore, the material is used very efficiently because of the
uniform sputter erosion along the cathode length. However, a potential
disadvantage with cylindrical sources is that target fabrication may be difficult.
Plasma rings can be confined over planar surfaces or within cylindrical
surface cavities. This is the basis of the planar magnetron[127][128] and sputter
or S-gun[129] configurations shown in Fig. 5.19. At the present time, these
devices are the most widely used form of magnetrons. Like cylindrical
magnetrons, planar magnetrons are attractive because of their ability to be
scaled to large sizes. Elongated planar magnetrons are particularly useful
Sputter Deposition Processes 313

for coating large substrate surfaces that are transported in a direction


perpendicular to the long axis of the cathode. In this arrangement, close
cathode-substrate spacing and deposition rates of µm/min or more may be
used. Proper cathode design, aided by minimal aperturing, can provide
deposition uniformities of better than ± 5%.[130]

Figure 5.24. Typical arrangement of substrates for batch processing with a


cylindrical-post magnetron sputtering source.

Figure 5.25. Cylindrical-hollow magnetron sputtering source with electrostatic


end-confinement. From Ref. 110.
314 Deposition Technologies for Films and Coatings

Figure 5.26. Cylindrical magnetron with magnetic end-confinement. From Ref.


110.

Figure 5.27 shows a schematic drawing of an in-line system, with


vacuum interlocks, which is typical of the apparatuses that are used to achieve
high production volumes with planar magnetrons. Large systems of this type
are used to coat architectural glass panels several square meters in size at
production volumes of 106 m 2/yr. The planar magnetrons are typically 2 to 3
m long and are driven by currents in the 100 to 200 A range. Cathodes as long
as 6.5 m have been considered for architectural glass coating.[131] Large
circular planar magnetrons with arrays of concentric plasma rings 0.6 m in
diameter have also been reported.[132] Patents have been granted for various
configurations of the sputtering sources shown in Fig. 5.19.[133]-[137]
Gun-type magnetrons do not have the scaling capabilities of the other
forms of magnetrons. However, arrays can be used to coat large areas. The
system shown in Fig. 5.4 uses an array of twenty-four S-gun sources in an in-
line configuration in which the substrates are transported relative to the
sputtering source.
Magnetron sputtering sources can be used to deposit magnetic as well
as nonmagnetic materials. However, when a sputtering target composed of
magnetic materials is used, it must be saturated magnetically so that its
magnetic behavior is suppressed and a field of the desired shape can be
maintained over its surface.[114]
Sputter Deposition Processes 315

Figure 5.27. Schematic illustration of an in-line system, with vacuum interlocks,


used to achieve high production volumes with planar magnetrons.

DC magnetrons are typically operated at discharge currents in the range


of 1 to 50 A. Current densities are generally higher in the plasma-ring devices
(Figs. 5.19 and 5.26) than in the plasma sheet devices (Figs. 5.20 and 5.25).
Total coating material fluxes (which are dependent on the total discharge
current) can be comparable at high currents to those obtained with evaporation
systems.
The current-voltage characteristic reveals a great deal about the ioniza-
tion processes in a plasma discharge. The more efficient the discharge, the
lower the voltage for a given cathode current density. Discharges operating
in the magnetron mode obey an I-V relationship of the form I proportional to Vn,
where n is an index to the performance of the electron trap and is typically in
the range 5 to 9. Typical I-V curves for various types of magnetron sputtering
sources are shown in Fig. 5.28 and compared with an I-V curve for a planar
diode.
A basic disadvantage of the plasma-ring devices is that sputtering occurs
only under the plasma rings. Troughs are eroded into the cathode, and the
source material is used relatively inefficiently. Relative motion between the
cathode and the magnetic field pattern is sometimes provided to improve the
target usage.[127] A further disadvantage of ring devices is that the complexity
of the magnetic-field shape makes effective anode placement more difficult
than for cylindrical magnetrons.[114][127] Some field lines will intersect the
substrates, as shown in Fig. 5.26, thereby allowing electron bombardment of
the substrates. However, the bombardment intensity is much less than in
planar diode sputtering sources. All plasma-ring magnetrons offer the
advantage that the required magnetic field can be produced by permanent
magnets located within the cathode rather than by magnetic field coils located
at or beyond the chamber walls, as is required for cylindrical magnetrons.
316 Deposition Technologies for Films and Coatings

Figure 5.28. Typical current-voltage characteristics for a planar diode sputtering


source and for various types of planar and cylindrical magnetrons. All sources were
operated with Al targets at the Ar working-gas pressures indicated.

At typical operating pressures (≈1 mTorr), the sputtered flux from


magnetron sources passes to the substrate while undergoing very little gas
scattering. Thus the deposition flux can be predicted with reasonable
accuracy by assuming a cosine emission of sputtered material from the
erosion area and collisionless passage to the substrates.[114][127] Figure 5.29
shows calculated and experimental profiles for the 2.1 m long cylindrical post
magnetron in Fig. 5.23.[122] Figures 5.30 and 5.31 show typical deposition flux
profiles for planar magnetrons of the ring and rectangular types, respectively.
Sputter Deposition Processes 317

Figure 5.29. Comparision of experimental deposition profile with calculated profile


for long (2.1 m) cylindrical-post magnetron with electrostatic end-confinement. The
profile was measured parallel to the cathode axis at a radius of 0.86 m. Data from
Ref. 122.

Figure 5.30. Deposition-rate profile for a ring-type planar-magnetron sputtering


source at various distances from the cathode surface.
318 Deposition Technologies for Films and Coatings

Figure 5.31. Deposition rate profile for a rectangular-type planar-magnetron


sputtering source along the long axis (A-A) at various distances from the cathode
surface.

3.4 RF Sputtering

DC methods cannot be used to sputter nonconducting targets because


of charge accumulation at the target surface. This difficulty can be overcome
by using radio frequency (RF) sputtering.[2][66][138]-[142] A single RF sputter-
ing apparatus can be used to deposit electrically conducting, semiconducting,
and insulating coatings. Consequently, RF sputtering has found wide
application in the electronics industry. Nonconducting and semiconducting
materials which have been deposited by RF sputtering include elemental
semiconductors: Si[143] and Ge;[144] III-V compounds: GaAs, [145] GaSb,[146]
GaN,[147] and AlN;[148] II-VI compounds: CdSe [149] and CdS;[67] IV-VI
compounds: PbTe;[150] refractory semiconductors: SiC;[151] ferroelectric
compounds: Bi4Ti3 O12;[152] oxides: In2O3,[153] SiO2 ,[154][155] Al2O3 ,[156][157]
Ta2 O5,[158] Y2 O3 ,[159] TiO2 ,[160] ZrO2,[161] SnO2,[162] PtO,[163] Bi2O3,[164]
ZnO,[165] and CdO;[166] pyrex glass; [167] and plastics.[168][169] Often several
targets are placed within a common vacuum enclosure so that multilayer
coatings can be deposited without breaking vacuum.
Sputter Deposition Processes 319

The usefulness of RF methods for sputtering nonconducting materials is


based upon the fact that a self-bias voltage, negative with respect to the
plasma floating potential, develops on any surface that is capacitively coupled
to a glow discharge.[170] The basis for this potential, which forms as a
consequence of the difference in mobility between electrons and ions, is
illustrated schematically in Fig. 5.32. The current-voltage characteristic for an
electrode immersed in a plasma is given in Fig. 5.32a. The floating potential
is negative relative to the plasma potential by an amount that depends upon
the gas species and plasma electron energy distribution function, but is
typically -20 to -50 V and therefore too low to produce significant sputtering of
most materials. When an alternating voltage is applied to such an electrode,
more electron current flows when the electrode is positive relative to the floating
potential than ion current flows when the electrode is negative relative to the
floating potential (Fig. 5.32b).
Capacitive coupling requires that there be no DC current flow; i.e., the net
current to the electrode in each RF cycle must be zero. Accordingly, a
negative bias must form such that the electron current on the positive side of
the cycle becomes equal to the ion current on the negative side. The negative
bias is approximately equal to half the peak-to-peak voltage of the RF signal
and therefore can be made large enough to produce sputtering.
The behavior illustrated in Fig. 5.32 applies strictly to the case where the
electrode is passive; i.e., is not responsible for sustaining the plasma
discharge. The planar diode shown schematically in Fig. 5.15 is the most
commonly used apparatus for RF sputtering. The electrodes sustain the
discharge and therefore have slightly different current-voltage characteristics
than the one shown in Fig. 5.32, particularly at negative voltages. However,
the overall effect when an RF potential is superimposed on the I-V character-
istic is essentially identical.
Figure 5.33 shows a schematic drawing of a typical RF planar-diode
sputtering configuration in which a nonconducting target is placed over one
electrode and substrates are placed on the other one. The electrodes reverse
cathode-anode roles on each half cycle. The discharge is operated at a
frequency that is sufficiently high that significant ion charge accumulation
does not occur during the cycle time when an electrode is serving as a
cathode.[11] Frequencies in the low MHz range are required. Most systems
are operated at a frequency of 13.56 MHz, since this has been allocated by
the Federal Communications Commission for industrial-scientific-medical
purposes. Operation at other frequencies requires careful shielding to assure
compliance with FCC regulations on radio interference.
320 Deposition Technologies for Films and Coatings

Figure 5.32. Schematic illustration of the development of a negative bias when an


RF potential is capacitively coupled to a probe immersed in a plasma. From Ref.
170.
Sputter Deposition Processes 321

At MHz operating frequencies, massive ions cannot follow the temporal


variations in the applied potential. However, the electrons can. Thus the cloud
of electrons in the negative glow plasma can be pictured as moving back and
forth at the applied frequency in a sea of relatively stationary ions. As the
electron cloud approaches one electrode, it uncovers ions at the other
electrode to form a positive ion sheath. This sheath takes up nearly the entire
applied voltage, the same as in the DC case.

Figure 5.33. Schematic drawing of a planar RF diode sputtering device. From Ref.
13.

A non-conducting target constitutes a capacitor in the electrical circuit


between the electrodes (an external capacitor would have the same effect).
Thus there can be no DC component to the current flow. The total ion and
electron charge flow to a given electrode during an RF cycle must balance to
zero, as discussed previously. However, a large electron current flows to a
given electrode as the electron cloud makes contact. Thus the electron cloud
need approach a given electrode for only a small fraction of a half cycle for
purposes of supplying sufficient electrons to fulfill the anode requirement; i.e.,
to balance the entire ion flux through the cycle. Accordingly, in the steady
state both electrodes develop a negative DC bias relative to the plasma
potential, such that the electrodes approach or exceed the plasma potential
(and become anodes) for only very short portions of their RF cycle as indicated
in Fig. 5.34.
322 Deposition Technologies for Films and Coatings

Figure 5.34. Approximate representation of target voltage waveforms relative to the


plasma potential for a balanced RF system with two equal-area sputtering
electrodes. Vf is the floating potential.

The motion of the ions, because of their inertia, can be thought of as


responding to the DC potential and passing to both electrodes throughout the
cycle. The electron cloud spends most of its time near the center position
between the electrodes. Visually, the discharge appears as a DC discharge
with a cathode dark space over each electrode. Functionally, sputtering
occurs continually at both electrodes.
RF discharges in planar diode systems can be operated at considerably
lower pressures than can DC discharges. Typical operating pressures are 5
to 15 mTorr. There are two reasons: a reduction in the loss of primary
electrons, and at high frequencies, an increase in the volume ionization
efficiency. A fraction of the lower-energy primary electrons are repelled from
the electrode toward which they are accelerated and thus remain in the
discharge longer to make additional ionizing collisions. In addition, electrons
can gain energy from the RF field by making in-phase collisions with gas
atoms. That is, if an electron, accelerated in one direction during a given half-
cycle, makes an elastic collision in which its direction is reversed near the end
of the half-cycle, it maintains most of its velocity (due to the large mass
mismatch between electrons and ions) and will again be accelerated during
the next half-cycle and thus have gained energy during the complete cycle.
Sputter Deposition Processes 323

The versatility of RF sputtering is not achieved without drawbacks.


Implementation of the process is complicated.[66] A typical electrical circuit
is shown schematically in Fig. 5.35. It consists of an RF power supply, an
inductive coupling to the load, and a matching network.

Figure 5.35. Schematic circuit of a single-ended RF discharge system including


an equivalent circuit for the plasma discharge. See Ref. 142 and 173.

An equivalent circuit for an RF glow discharge is also shown in Fig. 5.35.


The equivalent circuit assumes that both electrodes and the chamber walls are
in contact with the plasma, and that the impedance is dominated by the
plasma sheaths. The sheath capacitances result from the charge separation
across the dark space. These capacitors are shunted to the electrode surface
by a resistor to account for the ion current, and by a diode to account for the
high electron current that can flow from the plasma to an electrode that is
biased positive relative to the plasma potential. The capacitor Ct accounts for
capacitance of the target. Cb is a blocking capacitor that is added to make
the system independent of variations in the target capacitance.
The RF current through the plasma is principally an electron current
caused by the relative motion of the electron cloud. To the extent that there
is no volume power transfer from the oscillating electrons to the gas, this
current is out of phase with the applied voltage. The primary power transfer
324 Deposition Technologies for Films and Coatings

occurs via the relatively small ion and electron current components that are in
phase with the voltage. Thus, in the equivalent circuit approximation, the
power transfer to produce sputtering occurs as the ion currents pass through
the sheath resistances. Efficient power transfer requires that the RF power
supply operate into a resistive load. Therefore a matching network is used to
introduce inductance, and often capacitance, into the circuit in such a way
that, in combination with the load, they form a resonant circuit.[171] When the
variable matching network components are tuned to resonance, high circulat-
ing currents flow within the resonant circuit. However, the power supply sees
only the resistive component of the load, the current passing from the power
supply to the resonant circuit is in phase with the load and represents the
power passing to the load. Many commercial sputtering sources monitor the
reflected power from the load as an index of how effectively the matching
network is adjusted. The reflected power should be minimized.[32][141][172]
The ion current, and thus the sputtering rate at a given electrode, is
determined by the average difference in potential between the electrode and
the plasma. Thus it is useful to consider the plasma potential as a zero-point
reference voltage in examining the performance of RF sputtering systems.
The electrical character of RF sputtering systems can be classified in
general as being either balanced or single-ended. In a balanced system, both
electrodes are configured as identical sputtering targets and their potentials
are 180o out of phase. The average sputtering voltage is about equal to half
the peak-to-peak applied RF potential. The link center trap is placed at ground
potential to stabilize the system and the chamber walls and substrates are
connected to the center tap ground, as shown in Fig. 5.36. Since this point
is at zero potential relative to the RF voltage, no RF current will flow to these
elements. Furthermore, because of the capacitance in series with each of the
electrodes, there is no DC current path from the plasma to the wall and
substrates and then back through the electrodes into the plasma.[173] Thus
a charge will develop on the capacitors such that the substrates float at a
potential slightly negative with respect to the plasma, just like a floating
electrode in a DC plasma.
In an unbalanced RF system, the electrode on which the substrates
are placed is made considerably larger than the target electrode.[142] This
makes the sheath capacitance large, and the RF voltage drop across the
substrate electrode small, as shown schematically in Fig. 5.37. The
chamber and one side of the link are generally grounded (Fig. 5.35). Again,
the capacitance in both electrode circuits prevents a DC current flow to the
chamber, and a negative bias develops relative to the plasma potential. A
Sputter Deposition Processes 325

potential relative to the plasma potential will exist on the substrates and
chamber wall unless the substrate electrode area is large enough to reduce
this potential to essentially zero and to move the RF balance point to the
grounded end of the link. It is important that these voltage drops be small so
that sputtering from uncontrolled surfaces does not introduce contamination
into the coatings. An impedance may be added to the substrate electrode
circuit so that the potential of this electrode relative to the plasma can be
controlled for purposes of bias sputtering.[173]

Figure 5.36. Schematic representation of an equivalent circuit for a balanced RF


system with two equal-area sputtering electrodes and center-tap ground. The
matching network is not shown.

The above discussion has been presented in the context of planar diode
sputtering systems. Magnetron sputtering sources can also be used for RF
sputtering. Cylindrical-post,[114][116] cylindrical-hollow,[114][174] planar, [127]
and gun-type[129] magnetrons have all been successfully operated with RF
power. However, some problems are encountered. Magnetron sputtering
technology is basically a DC concept. The cathodes are shaped such that,
in concert with the magnetic field, they form electron traps with specific
symmetry. Anodes are placed to collect electrons which diffuse out of the trap.
326 Deposition Technologies for Films and Coatings

Figure 5.37. Approximate representation of voltages (as functions of time) relative


to the plasma potential for a single-ended RF sputtering system in which the wall
area is much larger than target area. Vs is the substrate ion bombardment potential.
See Ref. 142 and 173.

Effective double-ended RF magnetrons can be provided for some


geometries. These configurations provide independent traps for both elec-
trodes but allow magnetic coupling between them so that the electrons leaving
one trap can diffuse freely to the vicinity of the other.[116] However, most
magnetron configurations must be operated with single-ended arrangements.
The magnetic confinement produces gradients in the plasma density, so that
special care is required to minimize the voltage and therefore the sputtering
rate at the counter electrode. Furthermore, in the planar magnetron case, the
current-density concentration under the plasma ring requires that the power
level be limited to avoid cracking when using targets with low thermal
conductivities. When magnetron sources are driven single-ended, they
generally operate in hybrid modes with current-voltage characteristics which
are not representative of true magnetron behavior. Nevertheless, they provide
deposition rates that are typically a factor of three greater than those achieved
with RF planar diodes. (This is to be compared to the factor of twenty-to-thirty
improvement in deposition rate which DC magnetrons provide over DC diodes
when sputtering metals). Reduced electron bombardment and substrate
heating are other advantages of magnetrons, as opposed to planar diodes, for
RF sputtering.
Sputter Deposition Processes 327

3.5 Ion-Beam Sputtering

Glow discharge sputtering technology is limited in the sense that the


target current density and voltage cannot be independently controlled except
by varying the working-gas pressure. An exception is the cylindrical
magnetron where the voltage can be varied at a fixed current and pressure by
varying the magnetic field strength.
Ion-beam sputtering permits independent control over the energy and the
current density of the bombarding ions.[175] A sputtering target is arranged to
obliquely intersect an ion beam of given energy and flux density that is created
by an independent ion source. Substrates are suitably placed to receive the
coating flux, as shown in Fig. 5.38. In addition to the independent control over
the ion current and voltage, ion beam sources permit sputtered coatings to be
deposited at very low inert working-gas pressures (≤ 0.1 mTorr) onto sub-
strates that are not in contact with a plasma.

