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Georges Hadziioannou, Paul F. van Hutten (Eels.

Senticonducting Poly01ers
Chemistry, Physics and Engineering
Prof. G. Hadziioannou
Departmc'l.t of Polymer Chemistry and Ma.termls Science Centre
Univcrsi.ty of Groningen
Nijenborgh 4
NL-9747 AG Groningen
The Netherlands
Or. P. F. van Huucn
Oepartmen1 of Polymer Chen1istry and Materials Science Centre
University of Groningen
Nijenborgh 4
NL-9747 AG Groningen
'The Ne.therlam.ls
1111:. book carefully prut.luccU. Ncvcrthclc:..". wthor., , ooitor.. <llld puhlishcr do nul warmnl the
information con.taincd lhcrcin to be fn:c or error... Rev.Jer:. arc advscd lu l.cc1> 111 mind tllu l>tatc-
menls, data. illus.tr.tlioru;, proccdur.tl delails or other may ina.Jvcncntly be inaccur.ue.
ubrary of Congress Card No. applioo for.
A catalogue record for this book is available from the British ubrary.
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Ein Titchatz fur diesc f\Jblikalion ist bci Ocr Deutschcn Biblimhd. ertJa.ILiic.:h
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Compo:.ition: K+V Fotosal:t GmbH, 0 -64743 &-.:rfcldcn. Priming: bctz-uruck GmbH, D-64291 Dann-
s.tadt. Bookbinding: J. Schii!Tcr GmhH & Co. KG . D-67269 Griin.,ladl.
PriniCll in the Fo::<kr.tl R<:puhlic uf Gcnnatty.
When wnttng about a subject from a r:tpidly evolving research area, one is
templed into dealing with the latest results, those th;,tt still fascimtte. This is dan-
gerous, however, for such findings may not h;,tve a lasting value. They may not
be sufficiently unambiguous, enlightening, or novel to deserve their place in a re-
ference work.
We h:tve invited our colleagues to write ;,bout their licld or expc11ise. and put
dowtt on paper the thi ngs lhat they arc really cumfort<tble with, <tnd c.:onlillent of.
Fonun<ttcly, we found llluny willing to contribule in this vein. With their help, we
have been uble to eollecl much of the base or knowledge that hus been gathered
in " dt:c<tde of rese;.srch on semiconducling polymers. It is recognized, of course.
that research in thi s ticld coulll build on wh<tt had been learned about conducting
polymers in the preceding decade.
We like to thank those who collabor.ttcd in this book project. This includes all
uuthors, as well as the people at Wiley-VCH who offered us the opportunity and
m:tde it become a reality.
Georges Hadziioamwu
Paul van Huuen
Groningen, September 1999
The science and technology of conducting polymers are inherently interdisciplin-
ary; they fall at the intersection of three established disciplines: chemistry, physics
and engineering; hence the name for this volume. These macromolecular materials
are synthesized by the methods of organic chemistry. Their electronic structure
and electronic properties faiJ within the domain of condensed matter physics. Effi-
cient processing of conjugated polymer rnatcri<.tls into useful forms and the fabri-
cation of electronic and opto-electronic devices require input from engineering;
i. c. materials science (more specificaiiy, polymer science) and device physics.
With the emergence of semiconducting and mewllic polymers <.ts an interdisci-
plinary field, a host of new concepts h;we evolved which are of broad and funda-
mental importance. The licld originated in the 1970s with an initial focus on n-
type and p-type doping of conjugated polymers. Reversible doping of semicon-
ducting polymers was the early highlight with associated electrical conductivity
values that span the full range from insulator to metal. The unique electrochemis-
try of conducting polymers was subsequently discovered and remains as an active
area of science and technology.
The opportunity to synthesize new conjugated polymers with improved proper-
ties began to attract the attention of a larger number of synthetic chemists in the
1980s. Equally important was the subsequent development of stable, processible
metallic polymers. As a result of these efforts, we now have a class of materials
which exhibit a unique combination of properties: the electronic and optical prop-
erties of metals and semiconductors in combination with the processing advan-
tages and meclumicallnvperties of polymers.
Because of the progress toward higher purity, proccssiblc semiconducting poly-
mers, these materials are now av<tibble for usc in "plastic electronic" devices. In
this context, the discovery (at Cambridge University) of elcctroluminescence from
semiconducting, conjugated polymers, was of particulm importance. More gener-
ally, however, plastic electronics devices include diodes, photodiodes, photovol-
taic cells, sensors, light-emitting diodes, lasers, field effect transistors and <til-poly-
mer imegrated circuits - und the list is growing. Thus, the emergence of electron-
ic and opto-electronic devices fabricated from semiconducting polymers has been
a principal focus of the 1990s.
Despite the scientific progress and the demonstmtion of novel device concepts,
there was considcmblc skepticism that semiconducting polymers would ever reach
the levels of purity required for long-lifetime commcrci;.tl devices. ln the context
of the l;.tst 50 years of semiconductor physics, conjugated polymers were often
VIII Foreword
considered as "dirty" and poorly chamcterized materiuls. Therefore, the recent de-
monstration of high-brightness polymer emissive displays with opemting lifetimes
of 10000-20000 hours was a particularly important step; it is now clear that
semiconducting polymers c:m be used to fabricate consumer product-; that meet
commercial specifications.
As a result of the remarlwble p1Vgress in the clzemiscry, physics uml c:11gi11eer-
ing (device physics) of semiconductillg and metallic polymers, we are now witnes-
sing the beguwing of a revolution in "Plastic Electronics".
The field of semiconducting and metallic polymers remains vital; again and
again the science anc technology have moved into new directions. Specific exam-
ples of recent advances (within the I 990s) of special importance include the fol-
Metallic polymers which are stable, soluble and processible, and therefore suit-
able for industrial applications;
e The science and technology of high-efficiency light emission from polymer
light-emitting diodes and polymer light-emitting electrochemical cells;
Ultrafast photoinduced electron transfer in semiconducting polymers mixed
with controlled amounts of acceptors; this phenomenon has opened the wuy to
a variety of applications including high-sensitivity plastic photodiodes, and efti-
plastic solm cells;
Semiconducting polymers as mate&ials for solid-state lasers.
This book, "Semiconducting Polymers - Chemistry, Physics and Engineering",
edited by Georges Hadziiounnou and Paul van Hutten of the University of Gro-
ningen (The summarizes progress in areas of current activity wi thin
the field. The various chapters, all contributed by leading researchers, provide a
summary and review of the field that wi ll be useful and important to anyone seek-
ing a strong buckground in the basic interdisciplinary science and an up-IO-d4tte
"snapshot" of the current status of research. Emphasis is on the basic physics and
chemistry of conjugated polymers as electronic and opto-electronic materials <111d
on the performance (status, opportunities and limitations) of the electronic and
opto-electronic devices that are responsible for the on-going revolution in "Plastic
Alnn 1. Heeger
Professor of Physics & Professor of Materials
Institute for Polymers and Organic Solids
University of Califomia, Santa Barbam
UNIAX Corporation
Sunta Barham, CA
1.2. 1
1.3. 1
1.4. 1
Poly(arylenc vinylcnc)s - Synthesis and Applications
in Semiconductor Devices I
Michael M. Murray and Andrew B. Holmes
Poly( I ,4-phcnylenc vinylcnc) <md its Derivati ves 2
The Basic Polymer LED Device Architecture 4
Substituted Poly(phenylene vinylene)s 6
Poly( <nnhry lencvin y lcnc )s I 0
Step-Growth Routes to PPV Dcriv;nivcs 10
PPY Copolymers II
Relining the Properties of PPV - Multiluyer Devices 13
Multilayer Devices: The Incorporation
of Charge-Tr.mspo11ing l<tyei'S 14
Electron-Deficient Polymers - Luminescent Tnmspo11 l<tyers
Other Electron-Dclicicnt PPV Derivatives 19
Electron-Delicient ArOm;ttic Systems 19
Full Color Displuys - The Scurch for Blue Emitters 21
lsolmed Chromophores - Towards Blue Emission 21
Comb Polymers wi th Chromophorcs on the Side-Chain 22
Chiral PPV - Polarized Emission 23
Poly(thienylenc vinylene)s -
A Stable Cl<tss of Low-lli!nJ-Gap Materials 24
Organic Field EITect Tmnsistors (f.ET.-;) 25
Synthesis 26
Aldol Route 27
Ring-Substituted PTV Derivatives 27
Yinylene-Substituted PTV Derivatives - Tuning the Gap 30
Conclusions <md Outlook 31
Acknowledgements 32
References 32
4. 1
4.4. 1
Oligo- a nd Poly(phenylene)s 37
Ullrich Scherf and Klaus Mullen
Introduction 37
Polymers 37
Oxidative Condensation of Benzene Derivatives 38
Transition Metal-Mediated Couplings 39
Other Routes to Poly(p-phenylene)s 48
Oligomers 50
Dendtitic and Hyperbranched Poly(phenylene)s 55
Hyperbranched Poly(phenylene) Derivatives 55
Oligo(phenylene)s Composed of Orthogonall y Arranged Arms 56
Dendritic Poly(phenylene)s and Giant Polyaromatic Hydrocarbons
(PAHs) 57
Conclusion 60
References 61
Disorder and Solitons in Trans-Polyacetylene 63
Jasper Knoester and Maxim Mostovuy
Introduction 63
The Peierls Instability and Solitons 65
Disorder: The Auctualing Gap Model 71
Disorder-Induced Kinks 76
Concluding Remarks 82
Acknowledgements 83
References 84
Gas Phase to Solid State Evolution of the Electronic
and Optical Properties of Conjugated Chains:
A Theoretical Investigation 87
Jerome Comi/, Donhelli A. dos Santos, David Beljumw,
Zhigang Shuai, and Jetm-Luc Bredas
Introduction 87
Theoretical Met hodology 89
Wavefuncti on An<tlysis of the Excited States in PPV Oligomers 90
lntcrchain Interactions 94
Absorption Properties of Highly Symmetrical Complexes 94
PholOiuminescence Properties of Highly Symmetrical Complexes 99
The Influence of the Number and Relmive Orientations
of the Interacting Molecules 103
Clusters of Sexithienyl Molecules 107
Conclusions ~ n d Outl ook Ill
Acknowledgements Ill
References lt 2
5.2. 1
5.4. 1
5.5. 1
5.5. 1.1
5.5. 1.2
5.5.2. 1
5.5.3. 1
6. 1
6.5. 1
6.6. 1
6.6.2. 1
Electronic Structure of Surfaces and Interfaces
in Conjugated Polymers 115
Michael LiJgdlund and William R. Salaneck
Introduction 115
Photoelectron Spectroscopy 116
X-Ray Photoelectron Spectroscopy 119
Ultmviolet Photoelectron Spectroscopy 120
Theoretical Approaches 12 1
M<!lerials 122
Electronic Structure of rrans-Polyacetylene 123
Charge Stomge States in Conjugated Polymers I 25
Polymer Surfaces <tnd Interfaces 128
Poly(p-phenylenevinylene) 128
Interface Formmion Between Aluminum ;.md PPV 130
Interrace Formation Bclwccn C.tlcium and PPV 132
Polythiophene 134
lmerface Fornmtion Between Aluminum <md Polythiophene 135
Interface Formation Between Copper and Polythiophene 137
Polyaniline 139
Polyaniline on Indium Tin-Oxide 140
Summary 144
Acknowledgements 145
References 146
Electronic Structure and Energy Tr<msfer
in Solid u-Sexithicnyl 149
Carlo Talia11i. Fabio Biscariui, and Michele Muccini
Introduction 149
Experimental 151
Excited Electronic States in Isolated T
Single-Crystal Electronic Structure 154
Davydov Splitting 159
Herzberg-Teller Yibronic Coupling 160
Thin Films 164
Growth in High Vacuum 164
Thin-Film Morphology 165
Sc<tling Behavior of Surface Roughness 169
Disorder Enect on Energy Tmnsfcr 174
Single-Crystal Fluorescence 174
Thin-Film Fluorescence 177
MoqJhology-Dcpendcnt Polarization or Fluorescence
and Eleclroluminesccnce I ~ I
Morphology-Dependent Energy Transfer 184
Conclusions 185
Acknowledgements I g(J
Rclercnccs I g7
7.2. 1
7.3. 1
8. 1
8.4. 1
8.5. 1
Spectroscopy of Photoexcitation$ in Conjugated Polymers 189
Paul A. Lane, Sergey V. Frolov. and Zev V. Vardeny
Introduction 189
Experimental Techniques 190
CW Photomodulation Spectroscopy I 90
Optically Detected Magnetic Resonance 193
Transient Photomodulation Spectroscopy 196
Non-Linear Optical Spectroscopy 199
Poly(para-phenylene vinylene) 202
Absorption and Photoluminescence 202
Transient Photomodulation 204
Non-Linear Spectroscopy (TPA and EA) 208
CW Photomodulation 21 1
Polythiophcnc 2 14
Linear and Non-LinC<lr Absorption 214
Tr<msient Photomodulation 21 5
CW Photomodulation 220
Fullerene-Doped DOO-PPV 226
Transient Photomodul<ttion 226
Summary 232
References 232
Photophysics of Methyl-Substituted Poly(para-Phenylene)-Type
Ladder Polymers 235
Guiglielmo Lanza11i, Sandro De Silvestri, Giulio Cerullo,
Salvatore Stagira, Mauro Nisoli, Willi Gruupner,
Gunther Leising, Ullich Scherf, and Klaus Mullen
Introduction 235
An Overview of Previous Results 236
Optical Properties 237
Experimental 239
Conventionu1 Pump-Probe 239
Field-Assisted Pump-Probe 240
The Primary Photoexcitations in m-LPPP 241
Overview of the Experimemal Results 242
A Model for m-LPPP Electronic Structure 243
High Excitation Density Scenario 247
The Emission Process in m-LPPP 248
Charge Photogenemtion in m-LPPP 250
Conclusions 256
References 257
9. 1
9.5. 1
9.6. 1
9.6.4. 1
10. 1
11.2. 1
11 .2.3
Solid-State Aspects of Conjugated Semiconductors 259
Wilhelm Grmqmet; Stefan Tasch, and Giinther Leising
Introduction 259
Functionalities in Devices 262
Order in Conjugated Semiconductors 264
Excited-State Spectroscopy 268
Excited States 269
Neutral Photoexcitutions 271
Charged Photoexcitations 274
Electroluminesccnce Devices and Models 282
EL Devices from Conjug<tted Polymers
with a High Defect Concentr<ttion 283
EL Devices from Conjugated Polymers
wi th a Low Defect Concentration
from an Elcctruchemical Cell 286
Carrier Injection and Charge Transpon 287
Thermal Emission 288
Field-1ntluced Injection 288
Charge Recombination und Efficiency 295
Highly Excited Conjugated Films 297
Conclusions 303
Acknowledgements 303
References 303
Lasing in Conjugated Polymers 309
Uli Lemmet; Anclreus Hcwgenedet; Christian Kullinger.
and Joc:hen Feldmunn
Introduction 309
Stimuluted Emission in Organic Materials 310
G<tin NmTowing in Cunjug<ttcd Polymer Thin Films 3 17
Lasing in Conjug:ucd Polymers 321
Outlook 325
Acknowledgements 326
Appendix I 327
Appendix II 328
References 328
Physics of Polymer Light-Emitting Diodes 333
I. H. Ccunpbell and D. L. Smith
Introduction 333
Thin Films of Electroluminescent Polymers 335
Electronic Energy Stna.:turc 336
Optical Properties 336
Electrical Tmnsport Properties 338
12.2. 1
13. 1
Device Electronic Structure 339
Internal Photoemission Measurements
of Schouky Energy Barriers 340
Buill-In Potentials in Device Structures 342
Single-Layer Devices 345
Single-Carrier Suuctures 346
Two-Carrier Structures 352
Multi-Layer Devices 355
Blocking Layers 356
Transport Layers 359
Two-Carrier Multi-Layer Devices 361
Conclusion 362
References 363
Charge Transport in Random Organic Semiconductors 365
Heinz Biissler
Introduction 365
Charge Carrier Injection 367
Concepts 367
Comparison with Experiment 373
Space Charge Limited (SCL) Currents 379
The Concept 379
Experimental Results 381
Charge Carrier Transport 384
Concepts 384
Transport in the Presence of Extrinsic Traps 390
Charge Carrier Transport in Conjugated Polymers 398
Time-of-Flight Studies 398
Transient Absorption of Radical Cations 403
Some Remarks Concerning the Nature
of Charge-Carrying Moieties 406
Acknowledgements 407
References 408
The Chemistry, Physics and Engineering
of Organic Light-Emitiing Diodes 411
John Campbell Scott and George G. Ma/liaras
Introduction 411
Materials 413
Conjugated Polymers 413
Small Molecules 416
Molecularly Doped Polymers and Polymer Blends 419
Self-Assembled Layers, Langmuir-Biodgeu Layers,
and Liquid Crystals 420
Electrodes and Interface Modification 421
13.4. 1
13.5. 1
13.5.2. 1
13.7. 1
14.2. 1. 1.2
14.2. 1.2
14.2.2. 1
14.2.2. 1.1
Anodes 421
Cathodes 422
Electrode Modification 423
B<trrier Layers 423
Transparent Cathodes 424
Device Structures 424
Characterization 427
Device Characteristics 428
Figures-of-Merit 429
Built-in Potential 430
Barrier Heights 432
Ch<trge Tr.lllsport 433
Photoluminescence 434
Device Physics 435
The Elemelll<try Processes 436
Single-Layer Devices 438
Analytic Theory 438
Numerical Simulmions 439
Expcriment<ll Studies 440
Multilayer Devices 443
Electrochemical Cells 443
Microcavities 444
Degrad<ttion 445
Application of OLEOs in Fhtt-Panel Displays 449
Display Engineering Units and Conversions 449
Pixels. Patterning, and Drivers 450
Color 453
Encapsulation 455
Outlook 456
Acknowledgements 457
References 457
Physics of Organic Field-ElTcct Transistors 463
Gilles Horowitz
Introduction 463
Basic Principles 464
Junctions 464
Mewl-Semiconductor (MS) Junction 464
Formation of the Junction 464
The Junction al Equilibrium (Zero Bias) 465
Current-Voltage Characteristic 466
Met<tl -lnsulatur-Semiconductor (MIS) Junction 467
Ficld-EITect Transistors 471
Metal-Insulator-Semiconductor FET (MISFET) 472
Principle of Operation 472
Coments XV
XVI Contents
14.2.2. 1.2
14.3. 1
14.4. 1.1
14.4. 1.2
14.5. 1
14.6. 1
14.6. 1. 1
14.6.2. 1
15. 1
15.2. 1
15.2. 1.1
Current-Voltage Characteristic 473
Metal-Semiconductor FET (MESFE1) 475
Thin-Film Transistor (TFI') 476
Accumulation Mode, Linear Regime 477
Depletion Mooe 478
Accumulation Mode, Saturation Regime 480
Mobility Threshold 481
Charge Transport in Organic Materials 481
Localized Versus Dclocalizcd States 481
Hopping 483
Hopping Rate 483
Polarons 484
Polarons in Conjugated Polymers 484
Transport Mechanism of Polarons 484
Multi ple Tmpping and Release 486
Field-Dependent Mobility 487
Fabrication Techniques 488
Deposition of the Semiconductor 488
Elcctropolymeriwtion 489
Solution-Processed Deposition 489
Vacuum Evaporation 489
Langmuir-Blodgett 490
All-Organic Devices 490
Materials 491
Oligothiophenes 492
Other Molecules 495
Phthalocyanines 495
Pentaccne 496
n-Typc Semiconductors 498
Polymers 499
Models 500
Temper.llure and Gate Bias Dependence 50 I
Trap-Limited Tr.msport 501
Polaron and Hopping Models 504
Current-Voltage Characteristics 507
Short-Channel Effects 507
On-Off Current R:.1tio 508
Concluding Remarks 510
References 5 11
Conj ugated Polymer Based Plastic Solar Cells 515
Christoph J. Brabec and N. Serdar Sariciftci
Introduction 5 I 5
Conjugated Polymers as Photoexcited Donors 516
Optical Properties 518
Linear Optic:.1l Propert1es 518
15.2. 1.2
15.2. 1.3
15.3. 1
15.4. 1
15.5. 1
15.6. 1
16. 1.2
16.2. 1
16.2.1. 1
16.2. 1.2
16.2.1 .3
16.2. 1.3. 1
16.2. 1.3.2
16.2. 1.3.3
16.2. 1.3.4
16.2.2. 1
16.2.2. 1.1
Cumems XVII
Photoinduced Absorption 521
Quenching of the Intersystem Crossing to the Triplet State 521
Photoinduced IRAV Studies 522
lime-Resolved Photoinduced Studies 524
Sensitiwtion of Photoconducti vity 525
Magnetic Properties 526
Light-Induced Electron Spin Resonance (LESR) 526
Pure Conjugated Polymer Photovoltaic Devices 528
Definitions 528
Basic Transport Properties 528
MetaUConjugated Polymer Contacts 53 1
Spectml Response 532 -
Conjugated Polymer Bi h1yer Devices 536
Conjugated Heterojunction PhOtodiodes 539
Conj ugated Polymer Bulk Heterojum:tion Dio<.les 545
Conj ugated Polymer/C<>o Bulk Heterojunction Photodiodes 545
Conjugated Polymer/Conjugated Polymer Bulk
Heteroj unction Photodiodes 549
Flexible, Large Area, Plastic Sol:.u Cells 55 1
Stability of Pl:.1stic Solar Cells 553
The Guest-Host Approach:
Blending with Convention:ll Polymers 554
Outlook and Strategies 555
Acknowledgements 556
References 557
A Model Oligomer Approach to Semiconducting Polymers 561
Paul van Hutten and Georges 1/ad-::.i.ioamwu
Introduction 561
Background 561
The Copolymer Approach to Controlled Light Emission
in Polymers 562
Oligomcrs as Model Compounds for Structure-Property Studies 563
Synthesis and Solution Properties of OPVs 564
Synthesis 564
Introduction 564
General Strategy 565
Synthesis or Model Compounds 566
Three-ring OVPs 566
Synthesis of u-OPV5 567
Synthesis of oct-OPV5 :md Ooct-OPV5 568
Synthesis of Cy;.mo-Substit uh!d OPV3s and OPV5s 568
Opt ical Properties in Solution 569
Comparison of Copolymers :md Related Oligomcrs 569
Three-Ring Chmmophorcs 569
XVIII Contents
16.2.2. 1.2
16.3. 1
16.3. 1.2
16.3. 1.2.3 1
16.3. 1.3.3
16.3.3. 1 1
16.4.3. 1
Index 615
Five-Ring Chromophores 572
Substitution Effects in OPV5s 573
About the Geometry of the Excited State 576
OPVs in the Condensed State 577
Single Crystals 577
Introduction 577
Crystal Structures of Five-Ring OPVs 579
Ooct-OPV5 579
Ooct-OPV5-CN' 580
Ooct-OPV5-CN" 581
Crystal Structures of Three-Ring OPVs 582
Ooct-OPV3 582
Ome-OPV3 582
Ooct-OPV3-CN' 583
Ooct-OPV3-CN" 583
Oct-OPV3 584
Oct-OPV3-CN" 584
Optical Properties of Single 585
Them1al Properties: Liquid-Crystalline Phases 586
Thin Films 588
Introduction 588
Thin-Film Structure 589
Ooct-OPV5 589
Optical Microscopy 589
X-Ray Diffraction (XRD) 589
Atomic Force Microscopy (AFM) 590
Ooct-OPV5-CN' 592
Ooct-OPV5-CN" 592
Ooct-OPV3 593
Optical Properties 593
Five-Ring OPVs 593
Ooct-OPV3 597
Light Emission Applications of OPVs 598
Introduction 598
Light-Emitti ng Diodes 599
Single-Layer Devices 599
Influence of Morphology on Device Performance 602
Devices 603
Stimulated Emission 604
Single Crystals 604
Vacuum-Deposited Films 605
Summary and Outlook 608
Acknowledgements 6 10
References 6 10
List of Contributors
H. Biissler
Institute of Physical, Nuclear
;md Macromolcculm Chemistry
Philipps-Univers ity of
D-35032 Marburg
D. Bdjonne
Service de Chimie
des Matcriaux Nouveaux
Centre de Recherche en Electroni4ue
et Photonique Moleculaires
Univcrsite de Mons-Ho.tinaut
Place du Po.trc, 20
B-7000 Mons
F. Biscarini
lstituto di Spenroscopht Molecolme
Consiglio Nazionale delle Riccrche
Via P. Gobeui, I 0 I
1-40129 Bologna
C.J. Brabec
Christian Doppler Laboratory
for Plastic Solar Cells
Physical Chemistry
Johannes Kepler University Linz
AltenbergerstraBe 69
A-4040 Linz
J.-L. Brcdas
Service de Chimic
ties Materi<tux Nouveaux
Centre de Recherche en Electronique
et Photonique Molcculaircs
Uni versitc de Mons-Hainaut
Place du Pare, 20
B-7000 Mons
I. H. Campbell
Electronics Research Group
Los Alamos National Labomtory
Mail Stop 0429
Los Alamos
NM 87545
G. Cerullo
lstituto Nazionale per Ia Fisica
della Materia
Dipartimcnto tli Fisica
Politccnico tli Mihmo
Piazza Leonardo da Vinci, 32
l-20133 Milano
J. Cornil
Service de Chimie
des Nouveaux
Cemrc de Recherche en Elcctronique
et Photonique Moleculaires
Universitc de Mons-H<tinaut
Plat.:e du Pm'C, 20
B-7000 Mons
XX w t of Comributors
S. De Silvestri
Istituto Nazionale per La Fisica
della Materia
Dipartimento di Fisica
Politecnico di Milano
Piazza Leonardo <.Ia Vinci, 32
1-20133 Mi lano
D. A. dos Santos
Service de Chimie
des Materiaux Nouveaux
Centre de Recherche en Electronique
et Photonique Moleculaircs
Universite de Mons-Hainaut
Place du Pare, 20
B-7000 Mons
J. Feldmann
Lehrstuhl fUr Photonik
und OptocleklrOnik
Sektion Physik und Center
for N;moScience
AmalienstraBe 54
D-80799 Munchen
S. V. Frolov
Bell Labor.ttories
Lucent Technologies
600 Mountain Ave.
Murr.1y Hill
NJ 0974
W. Graupncr
Virginia Tech
Department of Physics
VA 24061-0435
G. Hadz.iioannou
Department of Polymer Chemistry
and Materials Science Centre
University of Groningen
Nijenborgh 4
NL-9747 AG Groningen
The Netherlands
A. Haugencder
Lehrstuhl fur Photonik
und Optoelektronik
Sektion Physik und Center
for NanoScience
Amalicnstralk 54
A. B. Holmes
University Che.nical L;tboratory
Department of Chemistry
Lcnslield Road
Cambridge CB2 I EW
United Kingdom
G. Horowitz
l.<tboratoire des Matcriaux Moleculaires
CNRS, ER 241
2 rue Henry-Dunant
F-94320 Thiais
C. Kallingcr
Lchrstuhl rur Photonik
und Optoclcktronik
Sektion Physik und Center
for NanoScience
AmalienstraBe 54
D-80799 Munchen
J. Knoester
Institute for Theoretical Physics
and Materials Science Centre
University of Groningen
Nijenborgh 4
NL-9747 AG Groningen
The Netherlands
P.A. Lane
Department of Physics
and Astronomy
University of Sheffield
Sheffield S3 7RH
United King<.lom
G. Lanz.u1i
lstituto Nazionale per Ia Fisica
Dipartimemu <.li Fisica
Politccnico di Milano
Piau.a Leonardo d<t Vinci, 32
L-20 133 Mi lano
G. Leising
lnstitut fi.ir Festktirpcrphysik
Technische UniversiUit Graz
Petergusse 16
A-go 10 Gr.1z
U. Lcmmer
Lehrstuhl fUr Photonik
und Optoelcktronik
Sektion Physik