Figure 5.38. Schematic representation of ion-beam sputtering showing relative


locations of target and substrate.

Early ion sources were of the duoplasmatron type, where an ion beam
was extracted through an aperture from a low pressure arc.[176] Hollow-
cathode ion sources were also used.[177] These devices were limited for
practical deposition because of the small ion-beam sizes (≈1 cm). The
recent adaptation of ion thruster technology has provided distributed ion
sources with ion beams of relatively large diameter (≈10 - 30 cm). [175]
328 Deposition Technologies for Films and Coatings

Although these devices cannot compete as deposition sources with the very
large substrate areas that are provided by magnetrons, they are attractive for
ion beam etching and for special deposition applications and research studies.
Sources designed for etching have provided 500 eV, 1 mA/cm2, ion beams that
are 30 cm in diameter with a uniformity of ±5% over 20 cm.[178] Reviews of the
fundamentals of ion beam deposition are provided in Ref. 21 and 179.

4.0 SPUTTER DEPOSITION MODES

Sputter deposition, in any of the configurations discussed above, can be


carried out in a variety of modes developed to provide better control over film
chemistry and/or microstructure. The most important of these modes of
operation are reactive sputtering and bias sputtering.

4.1 Reactive Sputtering

Reactive sputtering is a process in which a fraction of at least one of


the coating species enters the deposition system in the gas phase. The
target is typically either a pure metal (or metal alloy) or a compound
containing volatile species. In the former case, the high vapor-pressure
species, e.g., N in TiN,[180] S in CdS, [181] or O in VO2 ,[182] is provided
entirely in the gas phase (via N 2, H 2 S, and O2 , respectively) while in the
latter case (e.g., GaAs in As4 )[145] a considerably smaller partial pressure
of the reactive gas is added to the discharge to account for the less than
unity sticking probability of that species at the growing film surface.
Bibliographies and reviews of early work covering a wide variety of
compounds including oxides, nitrides, sulfides, carbides, etc. may be
found in Refs. 98 and 183.
The advantages of reactive sputtering are: (i) compounds can be
formed using relatively easy-to-fabricate metallic targets, (ii) insulating
compounds can be deposited using DC power supplies, and (iii) films with
graded compositions can be formed. The difficulty in the reactive-
sputtering process is the complexity which accompanies its versatility.
Chemical reactions occur at the target, at the substrate, and in cases
of very high working pressures, in the gas phase. When sputtering with
a reactive-gas/Ar mixture, the relationship between film properties and the
reactive gas injection rate is generally very nonlinear. The condensing
films can be considered as an additional pump for the reactive gas. The
Sputter Deposition Processes 329

nonlinearity occurs because the sticking probability (or getter-pump speed)


of the condensing coating depends in a complex way on its growth rate,
composition, film structure, and temperature. The composition dependence
is shown in Fig. 5.39 for N2 incident on a growing Ti film.[184] Note that as the
number of N2 molecules adsorbed per Ti atom deposited approaches 0.5 (i.e.,
a stoichiometric TiN film), the sticking probability α drops by more than two
orders of magnitude. The decrease inα occurs as the number of unoccupied
surface adsorption sites decreases.[185] Thus, for example, when sputtering
in an N2 /Ar mixture at low reactive-gas injection rates, virtually all of the
injected gas can react with the film. Consequently, the nitrogen is largely
removed from the working gas, and the cathode process becomes primarily
one of simple Ar sputtering of a metal. The coatings deposited under such
conditions are generally metallic in nature.

Figure 5.39. Sticking coefficient of N2 measured during the continuous deposition


of Ti as a function of the ratio of the getter-pumped nitrogen flux to the Ti deposition
flux. Data from Ref. 184.
330 Deposition Technologies for Films and Coatings

As the reactive-gas injection rate approaches that required to produce


a stoichiometric coating, there is an increase in the reactive-gas partial
pressure in the sputtering system because of the reduced getter-pumping
rate of the depositing coating. This change in the composition of the
sputtering gas greatly changes the processes which occur at the cathode
surface. The result is that, for most metal/reactive-gas combinations, the
sputtering discharge undergoes a transition into a mode in which the metal
sputtering rate, and therefore the reactive-compound deposition rate, is
reduced. The cathode surface reactions in this mode produce an energetic
flux of highly reactive gas atoms and molecular fractions which accompany
the sputtered metal atoms to the substrate. This large flux of reactive species
makes the reactive sputtering process so effective for producing a wide range
of compounds. The variation in discharge voltage and relative deposition rate
during a typical transition is shown in Fig. 5.40. The voltage decrease at high
oxygen injection rates is the metal-to-compound transition. The voltage
increase at low injection rates is the compound-to-metal transition.
The reduction in sputtering rate shown in Fig. 5.40 results primarily from
compound formation on the cathode surface and the reduced sputtering yield
of the reactive-gas molecules. The compounds often have higher electron
secondary emission coefficients which give rise to a reduction in both the
discharge voltage and the ion component in the cathode current for discharges
driven at constant currents. The hysteresis effect, which is shown for
discharge voltage but also applies to the deposition rate, occurs since the
target compound layer, once formed, will remain until the sputtering gas is
made sufficiently lean in the reactive species that a net sputter removal of the
layer can occur. A cathode on which such a layer has formed is often referred
to as being “poisoned.” The effect of cathode poisoning on the reactive
sputtering process depends on the metal/reactive-gas combination and the
properties of the cathode surface layer. Thus the very pronounced poisoning
effect shown in Fig. 5.40 occurs for the oxygen reactive sputtering of materials
such as Al, Cr, Ti, and Ta that form strong oxides. The decrease in deposition
rate is generally less for other reactive gases such as N2. No poisoning occurs
for Au, where the sputtering rate with pure O2 is not much different from that
with Ar.
The poisoning effect introduces two practical problems. One is the loss
in deposition rate. The second is that during the transition, the material being
deposited often passes abruptly from a metal to a nearly stoichiometric
compound. Intermediate materials such as suboxides therefore become
difficult to deposit. Consequently, considerable work has been directed
toward trying to operate sputtering sources at, or very near, the transition
Sputter Deposition Processes 331

point. Transition behavior has been observed in planar diodes,[185] planar


magnetrons,[186] and cylindrical magnetrons.[114] Many papers have been
written concerning the transition mechanism.[185][187]-[192] Most are incom-
plete, however, because they concentrate on the cathode processes and do
not consider the total system. It is important to realize that the reactive
sputtering process is dependent on the total system; i.e., its geometry, the
accumulation of coating on walls and fixtures and the positions of gas
injection. All these parameters must be carefully controlled in order for reactive
sputtering to be effectively used on a production basis.

Figure 5.40. Transitions in the steady-state operating mode of a Cr cylindrical-post


magnetron sputtering source due to injection of oxygen.
332 Deposition Technologies for Films and Coatings

Berg and co-workers[193]-[195] have recently developed nonlinear mod-


els of the reactive sputtering process, which do account for both internal
getter pumping and external pumping, to predict stability conditions in order
to investigate hysteretic behavior. They showed that with a sufficiently high
overall pumping speed, there is a smooth transition between the metal and
compound sputtering modes. Critical pumping speeds required to eliminate
hysteretic behavior can be estimated based upon their work.
Several techniques have been developed to increase the deposition rate
during reactive planar magnetron sputtering which take advantage of the
nonuniform cathode current densities in these devices.[196]-[198] Some of
these are illustrated schematically in Fig. 5.41. The reactive gas flux, and
therefore the tendency for reactive gas adsorption, is relatively uniform over the
cathode surface. However, the ion flux is nonuniform and causes sputter
removal of adsorbed reactive species, thereby reducing their surface coverage
under the plasma ring (Fig. 5.41b). At higher current densities (Fig. 5.41c),
the sputtering rate is adequate to maintain a fresh metal surface which in turn
yields a high rate of sputtering. By exerting control over the total system—
i.e., by arranging the reactive gas injection adjacent to the substrate and the
Ar injection adjacent to the target—it is possible, with the assistance of
suitable getter surfaces, as illustrated in Fig. 5.40d, to maintain a gradient in
the composition of the reactive gas in the sputtering atmosphere. If the
gradient is adequate, the target surface under the plasma rings can remain
unpoisoned and yield a high flux, even when the reactive-gas flux to the
substrate is adequate to produce a stoichiometric compound.[196] Baffles
have also been used between the target and substrate to maintain a gradient
in reactive gas partial pressure.[198]
For reactive sputtering in N2 , where the hysteretic behavior is more
gradual than in O2, (see, for example, Ref. 199), Sproul [200]-[203] has
developed feedback control techniques which allow film deposition rates of
transition-metal nitrides such as TiN, ZrN, and HfN at values very nearly equal
to those of the pure metals. The feedback controls maintain constant target
power, total pressure, and N2 partial pressure.

4.2 Bias Sputtering

Bias sputtering, in which the substrate is biased negatively with respect


to the plasma potential, is often used to provide low-energy ion bombardment
of the growing film. The analog of glow-discharge bias sputtering can be
carried out in an ion-beam deposition system using a second ion gun to
irradiate the substrate.[17] Low-energy ion/surface interactions during film
Sputter Deposition Processes 333

growth is a subject of study unto itself and recent reviews may be found in Refs.
22 - 25. Ion irradiation has been shown to strongly affect film nucleation and
growth kinetics, adhesion, film microstructure and chemistry, and hence film
properties. Mechanisms by which ion/surface interactions modify film
nucleation, growth, microstructure evolution, and film properties are dis-
cussed in Ch. 13 while reviews on adhesion[204][205] andion-induced changes
in film chemistry (including trapping, secondary implantation, and prefer-
ential sputtering) [24][206] have been published recently.

Figure 5.41. Schematic illustration of various elements of the planar magnetron


reactive sputtering process.

Recently, Window and Savvides[207][208] demonstrated that substrate


ion currents during magnetron sputter deposition can be influenced by
stray magnetic fields B leaking from the target magnet assembly. B can
be varied intentionally over a limited range by changing the relative
strengths of the inner and outer target magnetic poles, i.e., by "unbalanc-
ing" the magnetron. A similar concept was employed by Petrov et al.[209]
and Adibi et al.[210] in developing an ultra-high-vacuum DC planar-magnetron
334 Deposition Technologies for Films and Coatings

(PM) sputter deposition system with an external variable axial magnetic


field Bext superimposed on the permanent magnetic field of the PM as
shown in Fig. 43. A pair of Helmholtz coils, located outside the vacuum
chamber, produces Bext which is uniform along the axis orthogonal to both
target and substrate surfaces.

Figure 5.42. Schematic diagram of an ultra-high-vacuum reactive-magnetron DC


sputter-deposition system with both variable external and permanent internal
magnets.
Sputter Deposition Processes 335

As shown schematically in Fig. 5.43, the value and sign of Bext has a
strong effect on the plasma density near the substrate, and hence on the ion
flux, Ji, incident at the substrate, with only a minor effect on the target-atom
flux. For a Ti target sputtered in pure Ar at 20 mTorr with a target-substrate
separation of 6.5 cm, changing Bext from -50 G (opposing the field of the outer
PM pole) to +600 G (reinforcing the field of the outer PM pole) varied the ion-
to-Ti flux ratio Ji/JTi incident at the substrate by a factor of sixty from 0.1 to 6
with the bias held constant at any desired negative value between ~ -15 V
(limited by the difference between the floating Vf and plasma Vp potentials) and
the highest values examined, -100 V. For reactive sputter deposition in N2
(where the primary ion is N2+) under the same conditions, Ji/JTi varied by a
factor of fifty from 0.7 to 35. Vp was negative with Bext set to positive values
and ranged form ~ 0 (Bext = 0 G) to -13 V (Bext > +200 G) in Ar and 0 to -20
V in N2. Using an N2+ ion energy of 20 eV (10 eV per N) to bombard the growing
film, Adibi et al.[210] showed that by varying Ji/JTi from 1 to ≥ 5.2, the
microstructure of metastable NaCl-structure Ti0.5Al0.5N alloys deposited at
250°C could be controllably altered from a porous columnar structure with a
complete (111) texture to a dense completely (002)-oriented structure with no
residual ion-induced defects observable by high-resolution plan-view and
cross-sectional transmission electron microscopy.

ACKNOWLEDGEMENTS

The authors gratefully acknowledge the support of the Joint Services


Electronics Program and the Materials Science Division of the Department of
Energy over the course of several years.
336 Deposition Technologies for Films and Coatings

Figure 5.43. Schematic diagram illustrating the effect on the plasma during
sputter deposition of superimposing an external magnetic field B ext which (a)
opposes and (b) reinforces the field of the outer permanent magnet in the
planar magnetron target.
Sputter Deposition Processes 337

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Appl. Phys., 73:8580 (1993)
6

Ion Plating

Donald M. Mattox

1.0 INTRODUCTION

Ion plating is a generic term applied to atomistic film deposition


processes in which the substrate surface and the growing film are subjected
to a flux of energetic bombarding particles sufficient to cause changes in the
film formation process and the properties of the deposited film. This broad
definition does not specify the source of the depositing film particles, the
source of bombarding particles, nor the environment in which the deposition
takes place. The principal criterion is that energetic particle bombardment is
used to modify the film formation process and film properties.[1][2] Figure 6.1
shows a simple ion plating system using a DC diode arrangement with the
substrate as the cathode electrode and a thermal vaporization source as the
source of the depositing material.[1]
A description of the ion plating process was first published in the
technical literature in 1964[3] and a U.S. patent was granted for the process
in 1974.[4] Recently it has been found that a patent for a very limited version
of a similar process was granted in Europe in 1938[5] but was not published
in the technical literature nor pursued commercially. In 1965 it was reported
that the use of a bias on the substrate during sputter deposition (bias
sputtering) decreased the contaminant level in sputter-deposited films.[6]
The term ion plating is generally accepted [7] and is often used
without any description or reference, however there does not seem to be
a universally accepted definition and many other terms are applied to ion
plating-like processes such as bias sputtering, bias sputter deposition, “ion

346
Ion Plating 347

vapor deposition” (“Ivadizing”),[8][9] ion beam enhanced deposition (IBED),


accelerated ion deposition,[10] plasma-enhanced vapor deposition,[11] ion-
assisted deposition (IAD),[12] biased activated reactive deposition (BARE),[13]
plasma surface alloying, etc.

Figure 6.1. An ion plating configuration using a DC diode discharge and a thermal
vaporization source.[1]

Early work on the ion plating process was concerned with thedeposition
of atoms originating from thermal evaporation/sublimation, sputtered sur-
faces (sputter ion plating), or from chemical vapor species in the gas
(chemical ion plating).[4] Bombardment was by ions extracted from a plasma
by applying a negative potential to the surface to be coated which was
immersed in the plasma. The plasma could be of an inert gas species,
contain reactive species, or contain gaseous chemical compound species.
In the latter cases, the chemical species could be activated in the plasma to
either become more reactive with depositing species (for example, nitrogen
to form the nitrides) or could be decomposed to deposit a coating from the
constituents of the gaseous chemical compound (e.g., Ti from TiCl4).[14] The
latter process might be considered an early form ofplasma enhanced CVD[15]
with ion bombardment in addition to the plasma activation.
348 Deposition Technologies for Films and Coatings

Most recently, the termion plating has been applied to processes where
the surface to be coated is in contact with a plasma and the term ion assisted
deposition (IAD) or ion beam enhanced deposition (IBED) is used where the
substrate is bombarded by an ion beam in a vacuum environment during
deposition.[16]-[18] There are several other modifying terms which are some-
times used with ion plating such as: sputter ion plating and chemical ion
plating which specify the origin of the depositing species (sputtered material
or chemical vapor precursor gases respectively),vacuum ion plating which is
done in a vacuum environment,[19] and reactive ion plating,[20] used for the
deposition of films of compound materials.
Initially the film property of most interest was the adhesion of the film to
the substrate and the ability to have an in situ substrate surface cleaning
process, as well as to introduce thermal energy directly into the surface region
without having to heat the bulk of the material. In the early 70’s a number of
studies were made on the modification of film microstructure,[21][22] stress,[23]
composition[24] and properties[25][26] by the concurrent bombardment during
deposition, and the excellent coverage obtained by gas scattering and
sputtering-redeposition during ion plating. Bombardment during reactive
deposition was shown to improve the stoichiometry of the deposited film
material.
In the latter part of the 70’s and the early 80’s, sources of low energy (100
to 10,000 eV) ion beams of gaseous species became more generally available
and bombardment could be done in a vacuum environment. This led to studies
of bombardment effects under more controlled conditions. Studies included
both those of a physical nature such as the effect of bombardment on film
stress,[27] and those of a chemical nature (reactive deposition).[28][29] Re-
cently it has been shown that bombardment during vacuum deposition greatly
improves the properties of vacuum deposited optical coatings[16] by increasing
the index of refraction (density) and the environmental stability.
Recently ion implantation accelerators have been used to give high
energy (50 to 100 keV) particle bombardment of surfaces to give recoil
implantation of previously deposited material or “mixing” of the interfacial
region between a film and the substrate. [30][31] This high energy bombard-
ment may be concurrent with the atomistic film deposition or may be used
as a post-deposition treatment. The development of ion sources for fusion
reactor applications has lead to large area, high current, ion sources that
allow higher fluxes and larger areas of bombarding particles. [32][33] Also
during the early and mid 80’s, equipment and techniques were further
Ion Plating 349

developed that allowed ions of the film material to be used as the


bombarding species. [34][35] Some of these sources were derived from ion
sources developed for isotope separation.[36]
The basic rules for ion plating are:
1. Bombardment must be over the whole surface to be covered—the
more uniform the bombardment (species, number [ratio of bom-
barding species to depositing species] and energy) the better.
2. A minimum bombardment ratio and particle energy must be
established in order to attain the desired property and structural
modification of the surfaces and deposited film.
3. Bombardment must be continued from surface conditioning through
interface formation for good adhesion.
4. Bombardment may be continued through the film formation stage
in order to modify film composition, morphology, microstructure,
and properties.
5. Contamination in the plasma should be low in order to reduce
reaction with the substrate and with the depositing material
(reactive species are activated in the plasma—good for reactive
deposition, bad for contamination).
6. More material must be deposited than is removed by the bombard-
ment process; however, all of the deposited material may react
with the substrate giving a type of surface modification coating
(ex., Pt on Si giving a PtSi coating).
Ion plating may be divided into several stages, namely: (a) surface
preparation, (b) nucleation and interface formation, and (c) film growth. It is
important that the bombardment be continuous through the various stages for
the ion plating process to work properly.
The surface preparation stage allows in situ sputter cleaning of the
surface prior to the beginning of deposition. This “cleaning” portion of the
process allows good interfacial reactions for adhesion[37] and the generation
of ohmic contacts to semiconductor materials.[37] In addition to cleaning,
surface preparation may also be in the form of roughening the surface
morphology or changing the surface composition (surface reaction or prefer-
ential sputtering). Bombardment may also make the surface more “active” by
the generation of reactive sites and defects. For example: an unbombarded
silicon surface metallized with aluminum shows no interdiffusion but a
bombarded surface gives rapid diffusion.[39]
350 Deposition Technologies for Films and Coatings