Amalienstr.1Be 54
0 -80799 Munchen
M. Uigdlund
Labomtol'y M;.mager
Brcdg<ttan 34
S-602 2 1 NoJTkoping
Ust of Comributors
G. G. Mal Iiams
Department of Matenals
and Engineering
Cornell University
332T Bard H;tll
NY 14853- 1501
M. Mostovoy
Institute for Theoretical Physics
an<.l Materials Science Centre
University of Groningen
Nijenborgh 4
NL-9747 AG Groningen
The Nethcrlunds
M. Muccini
lstituto di Spcnroscopi;t Molccol;uc
Consiglio Nazionale delle Ricen:he
Viu P. Gobeui, I 0 I
1-40 129 Bologna
K. Mullen
fur Polyme1forschung
Ackl!nnannweg I 0
D-55128 Mainz

M. M. Murray
Eli Lilly S. A.
Kinsule, Co. Cork
M. Nisoli
C.E.Q.S. E.-C.N.R.
Politccnico di Milano
Piazza Leon;.trdo da Vinci, 32
1-20133 Mi lano
XX:ll List of Contributors
W. R. Salaneck
Department of Physics. IFM
Linkoping University
S-581 83 Linkoping
N. S. Sariciftci
Christian Doppler Laboratory
for Plastic Solar Cells
Physical Chemistry
Johannes Kepler University Linz
Altenbergerstra8e 69
A-4040 Linz
U. Scherf
fur Polymerfon;chung
Ackermannweg 10
D-55128 Mainz
J.C. Scott
IBM Research Division
Almaden Research Center
650 Harry Road
San Jose
CA 95120-6099
Z. Shuai
Service de Chimie
des Materiaux Nouveaux
Centre de Recherche en Electroniquc
et Photonique Molcculaires
Universite de Mons-Hainaut
Place du Pare, 20
B-7000 Mons
D.L. Smith
Electronics Research Group
Los Alamos National Laboratory
Mail Stop 0429
Los Alamos
NM 87545
S. Stagira
Istituto Nazionale per Ia Fisica
della Materia
Dipartimento di Fisica
Politecnico di Milano
Piazza Leonardo da Vinci, 32
I-20133 Milano
C. Taliani
Istituto di Speuroscopia Molecolare
Consiglio Nazionale delle Ricerche
Via P. Gobetti. 101
1-40 129 Bologna
S. Ta.,ch
Instttut fur Fcstkorpcrphy:-.ik
Tcchnisdu; Univcrsitat Gr.tz
Petcrga:-.se 16
A-8010 Graz
P. F. van Huuen
Department of Polymer Chemistry
and Materials Science Centre
University of Groningen
Nijenborgh 4
NL-9747 AG Groningen
The Netherland-;
Z. V. Vardeny
Department or Physics
University of Utah
Salt Lake -City
UT 84112
List of Abbreviations
dielectric constant
Atomic Force Microscopy
acousto-optic modulator
amplified spontaneous emission
bis-( 4' -diphcnylaminostyryl)-2,5-dimethox ybenzene
poly(2,5-bis(2'-ethylhexyloxy)-para-phenylene vinylene)
poly(2-butyl-5-(2' -ethylhexyl)-1 .4-phenylene vinylenc)
conduction band
coupled electronic oscillator
conducting polymer
charge photogenemtion
charge-transfer excitons
Continuous Wave
distributed Bragg reflector
distributed feedback
dihexyl-substituted 6T
poly(2.5-diheptyl-para-phenylene vinylene)
doping-induced absorption
poly(2,5-dioctyloxy-para-phenylene vinylene)
distribution of states
density of valence states
poly( I ,4-phenylene-1 ,2-diphenoxyphenylvinylene)
DiiTercntial scanning calorimeuy
diflercntial transmission
cxtcmal color conversion
electron ditrraction
energy distribution curve
Electron Spectroscopy for Chemical Application
electron spin resonance
licld-cffect transistor
XXIV List of Abbreviations
Fluctuating Gap Model
fluorine-doped tin dioxide
full width at half maximum
geminate pair
Gel Permeation Chromatography
highest occupied molecular orbital
high vacuum
internal color conversion
insulated gate FET
Intermediate Neglect of Differential Overlap
incident photon to converted electron
infrared active vibrational modes
intersystem crossing
indium-tin oxide
liquid crystal display
light-emitting electrochemical cell
light-emitting diode
Light-Induced Electron Spin Resonance
laddered poly(para-phenylene)
lowest unoccupied molecular orbital
molecular beam epitaxy
2 -methox y-5-(2' -ethyl hex y loxy )-1 ,4-bis( 4-styry lstyry I )benzene
Poly(2-methoxy-5-(2' -ethylhexyloxy)-1 ,4-phenylene vinylene
methyl-substituted poly(para-phenylene)-type ladder polymer
a metaVinsulator/metal
micromolding in capillary
metal-insulator-semiconductor FET
methyl-substituted poly(pam-phenylene)-type ladder polymer
Modified Neglect of Diatomic Overlap
silicon metal-oxide-semiconductor FET
multiple trapping and thermal release
naphthalene tetracarboxylic dianhydride
optically detected magnetic resonance
organic field-effect tmnsistor
oriented gas model
organic light-emitting diodes
optical multichannel analyzer
organic molecular beam deposition
oligo(phenylcnc vinylene)
photoinduced absorption
PA-Jetected magnetic resonance
polyaromatic hydrocarbon
Lisr of Abbni(llious XXV
2-(4-biphenyl)-5-( 4-tert-butylphenyl)-1 ,3,4-oxadiaz.ole
personal digital assistant
perylene tetracarboxylic dianhydride
poly(3-( 4' -(I " ,4", 7" -trioxaoctyl)-phenyl)thiophene)
photoelectron spectroscopy
photoinduced absorption
photoluminescence quantum yield
PL-detected magnetic resonance
photomodulation spectroscopy
copolymer containing phenylene, vinylene and non-conju-
gated ethylidene units
poly(phenylphcnylene vinylcne)
poly(pam-phenylenc vi nylene)
power spectral density
root mean S(JU<Ife
single configuration interaction
space charge limited current
stimulated emission
sc;mning tunneling microscopy
tri -para-a11isylaminc
XXVl List of Abbreviations

transverse electric modes
transmission electron microscopy
thin-film transistor
transverse magnetic modes
time of flight
two-photon absorption
ultra-high vacuum
Ultraviolet Photoelectron Spectroscopy (UPS)
valence band
Valence Effective Hamiltonian
X-ray photoelectron spectroscopy
X-Ray Diffraction
1 Poly(arylene vinylene)s - Synthesis
and Applications in Semiconductor Devices
Michael M. Murray and Andrew B. Holmes
1.1 Introduction
Polymers have traditionally been considered as insulating materials by
and physicists alike. Indeed a conventional application of polymers is the safe iso-
lation of metallic conductors. The serendipitous discovery of highly conducting
polyacetylene, however, marked the birth of a new tidd Ll ]. The study of
new class of comtx>Unds is often termed .. molecular electronics" and the area
proven to be highly interdisciplinary in nature. Chemists, physicists and theorist'
alike arc continually exploring new materials and devising novel technologies.
Early studies focused on improving the conductivity of organic poly1ners upon
doping, but it has been generally accepted that most real devices are likely to ex-
ploit the intrinsic semiconductive prope11ies of these materials.
Poly(arylene vinylene)s form an important class of conducting polymers. Two
representative examples of this class of materials will be discussed in some detail
here. There are poly( I ,4-phenylene vinylene) (PPY) I, poly(l ,4-thienylene viny-
lene) (PTV) 2 and their derivatives. The polymers are conceptually PTV
may be considered <IS a heterocyclic analog of PPV, but has a considerably lowe1
band gap and exhibits higher conductivities in both its doped and undoped states.
The semiconducting properties of PPV have been shown to be useful in the
manufacture of clcctroluminesccnt devices, whereas the potential utility of PTV
has yet to be fully exploited. This account will provide a review of synthetic
approaches to arylcne vinylene derivatives and will give details an how the struc-
ture of the mate1ials relate to their performance in real devices.