The interface formation stage allows the formation of a desirable


diffusion or compound type interface on the “clean” surface if the materials are
mutually soluble, or the formation of a “pseudo-diffusion” type of interface due
to the energetic particle bombardment during the initial deposition if the
materials are insoluble.[37] Interface formation is aided by defect formation and
the deposition of energy (heat) directly into the surface without the necessity
for bulk heating. In some cases the temperature of the bulk of the material may
be kept very low (ex., liquid nitrogen cooling) while the surface region is heated
by the bombardment.[4] This allows the development of a very high temperature
gradient in the surface region which limits diffusion into the surface. The ion
bombardment along with a high surface temperature may cause all of the
depositing material to be diffused into the surface giving an alloy or compound
coating.
In ion plating the bombardment may or may not be continued during the
film formation stage. If the bombardment is not maintained, the process,
through the interface formation stage, may be considered as astrike for further
deposition by another technique (vacuum deposition, sputter deposition,
electroplating, etc.). If the bombardment is maintained during the growth
stage, it is usually with lower energy bombarding particles and a higher ion flux
than is used in the surface preparation and interface formation stages. This
is to reduce the gas incorporation and compressive stress in the resulting
deposited material.
Generally energetic particles for bombarding surfaces and growing films
are of gaseous ions and arise from:(a) biasing (DC or RF) a surface in contact
with a plasma so that it is bombarded by ions from the plasma, (b) extraction
of ions from a confined plasma and accelerating them to a high energy through
a grid system into a vacuum environment (ion beam),[32][40] or (c) reflected high
energy neutrals which arise from ion bombarding a surface in a low pressure
environment[41]-[43] such that the reflected neutrals are not thermalized by
collisions in the gas phase.
The energetic particles (ions) may also be of a condensible film species
and arise from:(a) sources such as are used for isotope separation,[36][44]-[46]
(b) acceleration of negative ions from a negatively biased compound or alloy
sputtering target,[47] (c) ions from vacuum or plasma arcs,[35][48] or (d) special
ion sources.[49]
The most general source of energetic particles is the extraction of ions
from a plasma to bombard a surface which is at a negative potential with
respect to the plasma. The bombarded surface may be located in the plasma
generation region or at a downstream location in the plasma.
Ion Plating 351

2.0 PROCESSING PLASMA

Plasmas are gaseous media which contain enough ions and electrons
to be electrically conductive (e.g., fifty). Energy is introduced into the plasma
by the acceleration of electrons in a DC, RF, or microwave electric field. These
energetic electrons then fragment, excite, and ionize atoms and molecules by
collisions. A processing plasma is a plasma that is used in materials
processing.[51]-[53] In many, if not most, cases of film deposition the
processing plasma is a weakly ionized plasma such that there are many more
neutral particles than ions in the gas phase and there is a large number of
radical species compared to ions when a molecular gas is used. In a
processing system, the local plasma densities and plasma properties may
vary significantly due to electrode configurations, presence of fixturing, and
other geometrical factors.
Typical properties of a weakly ionized plasma are:
Ratio of neutrals to ions 107 - 104:1
(100 times as many radicals as ions when using a molecular gas)
Gas pressure 10-3 - 10-1 torr
Electron temperature 1 - 10 eV
Ion temperature 0.025 - 0.035 eV

3.0 GENERATION OF PLASMAS

In plasmas used for plasma processing, the electron energy is in-


creased by acceleration in electric field gradients. The most typical configu-
rations for generation of plasmas are: (a) DC diode discharge, (b) RF (radio
frequency) discharge,(c) electron emitter sustained discharge,(d) magnetron
enhanced discharge, (e) microwave discharge, (f) vacuum arcs, and (g)
plasma arcs. Figure 6.2 shows a schematic of some of these configurations.

3.1 DC Diode Discharge

The DC diode configuration consists of an anode and a cathode


immersed in a low pressure gas. In ion plating, the substrate may be the
cathode of the DC diode discharge. At the cathode, the negative potential (-)
attracts positive ions from the edge of the plasma region and they are
352 Deposition Technologies for Films and Coatings

Figure 6.2. Plasma generation configurations: (a) DC diode; (b) DC diode with
permanent magnets giving a planar magnetron; (c) RF plasmas with planar
electrodes immersed in the plasma, electrodes external to a dielectric wall and a
coil immersed in the plasma; (d) electron emitter (thermoelectron) with magnetic
confinement; and (e) microwave cavity.

accelerated across the cathode fall region to impinge on the cathode (target).
The cathode fall region, which surrounds the cathode, is where most of the
potential drop in a DC discharge is to be found.[54] The plasma region is located
between the edge of the cathode fall region and the anode where there is little
potential drop. In the DC discharge, energetic particles (ions and neutrals)
impinging on the cathode (target) cause the ejection of secondary
electrons which then accelerate across the cathode fall region, collide with
gas species, and create ions which sustain the discharge process. The
secondary electron emission coefficient of a surface depends on the
chemical nature and morphology of the surface. Oxides typically have a
higher electron emission coefficient than metals, and rough surfaces have
a lower secondary emission coefficient than smooth surfaces. The
secondary electrons can be accelerated to high energies and impinge on the
Ion Plating 353

anode or other surfaces in the system. This can give rise to extensive heating
of surfaces (substrates) in the system. The DC discharge requires a relatively
high gas pressure to sustain the discharge (>10 microns argon).
In the cathode fall region, some of the ions may be neutralized by charge
exchange processes which give rise to energetic neutral particles[55][56] which
are not affected by the applied electric field. The cross-section for charge
exchange is much larger than that for physical collision. The charge exchange
process is dependent on the gas pressure, and at low pressures the
accelerated ions will arrive at the cathode with the full cathode fall energy since
the collision probability is low. Because of these charge exchange processes
there is, at the cathode, a flux of energetic particles consisting of ions and
neutrals with a broad spectrum of energies.
In order to sustain a DC discharge, the secondary electrons must create
enough ions to compensate for losses by recombination. If the anode or
ground surface is brought too close to the cathode the discharge is extin-
guished. This effect can be used to confine the DC discharge to areas of the
cathode surface where bombardment is desired—other areas may have the
bombardment prevented by having a ground shield in closed proximity to the
surface. The Paschen curve gives the relationship between breakdown voltage
and the minimum anode-cathode separation in a gaseous environment.
Typically argon gas pressure of about 10 microns is used to sustain the DC
diode discharge. At this pressure the width of the cathode dark space is about
1 cm. Insulator surfaces cannot be used as cathodes in a DC diode
configuration since charge buildup on the surface prevents ion bombardment.
Electrically insulating films deposited in a DC discharge will build-up a surface
charge which will cause arcing through the film.
In addition to causing the ejection of secondary electrons, high energy
ions and neutrals which impinge on the target (or other surfaces) cause the
physical ejection of surface atoms (physical sputtering) by momentum
transfer processes. The sputtered particles leave the surface at higher than
thermal energies but may be rapidly thermalized by collisions in the gas
phase.[57][58] The sputtered particles may be scattered back to the target
surface—this effect is more prominent the higher the gas pressure. Some of
the energetic ions that bombard the cathode may be reflected as high energy
neutrals.[40]
354 Deposition Technologies for Films and Coatings

The electrical current measured in the DC cathode circuit is the sum of


the charge due to the ion flux to the target and the secondary electron flux away
from the surface. Therefore the cathode current density and cathode voltage
do not specify the flux nor the energy of the impinging ions. However these
parameters (along with gas pressure and gas flow) are typically used to specify
the plasma parameters in DC diode plasma processing.
Typically a DC diode discharge plasma is weakly ionized with many
more neutral particles than ions. Any surface in contact with the plasma will
be subjected to a flux of ions, neutrals, and electrons. A sheath potential will
be developed because of the greater mobility and energy of the electrons as
compared to the ions. This wall potential (typically 3 - 10 volts) will accelerate
ions from the plasmas giving rise toion scrubbing of the surface. In ion plating,
the surface in contact with the plasma may be biased to accelerate ions from
the plasma and bombard the surface at higher energies.
In plasma processing, the DC diode configuration has many advantages
including: (a) a rather uniform plasma can be generated over large cathodic
areas;(b) power input (watts/cm2) can be very high;(c) the power supplies are
rather simple, inexpensive and powerful; (d) process reproducibility can be
attained by controlling the geometry, gas pressure, and target power (current
and voltage); and (e) the sputter erosion of cathodic surfaces may be used as
a long-lived, stable source of depositing material. Disadvantages include:(a)
surface geometries can result in focusing effects giving non-uniform bombard-
ment;(b) heating of substrates by secondary electrons accelerated away from
the cathode can be extensive; and (c) inability to bombard electrically
insulating surfaces or films.
Typical conditions for ion plating in a DC plasma environment are:
Bombarding current: 0.5 mA/cm2
(typically ions, inert, reactive)
Applied accelerating potential: 50 - 5000 volts
(DC diode)
Ratio of bombarding particles 1:10 - 1:100
to depositing atoms
Typical plasma/system parameters that are controlled or monitored in
DC diode ion plating where the substrate is the cathode of the discharge are:
Ion Plating 355

System geometry
Substrate: Power input (voltage and current)
Plasma uniformity
Applied potential
Pre-sputtering time
Deposition rate/uniformity
Plasma: Gas pressure
Gas purity
Deposition source geometry

3.2 RF Discharge

At high frequencies, in a capacitively coupled discharge, the electrons


oscillate in the changing field thus gaining energy, and by collision with atoms
create ions, radicals and more electrons. Typical RF power supplies operate
at 13.56 MHz (U.S. industrial frequency) with peak-to-peak voltages of greater
than 1000 volts. The plasma acts as a low density electrical conductor and
the RF field penetrates quite some distance into the plasma. When the driven
RF electrode is a conductor, the surface is bombarded by ions from the plasma
during the half-cycle that the electrode is negative.
If the surface of the RF electrode is an insulator (backed by a conductor),
the metal-insulator-plasma acts as a capacitor and the surface potential that
appears on the insulator surface alternates between a low positive potential
(because the electrons have a high mobility) and a higher negative potential
(because the ions have a relatively low mobility).[59] Ions are extracted from
the RF plasma during the negative portion of the cycle and bombard the
insulator surface. During a portion of this half-cycle the bombardment energy
may be sufficient to cause physical sputtering of the insulator surface. The
RF potentials in the plasma can be determined using capacitive probes.[60]
The ion energies bombarding a surface may be determined using a sampling
orifice, a retarding grid, and a mass spectrometer.[61][62]
In capacitively coupled RF discharges, the plasma potential, and
hence the sheath potential at the electrodes, can have a time-varying value
of tens to hundreds of volts.[63] When the electrodes have different effective
areas, the plasma potential can also have a large DC potential with respect
to one or more of the electrodes.[64] These factors affect the distribution of
ion energies incident on the electrode surfaces in an RF discharge.[65] Small
356 Deposition Technologies for Films and Coatings

area electrodes will attain higher voltages than large area electrodes, and
the electrode potentials can be varied using an external capacitance in the
circuit.
The amount of energy that is coupled into the RF discharge depends
on the impedance matching (reflected power) and coupling losses to other
surfaces (stray losses). In RF plasma processing, it may be important to
determine just how much energy is actually being coupled into the
plasma.[66]-[69] RF power may be coupled to the plasma using metal
electrodes external to a dielectric wall [70] or the RF plasmas may be
excited using immersed electrodes (see Ref. 71, for example). Very high
plasma densities and ionization efficiencies can be attained in RF driven
plasmas and the discharge may be established at lower pressures than
the DC diode discharge.[72]
In plasma processing, the RF discharge has the advantage that
insulating surfaces or insulating films on conductive surfaces can be
bombarded by applying an RF potential. Disadvantages are: (a) high
power inputs (heating) to insulating materials cause cracking, (b) elec-
trode geometries can cause problems with coupling to the RF power, (c)
there are many sources of RF power loss in systems, (d) plasma
uniformity is difficult to obtain over complex surfaces, and (e) the bias
conditions on surfaces in the RF plasma are variable and often difficult to
control.

3.3 Microwave Discharges

Plasmas can also be excited at much higher frequencies—300 MHz to 10


GHz—where electron cyclotron resonance coupling gives more efficient ioniza-
tion.[73] Microwave discharges differ in many essential respects from DC and RF
discharges. Namely: (a) there is an increased amount of excitation in the
discharge and a lot of vacuum-UV is produced,(b) high degree of ionization (as
high as 20%), (c) the electron densities are higher, 1013 vs. 109 - 1010, and (d)
the particle temperatures are higher (factor of ten or more). Microwave plasmas
are most often used in the downstream processing configuration since sub-
strates in the microwave cavity can detune the system.

3.4 Electron Emitter Discharge

In the DC diode and RF plasma configurations, the electrons necessary


to sustain the plasma are produced in the plasma. When using electron
Ion Plating 357

emitters, the electron source is independent of the plasma processes.


Common electron emitters are hot thermoelectron emitting cathodic surfaces
and hollow cathodes.[74] For example: hot LaB 6 surfaces can give an electron
emission of >20 A/cm2 at 1700°C.[75] These discharges may have very high
electron densities (1012). Often the electrons are confined by a magnetic field
(100 - 500 gauss) directed along the anode-cathode axis. The magnetic field
increases the electron path length in its movement from the cathode to the
anode by causing the electron to spiral in the magnetic field. This increases
the ionization efficiency of the electron and allows the discharge to be
sustained at a low gas pressure. The ions in the plasma may be extracted
using an electrode at a DC or RF potential to give bombardment of a surface
(triode configuration). The triode configuration suffers from a nonuniform
plasma density along its axis, thus giving nonuniform bombardment and a
density variation in activated species over a large biased surface. The
thermoelectron emitter system is very amenable to forming dense plasmas
and for application to downstream processing. By applying magnetic fields,
the plasma (ions and electrons) may be confined and steered into a processing
chamber.[33] Steering (bending) of the plasma beam occurs since the
electrons follow the magnetic field lines and the ions follow the electrons. The
electron emitter configuration may also be used to melt and vaporize material
for film deposition and at the same time as producing the plasma.[76]-[81]
In plasma processing some of the advantages of the electron emitter
configurations are:(a) the flux of electrons is independent of other plasma and
electrode processes; (b) very high plasma densities can be attained; (c) the
plasma properties can be controlled by controlling the electron emission; (d)
the plasma may be steered from the plasma generation chamber; and(e) the
electron beam can be used as a source for thermally vaporizing material.
Disadvantages are:(a) need for well controlled and long life electron emitting
sources, and (b) plasma non-uniformity over large areas and complex
surfaces.

3.5 Magnetron Discharges

Low strength (100 - 500 gauss) magnetic fields may be used to


confine the electrons and increase their path length in plasma systems by
causing the electrons to spiral around the magnetic lines of flux (magne-
tron configurations). There are a number of ways to establish magnetic fields
in plasma chambers including: (a) internal permanent magnets, (b) external
permanent magnets, (c) external electromagnets, and (d) moving magnets.
358 Deposition Technologies for Films and Coatings

Permanent magnets have the advantage that they may be placed in such a
manner as to position the field lines in a desirable manner. However, getting
a uniform magnetic field over a large or complex surface is difficult with any
magnetic field configuration.
Magnetron enhanced plasma configurations have many advantages
including: (a) confining the plasma to a small region, (b) increased ionization
and plasma density, and (c) may be operated at low pressures where gas
phase collisions are reduced. Disadvantages include: (a) non-uniform
magnetic fields give non-uniform plasma densities,(b) isolation of the plasma
to a small region of the processing chamber requiring auxiliary plasma sources
near the substrates in some applications, and(c) low pressure processing can
give rise to a flux of high energy reflected neutrals which may affect bombarded
surfaces and growing films, and affect their properties in an undesirable
manner.[43]

3.6 Plasma Enhancement

Plasma enhancement techniques may also be used to locally increase


the plasma density. This plasma enhancement may be done by using local
RF fields,[82] thermoelectron emitting surfaces,[33] hollow cathode electron
emitters,[74][81][83][84] deflection of secondary electrons in e-beam evapora-
tion, localized higher gas pressure, etc. The plasma density may also be
increased by the use of magnetic fields which cause the electrons to spiral
around the magnetic field lines thus increasing their path length (magnetron
configurations).[85] Some of the most dense plasma sources have been
developed for the magnetic fusion community. Many of these sources use RF
power input or thermoelectron emitting surfaces along with confining magnetic
fields.
In some film deposition processes, ions of the film material (condensible
or non-condensible) may be used to bombard the substrate. Ions of reactive
gaseous species may be formed in plasmas by conventional techniques. High
concentrations of ionized condensible film species may be formed: (a) in
plasmas having a high density of low energy (100 eV) electrons,(b) in vacuum
arc-plasmas on solid cathodes,[86][87] or (c) above molten anodes in vacuum
arc-plasmas.[88][89] In many cases, these species may be multiply ionized.
The addition of a reactive gas to the plasma allows the deposition of compound
materials.[90]
When using plasmas and bombardment effects in ion plating, many
processing variables are unknown. Processing unknowns include: (a) the
Ion Plating 359

portion of the substrate current that is due to secondary electron emission,(b)


the flux and energy spectrum of the ions and electrons, and (c) the flux,
adsorption, and surface coverage of the neutral gaseous species. Generally
no attempt is made to determine these process variables during the process-
ing but rather they are controlled by controlling other processing variables such
as: (a) system geometry, (b) vaporization rate, (c) gas pressure, (d) gas
composition, (e) gas flow rate(s), (f) substrate and system temperatures, (g)
contaminants in the plasma, and (h) substrate power input per unit area
(voltage and current).