1 2
Scheme 1-1. Structures of PPV and PTV.
2 1 Poly(arylt!lle vinyle11e)s - Symhesis alld Applicutio11s u1 Semiconductor Devices
Poly(1,4-phenylene vinylene) and its Derivatives
Eectrolumi nescence was first demonstrated for conjugated polymers (e.g. PPV 1) at
Cambridge in 1990 12]. PPV is the cheapest and simplest poly(arylene vinylene),
comprising of alternating benzene and vinylene units. The material is highly fluores-
cent and is bright yellow in color. Its emission maxima are in the yellow-green re-
gion of the visible spectrum and two distinct emission peaks are readily idemified: at
551 nm (2.25 eV) and at 520 nm (2.4 eV). The synthesis of PPV was first described
in the 1960s but the final material obtained was insoluble, infusible, and difficult to
process. The high crystallinity of conjugated polymers is believed to arise from
strong interchain n- n stacking interactions. Solution processing is a highly desir-
able chamctcristic as it allows the matclial to be coated cheaply and incorporated
into EL devices; PPV fonns excellent transparent films when cast from solution
or upon spincoming. Synthetic routes have been developed to allow thcmtal conver-
sion to PPV from a variety of soluble precursors. Wessling and Zi mmennan intro-
duced (3, 4] the sulfonium precursor route to PPV. '01e route has subscyucntly been
adopted and modified by other research groups 15-7]. It has also been used to good
effect in the synthesis of several de1ivati vcs of PPV.
The chemistry behind the synthesis of parent PPV is relati vely straightforward
and is outli ned in Scheme l -2. A sultide such as tetrahydrothiophcne is reacted

Scheme 1-2. Synthesis of PPV 1: a) tetrahydrothiophene. MeOH, 65"C; b) NaOH, MeOHI
H20 or Bu4NOH, MeOH, O"C; c) neutralization (HCI); d) dialysis (water); e) MeOH, soc;
f) 220"C, HCI(g)/Ar, 22 h; g) 220- 300"C, vacuum, 12 h.
1.2 Poly( 1,4-pheuyleue viuyle11e) tmd its Derivatives 3
wi th a,a'-dichloro-p-xylene 3 to yield a bis-sulfonium salt 4. Dimethyl sulfide has
also been used but dimethylsulfoniurn groups were found to under<.;o deleterious
side-reactions in subsequent steps 15). Dissolving the monomer 4 in methanol and
treatment with a4ueous sodi um hydroxide at 0-5 C results in polymerization 1ia
the quinomethide intermediate 5. Considerable research ellort has determined that
the optimal results arc achieved if slightly less than one equivalent of base per
mole of monomer is used. Excess base promotes d iminution to highl y colored
conjugated material, whereas insufficient base lowers polymer yield. The reaction
is best condud ed under inert atmosphere and is temtinated by the adpition of di-
lute hydrochloric acid. Low mok-cul;.u weight impurities and salts are removed by
dialysis to afford almost colorless solutions of precursor polymer 6. The molecu-
lar weight of the precursor polymer may not be easi ly detennincd by gel-permea-
tion chromatography (GPC) because it is insoluble in conventional GPC solvcms
such as chl urofom1, TI IF, and toluene. llte material may, however, be rcll uxcd in
methanol. where upon the sulfonium group is replaced by a methoxy substituent.
The resultant neutral polymer 7 is soluble in common organic solvents its
number-average molar mass M, has been determined to be at least 100000 g/mol.
The mechanism of this polymerization has been extensively investigated. lltc
high molecular weights and rapid rate of polymerization poim to a radical mecha
ni sm 1ia a yuinomethide intermediate. It has been shown that radical trappi ng
agents such as molecular oxygen lower the polymer's molecular weight 14.
Further studies by VanderL.ande lend support to this hypothesis [9], and reccm
work appc;m to have ruled out anionic propagation.
Thin lilms of the polymer precursor 6 Jmay be convea1cd into fully conjugated
PPV 1 by heati ng within the temperature range 180-300"C for 12 hours un<.lea
vacuum (2, 6). lltcse conditions favor the removal of the reaction's by-products
tetrahydrothiophene and hydrogen chloride. There are reports that the presence ol
oxygen during the conversion has a deleterious effect on the luminescence quan
tum efticiency of the final tilm. It is believed that oxygen promotes the fonn;Jtior
of carbonyl groups which quench luminescence [ 10-12]. The conversion tempera
ture may be reduced to l OOoC by using the bromide rather than the chloride sah
of precursor polymer 6, allowing the preparation of LEOs on flexible polymer foi
substrates (e.g., ITO-coated PET). Langmui r-Blodgett techniques have also bcea
used to deposit PPV I 13]. It has recently been demonstrated that well-aligned thia
fi lms and fibers of PPV may be formed by pre-ordering the precursor polymer (
in a lyotropic liquid crystall ine phase before thennal conversion. Such a nanocom
posite has potential appl ications for polarized emission [1 4].
There have been a number of other routes to PPV reported in the literature, bu
the resulting device li feti mes and v:uy considerably. The Wessling routl
has been modi fied by employing a sullinyl group instead of a sulfonium grout
I I 5-17 ]. The pol ymerization is believed to proceed by the same quinomethidc in
termediatc and affords PPV upon thermal conversion. lltc route is complemental'\
to the Wessling method as the polymer is soluble in organic
Galvin et a/. I 18 I reported that a xanthate precursor route aflords higher devict
etliciencics than the standard route. PPV may also be synthesized by chcmic;a
vapl>r deposition of dihalogcnatcd p-xylcnes 3 and 9 1 191 or of the chlorimltCl
4 1 Poly(arylene vinylene)s- Synthesis and Applications in Semic01uluctor Devices

X=CI, Br
Ph#CH2 _"
c1e c,e

Scheme 1-3. Alternative synthetic routes to PPV 1: a) 500-700C, 0.01 rnbar; b) 580"C,
10 Pa; c) 800-000''C, O.Q1 rnbar. then 60"C, 0.1 rnbar: d) 200c. vacuum; e) CH
CN, 5.5 v.
cyclophane 8 [20]. In each case the intermediate a-halo precursor polymer 10 is
thermally converted to PPV at 200C under vacuum (Scheme 1-3). These meth-
ods yield PPV with low (0.002%) device efficiencies [ 19, 21 j.
A xylylene-bis-phosphonium salt 11 gave films of PPV 1 upon clectropolymer-
ization. The absorption and emission spectra of the resultant material were blue-
shifted with respect to PPV produced by other routes, suggesting that the electro-
polymerized material has a shorter effective conjugation length, possibly because
of incomplete elimination of phosphonium groups [22).
A potential drawback of all the routes discussed thus far is that there is linle
control over polydispersity and molecular weight of the resultant polymer. Ring-
opening metathesis polymerization (ROMP) is a living polymerization method
and, in theory, affords materials with low polydispersities and predictable molecu-
lar weights. This methodology has been applied to the synthesis of polyacetylene
by Feast [23), and has recently been exploited in the synthesis of PPV. Bicyclic
monomer 12 [24] and cyclophane 13 [25) afford well-defined precursor polymers
which may be converted into PPV 1 by thermal elimination as described in
Scheme 1-4.
1.2.1 The Basic Polymer LED Device Architecture
The simplest polymer-based EL device consists of a single layer of semiconduct-
ing fluorescent polymer, e.g., PPV, sandwiched between two electrodes, one of .
which has to be u-ansparent (Fig. 1- 1). When a voltage or bias is applied to the
material, charged carriers (electrons and holes) arc injected into the emissive layer
and these ca1Tiers arc mobile under the influence of the high (> 10
V cm-
) dec-

1.2 Poly( 1,4-phenylelle vi11yle11e) aiiCI its Derivatives 5
n n
Scheme 1-4. ROMP routes to PPV 1: a) [Mo(=NAr)(:::CHCMe
}; b) Bu
c) HCI(g). 190c: d) 108"C; e) 280 C.
t polymer film

Figure 1-1. S.:hema1ic of " single-layer clet:lroluminescenl device. An applied eleclric lidtl
lcac.ls lo injec1ion of hole' (posilivc charges; I he majuniy carriers in polymers su.:h as Pl'V)
anc.l ci<."Clrun' (usually lhc minuri1y dlilfgC carriers ) into lhc lighl-cmiuing !Xllymcr film from 1hc 1wo
elcclroc.lc conlacls. Fmmalinn nf an ck'ClrOal hlliC pair wilhin 1he polymer m:ty then resul! in 1hc emi,-
sion ur a pholnn. Siu.:c huk:s much murc easily 1hmugh PPV !han clcclmn-huk
rccumbimniun lakes in !he vicinily of lhc <.:alhuc.le.
tric field. Some of these carriers may recombine within the emissive layer yield-
ing excited electron-hole pairs, termed excitons. TI1ese excitons may be produced
in either the singlet or uiplet states and may radiatively decay to the ground state
by phosphorescence (PL) or fluorescence (FL) pathways (Fig. 1-2). An important
figure of merit for electroluminescent materials is the number of photons emitted
per electron injected and this is termed the internal quantum etliciency. It is clear.
therefore, that the statistical maximum internal efficiency for an EL device is 25%
as only quarter of the excitons <Ire prodm.:ed in the singlet state. In pmcticc.
this maximum value is diminished funher because not all of the light generated i!>.
I Poly(arylene vinylene)s - Synthesis ami Apfllicaticms in Scmiccmduuor Dt!vicc.1
LUMO C=:J c=:=:J
hY , hY'
- --!..
- -+-
excited slate
exoted state
Figure 1-2. a) Irr.H.Iiatiun of a nuun:M:cnt polymer an ckctruu frum IIOMO In LUMO. In a
typical conjug:aloo pt>lymcr, two new energy an: geueratcJ upon rclaxatllm wllhiu the original
HOMO-LUMO enc11;y gap anc.l arc each lillcJ with om: cle.:trun ur llJlJl'l'itc (singlet cx.:itcc.l
slate). TIIC cxcitc..-J polylllcr may 1hcn relax to the gruunc.l >IOIIe with emi"mn of light at a longer wave-
lcnglh than lhat absorbcc.l (phololumiucsccncc). b) In a (l\llymer LED. arc aujc4:tcc.l into the
LUMO (to form anions) :mJ holes into the HOMO (Ill Conn r.ac.lical cations) of the a:lcctmlumi-
nescenl p.>lymcr. lhc ch:ugcs migraJc from polymer chain to polymer ch:tin under the inllu-
of the applicc.l chxtric Iield. When a mc.lical anion ant.! a r.ac.lical cation a:ombtnc on a conju-
gated anc.l triplet excitet! slates arc formcc.l, of whicll the can emil lighl.
visible to the viewer. Some of the photons emitted are reflected by the polymer
itself and the external efficiency, therefore, is a factor of 2n
smaller than the in-
ternal efficiency, where 11 is the refractive index of the polymer (typically '' = 1.4 ).
Typical external quantum efficiencies for this class of materials is 0. 1- 2% [26).
1.2.2 Substituted Poly(phenylene vinylene)s
Conjugated polymers in general have.! a propensi ty to aggregate or s tack as a con-
sequence of their extensive n-delocalization. This is a limitation of PPV itself as it
requires thermal processing during device fabrication. LEOs fabricated from PPV
derivatives that arc soluble in the conjugatc.:d fonn were first reported by Ohnishi
et ul. at Sumimoto [27] and by Hceger and Bmun at Santa Barbam [28, 29]. The
solubility of the materials results from the presence of long alkyl chains which af-
ford some conformational mobility to the polymer chains. As a consequence, the
materials tend to have lower glass transition temperatures than PPV itself. Further-
more, the sulfonium precursor polymer 6 is soluble in methanolic solvenL-;,
whereas almost all soluble PPV derivatives are in solvl!nts that do not
cause swell ing of PPV or its sulfunium precursor 6. Multilayer or sandwich type
1.2 Poly( / ,4-plrenylene vinylene) ancl its Derivatives 7
structures comprising of different polymers (e.g. PPV and substituted PPV) may
be fabricated, and these exploit this difference in solubilities [30, 31 ].
Poly[2,5-diatkoxy- 1,4-phenylene) vinylene}s with long solubilizing alkoxy
chains dissolve in conventional organic solvents such as chloroform, toluene, or
tctmhydrofuran l27, 28, 32-36]. Their emission .and absorption spectm are red-
shifted relative to PPV itself, and the polymers' fluorescence and electrolumines-
cence quantum yields are greater than parent PPV. This benefit may be a conse-
quence of the long alkyl l:hains isolating the polymer chains from each other.
The sulfonium precursor route may also be applied to alkoxy-substituted PPVs,
but a dehydrohalogenation--condensation polymerization route, pioneered by
Gilch, h; favored 137}. The polymerization again proceeds via a quinomethide in-
tcnncdiatt:, but the synthesis of the conjugated polymer requires only two steps
and proceeds often in improved yields. Till! synthesis of the much-studied polyl2-
methoxy-5-(2-ethylhexyloxy)- 1,4-phenylene vinylenej, MEH-PPV IS is outlined
in Scheme 1-5 133. 35). The.! solubility of MEH-PPV is believed to be enhanCI!d
by the branch!.!d nature of its side-chain.

MeO n
Scheme 15. Preparation of MEH-PPV 15: a) 2-ethylhexyt bromide, KOH, EtOH, reflux, 16 h;
b) HCHO, cone. HCI, dioxane. 20' C, 18 h, reflux, 4 h; c) KOtBu, THF, 20"C, 24 h.
4-Methoxyphenol is alkylated and then chloromethylated to yield the bis-chlor-
omethyl derivative 14 [28, 32- 351. Polymerization and elimination to fully conju-
gated matl!rial is promoted by the addition of a 1 0-fold excess of a base such a.-;
potassium terr-butoxide in tctrahydrofuran. The concentration of base and mono-
mer must be carefully controlled to prevent cross-linking and gelation. TI1e resul-
tant MEH-PPV is bright red-orange.! in color. A single layer elcctroluminescence
device (ITO/MEH-PPV/Ca) achieves illl eiTiciency of 1.0% [28, 38, 39]. The
etliciency may be improved four-fold by the incorpomtion of a thin
hole-blocking layer of poly(mcthyl methacrylate) deposited by Langmuir-Blodgcu
techniques and by using aluminum as a cathode.
Other poly(2,5-dialkoxy- l ,4-phenylcne vinylenc)s have been prepared in a sim-
ilar fashion [34, 35, 40, 41 ). Ahl!mativcly, a soluble a-halo precursor polymer 17
may be obtained by using less than one.! equivalent of base (Scheme 1-6). This
may then be conve11ed into fully conjugated material 16 by them1al trcatml!nt.
This halo-precursor route may be preferred if the fully conjugated mate1ial has
limited solubility ur if incomplete conversion is desired.
8 1 Poly(arylene vinylene)s - Synthesis and Applications in Semiconductor Devices

R = Ct;H1s. CeHe
X= OR, Br, Cl, F3
1 b


X n X n
Scheme 1-6. The Halo-precursor route to substituted PPVs: a) NBS, CC!.t. hv; b) KOtBu,
THF; c) 160-220"C, vacuum, 4 h.
(Cti:!lnH n
Scheme 1-7. Preparation of DP-PPV derivative 23: a) H-cs C-{CH2)n-H; b) UAIH4;
; d) KOtBu, 2.2.
1.2 Poly( /,4-phenylene vinyle11e) UIU[ its Derivatives 9
Control of gelation and polydispcn;ity has recently been improved by the use
of a benzylic halide 22 as a terminator (Scheme 1-7) [42]. The halide serves as a
non-polymerizable acidic additi ve, and high molecular weight PPV derivatives 23
with relatively small polydispersities can be attained. A hexyl-substituted deri va-
tive 23a, DP6-PPV, shows a remarkably high photoluminescence quant um effi-
ciency of 65% in the solid state. Its emission maximum (490 nm) is in the blue-
green region of the spectrum. The synthetic route is versatile and utilises the
Diets-Alder reaction as a novel way of appending alkyl groups onto the benzene
The effects of the length and degree of bnmching of the alkoxy side chain on
EL etliciency have been examined by a number of research groups (Scheme 1-8)
[27]. Efficiencies pass through a maximum with increasing size of side chain be-
fore falling off tor very large substituents such as cholestanoxy, e.g. 26 [40, 43).
Il may be envisaged that such lar<Je substituents diminish the semiconducti ng
nature of the material by deleterious twisti ng of the polyrne backbone, and also
by increasing the insulating chamcter of the film. The introduction of a sterically
demanding silyl group as in DMOS-PPV 25 widens the HOMO-LUMO gap and
green light is emi ucd 144-47 ). External EL efficiencies of 2.1% have been
reported by Philips usi ng a dialkoxy-substitutcd PPV derivative 24 148] and an
Scheme 1-8. Examples of soluble, dialkoxy-substituted PPV derivatives.
10 1 Poly(arylene vinylene)s - Symhesi.1. w1d Applications ill Semiconductor Dcvias
Qrdered dialkoxy PPY derivative has been prepared by Yoshino e1 u/. r49l.
vinylene) 27a fonns a nematic liquid-crystal-
line phase upon 1nelting. TI1e material retains its order upon cooling to room tem-
perature, and its band gap (2.08 eY) is measurably smaller than in an unoriented
sample. Oriented clectroluminescence may be achieved by rubbing a thin film of
the material to induce molecular orientation [50]. Poly(anthrylene vinylene)s
The scope of Wessling route has been extended by Mullen and co-workers to de-
velop a soluble precursor route to poly(anthrylene vinylene)s (PAYs) [51). It was
anticipated that the energy differences between the quinoid and aromatic reso-
nance structures would be diminished in PAY relative to PPY itself. An optical
band gap of 2. 12 eY was detem1incd for 1,4-PAY 29, some 0.3 eY lower than the
value observed in PPY. Interestingly, the 9, I 0-bis-sulfonium salt does not poly-
merize, possibly due to steric cftccts (Scheme 1-9).

l<=5 Jn l<=5 Jn
Scheme 1-9. Synthesis of PAV 23: a) Et.NOH, CH
0; b) 290 .. C.
1.2.3 Step-Growth Routes to PPV Derivatives
Substituted soluble PPY derivatives may also be synthesized by step-growth poly-
merization methods. Arylene-bis-phosphylidenes may be condensed with ter-
ephthaldehydes in a Willig fashion to yield alternating PPY copolymers [52). An
aJkoxy-substituted PPY derivative 28 (Scheme 1-8) prepared in this fashion emits
in the orange (..(""'" = 585 nm) region of the spectrum [52).
Palladium-mediated catalysis has only been exploited relatively recently in the
synthesis of substituted PPY derivatives. The use of aryl dibromides as monomers
is particularly useful as it allows the synthesis of PPYs substituted with alkyl
mther than alkoxy sidcchains. The Suzuki )53, 54], Heck (55], and Stille )56) re-
actions have been used in the synthesis of new PPY derivatives, but auaining
high molecular weight PPY derivatives by these methodologies has proved
problematic. A phenyl-substituted PPY material PPPY 31 was synthesized by a
Suzuki coupling (Scheme 1- 1 0) of dibromoethenc and bis-boronic acid 30. Its ab-
sorption U'max=385 nm) and emission (}.
.. "=475 mn) maxima were strongly
1.2 Poly( 1.-1-p/umylene inylcne) and its Deri1utiel' II

Scheme 1-10. Synthests of PPV 25 by Suzuki coupfing; a)