4.0 PLASMA CHEMISTRY

The plasma is a very energetic chemical environment and many


chemical processes can occur (e.g., Refs. 91-93). The principal chemical
processes are: (a) electron impact ionization,(b) dissociation (fragmentation)
of molecules (formation of radicals), (c) Penning ionization (metastable
collision), (d) dissociative electron attachment (e) electron attachment, (f)
excitation, (g) momentum transfer collisions, (h) de-excitation of excited
species, and (i) recombination (neutralization). As an example of the
complexity of plasma chemical processes consider that there can be twenty-
four reactions and sixteen species formed by the decomposition and reaction
of CF4 in a plasma.[94]
As an example of Penning ionization, consider argon which has
metastable excited states of 11.55 and 11.75 eV, and copper which has an
ionization energy of 7.86 eV. Thus a copper atom colliding with a metastable
argon atom is easily excited or ionized. Metastable atoms may be very
effective in ionizing and exciting other species by collision.
Many of these plasma processes are characterized by cross-sections
for collision processes and threshold energies for attachment processes. For
example CF3 Cl has a high collision cross-section and low threshold energy
(2 - 3 eV) for electron dissociative attachment. CF4 has a low cross-section
and high threshold energy (5 - 6 eV) for electron dissociative attachment, and
CCl4 is not activated at all by electron attachment. Therefore CF3 Cl is much
more easily fragmented and ionized in a plasma than is CF4 or CCl4. The
degree of ionization, dissociation and excitation of the species depends
strongly on the gaseous species, electron energy, and density in the plasma.
Generally there is much more dissociation than there is ionization of molecular
species.
360 Deposition Technologies for Films and Coatings

Many of these plasma processes serve to activate(plasma activation)


the gas species, i.e., to make them more chemically active by dissociation,
ionization, or excitation. Plasma activation may partially decompose chemi-
cal precursor species and make them easier to thermally decompose. This
type of activation is used in plasma-enhanced and plasma-induced processes
such as plasma-enhanced chemical vapor deposition (PECVD).[95]
Plasma discharges are very effective in desorbing contaminates (ex.
H2 O) from surfaces in a plasma processing chamber. These impurities are
activated in the plasma and may contaminate the depositing material.
A number of techniques may be used to determine plasma proper-
ties.[96] Optical emission is the most common.[97][98] Optical absorption
techniques may also be used to characterize the gaseous species and
temperature in a gas discharge.[99] Electron and ion densities in a plasma may
be measured by the use of small-area Langmuir probes.[100]
In film processing utilizing plasmas, the depositing (condensible)
species usually traverses the plasma before condensing on the substrate. In
doing so, some of the species may be fragmented and/or ionized in the
plasma. However in the usual ion plating configuration (low density, weakly
ionized plasma) little ionization of the condensible species is to be ex-
pected.[101]

5.0 BOMBARDMENT EFFECTS ON SURFACES

The physical effects of energetic particle bombardment on surfaces and


depositing films is very dependent on the mass, flux, and energy of the
bombarding particles, the flux of non-energetic particles (i.e., depositing or
absorbing species) and the atomic mass and chemical nature of the
bombarded surface. In many cases the fluxes of impinging particles are not
determined or controlled except by the processing parameters.
Bombardment can be from ions accelerated to the surface under:(a) an
impressed bias,(b) an induced bias, or (c) due to the development of a sheath
potential. Bombardment can also be from energetic neutrals formed by charge
exchange processes or by the neutralization and reflection of energetic ions
from a surface.
Many studies have shown that intentional and/or unintentional particle
bombardment may affect the various stages of film growth (substrate prepa-
ration, nucleation, interface formation, and film growth). The parameters
(flux, energy, ratio) which are important are usually poorly defined, and
Ion Plating 361

in many instances, the importance of bombardment is not recognized. An


example is in magnetron sputtering where the stress in the deposited films
may be correlated to the gas pressure in the sputtering chamber and thus to
the bombardment by energetic particles reflected from the sputtering tar-
get.[102] At low pressures, high energy particles, which are reflected as
neutrals from the sputtering target, provide the particle bombardment of the
growing film, giving high compressive stresses. At higher gas pressures,the
high energy particles are thermalized by collisions before they can bombard
the growing film and tensile stress is developed in the growing film.[43]
High energy reflected particles are more prevalent at high angles to the
surface normal so substrates in these areas will be more affected by
bombardment than substrates positioned normal to the surface. Also the post
cathode or rod cathode target configurations will be more sensitive to
bombardment than planar targets. The nature of the stress can also be
correlated to the angle-of-incidence of the deposited material[103][104] and the
sputtering current density.[105] It has also been shown that anisotropic
bombardment gives rise to anisotropic stresses in films.[43]
Particle bombardment allows one means of in situ preparation of a
substrate surface prior to film deposition. In situ surface preparation may be
necessary to generate the high quality interface necessary for the fabrication
of some semiconductor devices.[38][39]
Figure 6.3 shows several regions affected by particle bombardment and
the regions are defined as follows:
Surface: Interface between solid and gas (vapor or vacuum).
Surface-region: Region of physical penetration by the bom-
barding particles in which there is a collision cascade.
Near-surface region: Region beyond physical penetration but
which is affected by the bombardment (heating, diffusion)
Bulk region: Region of the material which is not significantly
affected by the bombardment (or can be made so by cooling)
Figure 6.3 also depicts the effects of bombardment by energetic
species (not electrons) on the surface and the subsurface region. Surface
effects include:(a) desorption of weakly bonded surface species,(b) ejection
of secondary electrons, (c) reflection of the energetic species as high
energy neutrals,(d) sputter ejection (physical sputtering) of surface atoms
by momentum transfer through collision cascades, (e) sputtering and
redeposition of sputtered species by collisions in the gas phase, ioniza-
tion, and acceleration back to the surface and byforward sputter deposition due
362
Deposition Technologies for Films and Coatings
Figure 6.3. Schematic depiction of energetic particle bombardment effects on surfaces and growing films. See text for discussion.
Ion Plating 363

to the ejection angle on a rough surface, (f) enhanced surface mobilities of


atoms on the surface, and (g) enhanced chemical reaction of impinging and
adsorbed species to produce condensed species (reactive deposition) or
volatile species(etching). In the subsurface region:(a) the impinging particles
may be physically implanted,(b) the collision cascades cause displacement
of lattice atoms and the creation of lattice defects, (c) defects coalesce, (d)
surface species may be recoil-implanted into the subsurface lattice,(e) mobile
species may be trapped at lattice defects, and (f) much of the particle kinetic
energy is converted into heat.[106] Lattice channeling processes can carry
these effects deeply into the surface.
Film growth may be considered to be layered growth where each layer
is a surface (surface-region) which is covered by another surface layer. Thus
particle bombardment effects on surfaces and on growing films are closely
related.

5.1 Collisional Effects

Particles striking other particles transfer momentum (billiard ball effect).


Particles striking surfaces also transfer momentum to the surface atoms
which results in lattice atom displacement and vibration (heating). In many
cases there will be some penetration of the bombarding particle into the
surface lattice structure. The amount of this penetration will depend on the
relative masses of the bombarding and “target” atoms, and the crystallo-
graphic orientation (penetration will be greatest along open planes).
Particles with energies too low to give collisional lattice displacement
(<20 eV, depending on masses) may enhance chemical reactivity on the
surface thereby influencing: reactive deposition processes, reactive plasma
etching, ion enhanced chemical etching, reactive plasma cleaning, chemical
sputtering (volatile species), plasma polymerization, etc. These low energy
particles may also enhance the removal of weakly bonded surface atoms
(desorption). For instance, low energy bombardment by species accelerated
across the plasma sheath are used inion scrubbing to clean optical surfaces
before film deposition, and hydrogen ion scrubbing is used to remove surface
contaminants in Tokamak-type fusion reactors.
Chemical sputtering occurs when the bombarding species (H, Cl, Fl)
chemically reacts with the surface to form a volatile species which leaves the
surface with thermal energies.[107] Chemical sputtering is often a synergistic
effect when both a chemically reactive species and an energetic species
bombard the surface simultaneously (bombardment enhanced chemical
etching).[108][109]
364 Deposition Technologies for Films and Coatings

For particle energies large enough to create collisional damage, many


things can occur. Figure 6.3 depicts the various processes that can occur
when these particles strike a surface and generate a collision cascade in the
near-surface region. These processes include:
1. Reflection from the surface with some loss of energy—
these particles may be used for surface analysis (ISS, Ion
Scattering Spectrometry) or give bombardment-induced
changes in the deposited material.
2. Physical sputtering of the surface atoms by momentum
transfer processes.
3. Subsurface implantation of the bombarding species.
4. “Knock-on” implantation of surface species (recoil implan-
tation).
5. Point defect formation along the collision cascade track.
6. Localized high temperatures along the collision cascade
track, the heating from which diffuses through the surface
region.
7. Produce secondary electron from the surface which may be
accelerated away from a surface that is at a negative
potential.
Surface effects: Particle bombardment processes/effects may be
classed as:
Prompt processes (<10-12 sec) - collision effects
Cooling effects (>10-12 to <10-10 sec) - thermal spikes
Delayed effects (>10-10 sec to < 1 hour) diffusion, segregation
Persistent effects (> 1 hour) - compressive stresses, amorphori-
zation, phase change
Physical sputtering (often just called sputtering)[110] is the physical
ejection of a surface atom by momentum transfer in the collision cascade
where it intersects the surface (sputter erosion). This process is not a thermal
process so the ejected particles have energies greater than thermal and a
distribution (ejection pattern) that depends on the crystallographic orientation
of the surface atoms. Only a small amount of the energy of the bombarding
particles appears in the energy of the sputtered particles; the rest (70% or
more) goes into heating the bombarded surface.
The sputtering yield, the ratio of ejected atoms to incident particles,
is a function of incident particle energies (normal incidence), and is a
Ion Plating 365

function of the mass of the incident particle and the mass of the target atoms.
The sputtering process only begins after a threshold energy is reached where
there is enough momentum transfer to give ejection (> 20 eV).
The sputtering yield is a function of crystallographic orientation of the
surface material, giving differing yields for differing planes and allowing the
delineation of crystallographic structure of a surface by sputter etching. The
sputtering yield is also a function of the incident particle energy, increasing
from some threshold value to some maximum above which most of the energy
is deposited too far below the surface to affect the collision cascade where it
intersects the surface and the sputtering yield decreases. There have been
some reports of an equilibrium time for the sputtering yield to stabilize,
possibly due to saturation of the surface with bombarding gas.
For surfaces bombarded at normal incidence, the ejected particles will
come off with a cosine distribution at low bombarding energies,[111] and an
over-cosine distribution as the energies become higher,[112] and with some
dependence on mass when sputtering alloys or isotopic mixtures.[113] This
angular dependence may change with texturing of the sputtered surface. If the
bombarding flux is off-normal, the ejected flux will be skewed in a forward
direction. (The ejection from a single crystal surface will depend on the
orientation of the crystal planes). The energy of the ejected particles will
depend on the bombarding angle with oblique bombardment giving higher
energy ejected particles.
The sputtering yield is also a function of the angle of incidence of the
impinging particle. For this off-normal bombardment, the sputtering yield, as
a function of incident particle bombardment angle, initially increases to a
maximum then decreases rapidly above some angle as the bombarding
particles are reflected from the surface. The maximum generally occurs at
about 70 degrees off-normal but this varies with the relative masses of the
particles. This property may be used to give forward sputtering of materials
where the impingement angle on the target (inclined plane with ion beams,
edges of cylinders) is high. This angular dependence of sputtering also results
in the formation of cones on a sputtered surface. The taper of the cones is
determined by the angle-of-incidence dependence of the sputtering yield.
For a single component surface, the material will be removed from the
surface with the bulk composition. If the surface is an alloy or compound,
preferential sputtering may occur with some surface species being removed
more easily than others (may actually extend several monolayers into the
366 Deposition Technologies for Films and Coatings

surface—altered region). This will give rise to a surface composition that is


different from the bulk (enriched, depleted);[114]however, if no diffusion occurs,
the sputtered species will have the same composition as that of the bulk
material at equilibrium. Preferential sputtering of compounds decreases with
the off-normal incidence angle of the bombarding ions.[115]
During deposition with concurrent bombardment, preferential sputtering
can cause loosely bound species to be removed (contaminates, or non-
reacted compound-forming species),[6] or in the case of alloys, one of the
constituents may be preferentially sputtered.[116]
If diffusion in the target does occur, the sputtered species will have a
composition that differs from the bulk and may be continuously variable. Alloy
sputtering can give some mass separation with the flux normal to the surface
being enriched in the lighter element and the flux off- normal being enriched in
the heavier element.[113]
The sputtering process from a negatively biased elemental surface gives
neutral species. Sputtering from a grounded surface gives varying amounts
of ionized species which may be used for SIMS (secondary ion mass
spectroscopy) analysis or, if ionized in a plasma, may be used for GDMS
(Glow Discharge Mass Spectroscopy) or endpoint optical analysis of the
plasma. Sputtering of a target containing several species may give negative
ions of the species having the lesser electronegativity (ex., O-, Au- from AuCu
alloy).
At relatively high gas pressures (DC diode sputtering conditions) a
portion of the sputtered species may be scattered back to the surface. A
portion of the sputtered species may be ionized in the plasma and accelerated
back to the target surface giving self-sputtering. On non-planar surfaces,
some of the sputtered species may be forward-sputtered so that they are
deposited on the target surface. All of these affect the apparent sputtering
yield of surfaces.
Other sputtered species may condense on substrate surfaces giving
“sputter deposition” often just called sputtered films (poor terminology).
Controlled sputter erosion in conjunction with surface analysis tech-
niques is used to depth-profile from the surface in order to allow in-depth
determination of elemental composition.[117]
Particles on the surface or inclusions in the surface region may
protect the local area from sputter erosion, giving a texturing of the
surface morphology (cone formation). [118] Enhanced surface mobility may
also create whiskers on the bombarded surface.[119] Texturing of surfaces may
Ion Plating 367

give a long term change in the sputtering yield (2 - 3X) from the surface since
the surface morphology changes (changing angle of incidence and redeposition
processes).[120] Texturing is used to generate optical “trapping” surfaces,[121]
to treat surfaces for medical implants to improve bone growth[122] and
adhesion, and to reduce secondary electron emission from surfaces.
If the surface species is a “foreign” atom the process of removal may be
termeddesorption and may be calledion-induced desorption or cleaning.[123]
It has been shown that the process of recoil implantation is an important
parameter in the desorption (sputter cleaning) of monolayers of chemisorbed
species from a surface.
Surfaces may be etched byreactive plasma etching where a chemically
active species (Cl, F) is formed in a plasma and reacts with the surface to form
a volatile species. Typically a volatile chemical species is formed on the
surface and volatilization removes the surface species. The process is
somewhat difficult to control since the plasma composition and the flux of
impinging particles from the plasma may vary. If the particles are accelerated
to the surface, chemical reaction is enhanced and the process becomes
reactive ion etching or reactive plasma cleaning.[124]
The desorption of weakly bound surface species is important to plasma
cleaning and may be used to reduce the incorporated contaminants in
deposited films.[6][125] The desorption may also be useful in desorbing
unreacted species in reactive deposition processes giving rise to more
stoichiometric and chemically stable deposits.
In ion-assisted chemical etching,[126] a molecular beam of the
chemically reactive species and a beam of inert gas ions simultaneously
bombard the surface to be etched. Using this technique, very high etching
resolution can be obtained at high etch rates.[127]
The bombardment-assisted chemical processes that occur on
surfaces are very poorly understood.[109][128]-[130] On one hand the
increased chemical activity may be due to the increased “temperature”
due to momentum transfer from the bombarding ions. On the other hand,
secondary electrons from the bombardment of the surface may play an
important role. In some cases, surface changes due to the bombardment
may provide sites for chemical reactions. The etching process is sensitive
to the amount of adsorbed reactive gases.
368 Deposition Technologies for Films and Coatings

5.2 Surface Region Effects

The surface region is affected by the penetration of the bombarding


species. A major portion of the energy goes into atomic vibration and appears
as heat. The resulting collision cascades generate point defects and
collisional mixing by atomic displacement. The point defect densities may be
as high as 1 - 20 atomic percent and may combine to form large-scale defects
and, in the extreme, disrupt the crystalline material into an amorphous form.
The defects introduced into the surface region can affect the electronic
properties of the region.[37] For silicon, these electronic effects have been
studied by bombarding the surface, then fabricating Schottky barriers.[131]
The lattice defects may also allow the trapping of normally mobile
species.[132] Trapping studies of ion-bombarded surfaces show trapping site
densities of 1 - 20 atomic percent.[133][134] The bombarding species may be
implanted to quite high atomic concentrations if they are not lost by diffusion
to the surface. Typically 1 - 10% of entrapped bombarding species is found
in the surface region of argon-ion-bombarded sputtering targets. In the argon
bombardment of silicon, it has been shown that the argon content rises very
sharply from about 225 eV bombarding ion energies and approaches a plateau
around 2200 eV. Films of gold grown under bombardment conditions have
been deposited with 40 atomic percent helium[135][136] which is normally
insoluble in gold. Other gases have been incorporated into more complex
sputter-deposited amorphous materials to high concentrations.[137] Incorpo-
rated gases may embrittle materials, precipitate into bubbles, or outgas at
elevated temperatures.
The incorporation of radioactive krypton into surfaces (by pressure or ion
bombardment) for subsequent thermal desorption and wear studies has been
called kryptonation.[138]-[142] The materials thus formed have been called
kryptonates.
In the case of hydrogen ion bombardment of carbides, carbon depletion
is noted to depths far greater than the penetration depth of the hydrogen
ions.[143] Hydrogen ion bombardment also acts to hydrogen charge the
surface region giving a chemical potential which enhances the hydrogen
diffusion into the material. The same is true for nitrogen where nitrogen ion
bombardment, diffusion, and reaction results in nitriding of the surface region.
Outgassing of the incorporated gases may present adhesion problems when
a film has been deposited on the bombarded surface.
Ion Plating 369

The combination of high defect densities and heat allow rapid diffusion
(similar to radiation enhanced diffusion[144]) and the generation of analtered layer
whose composition may differ from the bulk (alloys and compounds).
The implantation of the bombarding species and the recoil implantation
of the surface species results in the compaction(peening) of the near-surface
region and the formation of a compressive stress in that region. The
implantation process also incorporate bombarding (and surface species -
recoil implantation) species into the near surface region often in amounts
that are above the normal solubility limits. Both the peening action and the
incorporation can affect the stress in this region film.