60' C.
blue-shifted relative to PPY itself. The molecular weights of this material were
moderate: M,=3900 and Mw= 11930.
1.2.4 PPV Copolymers
PPY and its alkoxy derivatives arc p-typc conductors and, as a conset(UCnce. hole
injection is more fac.:ilc than electron injection in these materials. Efficient injec-
tion of both types of charge is a prerequisite for efficient LED oper.1tion. One
approach to lowering the banier for electron injection is the usc of a low wor"-
functi on metal such as calcium. Encapsulation is necessary in this instance, how-
ever, as calcium is degraded by oxygen and moisture. An alternative approach is
to match the LUMO of the polymer to the work function of the cathode. The usc
of copolymers may serve to redress this issue.
it has been found that statistical copolymers often exhibit improved EL proper-
tics relative to their homopolymer analogs. This was demonstrated initially in a
copolymer or PPY and poly((2,5-dimethoxy- 1,4-phenylcnc)vinylencJ [57). A vari -
ety of copolymers with interrupted conjugation have subsequently been investi-
gated by the Cambridge group )58, 591 and elsewhere r60. 61 1.
The of such copolymers is relatively straightforward. A mixture of
monomers 4 and 32 is polymerized in a water-methanol mixture using sodium hy-
droxide as base (Scheme 1- 11 ). The ratio of the units in the resulting copolymer
may be manipulated by changi ng the feed ratios of monomers 4 and 32. The sul-
fonium groups arc replaced by methoxy substituents, and this substitution occurs
faster at benzylic carbons adj acent to activating alkoxy groups. As a consequence,
the resulting copolymer 33 consists of many sulfonium groups adjacent to pheny-
lene units and mostly methoxy substituents next to dimethoxyphenylene units.
Sulfonium groups may be readily removed with heat treatment of polymer thin
films, whereas methoxy groups are only pat1ially eliminated under these condi-
tions. A polymer with interrupted conjugation 34 may be readily produced. Com-
plete removal of mcthoxy substituents is achieved using thermolysis under acidk
conditions to yield the fully conjugated material 35.
The composition of the copolymer determines its clcctroluminesccnce effi-
ciency. Optimal efficiency (0.3%) was achieved in system 34 when the ICed ratio
of monomer 4 to monomer 34 was 9 : I. This rcprc.-;cnts a 30-fold improvement in
luminescence elliciency relative to PPV in the same device conligumtiou
0_Jpolymcr/AI) 158. 6:!). Copolymer 33 has found uses as waveguide.'> and
12 1 Poly(wylt!l1e vinylene)s - Synthesis and Applications in Semiconductor Devices

MeO n
Scheme 1-11. Synthesis of partially conjugated PPV copolymers: a) MeOH;
b) MeOH, 50C; c) 300C, vacuum, 12 h; d) 220C, HCI(g)/Ar, 22 h.
lithographically patterned copolymers [58, 59). High EL efficiencies have also
been demonstrated in alkoxy- and alkyl-substituted poly(phenylene vinylene)s
with interrupted conjugation. These systems may also be synthesized by the base-
induced dehydrohalogenation method [61 ].
The efficiency of PPV may also be mised by introducing disorder into the
polymer chains. The crystallinity of PPV may be lowered by employing a modi -
tied Wessling method utilizing a xanthate leaving group 163]. PPV produced by
this method is believed to contain a mixture of cis- and trans-alkene units. The
efficiency of the material is 0.22% when employed in a single layer device with
1.3 Refining the Properties of PPV - Multilayer Devitc:s

Roo R
R = H. C
, p-CJ-14F
1-12. Synthesis of PPV derivatives incorporating triarylamines: a) KOtBu, toluene.
aluminum calhodc.:s; this may be.: improved to 2% when a doublc.:-layer device em-
ploying an electron-transporting layc.:r is employeq (see Section 1-3).
Triarylamines have been employed in arylenc.: vinylene AB copolymers 38 by
Horhold et a/. using a Horner polycondensation route of aldehydes and ketones
36 with /Jis-phosphonate 37 (Scheme 1-12) 164 ]. Phenylamines have remarkably
low redox potentials and their charge tr.msport properties have been investigated
extensively 165). EL devices comprising triarylamines have demonstrated low
driving voltages.
1.3 Refining the Properties of PPV - Multilayer Devices
Any commercial applications of polymer-based LEOs require maximum bright-
ness, high power efliciency, and extended device lifetimes. The.-:;e requiremenL-;
necessitate the need for light emission at low driving voltages. The simple single
layer device architecture described thus far is limited in this respect, and notable
auempts have been made to improve the performance of PPV-based EL materials
by the creation of multilayer devices. Such refinements in device architecture may
pave the way for organic displays that can compete effectively with their inorgan-
ic counterparts in terms of cost-effectiveness.
16 1 Poly( urylene vinylene)s - Synthesis and Applications in Semiconductor Device.s
Scheme 1-14. Examples of a oxadiazole- and a quinoxaline-containing electron-transporting
A hyperbmnched polymer 42 compnsmg oxadiazole subunits has been synthe-
sized, but defect formation in such a structure appears to limit its use as a hole-
blocking material [74].
Other electron-deficient heterocyclic systems have also been as
electron-transporting materials. In particular, devices employing poly(phenyl qui-
noxaline) 43 as an ECHB layer have shown improvements in device efliciency
when used in conjunction with an emissive PPV layer [75).
1.3.2 Electron-Deficient Polymers - Luminescent Transport Layers
It would be preferable to incorporate both fluorescent and electron transport prop-
erties in the same material so as to dispense entirely with the need for elcclron-
tmnsport layers in LEOs. Raising the aflinity of the polymer facilitates the use of
metal electrodes other than calcium, thus avoiding the need to encapsulate the
cathode. It has bt:en shown computationally [76] that the presence of a cyano sub-
stituent on the aromatic ring or on the vinylenc portion of PPV lowers both the
HOMO and LUMO of the material. 1l1e barrier for electron injection in the mate-
rial is lowered considerably as a result. However, the We.-;sling route is incompati-
ble with strongly electron-withdrawing substitucnts, and an alternative synthetic
route to thi s class of matCJials must be employed. 1l1e Knocvcnagcl
1.3 Refining the Properties of PPV - Multilayer Devices
45 46
Scheme 1-15. Synlhesis ol CN-PPV 41: a) NaOAc; b) KOH, EtOH; c) pyridinium chlorochrc
mate; d) NaCN; e) KOtBu or Bu
NOH, tBuOH, ll-IF, SO"C.
177.1 utilized in the synthesis of CN-PPV 47, a dialkoxy-substituted PP\
dcnvat1ve wnh a substituent on the vinylene position. TI
e reaction in
.the of a tcrephthaldehyde 45 and a benzene- 1,4-diacetonitrilt
46 Ill the of a base such as tetrabutylammonium hydroxide o
potasstum in a solvent mixture of tetrahydrofuran and tert-butano
(Scheme l.-1.)) [78 ). Both monomers arc readily available from the dichloride 44
The may be puril}ed by precipitation. CN-PPV is a highly fluo-
rescent, bn!hant red matenal and Its band gap [590 nm (2.1 eV)) is very similar rc
other PPY derivatives. The molecular weight of the polymer is mod-
. albell lor step-growth polymerizations of this nature. The polymc
ts _soluble 111 such as chloroform, by virtue-of its long alkoxy side
chams. 1 He nature of the material is exemplified by cyclic vol-
tammetry studtes. These demonstrate that the cyano substituent reduces the onsc1
of reduction by 0.6 V relative to dialkoxy PPV (74].
In contrao;t with .L"O_njugated polymers, such as PPV, devices employing CN-
PPV 47 _as the enusstve layer can achieve respectable intemal erticiencies (ca.
wllh both and aluminum electrodes. EL elliciency may be further
unproved by cmploymg a hole-transporting layer such as PPV in COilJunction wi th
14 1 Poly(ary/eJ1e vi11ylene)s- Sy111hesis and ApplicaJions in Semiccmductur Devices
1.3.1 Multilayer Devices: The Incorporation
of Charge-Transporting Layers
To maximize light output. it would be ideal to create roughly equal amounts of
both charge carriers, i.e., electrons and holes. Most devices described thus far
have been single-layer devices where the semiconducting polymer is sandwiched
between the cathode and anode. It has already been mentioned that PPV has a
higher barrier for electron injection than for hole injection, and holes are preferen-
tially injected in a single-layer device. It is common. therefore, to use additional
layers of materials to enhance electron injection. These layers arc termed electron-
conducting/hole-blocking (ECHB) layers, and the configuration of a typical de-
vice incorpor.uing such a layer is depicted in Figure 1-3. To work efficiently, the
electron affinity of the ECHB layer must be higher than that of PPV. In such a
case charge carrier recombination takes place away from the polymer metal inter-
face, which is known to act as a quenching site. EL efficiency may thus be con-
siderably improved relati ve to single-layer devices.
The earliest ECHB materials studied were the oxadiazolcs. These are electron-
deficient materials and 2-( 4-biphcnylyl)-5-( 4-te rt-but ylphcnyl)- 1 ,3,4-oxadiazole
(PBD) 39 was the first member of this class of compounds to be used success-
fully in a sublimed film EL device [66, 671. The material is available in high pur-
ity, and may be sublimed or spin-coated as a dispersion in poly(mcthyl methacry-
late) (PMMA) (68]. It may also be blended to good effect with electroluminescent
polymers [47, 69, 70], although it is preferred to disperse PBD in an insulating
polymer such as PMMA to overcome potential problems with phase separation.
An increase in device thickness is llil inevitable consequence of this approach,
and this manifests itself as a ri se in driving voltages in an ITO/PPV/PBD-PMMA/
Ca device. This disadvantage, however, is outweighed by a ri se in EL efticiency
from 0. 1% (for an .ITO/PPV/Ca device) to 0.8% (for ITO/PPVfPBD-PMMA/Ca).
Figure l-3. In improved bilayer dcvi<.-c fur a polymer LEO an cx1r.1 ECHU layer
bc.:n inserted bclwccn the PPV thc calhudc metal. The ECIIB tllalcrial euham:o the llow of cltt-
ln.ms bu1 rcsisb mdoalion. Elcclrons and holes 1hen ac.:umula1e ncar lhe I'PV/ECHll layer imcrfaa:.
Charge rccomhina1ion and phlllun gencrutinn lX:cur.. in 1hc PPV layer and ;away fnnn the culhude.
1.3 Reju1ing the Properties of PPV - Multilayer Devices 15
Scheme 1-13. Examples of oxadiazole-<:ontaining electron-transporting materials.
Electron-hopping is the main charge-transport mechanism in ECHB materials.
There is precedence in the photoconductivity licld for improved charge tr.msporl
by incorporating a number of redox sites into Lhe same molecule. A number of at-
tempts to adapt this approach for ECHB materials have been documented. Many
usc the oxadiazole core as the electron-transport moiety and examples include
mdialenc 40 and dendrimer 41. However, these newer systems do not offer signif-
icant improvements in electron injllction over the parent PBD.
An alternative approach utili l.Cs polymeric analogs of PBD. The oxadiazoh:
unit may be in the polymer main chain or attached as a side chain. A reasonable
device perfonnance has been demonstrated in poly(aromatic oxadiamle)s [71- 741.
18 1 Pvly(uryle11e - am/ in Seminmcluctor Dnic't'.\'
51 50
Scheme 1-16. Color range available for CN-PPV derivaiJves.
the highly electron-deficient CN-PPV. The insolubility of PPV may be readily
exploited in this context: CN-PPV may be spin-coated onto a layer of PPV and a
two-layer device (ITO/PPV/CN-PPV/cathode metal) functions with very high
(4%) internal efficiencies [79, 80). Unlike other two-layer devices discussed pre-
viously, emission in PPV/CN-PPV two-layer devices appears to occur exclusively
from the CN-PPV layer. It may be postulated that CN-PPV behaves a-. a sink lor
excitons and charge carriers; emission from the PPV layer is an unfavoured conse-
The Knoevenagel condensation route to CN-PPV may be easily tailored and
several derivatives of u-cyano PPV have now been synthesized (Scheme 1- 16)
(61, 81]. Many of these also show high EL efficiencies when used in a double-
layer device configuration with PPV [82, 831. A representative example is MEH-
CN-PPV 48, which exhibits very high EL device efficiencies in the red/omnge re-
gion of the spectrum. A double layer device ITO/PPV/48/Al produces red-omnge
(600 nm) light with a luminous efficiency of 2.5 hn w- [61, 81 ]. The emission
color may be altered by modifying the substituents on the polymer backlxme.
Bulky substituents such as the isopropyl group of 49 cause a twisting of the poly-
mer backbone, inducing a blue shift in its emission spectrum (peak wavelength at
5 I 0 nm). An alternati ve method of reducing the effecti ve conjugation length in
these systems is the incorporation of meta linkages. Polymer 49 emits in the blue
region of the spectrum. Substitut ion of one benzene ring with a thiophene as in
50 reduces the band gap of the polymer to 1.75 cV (740 nm). Emission in the in-
fr..l red was first demonstrated in an ITO/PPV/50/AI LED [84]. The emission max-
imum may be red-shifted further by the replacement of the second benzene ring
with a thiophene. Polyll'lcr 51 has a band-gap of 1.56 eV (800 mn) (X I, 851.
1.3 R(/iuing tftt l'mpt'rtit., of PPV - Multi/ay<r J\) Other Elcctron-Dclicicnt I,PV Oc&iv<ativcs
Attachment of dectron-withdr..1wing groups directly onto the aromatic ri ng repre-
sents an alternative approach to polymers with a high electron affinity. 1l1e Wess-
ling procedure may be exploited to yield polymers 52 and 53 with alkoxy and
halide substituent-; on the ring (861. The group at Cambridge has synthesized
hokblocki ng derivatives such as 53, synthcsiwd by a bromo-precursor route 1871.
or 54, derived from a Homer polycondcnsation (88). The halogen-substituted
PPVs 52 and 53 emit light in the red region of the spectrum (emission maxima
620-630 nm) (86), whereas the trifluororncthyl derivative 54 was fol)nd to emit
yellow light (540-570 nm). However, the PL and EL quantum eHiciencies were
poor in these materials. A double-layer device employing PPV ac; a hole-i njecting
layer and AI a-; a cathode achieved an internal EL efficiency of only 0.0 I% [87.
89].1! is likely, therefore, that these materials will be more useful as ECHB layers
than as emissive layers.
Scheme 1-17. High-electron-affinity PPV derivatives with electron-withdrawing groups on the
aromatic ring. Electron-Delicicnt Aromatic Systems
Pyridine is considered by organic chemists to be an electron-poor aromatic system
and pyridine analogs of PPV such ao; 55 represent an alternative approach to r.1ising
the electron affinity of conjugated systems (Scheme 1-18). The material may be
synthesized by a palladium-mediated Stille coupling of I ,2-bis-(uibutylstannyl)-
ethylcne and 2;5-dibromopyridine 190(. The polymer is yielded as an orange pow-
der and is soluble in m-crcsol. It emits in the red region of the visible spectmm
(590 nm). 1l1e materi al may be alkylatcd or protonatcd at nitrogen to yield soluble
polymers 56 and 57 respectively. N-alkylation induces a blue shift in emission to
540 mn. When a butyl group is appended to the 5-posilion of 2,5-dibromopyri-
dine, the rcsultana p()l ymer poly(J-u-hutyl-J' pyridylvinylenc) 58 is soluble in con-
ventional organic solvents [91, 921. Its emission spectrum i:; red-shifted consider-
ably to 630 nm and a device wit h the configuration r rO/Bu-PPyV/AI has an exter-
nal quantum clllcicncy of 0.02% 1921.
Polymer 55 exists as three different regioisomers: head-to-head, hcad-to-hc<td.
and random. The various isomers have been synthesized, and it has been found
they have dilkrcnt absorption. PL. and EL spectra (931. The efl"cctivc conjugation
20 1 Poly(aryleue viuylene)s - Synthesis and Applicmions in Semiconductor Devices
57 58
Scheme 1-18. Pyridine-based analogs of PPV.
Cl...._ _ f N\ __

Q.. ;=N,

cr S+

!J n
62 55 61
l d
!J n
Scheme 1-19. Wessling route to PPyV 49: a) NCS, CC4; b) tetrahydrothiophene, MeOH,
sooc; c) aq. NaOH, MeOH; d) heat; e) 0.98 eq. KOtBu, THF; f) heat, MeOH.
length of the head-to-head isomer is found to be the longest. Its emission spec-
trum is maximal at 605 nm, whereas the head-to-tail and random isomers emit at
584 nm and 575 nm, respect ively 194].
Poly(pyridine vinylene) 55 may also be prepared by the Wessling route
(Scheme 1-19) (95]. Fully conjugated material may be obtained by thennal elimi-
nation of the sulfonium salt 61 or the halide 62. The method, however, does not
I .-J Full Color Displ<1ys - Tile Searclt for JJ/ue millers 2 1
yield a material of pa1ticularly high molecular weight (ca. 2900) as is evident i1
MALDI mass spectroscopy. The HOMO-LU MO band gap of the material is esti
mated to be 2.2 eV, whereas it emits in the orange-red region of the spectrum a
2. 1 eY. The solid state PL quantum efficiency (2%) is considerably lower thau oh
served in PPV (27%).
1.4 Full Color Displays - The Search for Blue Emitters
A multi-color display requires the three primary colors - red, green, and blue -
and these colors need to fall within the parameters delined by the CIE
L96]. Blue EL hal> been the slowest in development, both in traditional inorganil
materials as well a-; in polymers. There are a number of different approaches to
suitable polymeric analog. It has al ready been discussed in Section 1-2 how th1
HOMO-LUMO gap of PPV may be raised by incomplete conversion to the full)
conjugated polymer. Furthermore, the band gap may be increased by
sterically demanding side groups onto the polymer main chain. The useful opto
electronic properties of phenyl-substituted PPV deri vati ves has already been dis
cussed (sec Secti on 1-2.2) 1421. The following section will enunciate a number o
other approaches to matc1ials that emit in the blue region of the spectrum.
1.4.1 Isolated Chromophores - Towards Blue Emission
An alternative pproach to tailori ng the band gap of a polymeric material
the use of polymer blends. 1l1e blend of a fluorescent dye in an inert polymc
matrix yields a polymeric EL material with useful luminescent charactetistics. h
practice, however, the fluorescent yield in such a blend is very low as a consc
quence of the low mole fraction of the luminescent species. Device
may be enhanced considerably by the use of an clectroacti ve polymer, e.g., poly-
(vinyl carbazole) 64. TI1e improvement in performance manifests itself even a1
very low concentrations of fluorescent species. Alternatively, the active chromo-
phore may be incorporated into the polymer backbone ito;elf and the light-emittinf
species can be separated by varying lengths of inert .. spacer'' units. This has beer
demonstrated in the preparation of copolymers such as 65. These are prepared h)
conducting a Willig condensation of a bis-ylidc in the presence of
amounts of saturated dialdehydes (Scheme 1-20) 197].
More precise control over the emission color may be achieved by
equimolar quantities of a his-phosphonium salt, e.g., 67 and a dialdehyde contain-
ing a flexible unit such as 66. This approach has been exploited by a number ol
researchers 19X- 1021. The emission wavelength of these materials is in the blue tc
hl ue-grcen region of the spectrum (470-495 nrn).
22 I Pol)(urylene vulyle11e)s - Symhesis and Applications i11 Semiconductor Devices
n 0- (CH2}8
MeO m
64 65
Scheme 1-20. Poly(vinyl carbazole) and an example of a polymer with an isolated chromo-
OHC-Q-0- (CH2}e -0-o-CHO
Scheme 1-21. Synthesis of a blue-emitting copolymer with isolated chtomophore by Wittig
reaction: a) base.
1.4.2 Comb Polymers with Chromophores on the Side-Chain
The luminescent moiety may also be attached to the polymer backbone as a side-
chain, yielding a comb polymer. In this instance, the main polymer chain is often
non-conjugated, and classical approaches to high molecular weight polymers may
be employed. Distyrylbenzenc has proved to be a u:scful lumophore in this con-
text. It has been attached to polymethacrylates such as 69 bCaJing electron-trans-
porting diaryloxadiazole units [74, 103, 104]. A bilayer LED employing PPV as a
hole-transporting layer and 69 as an emitting layer showed emission in the blue
region (457 nan) of the spectrum with an efficiency of 0.037%. A tail into the yel-
low-green region of tl1e spectrum was observed, and this was attributed to emis-
sion from PPV itself.

0 'I
/ .5 Chiral PPV - Pulurized Emission
Scheme 1-22. Examples of electroluminescent polymers with side-ch,;n""' ho
... "'oromop res.
The precise control of ROMP methodolo has bee .
co-workers in the 1 , gy n cxploated by Schrock and
aW functionalized with a
. l n ca caum 1s used as a .. thod .
nal dev1ce efficiency of
J% . b . cd . . . ca e, an lnter-
(475 nm). .. IS o serv and the peak emission is in the blue
l.S ChiraJ PPV - Polarized Emission
Meijer and co-workers I 106j have recently re 011 d . . I I .
nescence (CPEL) . . h . P c cncu ar Y polanzed elcctrolumi-
. usmg a c lral 7H.:CmJugatcd PPV deriva( 71 S .. ,
such a system the absorebcd and emiued lioht hav' lrtl ave . ( 1-23). In
and ri oht (R) circularly ..,.
"'. d . o . c
c.:rcnt antcnsatiCS lor left (L)
o , . > auzc.: components To unpmvc >I b T
al and racemic monomers had to be c .I. . h' S Sl u a _aty pn>pcalles, char-

Pl> ymcn;rNU. mall ch1ral aggrc . t. .
orml-'"l Ill these matcriah. as a consequence of the rc<>iospll- .. b t . ga c.:s arc
o su s llutaon paucna
I Poly(arylene vinylene)s- Sy111hesis and Applicutions in Semicunductur Devices
Scheme 1-23. Chirooptical PPV derivatives.
of the enantiomcrically pure side groups on the chain. The conjugated polymer
obtained maintains its intrinsic chirality in both solution and solid state, and circu-
larly polarized emission requires no extemal macroscopic ordering of the chromo-
phores. Funhem1orc, it was found that the cin:ular polarization in absorption,
was larger in an aggregated solution than in a solid lilm, sugges_ting orderin_g
of polymer chains in an appropriate solvent. The dissymmetnc layer
a consequence of the polymer's constitution, the solvent and the proccss.ng condi-
tions employed.
1.6 Poly(thienylene vinylene)s-
A Stable Class of Low Band-Gap Materials
Polyacetylene is considered to be the prototypical low but its
potential uses in device applications have been hampered by senstllv_ty to both
oxygen and moisture in its pristine and doped states. Pol_y(thtenylene vmylene) 2_
has been extensively studied because it shares many ot the useful aunbutes ol
polyacetylene but shows considcr.1bly improved T_he low
band gap of PTV and its derivatives lends itself to potenttal apphcallons n both
its pristine and highly conductive doped state. Furthermore, the vinylcnc spacers
between thiophene uniL'i allow substitution on the thiophene ring without disrupt-
ing the conjugation along the polymer backbone. . .
Polymers such as PTV have potential applications as the acllve semtconductor
layer in thin-film transistors (TFTs).
1.6 Poly(thieuyleue vinylene)s - A Swble Class of Low Bcmd-Cup Mmerials 2:
1.6.1 Organic Field Efl'ect Transistors (FETs)
Organic materials have recently shown promise as the active layer in organic
based thin lilm tr,msistors (TFTs). Such devices have potential applications in th
switching element in flat panel displays and smart cards. Organic materials coul
have substantial cost advantages over their silicon counterparts if they can be de
posited from solution, as this enables the easy fabtication of large-area, tlexibl
displays. The geometry of a typical thin-film transistor device is depicted i
Figure 1-4. The current passing between two electrodes, the source and drain, i
controlled by applying a voltage to a third electrode, the gate. The semiconduc1
ing layer carries the current and the perfonnance of the device is very muc
dependent on the mobility, Jt, of the semiconducting material. Another figure c
merit is the ON/OFF r.1tio of the device; ideally the semiconducting layer shoul
have a low conductivity but a high field-eflcct mobility. Crystalline silicon has
mobility of 10-' cm
v- s- , whereas organics can only attain mobilities of th
order 1- 10 cm
v- s- but these values are sufficient for the intended applic<
tions. The best results to date have been achieved with discrete oligomers sue
as u-hexathienyl [107-112), C
fii3J and pentacene [114}. Mobilities as hig
a-; I cnl v- s- have been auained with ON/OFF ratios greater than lOll. bt
these results were obtained by sublimation of the semiconducting layer. An alte1
native approach utilizes low band-gap conductinf polymers; poly(thienylene vin)
lenc) 2 has yielded mobilities of 0.22 cm
v- s- 11151 but substantialtcchnologi
cal hurdles remain before these devices make it to market. Synthetic approachc
that yield well-ordered regioregular polythiophene or poly(thienylene vinylcm
derivatives may unlock the true potential of organic materials in semiconductl
Figure 1-4. Sc.:hcmalic.: dmwing of a 1Xllymer-basoo lhin film transi,lor device. A charge (usually pm
Jive) is injcclc:d imo the scmicunc.lucling layer from lhc source declroc.le anc.l Jhe charges
Jermcc.l polarons. arc swepl 1u 1hc dr.1in clcclrode under 1hc inlluenc.:e of a vollagc applied al a 1hi1
ch:t:m>dc. !he gale. In 'ueh a cunfJ!_!Uraliuu 1he device I S capable uf .:urrcnl amlllilkaliun. i.e .. sm.o
changes in til<: applic.J gale vuhagc can produce large in eurren1 passing bc1wccu lhc soun
and dr.1in. The clkt:liVCIICSS of lhC dcvit:c is lillliiCd hy !he :1lJili1y Of !he s.;miconducling layer I
tmnspurt charge, a parmnelcr 1ermcc.l Ute lielc.l ctTccl mobili1y.
26 1 Poly(wylene vinylene)s- Synthesis cmd Applications in Semiconductor Devices
1.6.2 Synthesis
In common with PPV 1, however, parent PTV is insoluble and infusible. The mate-
rial was first synthesized in powder fonn by Kossmehl using a Wittig polycondensa-
tion methodology [ 116). The first example of PTV synthesized by a soluble precur-
sor route was published by Elsenbaumer and co-workers [ 117). Once again, the
Wessling method was exploited (Scheme 1-24): 2,5-(Bis(tetrahydrothiophenonium,
methyl)thiophene chloride 73 was treated with one equivalent of water at O"C
and rapidly fonned a thick polyelectrolyte. The material may be cast from aqueous
solution and converted into PTV by heating to l50C. The material exhibited a con-
ductivity of 60S em- when doped with 1
The watersoluble precursor polymer,
however, has a tendency to gel or precipitate during dialysis and storage. Further-
more, the soluble precursor is prone to elimination even at room temperature. 1l1e
route was modified somewhat by Murase [ 118) and Saito [ 119 J by treating the
water-soluble precursor with methanol. As a conscquenc.:e, the sulfonium groups
arc replaced by mcthoxy substituents rendering the pn.:cursor polymer 75 soluble
in organic solvents. Thermal treatment at 200- 250'"C affords a shiny material with
a large absorption centered arounu 2.3 (540 mu) and an optical banu gap of
1.8 eV. A considerable amount of effort has been devoted lo optimising this
protocol[l20j. lt has been found that the reaction is best carried out in water, anu
that low temperatures are benelicial for high monomer conversion and polymer
processibility. The optical anisotropy of PTV was examined by orienting thin
films of thickness 0. 1 f.un [ 121 ). A red-shift in the absorption peaks on the ma-
terial was observed upon stretching indicating more highly-ordered polymer films.
A drawback of the Wessling methodology, however, is that trace amounts of
acid catalysts are required to completely eliminate the methoxy groups. A conse-


cr cr

1 b


S n 74
Scheme 1-24. Wessling route to PTV 2: a) MeOH, tetrahydrothiophene; b) NaOH, H
c) heat
/ .6 Puly(tlzieuyleue vinylene)s- A Swble Cluss of Law Bwzd-Cup Materials
quence is that this synthetic route is not particularly useful for semiconductor de-
vice applications. A route employing a xanthate precur.;or has been recently de-
scribed by the group at Lucent Technologies.
1.6.3 Aldol Route
Parent poly(thienylene vinylene) has also been synthesized by an
route [ 122). ln this method, 5-methyl-2-thiophenecarbaldehyde 76 ts treated With
a base and the monomer polymerizes yielding a precursor 77 which is soluble in
water. 1l1em1al treatment in an acidic solution at 80"C yields the fully conjugated
material. Alternatively, the solid polymer may be heated to 280oC to effect elimi-
nation of water. Fully conjugated matt:rial exhibits low conductivity (10-41 S em- ')
in its pristine stale.
H cJ[)-CHo
3 s
1 b

Scheme 1-25. Aldol route to PTV: a) KOtBu, DMF; b) heat.
1.6.4 Ring-Substituted PTV Derivatives
There have been a number of different synthetic 'approaches to substituted PTV
derivatives proposed in the last decade. Almost all focus on the aromatic ring as
the site for substitution. Some effort has been made to apply the tmditional base-
catalyzed dehydrohalogenation route to PTV and its substituted analogs. 1l1e
methodology, however, is not as successful for PTV as it is for PPV and its den-
vatives because of the grca1 tendency for the poly(u-chloro thiophene) precursor
spontaneously to eliminate at room tempcr.tture. Swager and co-workers at-
tempted this route to synthesize a PTV derivative substituted with a crown ether
with potential applications as a sensory material (Scheme 1-26) [123). The synthe-
sis employs a Fager condensation [ 1241 in its initial step to yield diol 78. Treat-
ment with a ditosylate yields a crown ethcr-funetionalized thiophene diester 79.
This may be elabor.1ll ... "<i to dichloride 81, but pure material could not be
and the dichloride monomer had to be polymerized in situ. The polymer Isolated
1 Poly(uryle11e vi11ylelle}s - Symhesis am/ Applicutiolls in SemicvtuluL'Ior Devices
Scheme 1-26. Attempted synthesis of a crown ether-functionalized PTV derivative 76:
K2C03, NMP; b) liAJH4, THF; c) SOCI
, pyridine, THF; d) KOtBu,
showed solvatochromic behavior, but could not be redissolved when solvent was
removed, and the material could only be chamcterizcd by IR spectroscopy.
The first substituted PTV deri vatives poly(3-methoxy-2,5-thienylcne vinylene)
poly(3-ethoxy-2,5-thienylene vinylene) 84 were synthesized by Elsenbaumer
10 the late 1980s [ 125 ]. The method employed was a step-growth condensation
a nickel-mediated cross-coupling reaction between a Grignard reagent and a
dtchlorocthene (Scheme 1-27). The materials obtained were deep blue solids, but
the majority of the sample was insoluble in common organic solvents. Endgroup


S n
82 83 84
A = Me, Et
BuO 06u

S n
Scheme 1-27_ Synthesis of alkoxy PTV derivatives and dibutoxy PTV 79: a) Bull,
MgBr2Et20; b) CICH::oCHCI (0.5 equiv.), NiCI
; c) CICH::oCHCI (1 equiv.), NiCI
1.6 Pol_r(tlliellylene Pinylene)s - A Stuble Cluss of ww Band-Cup Materials 2'
analysis of the insoluble proportion suggested that the number average molecula
weight M,, was over 9 100 g/mol. The soluble pl)rtion, however, showed in teres I
ing optoelectronic properties. It has an absorption maximum of 600 nm and it
band gap of 1.5 eV was significantJy lower than that of PTV itself. In additio1
the polymer could be cast into thin fil ms. The electron-donati ng groups arc lx
licvcd to reduce the ionisation potential of the polymer considcmbly compared t
unsubstitulcd fYTV. The material could be readily doped by FeC1
and pressed JX
lets of poly(3-cthoxy-2.5-thienylene vinylene) treated with FeCI
in nitromethan
solution exhibited conductivities of 1.8 S cm-
[ 126].
The same synthetic route was employed by Blohm and co-workers [1 27] in th
synthesis of poly(3,4-dibutoxy-2,5-thienylene vinylene) 85. The alkoxy chair
help to solubilise the polymer in conventional organic solvents, and this facilitat'
a rca.;onablc estimation of its molecular weight. GPC analysis of the polymer su:
gests M,= 12400, concsponding to a degree of polymetization of 49. The efll!t
tive conjugation length of this material is an improvement over poly(3-ethox:
2,5-thienylcne vinylene): the absorption maximum of poly(3,4-dibutoxy-2,5-th
enylcne vinylcne) 85 is red-shifted to 607 nm with a shoulder at 670 nm an
furthcnnorc, the color l)f the material could be reversibly changed from blue
nearly transparent in a doping-dedoping cycle. The measured conductivity of tl
doped material. however, was of the order I S em

The methodoll)gy has been further extended to hexyl-substituted P1V detivativo
by Shirakawa et ul. [ 12g]. A regioregular polymer consisting of alternating vinylet
and hexyl-substituted thiophene units 88 wa.o; prepared by a nickel-mediated eros
coupli ng (Scheme 1-27). The degree of polymerization was (M, == 360
and the ciTectivc conjugation length of the material .:t ..... =470 nm) was consi<ll
ably shorter than Observed in parent fYTV or its diaJkoxy-substitutcd dcriV<ttiVl
This is probably a consequence or the increased stcric repulsion between an alk
group and the hydrogen attached to the vinylic carbon.
The McMuny coupling route ha.; been utilised by lwatsuki and co-workers
the synthesis of PDBoxTV 8S (Scheme 1-29) 1129). Oialdehyde 90 is polyml
ized in the presence of tit anium tetrachloride and zinc dust. Molecular weights
35000 are reported and the polymer is freely soluble in solvents such as chlm
form. The repo11ed absorption maximum (605 nm) was close to that observed I
the Blohm route 1127 j .
The Stille reaction has been employed by a number or researchers in the sy
thesis of soluble PTV derivati ves [ 130]. Alkyl-substituted PTVs were symhesiz


a. b b,c
S n

86 87 88
Scheme 1-28. Synthesis of dihexyl PTV derivatives: a) BuU, MgBr
0; b) CICH=CH
(dppph; c) BuU, MgBr
30 1 Poly(arylene vinylene)s - Synthesis and Applications in Semiconductor Devices
C4H110 OCHe
Scheme 1-29. McMurry coupling route to dibutoxy PTV 79: a) BuU, TMEDA, DMF; b) T1CI
,f-1 A '

Scheme 1-30. StUie route to alkyl-substituted PTV derivatives: a) 1
, HN0
; b)
, Pd(PPh
by the reaction of 1,2-bistributylstannyl ethylene with a diiodothiophene 91
(Scheme l -30).
An attractive route to dialkoxy PTV derivatives has recently been reponed by
Elsenbaumer and co-workers 1131, 132). The method employs the thenual elimi-
nation of a sulfinyl group from <1 soluble sulfoxide precursor polymer (Scheme 1-
31 ). In addition, the authors claim the first isolation of the quinomethide inter-
mediate and characterised it by
NMR and mass spectrometry. Dibutoxy-PTV pro-
duced by this methodology exhibits a significantly smaller band gap (1.2 eV) and
higher molecular weight (M,. = 8700) than the san1e material obtained by other
methods. Poly(3,4-dimeJhoxy-2,5-thienylene vinylene) PDMoxTV was deep blue
in color (},,.,.,x = 680 nm) and exhibited a conductivity of 25 S cm-
when doped
with FeCI
This method is especially as it avoid:; the use of tmnsition
metal catalysts, which are potential contaminants for device applications.
1.6.5 Vinylene-Substituted PTV Derivatives - 1\ming the Gap
There have been very few examples of PTV derivatives substituted at the viny-
lene position. One example poly(2,5-thienylene-1 ,2-dimethoxy-ethenylene) 102
has been documented by Geise and co-workers and its synthesis is outlinctl in
Scheme 1-32 [133J. Thiophene-2,5-dicarboxaldehyde 99 is polymetized using a
benzoin condensati on; the polyacyloin precursor 100 was treated with base to
obtain polydianion 101. Subsequent treatment with dimethyl sulfate affords 102,
which is soluble in solvents such as chloroform, methanol, and DMF. The molar
mass of the polymer obtained is rather low (M,= 1010) and its band gap
(x= 2. 13 eV) is substantially blue-shifted rdative to PTV itself. Despite the low
effective conjugation, the mate1ial is reasonably conJuctive when doped with /
(o=0.4 S cm-



l f

8 8
1.7 Cundusimrs and Outlook


Scheme 1-31. Elsenbaumer route to dimethoxy PTV 92: a) Me
; b) UAIH TI-
c) PhSH, Znl
; e)KOtBu, THF; f) 80 C.