5.3 Near Surface Region Effects

The near-surface region is affected by the proximity of the surface


region. Compositional changes in the surface-region generate a chemical
potential which, along with the temperature and defect profile, may allow
rapid diffusion from this region to the surface and vice versa. Compressive
stresses generated in the surface-region are offset by tensile stresses in the
near-surface region and these may cause subsurface fracturing. In
hydrogen ion bombarded silicon, subsurface defects and fracturing are
attributed to the tensile stresses generated beneath the compressive
surface region giving fracturing. Temperature-rise studies by the crystalliza-
tion of metallic glass substrates during the ion plating of gold has shown
that the temperature rise in the near-surface region (10 - 15 microns)
approached 500°C.[145]

5.4 Bulk Effects

The principle bulk effect is that of heating. Particularly if the substrate


is not actively cooled then the bulk temperature can rise significantly.

6.0 SOURCES OF DEPOSITING ATOMS

In ion plating, the depositing (condensible) species may have thermal


energies or may be all or part of the energetic bombarding flux.
The source of the depositing species may be:
370 Deposition Technologies for Films and Coatings

Thermal evaporation or sublimation sources


Sputtering sources (sputter-ion plating)
Vacuum arc sources
Chemical vapor species (Chemical Ion Plating)

6.1 Thermal Vaporization

Thermal evaporation or sublimation of a material is performed by heating


the material to the point that it has an appreciable vapor pressure. Heating may
be done by:
Resistively heating the material directly
Material in contact with a resistively heated surface
Bombardment with low energy non-focused electrons
Bombardment with high energy focused electrons
Radiant heating from a high intensity source
Heating with a laser beam
RF inductive heating
Resistively heated sources are typically used to vaporize materials
which have appreciable vapor pressures below about 1500°C.
Low energy electrons may be produced by hollow cathodes[34] and
deflected in a low magnetic field. The electron energies are typically around
100 volts which is also the energy for the maximum cross-section for
ionization. Therefore as the vapor leaves the evaporating surface and passes
through the impinging electron cloud, the possibility for ionization is high.
Such a system has been used to ionize silver for deposition on beryllium. The
silver ions are used first to sputter clean the surface and then, by lowering the
acceleration voltage, a film of silver is allowed to form.[146]
High energy electron beam evaporation is done by generating a
small electron current and accelerating the electrons to very high energies,
on the order of 10,000 eV. The electrons are deflected by a magnetic field
and are moved over the surface in a variable electric field. This technique
allows a very high energy density spot to be rastered over the surface to
be evaporated thus allowing the evaporation of refractory materials. This
type of evaporation source can be used in a vacuum environment, along
with an ion gun, to supply inert gas ions for bombardment of the growing
film to do ion plating. A great deal of interest has been shown in optical coatings
Ion Plating 371

formed this way since the resulting films have higher index of refraction (more
dense) and are more environmentally stable than are vacuum deposited
films.[16] The adhesion of optical films may also be improved by the concurrent
bombardment.[147] By bombarding the growing film with reactive ions,
compounds of materials such as TiN can be formed.[148]
High energy electron beam evaporation may also be done in a plasma
environment as long as the hot filament is not exposed to the plasma. This
may be done by differentially pumping the chamber below the electron beam
evaporator where the electron emitting filament is located.[1]

6.2 Sputtering

Sputtering of a surface may be done in a plasma by extraction of ions


from the plasma under an impressed electric field and bombarding the target
surface with energetic ions to cause physical sputtering of the surface. This
source of depositing material is used in sputter ion plating.[149]
Sputtering may also be done in a vacuum environment using ion beams
formed in a separate plasma chamber and extracted into the vacuum chamber
using a grid system. The sputtered material may then be deposited in a
vacuum environment and an ion beam source may be used to bombard the
deposit with an inert or reactive beam.[150] Figure 6.4 shows some of the
configurations that may be used.

6.3 Vacuum Arcs

Vacuum arc vaporization sources can also provide film-ions in vacuum ion
plating. Arc evaporation (vacuum arc) occurs when a high current, low voltage
arc passes between electrodes in a vacuum. The arc is confined to spots which
have a very high energy density (1011 W m-2). The vaporized material may be
deposited as a film, often with a bias applied to the substrates. Arc vaporization
is an old method of vaporizing carbon to form thin carbon films. By using a reactive
gas atmosphere, compounds may be deposited. In arc evaporation, a large
fraction (0.5) of the vaporized material is ionized.[151]-[153] The potential
distribution in the arc gives a “hump” near the cathode allowing ions on the anode
side of the hump to be accelerated to a high potential (80 eV).[48] Problems with
this deposition technique include stabilization of the arc and the formation of
globules of the ejected material. Arc steering over the cathode surface and
plasma deflection have been applied to reducing theglobule problem. The ions
372 Deposition Technologies for Films and Coatings

Figure 6.4. Configurations for using an ion beam in a vacuum system to allow
concurrent bombardment of a depositing film.

formed in the vacuum arc may be accelerated to a biased substrate, and thus
constitutes a source of bombardment and deposition in the ion plating
process.
The vacuum arc melting process[154] utilizes a vacuum arc to melt
materials and the melting equipment may also be used as a source of ions
(from the molten anode) for deposition.
Ion Plating 373

6.4 Chemical Vapor Precursors

In chemical ion plating, a precursor gas containing the material to be


deposited is injected into the plasma where it is totally or partially decom-
posed, ionized, and deposited (accelerated) to the substrate surface. This
technique is similar to plasma enhanced CVD with the addition of the
acceleration of the ionized particles. In some cases, the chemical vapor is
introduced into an ionizing source chamber then the disassociation products
are extracted and accelerated into the deposition chamber( under vacuum) as
a beam to impinge on the substrate surface. This process has been used to
deposit i-carbon (hydrogenated carbon, i C-H)[155]-[157] and BN[158] films.

7.0 REACTIVE ION PLATING

In reactive ion plating, co-depositing species or surface species react


to form a non-volatile (compared to reactive ion etching where a volatile species
is formed) condensed species. The concurrent bombardment tends to
activate the reaction process (activate the species in the plasma, ion
enhanced reactions on the surface) making the reaction easier, and tends to
resputter the non-reacted species giving a more stoichiometric deposit.[159]
A large number of compounds have been deposited by reactive ion plating.

8.0 BOMBARDMENT EFFECTS ON FILM PROPERTIES

Many surface and film properties may be modified by particle bombard-


ment.[160] These properties include: adhesion, composition, grain size,
crystallographic orientation, growth morphology, surface morphology, impu-
rity content, electrical properties, magnetic properties, optical properties, film
stress, density, and mechanical properties. Particle bombardment may be an
important process variable and, if not controlled, may give unacceptable
product variability.

8.1 Effects: Adatom Nucleation

Particle bombardment may be used to sputter-clean surfaces in order


to remove barrier layers and contaminates. This allows adatoms to interact
directly with the substrate and, if there is chemical bonding, the nucleation
density is increased and interfacial reactions will be promoted.
374 Deposition Technologies for Films and Coatings

Ion bombardment during adatom deposition may increase the nucle-


ation density in many instances.[161][162] This increase may be due to the
formation of active sites due to the defect formation[163] and/or due to the recoil
implantation of adatoms into the surface region where they act as nucleation
sites. Conversely, ion bombardment may enhance surface mobilities. (Ex:
Ion bombardment enhanced surface diffusion during cone formation.[164]) The
presence of a plasma has been shown to influence the nucleation either due
to bombardment or to electrical effects.[165][166]
It has been shown that the nucleation density of gold deposited on oxide
substrates by sputter deposition in an oxygen plasma is much higher than in
an inert plasma. This allows the deposition of adherent gold films on
substrates where normally the adhesion is poor.[167] The reason for this
dependence on the oxygen plasma is not understood but may be due to
chemical or electrical charging effects.

8.2 Effects: Interface Formation

The nature and type of interfacial region that is formed during film
deposition is important to adhesion and the functionality of the film-substrate
couple. Interfacial regions may be classed as: (a) mechanical, (b) abrupt, (c)
compound,(d) diffusion,(e) pseudo-diffusion or combinations thereof.[36] The
type of interfacial region formed during deposition depends on the film/
substrate materials, chemical interactions, energy available, nucleation
behavior, contamination, and surface morphology. Particle bombardment
prior to and during film deposition affects many of these factors. Of particular
interest is the ability to clean a surface, influence nucleation, and to provide
energy to the surface region to enhance diffusion and chemical reactions.

8.3 Effects: Film Growth

Film growth may be considered to be layered growth where each layer


is a surface (surface-region) which is covered by another surface layer. Thus
particle bombardment effects on growing films are much the same as those
for the surface and surface-region effects. In addition there are sputtering/
redeposition effects on film morphology/microstructure and annealing effects
on the film structure due to the heating during deposition and local thermal
spikes during the bombardment.[168]
Ion Plating 375

Film microstructure, morphology, and properties that can be modified


by ion bombardment during growth include:
Stress
Stoichiometry
Microstructure
Morphology (surface and bulk)
Grain size
Grain orientation
Epitaxial growth
Hardness
Abrasion Resistance
Optical properties (index of refraction)
Density
Pinhole density
Adhesion
By using a partially ionized and accelerated beam of depositing
particles it has been shown that the “epitaxial temperature” can be lowered
compared to the deposition of a non-ionized beam.[169]
The important parameters in structure modification are:
Substrate temperature during deposition—all sources
Angle of incidence of depositing species
Resputtering during deposition—indication of forward sput-
tering
Redeposition (of sputtered species) during deposition
In the DC diode configuration (where there is appreciable redeposition
of sputtered material) studies have shown that an apparent resputtering rate
of 0.2 to 0.3 is necessary to achieve appreciable modification of the columnar
microstructure. In the magnetron configuration (where there is much less
redeposition) apparent resputtering rates of 0.6 to 0.7 are necessary to give
appreciable modification of the columnar microstructure.
Concurrent energetic particle bombardment during atomistic film
deposition may modify many film properties (e.g., Refs. 23 - 26, 170). The
amount of modification will depend on both the mass, energy, and flux of
the bombarding species and the mass and flux of depositing species. In
the case of reactive deposition, the availability of activated species and the
376 Deposition Technologies for Films and Coatings

effect of adsorbed surface species may also be important. The following are
some of the film properties that can be modified by controlled concurrent
bombardment during deposition.

8.4 Film Adhesion

The adhesion of a deposited film to a surface depends on the deforma-


tion and fracture modes associated with the failure.[171][172] Energetic particle
bombardment prior to and during the initial stages of film formation may
enhance adhesion by: removing contaminant layers, changing the surface
chemistry, generating a microscopically rough surface, increasing the nucle-
ation density by forming nucleation sites (defects, implanted and recoil
implanted species), increasing the surface mobility of adatoms, and by
creating lattice defects and introducing thermal energy directly into the surface
region, promote reaction and diffusion. These effects will also improve surface
coverage and thus decrease the number of interfacial voids which result in easy
fracture and poor adhesion. Film adhesion may be degraded by the diffusion
and precipitation of gaseous species at the interface. The adhesion may also
be degraded by the residual film stress, due either to differences in the
coefficient of thermal expansion of the film and substrate material in high
temperature processing, or the residual film growth stresses developed in low
temperature processing.

8.5 Film Morphology/Density

Physical sputtering and redeposition, increased nucleation density,


and increased surface mobilities of adatoms on the surface under bombard-
ment conditions may be important in disrupting the columnar microstructure
that develops during low temperature atomistic deposition processes.[26][173]-
[178] Figure 6.5 shows the fracture cross-section and surface morphology of

RF sputter deposited chromium films at zero bias and a -500 volt bias during
deposition. Note that the bombardment completely disrupted the columnar
microstructure. Bombardment-related effects may also improve the sur-
face coverage and decrease the pinhole porosity in a deposited film. This
increased film density is reflected in film properties such as: better corrosion
resistance, lower chemical etch rate, higher hardness, lower electrical resistivity
(metals), and the increased index of refraction (optical coatings). However,
it has been found that if the bombarding species is too energetic and
the substrate temperature is low, high gas incorporation gives rise to
Ion Plating 377

voids (e.g., Ref. 179). Some investigators have used the parameter
resputtering rate (deposition rate with and without an applied bias) as the
parameter for disruption of the columnar morphology; however this parameter
does not take into consideration the backscattering from the gas phase which
will be greater with higher gas pressure, and so must be used with caution.

Figure 6.5. Fracture cross-section (bottom) and surface morphology (top) of


a thick RF sputter deposited chromium deposit: (a) without bias (no bombard-
ment), and (b) with concurrent bombardment (-500 V bias on the substrate).[25]
378 Deposition Technologies for Films and Coatings

8.6 Residual Film Stress

Invariably atomistically deposited films have a residual growth stresses


which may be tensile or compressive in nature and may approach the yield or
fracture strength of the materials involved. The origin of these stresses is
poorly understood although several phenomenological models have been
proposed.[180] Generally, vacuum-deposited films and sputter-deposited films
prepared at high pressures have tensile stresses which may be anisotropic
with off-normal angle-of-incidence depositions. In low pressure sputter
deposition and ion plating, energetic particle bombardment may give rise to
high compressive film stresses due to the recoil implantation of surface
atoms.[181]-[184] This effect is sometimes called atomic peening. Studies of
deposited films with concurrent bombardment have shown that the conversion
of tensile stress to compressive stress is very dependent on the ratio of
bombarding species to depositing species.[27][185] In plasma processing, the
residual film stress may be very sensitive to the substrate bias and gas
pressure[43] during deposition in a plasma environment. High intrinsic film
stresses may lead to long-term film stability problems such as room-
temperature grain growth[186] and void formation.[187]
Figure 6.6 shows the residual stress and gas content in sputter
deposited chromium films as a function of substrate bias.[25] Figure 6.7 shows
the anisotropic residual stresses in post-cathode magnetron sputter-depos-
ited molybdenum films as a function of sputtering gas pressure and orienta-
tion.[43] Where rather thick films of high modulus materials are involved, these
stresses must be controlled or spontaneous failure (adhesion, cracking,
blistering) will occur.[171] The stresses may be controlled by controlling the
film thickness, materials involved, film morphology, bias during deposition,
deposition temperature, and/or sputtering pressure.[43]
The lattice strain associated with the film stress represents stored
energy and this energy, along with a high concentration of lattice defects, may
lead to:(a) lowering of the recrystallization temperature in crystalline materi-
als,(b) a lowered strain point in glassy materials,(c) a high chemical etch rate,
(d) electromigration problems, (e) void growth in metallization lines by creep,
and (f) other such mass transport effects.

8.7 Crystallographic Orientation

Under proper bombardment conditions, the crystallographic orienta-


tion of the deposited material is developed such that the more dense
Ion Plating 379

Figure 6.6. Residual stress and gas content of an RF sputter-deposited chromium


deposit as a function of substrate bias during RF sputter deposition.[25]

Figure 6.7. Stress and stress anisotropy in post-cathode magnetron sputter-


deposited molybdenum films as a function of orientation and sputtering gas
pressure. [43]
380 Deposition Technologies for Films and Coatings

crystallographic planes are parallel to the bombarding direction.[188][189] This


effect is attributed to the channeling of the bombarding species into the film
thus decreasing the sputtering rate under this orientation. Under more
energetic bombardment condition, however, the crystallographic orientation is
disrupted due to the formation and consolidation of defects.

8.8 Gas Incorporation

When a depositing film is bombarded during deposition by energetic


gaseous particles, the incorporated gas content is dependent on the particle
energy, substrate temperature, film material, and bombarding species.
Generally, low mass bombarding particles are more easily incorporated
than are large mass particles. The gas incorporation increases with energy
of the bombarding species to the point that heating causes gas desorption.
Under some conditions, very high concentrations of normally insoluble gas
may be incorporated into the depositing film by concurrent bombardment
during deposition. An example is the incorporation of 20 - 40 atomic percent
hydrogen and helium in gold[135][136][190] and the incorporation of krypton in
amorphous metals films.[137] This incorporation is probably due in part to the
high lattice defect concentration in the bombarded material which trap
mobile species. At very high gas contents, the gas will precipitate into voids.
Gas incorporation can be minimized by using low-energy bombarding
species (i.e., less than 100 eV), an elevated substrate temperature during
deposition (300 - 400°C), and/or using higher atomic mass bombarding
species (Kr, Xe, Hg).