1 c

' -s on
Scheme 1-32. Synthesis of 96: a) Bul.i, TMEDA, DMF; b) KCN; c) Buli, KotBu; d) Me2S04
1.7 Conclusions and Outlook
This survey demonstrated that the licld of conjugated arylene vinylcnc pol
mers has matured considembly over the past thicny years. Several symhc
approaches to poly(arylene vi nylcne)s have been developed, and many routes m
allow solution casting of polymeric materials, thereby facilitating
32 I Poly(arylene vi11ylene)s - Symhesis wul Applicutions in Semico11ductor Devices
semiconducting polymers into real devices. The technology employing poly-
(arylene vinylene)s as the active layer in LEOs has advanced considembly over
lhe past Len years, and lhc impact of controlled synthesis on device properties can-
not be underestimuted. lL is perhups fair to say lhat PPV derivatives have had a
greater impact to date in the field of molecular electronics, but research effons arc
continuing to devise new synthetic approaches to PTV and its derivati ves. As a
consequence, it is anticipated lhat novel applications of such low band gap materi-
als in solid-state devices will be pursued with increased vigour in the next de-
We lhank the Engineering and Physical Sciences Research Council (UK), the
Commission of the European Community (Marie Curie Fellowship to MMM),
and Cambridge Display Technology for financial support. We acknowledge the
collaboration in Cambridge of our colleagues Prof. R. H. Friend, Dr. S.C. Moratti,
Dr. N.C. Greenham, and Dr. F. Cacialli and we thank Dr. A. Kraft and Dr. A. C.
Grimsdale for their interest in this work.
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2 Oligo- and Poly(phenylene)s
Ulhich Scherf and Klaus Mullen
2.1 Introduction
The structural regularity and order in polymeric or oligomeric molecules play a
critical role in determining the physical properties of such electronically active
compounds. This creates an exciting challenge for the synthetic chemists; with the
emphasis on the physical function of such materials, their properties have to be
selectively engineered through synthesis and supramolecular assembly. A fruitful
design strategy is aimed at controlling both the microscopic and 1he solid-slate
macroscopic structure. On the microscopic level this concerns a homogeneous
chemical structure (conliguration, tacticity etc.) and, on the macroscopic level, the
solid stale morphology (disordered, amorphous arrangemem of the molecules or a
controlled supramolecular assembly).
The synthesis-driven approach towards material science can be applied to cre-
ate oligomcrs and polymers with optimized properties, e.g. maximized carrier mo-
bilities and electrical conductivities or high photo- and electroluminescencc quan-
tum yields. It becomes obvious, however, that the abili ty to synthesize structur-
ally defined n-architectures is the key to these high performance matetials.
Besides the classical' search for linear, one-dimensional electronically active
materials, synthetic approaches are now also focussed on the generation and char-
acterization of two- and three-dimensional structures, especially shape-persistent
molecules with a well-defined size and geometry on a nanometer-scale. It is there-
fore timely and adequate to extend concepts of materials synthesis and processing
to meet the needs defi ned by nanochemistry' since the latter is now emerging as
a subdiscipline of material sciences.
2.2 Polymers
A large part of organic and macromolecular chemistry starts with the chcmkal
functionalization or benzene, and benzene units serve as building blocks lor im-
portant polymers. Naturally, benzene-based aromatic materials also represent au
impottant sulx:hL'iS of n-conjugatcd an:hih.:dures. Despite some synthetic Jiflicul-
ties related to the gem:ration of structurally well-dctined oligo- and poly(phenyl-
38 2 Oligo- and Poly(phenylene)s
ene)s. both academic and industrial researchers have had constant interest in phe-
nylene-type materi als.
Poly(p-phcoylcne)s, PPPs. constitute the prototype of rigid-rod polymers and
are currently being intensively investigated [I]. The key role of PPPs follows
from their conceptually simple and appealing molecular structure, from their
chemical stability, and from their superior physical properties [2]. In tum, this
the result of important advances made in aromatic chemistry over the last few
years. The following section gives an overview of the most common methods to
generate poly(p-phenylene)s via different synthetic approaches.
ppp 1
Scheme 2-1.
Unsubstituted poly(p-phenylene) PPP 1 as a parent system of a whole class of
polymers is an insoluble and intractable material, available by a variety of syn-
thetic methods [3, 4}. The lack of solubility and fusibility hinders both unequivo-
cal characterization and the processing of PPP l . Moreover. the inuactabili ty of
unsubstituted PPP materials has thwarted any serious commercial development of
the polymer.
2.2.1 Oxidative Condensation of Benzene Derivatives
The first allempts to generate poly(p-phenylene) (l) were undertaken in the
1960s. Kovacic et al. [3) reported that the oxidative treatment of benzene with
copper(ll) chloride in the presence of strong Lewis acids (alumi num trichloride)
gives rise to a coupling of the aromatic rings. Duri ng the condensation reaction
radical cations are formed as reacti ve intem1cdiates. The maximum degrees of po-
lymerization are ca. The benzene subunits are preferentially connected in
the 1.4-position, however, crosslinking and oxidative coupling to polycyclic aro-
matic hydrocarbon building blocks occur as side reactions. Adapting the initial
procedures of Kovacic et a/. other 1,4-substitutcd benzene derivatives were
coupled to poly(p-phenylene)s.
Katsuya er a/ . [5 1 published the oxidative coupli ng (agent: copper( II) chloride/
aluminum chloride) of electron-rich benzene derivati ves such as 2,5-di methoxy-
benzene to poly(2,5-dimethoxy- 1,4-phenylene) (2). The resulti ng polymer is only
soluble in concentrated sulfuric acid, and is fusible at 32o<c. Ucda et al. 161 de-
scribed the coupling of the same monomer with iron(lll ) chloride/aluminum chlo-
ride. The polymers obtained by the authors were not thoroughly pam-linked.
2.2 Polymers

or: f eCI,
Scheme 2-2..
Yoshino era/. [7 I prepared 9,9-substituted poly(fluorene)s 3, in which solubiliz-
ing alkyl substituents are auached at the methylene function. The soluble and fusi-
ble (3) are obtained by oxidative coupli ng
or w1th tron(ua) chloride and are characterized by number
M., or up to 5000. The longest wavelength absorption
Amax ol 3 IS centered at about 388 nm. Thereby, A
...,. is shifted batho-
chromlc<llly by about 50 nm relati ve to that of the parent PPP l structure due to
a partial planarization of the PPI, -typc polymer 3.

R: -alkyl
Transition from the parent PPP 1 to the poly(Ouorcne) derivati ve 3 touches a
crit ical aspect of poly(phcnylenc) chemistry. Introducing alkyl or alkoxy substitu-
ems can dramatically enhance solubility while at the same time introducino inter-
ri ng tors ion and thu_s inhibiting extended n-conjugation. TI1e fluorcnylene can
be regarded as a bndged and planarizcd biphenyl moiety to which one can attach
substituents wi_thout creati ng steric inhibition of resonance. Further stmtegies
d1rcctcd at suppressmg the mutual distortion of aromatic subunits in substituted
poly(p-phenylcne)s wi ll be outl ined below.
2.2.2 Transition Metal-Mediatt-'<1 Couplings
Entries to the preparati on or structurally more dctincd PPI,s have evolved based
on synthetic. of organic <md organometallic chemistry. The
avatl ab1llly of more ellcct1vc, more recent methods for the aryl-aryl coupling or
small n_10lecules. an imponant drivi ng force in the development of new
synthetic stmtegtcs lor poly(p-phcnylenc)s and other poly(arylcne)s. In pa
the Pu(O)-catalyzcd aryl-aryl coupling according to Su1.uki (arylboronic acid
40 2 Oligo- und Poly(l'lumylem! )s
plus aryl halide or -tosylate) and the nickei(O)-catalyzed or coupli ng ac-
cording to Yamamoto [9J (aryl halide or -tosylate plus aryl hahde or -tosylate)
have been most successfully employed.
Typically, such reactions were designed for the synthesis of low molecular
weight organic compounds and then, after having proven their synthetic potential,
applied to repetitive processes in the genemtion of macromolecules. This protocol
was shown to greatly improve the chemistry of conjugated polymers. Failure Ill
avoid side reactions such as dehalogenation or deboronation of the functionalized
monomers often creates, however. an unbalanced stoichiometry and limits the at-
tainable molecular weights.
Kaeriyama et al. [ 101 reported on the Ni(O)-catalyzed coupling of I ,4-dibromo-
2-methoxycarbonylbenzene to poly(2-methoxycarbonyl-1,4-phenylene) (4) as a
soluble, processable precursor for parent PPP 1. The aromatic polyester-type PPP
precursor 4 was then saponified to carboxylated PPP 5 and
latcd to 1 with CuO catalysts. However, due to the harsh reaction cond1t1tms 111
the final step, the reaction cannot be carried out satisfact01ily in the solid state
The strategy of Kaeriyama represents a so-called precursor route and_ was de-
veloped to overcome the characteri stic ol
abili ty) of previous PPP syntheses. The condensatton rcact1on 1s camed out w1th
solubilized monomers, leading to a soluble polymeric intennediate. In the linal
reaction step this intermediate is then converted, preferentially in the solid state
allowing the formation of homogeneous PPP films or layers, into PPP (or other

Ni(O) ott
- -


As has been outlined above, a second, very fruitful synthetic principle for obtain-
ing structumlly homogeneous, processable PPP de.rivatives involves _the
of soluble PPPs via introduction of solubilizing s1de groups. The p10neenng work
here was canicd out at the end of the eighties by Schluter, Wegner, et a/. [II ,
12], who for the lirst time prepared soluble poly(2,5-dialkyl-1,4-phenylene)s 6.

Scheme 2-5-
R: ..alkyl, ..alkoxy
2.2 41
SchlUter et al. [ Ill were the first to describe the coupling of aromatic com-
pounds containing aryl magnesi um halide and aryl halide functions catalyzed by
Ni(O) compounds. Herein, the authors attached solubilizing side-chains at the 2-
and 5- positions or the benzene rings and in on.lcr to make soluble products. They
yicldt::d oligo(para-phenylene)s with maximum degrees of polymerization of 8-
10. The products arc chamctcrizcd by an exclusive 1.4-linking of the benzene
rings of the main-chain. However, the molecular weights were quite low.
Several authors developed the method further of Ni(O)-mediated couplings to
generate several derivatives (9, 13, 141. They described homocouplings of
various 1,4-dihalobenzene derivatives by means of nickci(II)chloride/triphenylpho-
sphine/zinc or the nil:kei(O)kyclooctadienc complex.
homocouplings of 2-substituted 1,4-phcnylcnebis(trillate)s have
been reported by Pcrcec et a/. [15] to provide substit uted poly(p-phenylene)s 7
containi ng alkyl, aryl or ester substitucnts in the 2- and 3-positions of the 1.4-
phenylenc skeleton. This method of preparation appears to be broad in scope.
especially due to the case of preparation of the bis(trillatc) monomers starting
from the con-csponding hydroquinone deri vatives.
R: ..alkyl, 1)henyl, -COOMe
Scheme 2-6.
By means of a repetiti ve Suzuki aryl-aryl cross-coupling method, developed by
Schliiter, Wegner and co-workers, the synthesis of solubilized PPP's 6 with a dra-
matically increased molecular weight (number average up to 100 1,4-phenylcne
units) was possible (12j. 2,5-Dialkyl-substituted PPPs 6 were intensively studied
as prototypes of so-called ' hairy-rod' macromolccu!es, composed of a linear, rigid
PPI' main-chain and tlexible, ' hairy' alkyl side-chains. The individual, shape-per-
sistent macromolecules can be imaged by transition electron microscopy within
monolayers r 16]. Poly(2,5-di-n-dodecyl-1 ,4-phcnylene) 6 (R: -C I:!H:!:;) revealed a
sandwich-type structure with layers or aliphutie side-chains perpendicular and
layers or the PIP main-chain parallel to the substrate surface. Poly(2.5-di -n-uodc-
42 2 Oligo- and Poly(phenylene)s
cyl-1,4-phenylene) of Mw 73000-94000 show a single anismropic liquid crystal-
line mesophasc in the molten state and macromolecules with Mw 44000-73000
gave coexisting isotropidanisotropic phases [ I 7 j.
R: -alkyl, -alkoxy
In addition to alkyl-substituted derivatives, soluble PPPs 6 are also known to-
day containing alkoxy groups as well as ionic side groups (carboxy ancJ sulfonic
acid functions) [l8j. Schliilcr cr a/. ~ t t n t l y described the gencmtion of soluble
PPPs decorated with densely packed stcrically demanding dendmns on the fomm-
tion of cylindrically shaped dendri mcrs, so-called cylinder dendrimers 119j.
Scherf er at. [20} reported the synthesis of the PI)P derivative Sa, which is
composed of chiml eyclophane subunits, by means of a Suzuki-type aryl-aryl
cross-coupling of the corresponding diboronic acid and dibromo monomers. The
monomers wi th the cyclic -0-C
-0- loops can be resolved into the pure enan-
tiomers by preparative high pressure liquid chromatography on chi ral stationary
phases. The pure enantiomers were used to generate the corresponding stereoregu-
lar iso- and syndiotactic PPP derivatives 8b and 8c. Hereby, the isotactic deriva-
tive 8b is of special interest due to its main-chain chiral character [20].
Unsubstituted PPP 1 possesses a 23 twist between adjacent phenylene units
[2 I ). Since the n-overlap operates as a function of the cosine of the twist angle,
even at 23 there is a fair amount of conjugative interaction remaining. If one
places substituents along the PPP backbone (e.g. at the 2- and 5-positions as in 6,
7 and 8), the solubility is drJmatically enhanced, as discussed above, however.
the n-overlap is reduced. Twist angles of 60-80'' are reported for alkyl substitu-
ents in 2,5-positions [22j. Thus, for poly(2,5-dialkyl-1,4-phenylcne)s. only negli-
gible optical absorption can be detected in the wavelength region above 300 nm,
which is characteristic for delocalized n-n* tmnsilions.
The results described thus far sketch the synthetic demands for being able to
prepare processable. structurally defined PPPs, in which the n-conjugation re-
mains fully intact or is even increased as compared to that of the parent PPP 1
system. The key step in the realization of this principle is the prepamtion of a
PPP in which the aromatic subunits can be obtained in a planar or only slightly
twisted conformation in spite of the introduction of substituents.
One of the first examples was the above mentioned work from Yoshino er a/. PI
conceming the synthesis of poly(9,9-dialkylfluorene)s via oxidative coupling of
fluorene derivatives. Poly(9,9-dialkylfluorene) derivatives have been also synthc-
si:i".cd via Ni- and Pd-catalyzcd aryl-aryl homo- and cross-coupling reactions of sui-
Atactic PPP-Oerlvative Sa
lsotacllc PPP-Oerivative 8b
Syndiotactic PPP-Oerivative ~
Scheme 2-a.
2.2 Polymers 43
tably substituted monomers (2,7-dibromolluorene and fluorene-2.7-diboronic acid
derivatives. respectively) 123, 241. These reactions allow the synthesis or structu-
rully defined products possessing high molecular weights of up to 100000. Some
derivatives, e.g. the 9,9-dioctyl-substituted polylluorcnc form well-defined thermo-
II'Opic LC states and can be aligned on tubbed substmtes. These layers show a high
degree of orientation, both in absorption and photoluminescence {25].
The next allempt at these reactions were carried out by Yamamoto et ul. 1261.
They coupled 2,7-dibromo-9, I 0-dihydrophenanthrcne to give an ethano-bridged
pol y(p phcn y lene) <.Jeri v ali vc I pol y(9 ,10-d ih ydrophenanthrcne-2, 7 -di yl )I (9) by
way of low-valent nicl.cl complexes, which were used either stoichiometrically as
rc.tgent (Ni(CODh) or were generated electrochemically in the reaction mixture.
As a result or the insullicient solubilization of the ethano substitucnts only the oli-
gomer fraction with M .. < I 000 is soluble, the polymeric products precipitating out
as an insoluble powder. The value of A."'"" l(lr the soluble fr.tction of 9 is about
360 nm.
Scheme 2-9.
44 2 Oligo- a11d Poly(phe11ylene)s
Consequently, by combining the synthetic procedure of Yamamoto (26] with
the introduction of more extended solubilizing substituents, advantageous results
were expected. Accordingly, alkyl-substituted dihydrophenanthrenes or tetr-clhydro-
pyrenes offered themselves as starting monomers for the preparation of soluble
'step-ladder' PPPs of this type. 2,7-Dibrom<r4,9-dialkyl-4,5,9,10-tetrahydropyr-
encs (10) represent suitable starting monomers for the realization of this synthetic
route. These difunctionalized tetrahydropyrene monomers were first prepared by
Mullen et a/. and reacted in a Yamamoto coupling [27}.
Reaction of the dibromide 10 with Ni(CODh in DMF/toluene gave a poly(4,9-
dialkyl-4,5,9, 1 0-tetrahydropyrene-2,7-diyl) PTHP 11 as a completely soluble, new
type of PPP derivative, in which each pair of neighboring aromatic rings is doubly
bridged with ethano linkages [27j. The solubilizing alkyl substituents appear on the
periphery of the macromolecule so that they cannot cause twisting of the main-chain.
PfHP 11 possesses a relatively high number average molecular weight. up to
=45000, which com:sponds to coupling of about 100 THP units.
A further advantage of PTHP 11 is that distereomeric fom1s can be generated
which arc exclusively of cis- or lrcm.\-cunfigurcu monomeric TIIP
bui lding blocks. The stereochemistry or the substituents in 4- and 9-position (Ci.i,
trans) strongly intluences the solid state packing behavior of ll.
Scheme 2-10.
R: -alkyl
PTHP 11 possesses the longest wavelength absorption A"""' of 385 nm, almost
identical with the value for the polyfluorenes 3 of Yoshino et a/. [7}. Thus, inde-
pendent conlinnations exist for the correctness of this 'step-ladder' concept; the
introduction of solubilizing groups combined with simultaneous bridging of the
subunits guarantees an increao;ed degree of conjugative intemction.
In solution PTHP 11 exhibits intense blue photoluminescence (PL) with a rela-
tively small Stokes shift between absorption and emission <Ama absorption: 385
nm; Amax emission: 425 nm). PTHP 11 can be used as active component in light-
emitting diodes (LED) based on organic polymers, elcctroluminesccnce (EL)
quantum yields of 0. 1-0. 15% (single layer construction ITOIPTHP 11/Ca) of
blue-green LEOs were reported. Blue polymer-based LEOs represent an auracti vc
target, as blue cmilling LEOs based on inorganic semiconductor materials are not
easily accessible. As a result of their band gap energy of 2.7-3.2 eV, PPP deriva-
tives arc particularly suitable as blue emitters.
In contr.tSI to low molecular mass materials, polymcic emiucrs possess the ad-
vantage that they can be easily worked into tmnspurcnt tilms wi th a low degree
2.2 Polymers 45
of scauering. In addition, they show a higher morphological stability compared
with that of vapor-deposited low molecular weight compounds.
The logical continuation of the 'step-ladder ' stmtegy outlined above to mini-
mize the mutual distortion of adjacent main-chain phenylene units is the incor-
poration of the PPP-parcnt chromophorc into the network of a completely planar
ladder polymer. The perfect flallening of the conjugated n-system by bridging all
the subunits should then lead to a maximum conjugative interaction. As with the
PTHP ll systems, alkyl- or alkoxy side-chains should lead to solubilization of
the polymers. The realization of this idea culminated in 1991 in the first synthesis
of a soluble and conjugated ladder polymer of the PPP-typc by Scherf and MUl-
len [28]. This PPP ladder polymer LPPP 12 was prepared according to a so-
called classical route, in which an open-chain, single-stranded precursor polymer
was closed to give a double-stranded laducr polymer. The synthetic potential of
such a multi-step sequence wa."i doubted for a long time, and in the eighties syn-
chronous routes were strongly favored as preparative method for ladder polymers.
In a classical multi-step route the critical point is to conduct the ring closure
lfUant ilati vcly and rcgiosclectivcly. In the symlh.:sis of LIPJ. the pn:clll'Silf poly-
mer 13 is initially prepared in an aryl-aryl coupling from an aromatic diboronic
aciu and an aromatic dibromoketonc.

R': -alkyl
R: -1,4-CaH -alkyl
Scheme 2-11.
The cyclization to structurally dclincd, soluble LPPI' then Iukes place in a
two-step sequence, consisting of reduction of the keto group followed by ring clo-
sure of the secondary alcohol groups of 14 in a Fricdcl-Crafts-type alkylation.
The resulting ladder polymer LPJ>J> 12 possesses a number average molecular
weight of 25000, which corresponds to the of 65 phenylene units.
No structure dcfce1s could be detected using NMR spectroscopy. LJ>PP 12 is
46 2 Oligo- a11d Poly(pltenylene)s
characterized by unusual electronic and optical properties; the absorption maxi-
mum undergoes a marked bathochromic shift as a consequence of planarization of
the chromophore, to a Amax value of ca. 440 nm (see Fig. 2- 1), depending some-
what on the substituents -R and -R'. In addition, the longest wavelength n- rc* ab-
sorption band possesses an unusually sharp absorption edge as an indication for
the fully planarized, geometrically fixed ladder structure.
The photoluminescence (in solution) of LPPP 12 is very intense and blue
(AnlaX emission: ca. 460 nm). The Stokes shift between absorption and emi ssion is
extremely small (ca. 150 cm-
); a consequence of the geometric tixation of the
chromophore in the ladder structure. The PL quantum yields are high in compari-
son to those of many other conjugated polymers; in solution values between 60
and 90% have been measured, in the solid state up to 40% [29). In comparison,
PPJ> 1, synthesized by the lCI-precursor route, shows a PL quantum yield of only
4% [30). Thus, the next step was to investigate the suitability of this new type of
material for application as an active component in organic materials-based LEOs.
Init ially, this led to the surprising result that although etlil:ient LEOs can be pre-
pared with LPJ>P. the color of the emission in the :-.olid state (lilm) is 111.:verthelcss
yellow (PL and EL). In addition to primary emission of the LPPP 12 chromo-
phore in the blue region, the PL and EL spcctm exhibit an additional unstruc-
tured broad emission band in the yellow region (ca. 600 nm) 13 11. The yellow
emission band could be unequivocally as aggregate emi ssion by
ious pieces of photophysical evidence (32-34j, and the occuncnce of excimer for-
mation unquestionably ruled out.
EL experiments showed that the yellow-emitting LEOs prepared from LPPP
12 exhibit quite remarkable chamcteri stics (single layer constructi on ITO/LPPP
12/Ca; quantum efficiency: ca. 1.0%, applied voltage: 4-6 V 135 J). These figures
are in the r.mge of the best values described hitherto for polymeric emitters in a
single layer arrangement. for example, poly(para-phenylenevinylene) PJ>V and
PI)V deri vati vcs.


' ..
--.................... .
400 600
Wavelength li'Vli
.Figur e 2-1. AbMlrplion and photuluaninc:;c\;flcc SJliX:Ira of LPI'I' 12 (solvent: dichluromclhanc,
-R: -11-Cc,H
; -R': -C.,Ho).
2.2 Polymers 47
From the perspective of the strategies aimed at fabrication of efficient blue
LEOs, the results outl ined above regarding yellow LPPP light emitting diodes
are, nevertheless, unsatisfactory. In order to prepare blue LEOs from LPPP
materials, it is necessary to efficiently mask out or suppress the dominant yellow
aggregate emission.
Suppression of the aggregate emission is possible in two quite ditl"erent ways.
At first, the aggregate emission could be almost completely shut out by simply di-
luting the LPPP 12 with a matrix polymer. LEOs with I% LPPP 12 in poly(9-
vinylcarbazole) PVK as emitter material are characterized by a pure blue light
emission with a quantum efliciency of ca. 0.15% in single-layer contigumtion
(ITO/I % LPPP 12 in PVK/Ca) 135).
If suppression of the aggregate emission in this first example was based on a
purely physical principle, chemical modification of the LPPP 12 structure towards
the same aim is also possible. 1l1us, one option is the introduction of additional sub-
slituems into the LPPP skeleton. Attaching an additional methyl group to the mellly-
lene baidge of LPPP 12, which can, indeed, easily be achieved by quantitative ad-
dition of methyllithium tu the precursor 13, in place of reduction of the keto groups.
yields ladder polymers Mc-LPI'I, 15. Their solid state PL spectra show only vcty
weak aggregate emissions; the solution- m1d solid state PL spectra are almost iden-
ticall361. The fact that the of the aggregate emission could be achieved
by molecular and supramolecular design is, indeed. a convinci ng example of the
above menti oned synthesis-driven approach toward electronic materials.
The suppression or aggrcgaae formation is accompanied by a dramatic increase
in the PL quantum efficiency to >90% for solution and up to 40% for the solid
state. This enom10us solid state PL quantum efficiencies favor Me-LPPP 15 as
emitter material lor solid state lasers based on organic mateaials. Leising er a/.,
Mahrt er a/. and Lemmer er a/. have independently demonstrated the potential of
Me-LJ>J>p as solid state laser material in seveml configumtions (waveguide con-
figuration, distributed feedback contiguration) l37-40J. The high molecular
weights of 15 (M .. up to 50000) allow lor the fabrication of thick lilms and strips
(up to 10 l-tlll). The devices are characterized by an extreme stability and lasing
was observed over a period of more than 10
pulses t40J.
Me-LPPP 15
R: -aryl, R': -alkyl
Scheme 2-12.
At this point it might be appropriate to comment on the conll icting require-
ments of the synthesis. The large interest which other conjugated polymers such
as polypyrrolc, polyaniline or poly(pam-phcnylcnevinylene) (PPV) have attracted
originates, tirstly, from their <tllractive physical properties, but also from the sim-
48 2 Oligo- and Pvly(phenylelle)s
pie fact that they are readily available in sufficient quantities - even in laborato-
ries without highly developed synthetic know-how. However, one must be aware
that each electrochemical formation of a polypyrrole or a precursor route towards
PPV provide individual samples whose performance in devices depends upon the
chemical conditions of materials synthesis. Thus. while one would not argue
against a 'practical' synthesis, two important aspects must be obeyed; (I ) a selec-
ti ve structure-property relationship necessitates a scrupulous definition of the mo-
lecular structure and of possible impurities, and (2) adequate synthetic solutions
for physical problems can require a higher level of sophistication and still remain
valuable, even from a practical point of view.
2.2.3 Other Routes to Poly(p-phenylene)s
Besides the oxidati ve and transiti on-metal-catalyzed condensation reactions discussed
above, several other syntheses were developed to generate PPP and PPP derivatives.
Marvel et a/. described [4 1] the polymerization of 5,6-dibromocyclohexa- 1,3-
? iene (16) to poly(5,6-dibromo- 1,4-cyclohcx-2-ene) 17 followed by a thermally
tnduced, solid state elimination of HBr on the formation of tPP l. The products,
however, display some indications for several types of structuml defects (incom-
plete cycliUttion, crosslinking).
11 1
Scheme 2-13.
Later on, Ballard e1 al. [42, 43) developed an improved precursor route starting
from 5,6-diacctoxycyclohexa-1,3-diene (18), the so-called ICI route. The soluble
precursor polymer 19 is finally aromatized themmHy into PPP 1 via elimination
of two molecules of acetic acid per structuml unit. Unfortunately, the polymeriza-
tion of the monomer does not proceed as a uniform 1,4-polymerization; in addi-
tion to the regular 1,4-linkages ca. 10% of 1,2-linkages arc also formed as result
of a 1,2-polymerization of the monomer.
1 .1j
Scheme 2-14.
2.2 Polymers 49
Grubbs [441 and MacDiannid [45) et a/. described in 1992 and 1994, respec-
tively, an improved precursor route to high molecular weight, structurally regular
PPP 1 starting from the cyclohexa- 1,3-diene derivati ve 18 and leading to a stereo-
regular precursor polymer 20 via transition metal-catalyzed polymerization. The
final step of the reaction sequence is the thermal. acid-catalyzed elimination of
acetic acid to convert 20 into PPP 1. The authors obtained free-standing PPP
films of defined structure, however these tilms still contained large amounts or
the acidic reagent polyphosphoric acid. Nevertheless, in this work a reliable value
for the longwave absorption maximum Amax of PPP 1 could be obtained, at about
336 nm. This value is of utmost importance in the interpretation of the optical
properties of substi tuted PPPs.
Q , .. .... .,
R: F
Scheme 2-15.
As well as the polymerization of I ,3-cyclohexadiene derivatives. repetitive
Diels-Alder polyadditions wen.: widely used to prepare arylated PPPs. Stille and
co-worker"l' developed a set of suitable monomers (I ,4-diethynylbenzenc and 1,4-
phenylenebis(triphcnylcyclopentadicnone) derivatives) to gencr.lle phcnylateu
PPPs (e.g. 21) possessing molecular weights of 20000-100000 [46]. Unfortu-
nately, the repetiti ve polyaddition does not in a regioselective way; poly-
mers containing para- as well as meta-phcnylene units withi n the main-chain
skeleton are fom1ed.
Scheme 2-16.

50 2 Oligo- and Poly(phenylene)s
Recently, Tour et al. [47) described attempts to use the Bergman cyclicll
produce PPP derivatives starting from substituted endiynes, e.g. pvi.: .
1.4-phenylene) 22 starting from 1-phenyl-hex-3-en-1.5-diyne or the structurally re-
lated poly(2-phenyl-1,4-naphthalene) 23 starting from 1-phenylethynyl-2-ethynyl-
\J- -<J -idt. ld1
l 0 I.
Scheme 2-17.
2.3 Oligomers
Pamllel to the polymer synthesis, many activities have been directed towards solu-
ble. well-defined oligomers. Such oligomers are important to optimize the poly-
mer synthesis and to understand structure/property relations in the class of PPP
and other poly(arylcne) materials. The key approach, thereby, is a study of physi-
cal properties as a function of chain length. The problem of oligo(phenylene)s is,
as mentioned above, the low solubility of the compounds. The solubilities of flflfl
oligomers in conventional organic solvents decrease dramatically with increasing
chain length and reach, e.g. for octaphenylene, the negligible value of less than
10 ng/1 in toluene at 25 oc. In view of this, all attempts to synthesize and charac-
terize longer unsubstituted flflfl oligomers by direct couplings are inappropriate.
The first series of soluble oligo(para-phenylene)s OflVs 24 were genemted by
Kern and Wirth [48) and shortly after by Heitz and Ulrich [49]. They introduced
alkyl substituents (methyls) in each repeat unit and synthesized oligomers 24 up
to the hexamer. Various synthetic methods, like the copper-catalyzed Ullmann cou-
pling, the copper-catalyzed condensation of lithium aryls, and the twofold addition
of organometallic species to cyclohexane- 1,4-dione, have been thereby investigated.
The authors developed two gencml concepts for the synthesis of these mono-
disperse, defined oligomers. The oligomers can be built up in a stepwise fashion,
e.g. via addition of organometallic species to cyclohexane-1 ,4-dione followed by
aromatization to the oligo(arylene) (e.g. for 25).
The alternative stmtcgy involves the generation of oligodisperse mixtures of
seveml oligomers of different chain lengths, e.g. by copper-catalyzed couplings of
mono- and dilithioaryls, followed by a chromatographic resolution of the oligotlis-
perse mixtures into the monodisperse components 24 of defined chain lengths. In
2.3 Oli gomers 51
Scheme 2-18.
this way. oligomers 24 up to a duodeciphenylene derivative have been by
preparative thin-layer chromatogmphy.
Scheme 2-19.
.! MeA rtel
Recently Rehahn <!I a/. (501 presented the synthesis of constitutionally homoge-
neous oligo(phcnylene)s 26a/b with 2,5-alkyl substituents, located on the centml
aromatic ring, genemted via the cross-coupling reaction according to Suzuki. They
arc exclusively linked in para-positions and constituted of 3- 15 benzene rings.
All the above oligomers are characterized hy the presence of solubilizing alkyl
groups, resulting in an increased solubility. However, the electronic properties of
the 1r-system arc disturbed by the mutual distortion or the phenylenc units in-
duced by the substituents. Compared to the parent PPP-system with its 23"' twist
between adjacent building blocks, the substituted deri vatives display distortion an-
gles of 60-XO"", which minimizes the conjugative interaction within the conjugated
backbone. One possibility to overcome this drawback is the substitution only at
the terminal rings as pcrfonncd by Liillkc eta/. 1511. They generated oligo(phenyl-
enc)s 27 with tat butyl substituents at the tenninal 3- and 5-positions using a
52 2 Oligo- and Pvly(phenylenc)s
Scheme 2-20.
Grignard coupling us the key step. However, longer oligo(phenylene)s 27 are not
available fo llowing this approach, since the compounds become also insoluble
when reachi ng chain lengths of more than 7 aromatic buildi ng blocks.
Scheme 2-21.
As described for the corresponding polymers, a powerful strategy to achieve
soluble oligomers with maximum conjugative interaction is to incorporate the
PPP backbone into a step-ladder (or ladder, see Section 2.2) fr.unework in combi-
nation with the attachment of solubili zing side groups onto the bridging function-
alities. Following this, it was possible to generate short-chain tetrahydropyrene
oligomers via separation of polydispersc mixtures into their (monodispersc) indi-
vidual components 28 with the aid of preparative gel permeation chromatogmphy
28 (n: o -8)
R: -alkyl
Scheme 2-22.
2.3 0/igomer.s 53
With such a series of oligomer.; 28 available, the convergence of optical proper-
ties with increasing chain length can be monitored and the conj ugation length in
the corresponding polymer YfHP 11 can be determined as comprising of about
10 monomer building blocks (i.e., 20 aromatic rings) [53j.
The above approaches to synthesize oligomer.; (i.e. stepwise synthesis, chroma-
togmphic resolution of oligodispersc mixtures) have more recently been comple-
mented by repetiti ve modular stmtcgies. Such concepts involve the repetition of
directed protcction/couplingldcprotection sequences in a convergent process to
minimize the number of reaction steps necessary to genemte the extended oligo-
mers. Such a stmtegy was developed e.g. for linear poly(para-phenyleneethynyl-
ene)s PPEs by Tour eta/. 154j. Using a similar approach, Schluter et a/. [55] dc-
:.cribed the synthesis of monodisperse oligo(phcnylene) rods 29 with up to 16
phcnylcne rings and with well-defined functional end groups. The synthesis is
based on a convei"Jent (exponential) growth using the Suzuki reaction as the cou-
T ~
l Pd(O)
Zl!. n: 2,4,6,8
R: -n-hexyl
Scheme 2-23.
54 2 Oligo- und Poly(phenylene)s
piing step. The key principle rests upon the significantly faster coupli ng of iodoar-
yl functions as compared to the corresponding bromoaryls in the aryl-aryl cross-
coupling reaction according to Suzuki. Accordingly, building blocks containing
both iodo and bromo functions undergo the coupling with an arylboronic acid pre-
ferentially at the iodo side, leaving the unreacted bromo side for subsequent
chemical derivatization, such as conversion into a boronic acid function.
Ladder-type LPPP oligomers J O (56] were also synthesized following a so-
called 'oligodisperse approach'. The two bifunctional (chain forming) monomers
of the polymer (20) synthesis were co-reacted with a monofunctional (end cap-
ping) monomer to produce an oligodisperse mixture of 'end-capped' molecules of
differing chain lengths. These mixtures were resolved into their monodisperse
components by means of liquid chromatography; preferentially by size exclusion
chromatogmphy. Following this protocol, LPPP oligomers 30a, J Ob, and JOe
were achieved containing three, five, and seven I ,4-phenylene units within the
planar ladder-type main-chain.
R': -n-hexyl
Scheme 2-24.
Using UV-VIS measurements of this series of monodisperse, oligomelic model
compounds JO the effecti ve conjugation length of the corresponding polymer
LPPP 20, i.e. the convergence limit or absorption and PL properties, be
identified as compri sing about II phenylene units (53). While a plot of the physi-
cal properties as a function of chain length and a determination of the effecti ve
conjugation length has no sound theoretical background, it is a remarkable out-
come that the convergence of the optical absorption energy with increasing chain
length occurs much more mpidly in the planar u >pp 20 molecule than in non-
bridged PPP detivutivcs or in the partially bridged step-ladder polymer PTHP 11.
2.4 Dendritic ond H)perbmnclred Poly(plreny/ene)s 55
2.4 Dendritic and Hyperbranched Poly(phenylene)s
The results presented up to here concem only one-dimensional oligomers and
polymers of the PPP-type. This section is mainly focussed the electJ"?nic
et1ies or extended n-chains and on the morphology of sohd PPPs usmg cham-
stiffness as a structure-fonninu principle for supmmoleeular architectures.
b .
The transition from one- to two-, and three-dimensional PPP-structures gtves
access to novel spectrum of attractive properties. The n-conjugated cl}amcter of
1,4-disubstituted phenylenes drJws in the background, such 2D- and
of the PPP-type represent, moreover, a unique, novel class of shape-perststent .
nomaterials. Their bmnched backbone, which is exclusively composed of ngtd
phenylene units, causes the above mentioned stinness of the whole molecule. En-
ormous synthetic <K:hievements in this field open opportunities for a contro!lcd
molecular and supramolccular design. 2D-Structures can be, e.g. processed mto
monomolecular absorbatc layers on surfaces. 3D-Dendritic structures are available
with a size and shape which can be systematically vatied. The shape-persistent na-
noparticles can carry well defined chemical functions and can act e.g. as caniers
for biologically active principles (tracers, drugs etc.). Moreover, the 3D nanomole-
cules can be further tmnsrormed into planar, giant polycyclic aromatic hydrocar-
bons (PAHs).
2.4.1 Hypcrbra nched J>oly(phcnylcnc) Derivatives
Kim and Webster (57] were the first to show that trifunctional benzene-based
monomers can also be used to synthesize poly(phenylene)s, in this case hypcr-
bmnched structures Jl based on 1,3,5-trisubstituted benzene cores. They self-con-
densed 1,3-dibromophenyl-5-boronic acid leading to the formation of soluble,
hyperbnmched PPI)-type macromolecule Jl .
Scheme 2-25.
56 2 Oligo- and Poly(pheny/ene)s
The transfonnation of the hydrophobic periphery composed of bromo substitu-
ents into a hydrophilic wrapping of carboxylic acid functions was achieved by re-
acting 31 with (i) n-butyllithium and (ii) carbon dioxide. The polymer-analogous
tmnsfom1ation provides water soluble, amphiphilic derivatives of 31 which consti-
tute useful covalently bonded unimolecular models for micellar struciUres.
2.4.2 Oligo(phenylene)s of Orthogonally Arranged Anns
Star-shaped molecules with oligophenyl arms derived from 9,9-spirobifluorene as
the central unit have been synthesized by Tour et al. [58] and Salbeck et al. [59]
and have been suggested as potential emitter materials for blue LEOs.
Scheme 2-26.
The authors used a synthesis of 9,9-spirobifluorenes 32 which was developed
by Clarksen and Gomberg [60J and which includes the addition of biphenyl-2-yl-
magnesium iodide to fluorenone and subsequent cyclization with protic acids. To
obtain 2,2,'.7,7'-arylated 9,9-spirobifluorcnes 33, 9,9-spirobifluorenc (32) was
tetrabrominatcd [58] to yield 34 followed by a Suzuki-type aryl-aryl cross-
coupling with various oligoaryl and oligoheteroaryl boronic acids to obtain the
2,2',7,7'-tet.r.:tarylated derivatives 33.
Scheme 2-27.
r Pd(O)
2.-J Dtntlritic uml Hypabmucltecl Paly(pltenyleuc )s 57
The star molecules 33 are characterized by a drastically increased solu-
bility when compared to the corresponding unsubstituted PPP oligomers. The
spiro compounds 33 are non-polymeric organic glasses with high thennal stability
and unusually high glass transition temperatures (59. 61]. TI1ercfore, high quality
amorphous films can be with these spiro compounds by vapor deposi-
. tion or spin coating. Derivatives of 33 composed or two orthogonally arr.mgcd
oligophenyl chains, e.g. sexiphenyl anns (R: - 1.4-C<>H
), display an efficient
photoluminescence, which makes them promising materials to be used as emitters
for organic light emitting diodes LEOs.
2.4.3 Dendritic Poly(phenylene)s and Ghmt Polyaromatic Hydrocarbons
More recentl y, Mullen et a/. have worked out very ellicient procedures to gener-
ate highly arylatcd, branchal oligo(phenylcne) and related oligo(arylene) deriva-
ti ves following di fferent synthetic approaches.
A first milestone was the development or a novel intmmolecular Oiels-Alder
cydiwtion or terphenyl monomers 35 and 38 containing both 4-phenylbutadienyl