8.9 Surface Coverage

The macroscopic and microscopic surface coverage of a deposited film on a


substrate surface may be improved by the use of concurrent bombardment during film
deposition. The macroscopic ability to cover complex geometries depends mostly
on scattering of the depositing material in the gas phase.[1][191][192] The gas scattering
by collision in the gas phase may be aided bygas pumping[193]-[195] in the discharge,
which will give a directed velocity to the film-atoms toward the substrate surface. If
gas scattering is extensive then gas phase nucleation will occur and the resulting
deposit will be poorly consolidated. If a plasma is present and the substrate is
at a negative potential, the gas phase nucleated materials will become
negatively charged and repelled from the substrate. In addition, bombard-
Ion Plating 381

ment will heat, densify, and consolidate the deposited material into a high
quality film over the whole surface. On a more microscopic scale, sputtering
and redeposition of the depositing film material will lead to better coverage on
micron and submicron sized features,[24][179][196]-[199] and reduce pinhole
formation. On the atomic scale, the increased surface mobility, increased
nucleation density, and erosion/redeposition of the depositing adatoms will
disrupt the columnar microstructure and eliminate the porosity along the
columns. In total, the use of gas scattering, along with concurrent bombard-
ment, increases the surface covering ability and decreases the microscopic
porosity of the deposited film material as long as gas incorporation does not
generate voids.

8.10 Other Properties

Many other properties of the film material may be changed and improved
by bombardment during deposition. They include: (a) electrical resistivity of
metal films,(b) hardness of hard-coatings,(c) chemical etch rate,(d) corrosion
resistance,(e) pinhole density,(f) index of refraction of dielectric coatings, (g)
color of TiN films, etc.

9.0 ION PLATING SYSTEM REQUIREMENTS

Generally the equipment used for ion plating is the same as that used
for sputter deposition except that now the substrate is the sputtering target and
another vaporization source has been added. Figure 6.8 shows some of the
possible configurations.

9.1 Vacuum System

This system is similar to sputter deposition equipment. A good base


pressure and little contaminant desorption during processing is desirable in
order to keep the contaminant level in the plasma low.

9.2 High Voltage Components

This is also similar to sputter deposition equipment with more attention


paid to substrate cooling and the means of providing a high voltage
connection to the substrate. Because of the high “throwing power” condi–
382 Deposition Technologies for Films and Coatings

Figure 6.8. Some configurations for bombarding a surface from a plasma by using
accelerated or reflected high energy particles: (a) diode, (b) grid to allow bombard-
ment of complex surfaces or insulators, (c) thermoelectron sustained plasma with
magnetic enhancement/confinement, (d) e-beam evaporation with a differentially
pumped vacuum chamber, (e) utilizing reflected high energy neutrals and sputter-
ing, (f) magnetron sputtering source, and (g) moving magnetron plasma to allow
uniform bombardment of substrate surface.
Ion Plating 383

tions often used in ion plating systems, the insulators of electrical feed-
throughs must be carefully shielded from deposition or else they will become
shorted. These conditions may also lead to gas-phase nucleation of particles
which will deposit on the system walls (called “black sooty crap”, BSC, by the
operators). This material has a very low density and if the material is
pyrophoric (Ti, Zr etc.) the BSC may ignite if disturbed in air. In such a case
system cleanup should be done wet.
Power supplies must be capable of withstanding electrical arcs in the
deposition chamber and their attendant electrical transients. Substrate
potentials may be DC or RF and with or without magnetron enhancement. In
some configurations (beam, grounded cathode) the substrate may be at
ground potential. Very high voltage (to 1-00 keV) pulsing of substrates
immersed in plasmas is being studied as a way to modify surfaces by ion
bombardment.[199] This technique could be used in ion plating to allow periodic
bombardment of the depositing film material and might be termed pulsed ion
plating.

9.3 Gas Handling System

This equipment is also similar to sputter deposition. Inert gases should


be purified in order to decrease the contaminants in the plasma. Reactive
gases may be injected directly toward the deposition region and some concern
must be given to having a uniform flux of reactive gases to the deposition region.

9.4 Evaporation/Sublimation Sources

In electron beam evaporation into a plasma, the filament region of the


gun must be differentially pumped in order to prevent sputter erosion of the high
voltage filament. Evaporation/sublimation in a gas environment takes more
power than in a vacuum because of heat loses by convection and backscat-
tering of the vaporized material.

9.5 Sputtering Sources

Sputter target fixturing will be coated by the sputtered material. Target


fixtures and nearby material will be sputtered by the bombarding ions or high
energy neutrals. This may lead to contamination of the deposited material. In
order to get around this problem, the target fixtures may first be coated by the
material to be deposited.
384 Deposition Technologies for Films and Coatings

9.6 Plasma Uniformity

Plasma uniformity over the substrate surface is desirable when using


the plasma as the source of bombarding particles or the source of reactive
species. Often this plasma is non-uniform due to the geometry of the surface,
non-uniformity of the electric field, or non-uniformity of the magnetic field.
The electric field uniformity can be improved in some cases by enclosing
the surface in a high transmission grid at the same potential as the part. The
magnetic field uniformity can be improved by using multiple polepieces or by
using moving magnetic fields.

9.7 Plasma Generation Near the Substrate Surface

In many cases the substrate potential may be used to create a plasma


near the substrate if the gas pressure and magnetic field are of the appropriate
nature. In some sputtering-source configurations, i.e., DC magnetron sputter-
ing, the plasma is held away from the substrate and it may be desirable to
sustain a plasma near the substrate surface. This may be done by having an
auxiliary plasma generating technique such as a hot filament or hollow
cathode triode configuration near the substrates. For reactive deposition, it
may be desirable to inject the reactive gases directly into this region.

9.8 Substrate Fixturing

This is similar to sputter deposition equipment with more attention


paid to substrate cooling and means of providing a high voltage connection
to the substrate. Moveable fixturing may be necessary in order to not leave
points of electrical contact uncoated. The barrel-plating fixturing may also
be used to give 100% coverage of the substrate. [200] Heating of the
substrate holder may be done by having poor thermal contact to a heat
sink, by using embedded heaters, or by radiant heating. Since appre-
ciable heat in introduced into the substrate surface, substrate cooling may
be an important concern. Coolants used to actively cool the substrate
holder must be isolated from ground by using insulating tubing. Some
leakage to ground can be expected though ionic conduction. A cold finger
substrate holder may be used to allow direct cooling of the substrate.
Ion Plating 385

Holding-fixtures and nearby material will be sputtered by the bombard-


ing ions or high energy neutrals. This may lead to contamination of the
deposited material. In order to get around this problem the fixtures may first
be covered by the material to be deposited.

10.0 PROCESS MONITORING AND CONTROL

The ion plating process is very complex and monitoring what goes on
is usually done in a comparative manner rather than an absolute manner. This
means careful control of process variables.

10.1 Plasma

Typically the plasma is monitored by the gas pressure, gas flow through
the system, and power input. Calibrated flow meters are useful for process
control. The species in the plasma may be monitored by the optical emission
from the plasma, and this analysis may be correlated to the composition and
properties of the resulting film.[201] In some cases, mass spectrometry may
be used to determine gas species but if a plasma is used in the process, the
mass spectrometer must be differentially pumped and the calibration is
confused by the initial presence of ionized species.

10.2 Substrate Temperature

Substrate surface temperature monitoring is complicated by the pres-


ence of the plasma and high voltage. Thermocouple readouts must be isolated
from ground and float at the substrate potential. Infrared temperature
monitoring techniques may be used.[202]

10.3 Specifications

Process specifications and reproducible processing are the keys to


good ion plating processing. Because of the many process variables and the
problems of determining some of the possible variables absolutely, specifica-
tions and reliable process monitors are particularly important in the ion plating
process.
386 Deposition Technologies for Films and Coatings

11.0 PROBLEM AREAS

Problem areas which exist with ion plating arise because of:
“Activated” reactive contaminants in the plasma
Redeposition of sputtered contaminates
Plasma uniformity
High field regions
Points
Focusing fields
High plasma density region
Trapped secondary electrons
High secondary emission
Unwanted shielding of substrate areas
Wasted power
Unshielded leads/areas
Substrate heating
Coating (shorting) high voltage insulators
Non-uniform availability of reactive species (reactive depo-
sition)
Electrical contact points are not coated
Gas incorporation
These problem areas can generally be avoided by design of the fixturing
and other “tricks” such as:
Rotating fixturing
Use of grids to smooth out electric fields
Periodic plating (on-off) mode to reduce substrate heating
Heating of substrate to outgas material as it deposits
A major problem area in using plasmas for thin film deposition is that of
obtaining a uniform plasma density over a surface so that uniform bombard-
ment and reactive gas availability can be attained. Plasma non-uniformity can
arise from a number of sources including: (a) geometrical arrangement of
power input electrodes and substrate fixturing,(b) substrate geometry,(c) the
presence of surfaces that allow recombination and loss of species in the
nearby plasma, and (d) in the case of reactive deposition, reactive surfaces
that deplete the supply of reactive gas at the growing film surface.
Ion Plating 387

As a general rule, the best system design is one that is geometrically


symmetric. However, in many instances a symmetric geometry is difficult to
attain. The use of magnetron configurations is an example. The use of a
magnetic field to confine electrons and increase the local plasma density in
one region leads to a decrease in plasma density in some other region. Figure
6.9 shows an example of how two independently sustained plasmas may be
used to allow magnetron sputtering of a source and the use of a hot-filament-
sustained plasma in the vicinity of the substrate to provide a plasma from which
ions can be extracted to bombard the substrate and film.
If the part has a very complex configuration, the electric field around
points and corners focus the bombardment giving high erosion rates and
heating in these areas. A thin region gives poor thermal conductance and
results in heating. Holes and re-entrant features give low field gradients. In
these regions heating will be high and erosion will be low, giving poor cleaning
and allowing reaction with contamination. Excessive heating can sometimes
be alleviated by pulse processing where the substrate bias is periodically
turned on and off.

Figure 6.9. Example of using an auxiliary plasma near the substrate to allow ions
to be extracted and bombard the growing film.
388 Deposition Technologies for Films and Coatings

In some cases high transparency grids at the substrate potential may


be used to surround the substrate giving a more uniform bombardment over a
complex surface. This is the basis of the equipment used in the ion vapor
deposition (IVD) process and in the barrel-plating ion plating configuration.
Figure 6.10 shows a barrel-plating configuration used to coat small parts which
are tumbled in the rotating cage. A grid configuration may also be useful in
coating dielectric materials where charge buildup may be a problem, or in
coating moving substrates where electrical contact may be a problem.

Figure 6.10. Ion plating “barrel plating” configuration using a rotating cage to
contain the parts.[200]
Ion Plating 389

As with any plasma process, wall effects enhance the desorption of


contamination. This contamination, when introduced into the plasma, is
“activated” and can be an important source of contamination which must be
controlled.

12.0 APPLICATIONS

There are many applications of the ion plating process some of which
are:
! Obtaining good adhesion: Ag on steel for mirrors, soft metals
on surfaces for space lubrication, Ag on Be for diffusion
bonding, Cu and Au on Ta and Mo for subsequent brazing,
Cu-on-ceramic metallization.
! Metallization: Al, Ag, Au on plastics and semiconductors.
! Good surface coverage on complex surfaces: TiN on tool
bits, molds and jewelry items; semiconductor metallization.
! Good reaction and stoichiometry: TiN on tool bits, molds
(hardness, wear); jewelry items.
! Corrosion protection: Al on U, steel and Ti (galvanic); C and
Ta on biological implants.
! Abrasion resistance: MgF2 coatings on plastics.
! Deposition of diffusion barriers: HfN and TiN on semiconduc-
tor devices.

13.0 SUMMARY

Like any deposition technique the ion plating process has its advan-
tages and disadvantages.
Advantages:
! Excellent surface covering ability(throwing power) under the
proper conditions.
! Ability to have in situ cleaning of the substrate surface.
390 Deposition Technologies for Films and Coatings

! Ability to obtain good adhesion in many otherwise difficult


systems.
! A great deal of flexibility in tailoring film properties by
controlling bombardment conditions.
! Equipment requirements are roughly equivalent to those of
sputter deposition.
Disadvantages:
! Many processing parameter that must be controlled.
! Processing may be very dependent on substrate geometry
and fixturing.
! Obtaining uniform bombardment and reactive species avail-
ability over a complex surface may be difficult.
! Gas incorporation may be excessive.
! Substrate heating may be excessive.
! Contamination is desorbed from surfaces and activated in the
discharge and can contaminate deposited material.

In order to achieve the desired film property modification, there must be


an appreciable ratio of bombarding particles to depositing species. This ratio
must be much higher to disrupt the columnar morphology than is necessary
to change the film stress. The necessary bombardment conditions for each
application are usually determined empirically and controlled by controlling
the processing geometry and parameters. A typical condition to control film
stress might be a substrate bias of -50 to -100 volts DC, a current density of
1 mA/cm2 and a deposition rate of 10 nanometers per second. For columnar
structure disruption and maximum covering ability, a resputtering rate might
be 30%.
The ion plating process provides an alternative film deposition technique
which should be evaluated for specific applications.
Ion Plating 391

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7

Chemical Vapor Deposition

Jan-Otto Carlsson

1.0 INTRODUCTION

Chemical vapor deposition (CVD) is a process whereby a solid material


is deposited from a vapor by a chemical reaction occurring on or in the vicinity
of a normally heated substrate surface. The solid material is obtained as a
coating, a powder, or as single crystals. By varying the experimental
conditions—substrate material, substrate temperature, composition of the
reaction gas mixture, total pressure gas flows, etc.—materials with different
properties can be grown.
A characteristic feature of the CVD technique is its excellent throwing
power, enabling the production of coatings of uniform thickness and properties
with a low porosity even on substrates of complicated shape. Another
characteristic feature is the possibility of localized, orselectivedeposition, on
patterned substrates. CVD is employed in many thin film applications. It is,
for instance, used in the microelectronics industry to make films serving as
dielectrics, conductors, passivation layers, oxidation barriers, and epitaxial
layers. The production of optical fibers as well as wear-, corrosion-, and heat-
resistant coatings with this technique is well known. Other CVD applications
are the preparation of high temperature materials (tungsten, ceramics, etc.)
and the production of solar cells, of high temperature fiber composites, and of
particles of well-defined sizes. Recently, high-Tc superconductors have also
been made by this technique. Since oxygen activity in the vapor can be
precisely controlled during the deposition, no annealing in oxygen is needed
to achieve superconductivity.

400
Chemical Vapor Deposition 401

There exist several types of CVD processes. In thermally activated CVD


(TACVD), the deposition is initiated and maintained by heat. However,
photons, electrons, and ions, as well as a combination of these (plasma-
activated CVD), may induce and maintain CVD reactions. In this chapter, the
underlying principles of TACVD are introduced. In addition to large-area
deposition, selective CVD on patterned substrates is discussed.

2.0 IMPORTANT REACTION ZONES IN CVD

In CVD, gaseous reactants are admitted into a reactor (see Fig. 7.1).
Near or on a heated substrate surface, a chemical reaction of the following type
occurs:

Gaseous reactants → Solid material + Gaseous products

Because of the gas flows as well as the temperature used in CVD, five
important reaction zones are developed during the CVD process (see Fig. 7.2).
The properties of CVD materials are affected by the interacting processes
occurring in these reaction zones. In a CVD process, a main gas flow (the
reaction gas mixture) passes over the substrate/coating surface. For fluid
dynamical reasons, a more or less stagnant boundary layer occurs in the vapor
adjacent to the substrate/coating. During the deposition process, the
gaseous reactants and the gaseous reaction products are transported across
this boundary layer. In reaction zone 1 (see Fig. 7.2) as well as in the main
gas stream, homogeneous reactions in the vapor may occur. These reactions
may lead to an undesirable homogeneous nucleation resulting in a flaky and
non-adherent coating. In some cases however, these reactions, when not
accompanied by homogeneous nucleation, are favorable to the CVD process
(for instance CVD of Al2 O3,[1] of B13C2,[2] and of Si,[3] respectively). The
heterogeneous reactions occur in the phase boundary vapor/coating (zone 2).
These reactions determine, in many systems, the deposition rate and the
properties of the coating.
Relatively high temperatures may be used during CVD. This means that
various solid state reactions (phase transformations, precipitation, recrystal-
lization, grain growth, for example) may occur during the process (the zones
3 - 5). In zone 4, which is a diffusion zone, various intermediate phases may
be formed. The reactions in this zone are important for the adhesion of the
coating to the substrate.
402 Deposition Technologies for Films and Coatings

Figure 7.1. The principle of CVD.

Figure 7.2. Important reaction zones in CVD.

3.0 DESIGN OF CVD EXPERIMENTS

Every CVD experiment is unique. However, some general aspects in


designing CVD experiments can be given. The design is usually an iterative
procedure. For instance, the choice of the reaction gas mixture affects the
design of the CVD system, the cleaning procedure, the adhesion of the
coating, etc.
Chemical Vapor Deposition 403

3.1 Classification of CVD Reactions

CVD processes frequently proceed by complicated chemical reaction


schemes. However, use of overall CVD reactions enables a classification to
be made.
Thermal decomposition reactions or pyrolytic reactions mean, in this
case, that a gaseous compound AX is thermally dissociated into A (a solid
material) and X (a gaseous reaction product).

AX(g) → A(s) + X(g)

Use of thermal decomposition reactions normally results in relatively


pure coatings. Examples of some thermal decomposition reactions are given
below:

SiH4(g) → Si(s) + 2 H2(g)

B2 H6(g) → B(s) + 3 H2(g)

Ni(CO)4 (g) → Ni(s) + 4 CO(g)

Si(CH3 )Cl3(g) → SiC(s) + 3 HCl(g)

Processes like carburizing and nitriding may also be classified in this


category of reaction. In carburizing, for instance, a carbon-carrying vapor
species, e.g., methane, is allowed to react at/on a heated surface. Methane
then decomposes in principle according to

CH4(g) → C(s) + 2 H2(g)

The deposited carbon reacts immediately with the substrate yielding a


solid solution of carbon in the substrate and/or—if they exist—carbides of the
substrate material.
Reduction reactions, where hydrogen acts a reducing agent, are
frequently used (see alsoCoupled reactions below).

2 AX(g) + H2(g) → 2 A(s) + 2 HX(g)

Straightforward reduction reactions have been almost exclusively used


in the CVD of elements.
404 Deposition Technologies for Films and Coatings

WF6(g) + 3 H2 (g) → W(s) + 6 HF(g)

2 BCl3(g) + 3 H2(g) → 2 B(s) + 6 HCl(g)

SiCl4 (g) + 2 H2(g) → Si(s) + 4 HCl(g)

Exchange reactions mean that an element E replaces another element,


for instance X, in the molecule AX according to

AX(g) + E(g) → AE(s) + X(g)

Examples of exchange reactions are:

Zn(g) + H2S(g) → ZnS(s) + H2(g)

SiCl4 (g) + CH4(g) → SiC(s) + 4 HCl(g)

SnCl4(g) + O 2(g) → SnO2(g) + 2 Cl2(g)

Disproportionation reactions are rarely used in CVD. Disproportionation


means a reaction where the oxidation number of an element both increases
and decreases through the formation of two new species. CVD of A from AX
can be obtained in disproportionations like

2 AX(g) → A(s) + AX2(g)

3 AX(g) → 2 A(s) + AX 3(g)

4 AX(g) → 3 A(s) + AX 4(g)

Examples of disproportionation reactions are

2 GeI2 (g) → Ge(s) + GeI4(g)

2 TiCl2 (g) → Ti(s) + TiCl4(g)

2 SiI2 (g) → Si(s) + SiI4(g)

Coupled reactions are often used in CVD. For instance, CVD of Al2O3
from AlCl3, CO2 and H2 can be described in an overall reaction:
Chemical Vapor Deposition 405

2 AlCl3(g) + 3 CO2(g) + 3 H2(g) → Al2O3(s) + 3 CO(g) + 6 HCl(g)

where the reaction in which water is formed

CO2(g) + H2 (g) → CO(g) + H2O(g)

is coupled to the hydrolysis reaction

AlCl3(g) + 3 H2 O(g) → Al2O3(s) + 6 HCl(g)

i.e., a reduction reaction is coupled to an exchange reaction (for example, see


Ref. 7.1). Other examples of overall coupled CVD reactions are

TiCl4 (g) + NH3(g) + ½ H2 (g) → TiN(s) + 4 HCl(g)

Ga(CH3 )3 (g) + xPH3 (g) + (l-x)AsH3(g) → GaAs1-xP x(s) + 3 CH4(g)

In general, several possibilities of preparing a substance by CVD exist.


For practical reasons however, relatively few alternatives will remain after a
critical evaluation of the requirements of the process (temperature, total
pressure, compatibility with the substrate and the reactor, the reactions gas
mixture, costs, toxicity of the substances, etc).

3.2 Thermodynamics

Thermodynamic calculations are a useful tool when choosing the


experimental conditions (temperature, total pressure, reaction gas composi-
tion) for the deposition of a certain substance, and also serve as a guide when
changing the experimental conditions in a CVD process. For the calculations,
different computer programs are in use and there are now practically no
limitations in the number of substances that can be included in the calcula-
tions. For reviews of computational methods, the reader is referred to Refs.
7.4 - 7.7.
Usually the computer programs are based on the so-calledfree energy
minimization technique. The free energy G is given by the following equation:

G = ∑ n iµ i
i
406 Deposition Technologies for Films and Coatings

where ni is the number of moles of a substance i and µi is the chemical


potential of the substance. The chemical potential is defined as

µi = µi0 + RTlnai

where µi is the reference chemical potential, and ai is the activity. Assuming


ideal gas conditions, the activity of the gaseous species may be expressed
as its partial pressure

ai = pi = (ni /n)P

where n is the number of moles in the gas phase, and P the total pressure.
For pure condensed substances, the activities are equal to unity.
Eriksson[8] developed a computer program (SOLGAS) based on the
minimization of the free energy. This program became a prototype for many
other equilibrium calculation programs. From the basic equations given
above, dimensionless quantity G/RT was defined (see eq. below) and used
in the calculations.
g s
m  0
g µ n ig n  0
s µ
∑ ∑
G
= ni   + ln P + ln + ni  
RT i =1  RT  i n i =0  RT  i

The superscripts g and s refer to the gas phase and the solid phase, respectively.
The value of µ0/RT for a specific substance is calculated from

µ0
=
(
G 0 − H 298
0
+
)
∆H f0,298
RT RT RT

where: (Go - Ho)/RT = free energy function


∆H0f,298 = heat of formation at 298.15 K.

By minimizing the quantity G/RT (or G) and using mass balance equations
as subsidiary conditions, the equilibrium composition of a system can be
calculated.
The input data in the calculations are the number of moles of the
different reactants, the total pressure, the substrate temperature, the different
substances, and their thermochemical data. From the calculations, various
quantities like the partial pressures of the vapor species, the amounts of the
different substances available for CVD, i.e., the yield, thermodynamic
functions (supersaturation, reaction enthalpies, driving force of different
processes, etc.), are obtained.
Chemical Vapor Deposition 407

Figures 7.3 - 7.5 illustrates results from equilibrium calculations. Figure


7.3 shows the change in equilibrium composition when SiH4 is added to an H2/
WF6 gas mixture. For an overview of the experimental conditions for
depositing a certain substance, CVD phase diagrams are constructed.[10]
Figs. 7.4 and 7.5 are examples of calculated CVD phase diagrams. The
number of variables required to construct a complete CVD phase diagram is
given by the phase rule. Normally various sections (constant temperature,
constant total pressure, constant molar ratio between two of the reactants,
while varying the number of moles of a third reactant) are used. Finally, for
more theoretical work,predominance diagrams with element chemical poten-
tials as variables are employed. In these diagrams, the phase stability ranges
are limited by straight lines.

Figure 7.3. Partial pressures of vapor species in the homogeneous reaction


between H 2, WF6 and SiH4. Total pressure 0.1 Torr, temperature 300°C, H2/WF6
= 39.[9]
408 Deposition Technologies for Films and Coatings

Figure 7.4. Calculated CVD phase diagram for the W - Si system. Reactants WF6,
SiH4, and H2, total pressure 0.1 Torr, H2/WF6 = 39.[9]

Figure 7.5. Calculated diagram for deposition of YBa2Cu3O7-x. The grey-shaded


stability regions contain the superconducting phase. The contour lines represent
the yield of YBa2Cu3O7-x. Precursors YCl3, BaI 2, and CuCl, O2, and H2O, molar ratios
YCl3:BaI2:CuCl = 1:2:3, O2:H2O = 1:1, total pressure 1 kPa.[11]
Chemical Vapor Deposition 409

The reliability of the equilibrium computations described above is


dependent on the availability and accuracy of thermochemical data as well as
the identification of all the substances—vapor species and condensed
phases—that are of importance in the system. Examples of sources of
thermochemical data are given in Refs. 12 - 14. In cases were data do not exist
or the data are unsatisfactory or unreliable, estimation procedures can be used
(see, for instance, Ref. 12). Finally, a few references illustrating the use of
thermodynamic computations in CVD have been selected.[15]-[24]

3.3 Adhesion

Production of well-adhering coatings with desired properties is the


ultimate aim of all CVD work. There are, however, several factors which reduce
the adhesion between the coating and the substrate.
Stresses introduced as deposition stresses or originating from a
mismatch in the thermal expansion coefficients between the substrate and the
coating when cooling down after the deposition process. These stresses can
be reduced by depositing a substance prior to the final CVD process. The
predeposited substance forms an intermediate layer. The stresses can also
be reduced by decreasing the thickness of the coating as well as by changing
the grain size and morphology of the coating.
Homogeneous nucleation in the vapor produces a flaky/powdery de-
posit. By reducing the degree of supersaturation or the driving force of the
process, the homogeneous nucleation can be eliminated.
Intermetallic compounds formed in the coating/substrate interface may be
brittle, leading to the initiation of cracks there. The risk of crack initiation
increases with increasing thickness of the layer containing the intermetallic
compounds. The technique of predeposition of a substance—forming an
intermediate layer later—may be usable to improve the adhesion in this case.
Hydriding of the substrate may cause bad adhesion. Hydrogen is
frequently used in the cleaning procedure prior to the deposition stage. Some
metals/alloys can dissolve a considerable amount of hydrogen. If the
deposition process is then run at a temperature where the hydrogen is
liberated, cracking of the coating occurs. Hydriding can be eliminated by using
another cleaning procedure or heating the substrate in vacuum or an inert gas
after cleaning in hydrogen.
Pores in the coating/substrate interface reduce the adhesion not only
because of the fewer bonds in the interface but also because the pores act as
crack initiators. The pores can originate from the coalescence step at the
410 Deposition Technologies for Films and Coatings

beginning of the process as well as from Kirkendal diffusion (differences in the


diffusion fluxes of the atoms over the coating/substrate interface).
Oxide films or other surface contaminants reduce the adhesion as a
rule. A proper cleaning procedure usually can solve this problem.
Chemical attack on the substrate by the reaction products formed
during the CVD process may cause bad adhesion. The chemical attack on
the substrate can occur as long as the substrate is exposed to the vapor and
is described in the following reactions:

2 AX(g) + H2 (g) → 2 A(s) + 2 HX(g)

The volatile reaction product HX formed reacts with the substrate S according
to the reaction

2 S(s) + 2 HX(g) → 2 SX(s) + H2(g)

The solid substance SX formed may result in poor adhesion. The reaction
above can be predicted from thermodyamics.

3.4 Substrate Cleaning Procedures

A clean substrate surface free from oxides and other contaminants is


a prerequisite condition for good adhesion. The cleaning procedure depends
on the substrate used, the material to be deposited, the CVD equipment
available, etc. Examples of some cleaning techniques are given below.
Before the substrates are placed in the reactor, pickling, grit blasting,
etching, degreasing, etc., are carried out. In the CVD reactor surfaces
containing hydrogen-reducible oxides, e.g., tungsten oxides, are heated in a
hydrogen gas flow at temperatures above the deposition temperature. Metals
forming volatile oxides are cleaned by heating in an inert atmosphere. Finally,
the heating operations in the cleaning step remove dust particles from the
surface, in some cases by the formation of carbides in the surface. After the
cleaning procedure the reactor is purged with an inert gas/hydrogen before the
deposition process (interlayers or final coating).

3.5 The CVD system

The choice of the CVD system is affected by a number of factors: the


reactants used in the process, the maximum acceptable leak rate for air into
the system, purity of the deposit, size and shape of the substrate, process
Chemical Vapor Deposition 411

economy, etc. In the following, some general comments on the design of CVD
systems are given.
A CVD system is advantageously constructed in three modules:
1. The reaction gas dispensing system.
2. The reactor, including components for defining the gas flows.
3. The exhaust system containing a total pressure controller,
vacuum pump, scrubber and/or reactant recycle system.

3.6 The Gas Dispensing System

Reactants, which are gases at room temperature, are stored in gas


bottles. After pressure regulation, their flows are measured with, for instance,
mass flow meters. Use of mass flow meters yields high accuracy and allows
microprocessor control of gas flows.
Those reactants that are liquids or solids at room temperature have to
be fed to the system in other ways (see Fig. 7.6). They can be admitted to
the system by simply heating them above the boiling or sublimation point. The
evaporation rate can be varied by varying the source temperature and/or the
dimensions of the capillary from the sources. Another way of introducing these
substances is to use an evaporator or sublimator and a carrier gas. When the
evaporator is used, the carrier gas is bubbled through the liquid to be
evaporated or flowed above its surface. The carrier gas picks up the liquid
substance and transports it into the reactor. The evaporation rate depends on
the temperature of the liquid, the liquid level in the container, and the flow rate
of the carrier gas. For the highest reproducibility it is important to have a
constant level of the liquid in the container. However, some alternatives to
these evaporators exist which use carrier gases and are independent of the
liquid level. In one alternative, the liquid is evaporated from a vessel, cooled
and condensed in a cooler, leaving the carrier gas saturated at the temperature
of the cooler. If two or more reactant liquids have to be used in the process,
it is seldom possible to vaporize them in the same evaporator while maintaining
the predetermined molar ratio since they normally have different vapor
pressures.
The principle of the sublimator is similar to that of the evaporator. In a
sublimator the substance is transferred to the vapor by sublimation (solid→
gas) and then transported to the reactor by the carrier gas.
412 Deposition Technologies for Films and Coatings

Figure 7.6. Sketch of a CVD system.

Non-gaseous reactants at room temperature can also be admitted into


the reactor by generating them in situ in the gas dispensing system. If, for
instance, the halide AlCl3 is to be used in a process, the generator is filled with
aluminium sponge. Aluminium chlorides are then obtained by leading
hydrogen chloride through the generator. Generator variables are tempera-
ture, flow rate, and concentration of the hydrogen chloride (varied by dilution
with an inert gas).
Chemical Vapor Deposition 413

Direct metering of liquids/solids followed by immediate vaporization in


a vessel can also be used. For metering of liquids, flow meters and various
dispensing pumps are available. The final vaporization takes place in, for
instance, a flash vaporizer[25]—a vessel containing pieces of porcelain of high
temperature.
Many CVD processes are strongly affected by contaminants in the
vapor. The contaminants originate from the reactants themselves and from
various chemical reactions between the gases and the materials in the gas
dispensing system (in the tubes, evaporators, sublimators) and from air
leakage. The contamination level can be reduced by:
! Purifying the reactants. Hydrogen and argon can be purified
to a level of 1 ppm in commercially available purifiers
! Having a low leak rate
! Using carrier gases which are non-reactive against the
materials to be vaporized (in evaporators and sublimators)
! Using materials in the tubes, vaporizers, reactors, etc.,
which are compatible with the gases used
! Using degassed O-rings, where they are used for vacuum
seals
! Installing purge line, which is important when reactive gases,
e.g., halides, are used
Finally, in CVD, explosive, flammable and toxic gases (hydrogen,
silane, phosphine, arsine) are frequently employed. Correct handling of the
gases is, therefore, necessary. Every precaution should be taken. Effective
ventilation systems and gas detectors (commercially available) should be
used.

3.7 The Reactor

The process selected and the size, shape, and number of substrates
define the type of reactor and its geometry. Two main reactor types can be
distinguished:
1. In the hot wall reactor (see Fig. 7.7), the reactor tube is
surrounded by a tube furnace. This means that the
substrates and the wall of the reactor have the same
temperature. In addition to the film growth occurring on the
substrates, film growth might thus take place on theinside of
the reactor walls. With thicker films on the reactor walls,
414 Deposition Technologies for Films and Coatings

there is a risk that particles will break loose from


reactor walls, fall down on the surface of the growing film,
and introduce pinholes in it. There might also be a source
of contamination in this reactor type because of the reaction
between the material of the reactor wall and the vapor. In the
hot wall reactor, homogeneous reactions, affecting the
deposition reactions and hence the structure of the films,
may take place in the vapor. There is a successive depletion
with respect to the reactants as they are transported through
the reactor. Such a depletion may yield different deposition
conditions within the reactor. Finally, in a hot wall reactor,
many substrates can be deposited simultaneously.

Figure 7.7. A hot wall CVD reactor.

2. In the cold wall reactor (Fig. 7.8), the walls of the reactor are
cold and usually no depositionoccurs on the walls, eliminating
the risk of particles breaking loose from the walls. Furthermore,
a low wall-temperature reduces the risk of contaminating
vapor/wall reactions. In the cold wall reactor, the homogenous
reactions in the vapor are suppressed and the importance of
the surface reactions is increased. The steep temperature
gradients near the substrate surface may introduce severe
natural convection resulting in a non-uniform film thickness
and microstructure. However, with the higher flexibility of the
cold wall reactor, high cleanliness, high deposition rates
(yielding high wafer throughput), high cooling rates combined
with the needs of thickness uniformity, automatic wafer
handling and use of increasing wafer diameter, there is
tendency to more frequently use cold wall reactors in the
microelectronics.
Chemical Vapor Deposition 415

Figure 7.8. A cold wall CVD reactor.

Various techniques of heating the substrates exist.[26] Conductive


substrates can be heated resistively or by radio frequency induction. Non-
conductive substrates are normally heated by applying optical techniques
(tungsten filament lamps, lasers), thermal radiation techniques, or by using
susceptors and radio frequency induction heating. Examples of some
reactors are shown in Fig. 7.9. Finally for coating a large number of small
pieces, fluidized bed techniques can be applied.[25]
To illustrate how the choice of reactor is dependent on the substrate to
be coated, an example of applying a coating inside a tube is given. In this case
the tube itself is the reactor. The reactants are introduced in the tube and
transported to the heated zone where the deposition occurs. Induction heating
as well as tubular furnace heating can be employed. By moving the tube or
the heating sources continuously, a coating of uniform thickness can be
produced (see, for instance, Ref. 27).
The arrangement of the gas flows as well as the gas flow rate are of
highest importance for obtaining good coatings. Gas flow dynamics are
discussed in Sec. 4.

3.8 The Exhaust System

The exhaust system contains a vacuum pump, total pressure control,


scrubbers, and a recycling system, if used. Processes working at atmo-
spheric pressure do not require vacuum pumps and total pressure control. At
reduced pressures, however, pumps as well as some kind of total pressure
control have to be used.
416 Deposition Technologies for Films and Coatings

Figure 7.9. Examples of some CVD reactors. (a) and (b) RF heated cold wall
reactors, (c) vertical hot wall reactor, (d) barrel reactor.

The choice of the vacuum pump depends on the process (pumping


capacity required, pressure range to be used, gases to be pumped). At
higher process pressures (>30 Torr), water ring pumps and different
mechanical chemical pumps are used. The chemical pumps are also
employed at lower pressures (1 Torr), and at the lowest pressures in
combination with, for instance, mechanical boosters. When mechanical
pumps are used in CVD processes, the pump oil can polymerize or be
damaged in other ways by certain gaseous species. The pump oilshould
Chemical Vapor Deposition 417

be chosen with respect to its compatibility with the specific gaseous species.
The polymerization of the oil can easily be followed by measuring its viscosity
at different times. Mechanical pumps also produce back-diffusion of oil
molecules into the system. The back-diffusion can be stopped in a trap
(zeolite trap, liquid nitrogen cold trap) just before the pump. With the current
trend of using lower pressures to create abrupt interfaces and superlattices,
diffusion (to pump hydrogen) and turbo pumps are also utilized. Finally,
external oil filtering systems reduce the wear of the mechanical pumps in
processes where solid particles are formed and transported in the vapor to the
pump.
In a CVD process, more or less toxic, explosive, and corrosive gases
are used/formed. To remove them before exhaust, scrubbers are used. The
scrubber type is appropriate to the CVD process used. Halides can easily be
neutralized in a water scrubber. Carbon monoxide and hydrogen can be burnt
in a flame. Arsine can be removed by simply heating the reactor gas in a
furnace especially arranged for this purpose (i.e., with a high efficiency for
stripping arsenic from the gas stream).
Recycling is frequently used to improve process economy. It becomes
necessary in large scale processes, where expensive reactants are utilized
and the conversion efficiency of the reactants is low. The technique of
recycling varies from process to process. A simple recycling can be achieved
in some processes by selective condensation. It can easily be applied in
systems where the component to be recycled has the highest boiling point.
In the production of boron fibers for instance—where hydrogen and boron
trichloride are used—the unconverted boron trichloride is condensed in the exit
stream from the reactor, while the hydrogen and the hydrogen chloride (formed
in the process) are not condensed.

3.9 Analysis of the Vapor in a CVD Reactor

Various spectroscopic techniques have been used to analyze the vapor


in a CVD reactor. The purpose of these analyses is to achieve a better
understanding of the processes. Spectroscopic techniques are also used for
process control. Mass-, Raman, and IR-spectroscopy are in use.[28]-[30]

4.0 GAS FLOW DYNAMICS

The rate and arrangements of the gas flows in a CVD reactor influence
the deposition conditions considerably. In the following, some fundamentals
418 Deposition Technologies for Films and Coatings

of gas flow dynamics are given. For further details the reader is recommended
textbooks in chemical engineering or other books treating transport pro-
cesses.
In a gas, different states exist. In the molecular state, the mean free
path of the molecules is much longer than the dimensions of the vessel. In
the viscous state, the mean free path is much shorter than the vessel
dimensions. The viscous state can be divided into two flow regimes. The
laminar flow regime, where the flowing gas layers are parallel, is appropriate
to low gas velocities. At higher velocities, the flow becomes turbulent. The
limit between the laminar and the turbulent flow is defined by the value of
Reynold’s number, Re:

ρ • V •D
Re =
η

where: ρ = the density of the gas


V = the velocity
η = the viscosity
D = the diameter of the tube
At Re < 1100 the flow is laminar, while at Re > 2100 the flow is turbulent. The
range 1100 to 2100 is a mixed flow regime.
The Reynold’s number given characterizes the flow in an isothermal
environment. In the non-isothermal environment existing in a cold wall reactor,
natural convection induces a turbulence even at low flow rates. Consider the
situation above a heated surface (Fig. 7.10). At small temperature gradients
dT/dx, the varying density of the gas along the coordinate X is compensated
by the gravitational field and no movement of the gas occurs. At larger
gradients, the gas starts to move and the laminar flow can no longer be
retained. From Fig. 7.10 it can be understood that turbulence at a heated
substrate surface may be obtained at different parts of it. For instance, when
the temperature gradient is perpendicular to the gravitational field turbulence
occurs at smaller temperature gradients than in the antiparallel case.
Different dimensionless quantities are used for identifying conditions of
laminar and turbulent flows at different geometries. For instance, the Rayleigh
number, Ra, and the Grashof number, Gr, are employed.[31] Ra and Gr are
related to each other. Gr multiplied by the Prandtl number (nearly equal to one
for gases) yields Ra.
Chemical Vapor Deposition 419

Figure 7.10. Forces at a heated substrate surface. The value, g, the gravitational
force, dT/dx the temperature gradient.

To summarize the flow situation, diagrams depicting flow stability


regions like that in Fig. 7.11 are constructed for different geometries and
reaction gas mixtures. In an isothermal environment, Gr is equal to zero and
Re describes the situation completely. In a non-isothermal environment Gr is
larger than zero (increases with increasingDT). Turbulence occurs at a certain
Gr value, depending on the flow rate of the specific gas mixture and the
temperature difference between the hot and cold part in the reactor.

Figure 7.11. Flow diagram showing flow stability regions.


420 Deposition Technologies for Films and Coatings

In many CVD processe,s the laminar flow region is normally used. High
flow rates (turbulence) usually decrease the conversion efficiency of the
reactants to the coating and very large gas volumes have to be handled. The
flow situation around the object to be coated can be visualized in smoke
experiments where the smoke is generated inside the reactor from, for
instance, titanium tetrachloride and water.

4.1 Gas Flow Patterns

For growth of films of uniform thicknesses and compositions the gas


flow patterns are of greatest importance. This is particularly the case when
“high” pressures (about 1 atm) are used. At reduced pressures the diffusivity
of the vapor species increases, which results in a better mixing of the process
gases, and hence the flow fields become less important.
The gas flow patterns are very complicated in many CVD reactors
because the flow is driven by both the pressure differences (forced convection)
and gravity (free convection) in mostly complex reactor geometries. Free
convections contributes to the gas flow pattern not only in cold-wall reactors
with their steep temperature gradients but also in hot wall reactors with small
axial temperature gradients. These are employed for correction of the
successive depletion of the vapor with respect to the reactants as they flow
through the reactor. Fluid flow phenomena characteristic of various CVD
reactors have been reviewed by, for instance, Westphal[32] and Jensen.[33]
In gas flow calculations, the continuity equation for the total mass, for
the single components, for the energy, and for the momentum must be solved.
For a suitable choice of experimental conditions (flow regimes and reactor
geometries) simplifying equations and boundary conditions—resulting in
reasonable computer times—are obtained. As an introduction to this field
results from detailed flow calculations for two main reactor types are
summarized. Wahl[34] has calculated the flow fields in some cold wall
reactors for the laminar flow region (atmospheric pressure) for the CVD of
silicon nitride from SiH4 and N2. The reactor geometry investigated can be
seen in Fig. 7.12. The flow patterns calculated for this geometry and the
inverted geometry (difference in the buoyance-driven convection) are shown
in Fig. 7.12. The flow pattern becomes more complicated in the inverted
geometry, i.e., when the forced convection and the gravity interact. The flow
pattern, including generation of loops and rolls,was strongly dependent on the
ratio between the free convection and the forced convection.
Chemical Vapor Deposition 421

Figure 7.12. Gas flow pattern in a cold wall reactor, where the forced and buoyance-
driven convection (a) interact, and (b) counteract, substrate temperature 900 K, Re
= 50.[34]

To show the influence of the reactor geometry on the flow pattern, a


calculation of Wahl and Hoffman[35] will be taken as an example. The reactor
geometry considered as well as the results from the calculations are shown
in Fig. 7.13. As can be seen, the flow pattern in this geometry is not as
complicated as that obtained in the previous geometry (Fig. 7.12), where the
diameter of the inlet gas tube was half the diameter of the hot plate.
422 Deposition Technologies for Films and Coatings

Figure 7.13. Gas flow pattern in a cold wall reactor with a geometry different from
that in Fig. 12.[35]

A technique frequently used for correction of the successive depletion


of the reactants as they are transported through a hot wall reactor is the
application of a temperature gradient in the axial (flow) direction of the reactor.
Even small temperature gradients, however, can induce buoyancy-driven
convection. The flow pattern in a hot wall reactor with a temperature gradient
for the atmospheric CVD of GaAs in the Ga-AsCl3-H2 system has been
calculated for different temperature gradients, different gas flow velocities, and
different reactor heights by Westphal et al.[32] A typical result from their
calculations is shown in Fig. 7.14. It can be seen that a convection roll,
induced by free convection, is generated. The effect of free convection on the
gas flow pattern decreased with decreasing temperature gradients, increasing
gas flow velocities and decreasing reactor heights. No extreme conditions
were required to generate convection rolls. They were, for instance, obtained
at a temperature gradient of 6 K cm-1, a gas flow velocity of 2 cm s-1 and a
reactor height of 5 cm.
Chemical Vapor Deposition 423

Figure 7.14. Gas flow pattern in a hot wall reactor with a temperature gradient of
6 K cm-1, linear gas flow velocity of 2 cm s-1, and channel height 5 cm, deposition
system Ga-AsCl3, H2.[32]

Convection rolls are frequently generated in CVD. These rolls cause


dilution of the reaction gas with reaction products, resulting in an alteration of
the deposition conditions. Developed rolls may yield problems for multilayer
growth with well-defined phase boundaries and for the creation of sharp doping
profiles. By using extreme low total pressures (in the 10-3 Torr range), these
problems can be solved.

4.2 Boundary Layers

In CVD the substrates are immersed in a gas stream. From fluid


mechanics it is known (see, for instance, Ref. 36) that so-called boundary
layers are developed near the substrate surface. The boundary layers are
defined as the region near the substrate surface where the gas stream velocity,
the concentration of the vapor species and the temperature are not equal to
those in the main gas stream. Thus a velocity boundary layer, a concentration
boundary layer and a thermal boundary layer exist. The development of a
velocity boundary layer in a laminar flow region is sketched in Fig. 7.15. The
gas velocity is zero at the substrate surface and increases to a constant value
(the bulk gas flow velocity). The layer over which the gas flow velocity varies
is the boundary layer.
The thicknessδ of a boundary layer (laminar flow) at a position X on the
substrate or susceptor[36] is given by

δ = a(ηX/ρν)1/2
424 Deposition Technologies for Films and Coatings

where a is a proportionality constant, η is the viscosity of the gas, ν is the


velocity of the gas and ρ is the density of the gas. From a knowledge of the
temperature and pressure dependence of η, ρ and ν[31][36] it is deduced that
the thickness of the boundary layer increases with increasing temperature and
decreasing total pressure. Moreover, the thickness also increases with
increasing transport distance of the gases along the substrate surface.

Figure 7.15. Definition of the velocity boundary layer.

The development of boundary layers in CVD situations has been


investigated both experimentally and theoretically. Eversteijn et al.,[37] used
smoke experiments to visualize the flow pattern in a horizontal epitaxial
reactor. The smoke was generated from TiCl4 and water. They observed an
immobile layer of gas, called the stagnant boundary layer, above the
susceptor. It was shown later, however, that in steep temperature gradients
(near the susceptor) fine particles are driven away from the susceptor by
thermophoretic forces.[38] This shows that smoke experiments can only be
used to map the flow at a greater distances from a heated susceptor.
Ban and Gilbert[28] investigated the heat transport in a cold wall reactor
by heating a susceptor in helium and measuring the temperature at different
locations above the susceptor with a thermocouple with a small diameter. The
very steep temperature gradient can be seen in Fig. 7.16.
Ban and Gilbert also investigated the concentration profiles of various
vapor species in silicon CVD from an H2 /SiCl4 gas mixture. They introduced
a fine capillary probe for a mass spectrometer at different locations above the
susceptor. The concentration profile of SiCl4 and the reaction product HCl can
be seen in Fig. 7.17. The thickness of the concentration boundary layer in this
case is more than 2 cm. The successive depletion with respect to the
reactants as they were transported through the reactor is shown in Fig. 7.18.
At a height of 7 mm above the susceptor and 15 cm downstream of
Chemical Vapor Deposition 425

Figure 7.16. Temperature profile in helium. Linear gas flow velocity: 24.9 cm s-1.[28]

Figure 7.17. Concentration profiles of SiCl4 and HCl in the CVD of silicon from SiCl4
and Hc. Transport distance along the susceptor: 12.5 cm, linear gas flow velocity:
24.9 cm s-1, - - - 1000°C, —— 1140°C. [28]
426 Deposition Technologies for Films and Coatings

the susceptor, the partial pressure of SiCl4 was reduced to about 50% of the
initial value. Sedgwick et al.[29] measured temperature and concentration
profiles in an air-cooled horizontal cold wall reactor using Raman scattering.
They observed a steep temperature gradient near the susceptor. The
temperature profile developed was dependent on the position along the
susceptor.

Figure 7.18. Partial pressure profile of SiCl 4 as a function of the transport distance
along the susceptor at a height of 7 mm above the susceptor.[28]

Giling[39] investigated the gas flow patterns and temperature profiles at


atmospheric pressure in air-cooled as well as water-cooled horizontal epitaxial
reactors by means of interference holography. The gases used were H2, He,
N2 and Ar. H2 and He yielded stable laminar flows through both the water-
cooled and the air-cooled reactor. At flow velocities higher than 40 cm s-1 a
cold gas finger, indicating incompletely developed flow and temperature
profiles, was observed in the air-cooled reactor. N2 and Ar behaved quite
differently from H2 and He and different convective effects were obtained. At
flow velocities higher than 4 cm s-1 for instance, a laminar layer about 8 mm
thick was developed near the susceptor, while the gas above this layer
appeared to be in turbulence.
Chemical Vapor Deposition 427

Giling also pointed out the importance of entrance effects, i.e., that it will
take some distance (the entrance length) from the susceptor edge for full
velocity and temperature profiles to develop. According to Schlichting[36] the
entrance length for the development of the full velocity profile is given by the
equation

X = 0.04hRe

where h is the height of the channel and Re is the Reynolds number. Hwang
and Cheng[40] predicted that the thermal entrance length was seven times
longer than the flow entrance length. Giling confirmed this for H2 in his
measurements.
Coltrin et al.[41] have developed a mathematical model of silicon CVD
from silane in a cold wall reactor. The model includes gas phase chemistry
as well as fluid mechanics, and predicts temperature, velocity, and concen-
tration profiles for many vapor species. Figure 7.19 depicts the temperature
contour in a typical calculation. The thickness of the boundary layer is in the
centimeter range and increases with increasing gas transport distance along
the susceptor.

Figure 7.19. Calculated temperature contours for silicon CVD from silane (0.6 Torr)
and helium as a carrier gas (600 Torr). Temperature: 1018 K, gas flow velocity: 15.3
cm s-1.[41]
428 Deposition Technologies for Films and Coatings

4.3 Mass Transport Processes Across a Boundary Layer

Different mass transport processes across a boundary layer can be


distinguished:
1. Fickian diffusion occurs because of the concentration gradient
across the boundary layer.
2. Thermal diffusion or Soret diffusion is induced by a temperature
gradient, in for instance, a cold wall reactor.[31] This diffusion
is of greatest importance in systems having large differences
in molecular weights and molecular sizes between vapor
species.
3. A concentration gradient implies a density gradient, resulting
in a buoyancy-drivenadvective flux.[42]
4. In the overall CVD reaction, the number of moles of gas may
be changed. This induces a flux (Stefan flux) towards or away
from the substrate surface. In, for instance, the CVD of boron
from BCl3 and H2 according to the reaction

2 BCl3(g) + 3 H2(g) → 2 B(s) + 6 HCl(g)

the number of moles in the vapor is changed from 5 to 6,


causing a flux from the substrate.[43]

5.0 RATE-LIMITING STEPS DURING CVD

In a CVD process various sequential steps occur. Each of these steps


may be rate-limiting in the absence of thermodynamic limitations. Plausible
rate-limiting steps are as follows (see also Fig. 7.20): (a) transport of the
gaseous reactants to the boundary layer surrounding the substrate (free and
forced convection);(b) transport of the gaseous reactants across the boundary
layer to the surface of the substrate (diffusion and convections flows); (c)
adsorption of the reactants on the surface of the substrate; (d) chemical
reactions (surface reactions between adsorbed species, between adsorbed
species and reactants in the vapor and or between reactants in the vapor),(e)
nucleation (at least at the initial stage); (f) desorption of some of the reaction
products from the surface of the substrate; (g) transport of the reaction
products across the boundary layer to the bulk gas mixture; (h) transport of
the reaction products away from the boundary layer. In each of these steps
several processes may proceed simultaneously.
Chemical Vapor Deposition 429

Figure 7.20. The various steps in a CVD process.

Even though several rate-limiting steps can be identified in a CVD


process, only five main categories of control are normally discussed:
1. Thermodynamic control. Thermodynamic control means
that the deposition rate is equal to the mass input rate into
the reactor (corrected for the yield of the process). This
occurs at extreme deposition conditions (very low flow rates,
high temperatures, etc.). The temperature dependence of
the deposition rate is obtained from thermodynamic
calculations.
2. Surface kinetics control. If the deposition rate is lower than
the mass input rate into the reactor and the mass transport
rate in the vapor in the reactor to or from the substrate, a
surface kinetics control or nucleation control exist. The
surface kinetics control is favorable for obtaining coatings of
uniform thicknesses on more complicated shaped substrates.
The mechanisms of surface reactions are discussed in Sec.
6.
3. Mass transport control. A process may also be controlled by
the mass transport in the vapor in the reactor to or from the
substrate surface. This occurs frequently at high pressures
and high temperatures.
4. Nucleation control. At low supersaturations the deposition
rate may be controlled by the nucleation.
5. Homogeneous reaction control. In some processes the
formation rate of key species in the vapor may control the
deposition rate.
430 Deposition Technologies for Films and Coatings

Since the mass transport in the vapor or the surface kinetics usually
controls the deposition rate, the following discussions are limited to just these
two cases. Surface kinetics control is normally desirable and means a
maximum in throwing power or step coverage. Figure 7.21 shows conditions
of complete mass transport control, complete surface kinetics control and
mixed control. In the surface kinetics control, a fast diffusion in the vapor is
combined with a slow surface reaction. For a mass transport control, the
surface kinetics is fast while the mass transport in the vapor is slow.

Figure 7.21. Diagrams illustrating situations of complete mass transport


control in the vapor (a), and surface kinetics control (b), respectively, and (c)
shows conditions of mixed control.
Chemical Vapor Deposition 431

Reaction resistances are often used to predict rate-limiting steps or


control in CVD. To illustrate their principle use, reaction resistances are
employed to define the surface reaction control and the mass transport
control, respectively.
The diffusion flux JD across the boundary layer is given by

JD = D Pb − Ps
R• T δ

where: D = diffusion coefficient


R = gas constant
T = absolute temperature
δ = boundary layer thickness
Pb and Ps (see Fig. 7.21)

The mass flux JM towards the surface is expressed as

km (
JM = Ps − Peq)
RT

where km is the mass transfer coefficient.


Pb and Peq are known from the reaction gas composition and from
thermodynamic calculations, respectively. Ps can be eliminated by assuming
steady-state conditions (JM = JD)

km • δ
Pb + • Peq
Ps = D
km