Scheme 2-28.
58 2 Oligo- and Poly(pllenylene)s
and styryl functions. The formation of the 14+2) cycli:zation adducts 36 and 39 is
then followed by a simple aromatization of the eyclohexene moieties 162]. In this
way, the phenylatcd, two-dimensional arylene structures 37 and 40 based on a
tetmbcnl.oanlhmccnc cure and possessing a hithc11o unknown topology were
The branched oligo(arylene)s 37 and 40 can undergo a further oxidative cycliza-
tion with copper( II) chloride or triflate/aluminum trichloride leading to the formation
of large, hitherto unknown polycyclic aromatic hydrocarbons PAHs 41 and 42.

Scheme 2-29.
The large polycyclic aromatic hydrocarbons (PAHs) 41 and 42 are character-
ized by their extremely high them1osUtbility. They can be sublimed at tempera-
tures of 550-650C under ultrahigh vacuum (UHV) conditions. Such a sublima-
tion step is of crucial importance to obtain pure compounds because the solubility
of the reaction products in organic solvents is very low. The sublimation proce-
dure can be used to grow densely packed monomolecular absorbatc layers. Such
organic absorbate layers can be chamctcrized by means of electron diffr.1ction
(LEED) or scanning tunneling microscopy (STM). It was possible to get a molec-
ular resolution of the rhomboid PAH 41 with STM 163]. Fommtion of mono-
molecular absorbate layers of giant PAHs is also possible by physisorption from
solution if the disc-type molecules arc made sulliciently soluble by suitable alkyl
substit ution. The large size of the molecular gr.tphite models such as 41 and 42
also allows one to achieve a submolecular resolution in STM and thus to record
current-potential curves for single molecules. h follows that the tonnation of or-
dered surface absorbates from adequately designed PAHs is a challenging starting
point to enter the field of molecular electronics.
In a second novel approach, Mi.illen and co-workers further developed ;m inter-
molecular repetitive Diets-Alder procedure for the gener..ttion of dendritic and hy-
pcrbranched poly(phenylcne)s. Hereby, they applied the concept of reacting A2B-
typc monomers, in this case monomers containing both cyclopcntadienone (dicn-
2.4 0("11(/riti und Hypabrcmdttd Poly(plu!llylene)s 59
ophilc) and ethynyl functions (sec 1461). Simple polyaddition of the monomers
yield-; hyperbranchcd poly(phenylcne)s.
If the polyaddition is carried out (i) starting from suitably substituted core mol-
ecules containi ng. llucc. four ur six cthynyl fum:tiuns. ami (ii) with
mers containing TMS-protccted cthynyl functions, a facile divergent synthesis of
monodispersc dendritic poly(phenylene)s becomes possible. 13y selecting the cen-
tml (core) unit and di- (A
B-) or tetrafunctional monomers, dcndrimers of
different size (genemtion) and topology were accessible by applying a directed,
repetitive !4+2) cycloaddition/dcprotection sequence. Within the synthetic se-
quem:e, the authors made usc of the ditlcrent reactivity of protected and depro-
tected ethynyl functions within the key (4+2] cyctoaddition step. The largest
phcnylcne dendrimcrs generated via this procedure contain more than 140 ben-
zene rings (dian1eter up to 50 A) and surpass all previously known exan1ples of
phenylene nanoparticles 161 J.
In this way. Mullen and co-workers have, e.g., gencmted 43 starting from a
3.3',5,5'-tctmcthynylsubstitutcd biphenyl core and 44 164).
= TMS)-
Scheme 2-30.
60 2 Oligo- and Poly(pflcnylcnc)s
This modular concept allows for the synthesis of monodisperse dendritic phen-
ylene dendrimers of the fi rst (43a, 22 benzene rings) and second (43b, 62 ben-
zene rings) generation f651. Due to the dense packing of the pht:nylene rings,
shape-persistent nanostructures result. Several of these large phcnylene-type den-
drimers (e.g. 43a) can be further cyclized to giant polycyclic PAHs.
2.5 Conclusion
This article has been focussing on poly(phenylene)s with 1,4-(para-)phenylene
units since these polymers play a key role in the synthesis-driven search for elec-
tronic materials. From this article it hao; become clear that poly(phenylene) chem-
istry has not restricted its attent ion to linear ( I 0 -) structures. but has more re-
cently developed into 20- and 3D-structures as well, the Iauer serving as
tional shapt:-persistcnt nanoparticlcs.
The versatility of poly(phenylcne) chemistry can also be seen in that it consti-
tutes a platfonn for the design of other conjugated polymers with aromatic build-
ing blocks. Thus, one can proceed from I ,4- to I ,3-, and I ,2-phcnylene com-
pounds, and the benzene block can also be replaced by other aromatic cores such
as naphthalene or anthmcene, heterocycles such as thiophene or pyridine a<; well
as by their substituted or bridged derivatives. Conceptually, poly(phenylene)s can
also be regarded as the parent structure of a series of related polymers which arc
obtained not by linking the phenylene unit-. directl y, but by incorpomtion of other
conjugated, e.g. olefinic or acetylenic, moieties.
The careful control of electronic properties is, of course, a key motivation of
such structural changes; the so-called band-gap tuning being a particul arly impor-
tant concern. Etliciency of synthesis and structural homogeneity of the products
are essential ingredients of such an approach since failure to achieve e.g. quantita-
tive transformation of precursor polymers or to couple benzene units exclusively
in a para-fashion inteiTUpts the extensive n-conj ugation and hampers a reliable
On the other hand, it has also become clear that a materials-oriented synthcsis
of conjugated poly(phcnylene)s cannot narrow its attention to properties of mole-
cules only in sol ution, but has to include aspects of processing and supmmolecu-
lar ordering as well. The rigid-rod chamcter of PPPs therefore suggests the use of
chain stillness as a structurt:-fom1ing principle in the design of supramolecular
This article, while not being intended to provide a full account of poly(arylcne)s,
emphasises the synthetic aspects. The synthesis of conjugated oligomers aud poly-
mers is, however, always part of an interdiscipli nary approach with their active
physical function being a key conccm. In that sense the research being revi ewed
above concentmtes on physical properties rather than playing with exotic chemical
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3 Disorder and Solitons in Trans-Polyacetylene
Jasper Knoester and Maxim Mostovoy
3.1 Introduction
The elcctronit: and optical properties of conjug.ated polymers have received con-
tinuous <tllcntiou over the past two Jc.:adcs. From a h.:dmulogiGtl point of view,
the semiconducting nature and the large optical non-lincarities of these materials
are of great interest, while, li-om a fundamental point of view, the unusual excita-
tions in these quasi-one-dimensional many-body systems have stimulated much
research ll j . Undopcd polymer chains arc half-filled Pcierls systems:
their ground state is dimerized, which means that along the chain the carbon-car-
bon bonds have altemating length. In chemical structures, this alternation is seen
ac; an <tlternation of single (long) and double (short) bonds. This Peierls dimcriza-
tion contributes to the gap in the electronic excitations. Another contribution to
this gap originates from the electron-electron intcr..tctions and is refen-ed to as the
Mott gap [2).
Trcms-polyacetylene is one of the most studied conjugated polymers and in
model studies it is often considered as the generic example. The Pcicrls instability
of a half-filled tnms-polyacetylcne chain results in the appcar..tnce of two degener-
ate ground states, which only ditl'cr in the sign of their dimerization (+ and -
phase; see Fig. 3-1 ). As a result, topological excitations of trcms-polyacctylene ex-
ist in which one or more domain walls occur that interpolate between the two de-
gener..tte phases (Fig. 3-2). The possibility of such domain walls (also called soli-
tons or kinks) wa-; noted as early as 1962, by Pople and Walmsley (3). The real
breakthrough in the interest in solitons, however, did not occur until 1979, when
Su, Schriefter, and Hecger presented their SSH Hamiltonian [4). Using a varia-
tional approach, they found the energy and the size of the domain wall. In the
weak coupling limit their variational solution becomes exact 15. 6). It appeared
that the energy of a charged soliton wac; lower than the energy of electron or hole
excitations. Thus, the idea was put forward by Rice l71 and Su, Schrielfer, and
Hecger (4, gl that in char<Jc may be tr..tnsported by charged
solitons, mther than by electrons and holes. It should be notcu that solitons in
one-dimensional systems with a dcgcncr..ttc ground state also received much atten-
tion from high-energy physicists when the importance of topological objects in
yuantum field theory was recognized 19- 11 ).
The most interesting aspect of solitons is their charge-spin relation ll). Charged
solitons arc spinlcss, while neutral solitons have spin 1/2. Titis property provided
a natural explanation for the fact that in doped /mm-polyacetylene the electrical
3 Disorder and Solitons in Trans-Polyacerylene
Figure 3 1. Perfectly dimeri"L.Cd murs-polyacctylcne chain. Double and singk correspond to
hort and long bouds, respectively. The two ground state (b) arc IJ.:gcncr<IIC,
!Fq:ure 3-2. Solilon: a domain wall between the 1wo diiTcrcnt dimcrizcd pha.'leli shown in FigUI'C 3- 1.
dot indicates lhc unpaired electron which is localized nc-dJ' lhe domain wall in C>tsc il is neutr.ll.
rises much faster than the Paul i susceptibility (1 2, 131: adding charge
to a half-lilled chain creates charged solitons. Also, the ESR detection of neutr.tl
free spins in pristine tnms-polyacetylene [14, 151 could be understood on the ba-
sis of the soliton picture: neutml solitons may occur as defects, resulti ng from an
incomplete cis-trans isomerizati on (16].
Monte Carlo simulations [ 17, 18], the valence bond approach I 19, 20], and
g-ology [21-24) indicate that the Pcierls instabili ty in half-filled chains survives
the presence of electron-electron interactions (at least, for some r.lnge of intemc-
tion paJameters). This holds for a variety of different models, such as the Pcicrls-
Hubbard model with the onsite Coulomb repul sion, or the Pariser-Parr-Pople
model, where al so long-mnge Coulomb interactions are taken into account 12]. As
the dimcrization persists in the presence of inter,u:tions. also the
soliton concept survives. An important difference with the SSH model is that neu-
3.2 The Peierls Justubility and Solitons 65
tral and charged solitons no longer have the same energy: the neutral soliton is
lower in energy [25, 26].
Solitons are usually associated with excited or doped states, because in regular
chains their energy is too high ( - I eV) for thennal population in the ground
state. Conjugated polymer chains, however, in general are far from regul ar. One
important type of disorder is conformational disorder, which leads to disorder in
the electron hopping amplitudes along the chain. The si mplest way to treat such
disordered Peierls systems is a n'lCanfield treatmem, where the lattice dimerization
is assumed to randomly Ouetuate along the chain around some average value (the
so-called Auctuat ing Gap Model, FGM [27J). Using this approach, disonJer sup-
presses the dimeri zcd phase by localizi ng the and filling the Peierls gap
with clcctmn states.
If, instead, one allows the lattice to respond to the electronic disorder, one
finds that disorder induces a linite density of neul.-.al solitons in the ground state
of a single chain [28- 30]. These solitons destroy the long range order, unless they
arc suppressed hy suiTiciently strong inlen:hain intenu.:tions. 1l1e disorder-induced
solitons also affect the opt ical and magnetic properties or tmns-polyacctylene. In
the limit of weak disorder, we t'Ccently studied the creation of solitons by disorder
by using a mapping on the random ticld Ising model 131, 32}.
In this contribution, we review our recent work on disordered ttuasi-one-dimen-
sional Peierls systems. In Section 3-2. we introduce the b<L'iic models and con-
cepts. In Section 3-3, we discuss the localized electron states in the FGM, while,
in Section 3-4. we allow fM lauice relaxati on, leading to disorder-induced soli-
tons. Finally, Section 3-5 contains the concluding remarks.
3.2 The Pcierls Instability and Solitons
As noted in the the Peierls instability of a half-lillcd
kne chain results in the appearance of two degenemte ground states, in which the
lengths of carbon-carbon bonds altcmate (sec Fig. 3- 1 ). The Pcierls order parame-
ter fl (dimerization). dctined as the difference between the electron hopping am-
plitudes on neighboring even and odd bonds. has opposite sign in these two
states: fl =flu. The minima l energy inhomogeneous lattice configuration ll,. (x)
that satislies the boundary conditions
+A, for x ....... +oo
fl_,(x) -+ - AI
Lll for x ....... - oo
(3. 1)
nccc.-;sarily contains a domain wall separating regions with opposi te sign of fl.
This wnliguration is rcfened to as a soliton (ur a kink). The lallicc configumtion
fl, (x) =- fl., (x), satisfying the boundary conditions op[X>sile to Eq. (3. 1 ), is called
an antisoliton (anli kink).
66 3 Disorder a11d Solitons in Trans-Polyacetylene
The soliton lattice configumtion is characterized by the soliton position Xo and
the width of the domain wall which, quite genemlly, is of the order of the cor-
relation length <o in the uniformly dimerized chain. The soliton energy (counted
from the energy of the uniformly dimcrized ground state) is finite, since the en-
ergy density is concentmted in a region of size <s near Xu The soliton energy is
!independent of its position Xu. which makes solitons mobile objects capable of
l tmnsporting the charge or spin that is localized near the domain wall, along the
chain. (Actually, lattice discreteness results in a periodic dependence of the soliton
energy on xo, that is, however, r.llher weak and can be neglected [4, 8].)
In a seminal paper [4], Su, Schrieffer, and Heeger discussed the energetics of
solitons using a simple model of free electrons interacting with the Janice de-
scribed by the Hamiltonian:
f/d = - L
, ., 11 (c:!, . r.nc,.n + c!,.nc,1 l .n)
K ( )2]
f/laJ = 2M+2 Un+l - u, .
In the context of tran.\-polyacetylene ct
and c .o are, respectively. the creation
" n
and annihilation oper.nors of an electron with spin projection a in the n-orbital of
the nth carbon atom (n= l , . .. ,N) that is perpendicular to the chain plane (sec
Fig. 3-3). Furthem10re, u, is the displacement along the chain of the nth CH unit
from its position in the undimcrizcd chain, P, denotes the momentum of this unit,
and M is its mass.
I The electron-lattice intemction is introduced through the dependence of the
electron hopping amplitude on the carbon-carbon bond length:
t,_, ... = lo + a(u,- u,.H) . (3.5)
l'igure 3-3. A schcm;uic pi.:lurc uf a mms,lOiyacctylcnc ch01in. showing the 2tl: cle.:lrunic orbilill,,
which arc rcJ>emlicular to the plane funn . "tl hy the n-bontls (soliu lines).
3.2 Tile Peicds Instability cmd Solitous 67
The Coulomb intemction between the n-electrons is neglected. 11te standard
trtms-polyacetylene parameters are t
=2.5 eV for the hopping amplitude in
the undimcrized chain, C1=4. I cV/A for the electron-phonon coupling, and
K=2l eV/A
for the spring constant[!, 4, 8l
The SSH model (Eq. (3.2)) is, essentially, the model used by Peierls for his dis-
cussion of the clectron-Jauice instability [331. lls ground stale is characterized by
a non-zero expel:lation value of the operator:
and by a periodic lattice distortion wave with wave vector

1l1e undoped
tnms-polyacetylene chain contains one electron per site (half-filling), so that the
disto1tion wave vector 2kF equals rr/u (a is the length of a C-C bond in the umlis-
torted chain), which corresponds to alternating shifts of the CH units:
u, = (- )"un. (3.7)
The alternation of the bond lengths results in an ahemation of the electron hop-
ping amplitudes:

t,J, 1 1 = tu + - -;;- . (3.8)
with the Peierls order parameter .1
. 1l1e lattice dimerization opens a gap
in the spectrum of the single-electron excitations equal to 2.1o. In tmns-polyacety-

An imp01tant property of the electron Hamiltonian (Eq. (3.3)) is that for arbitrary
hopping amplitudes tll.ll.+l the spectrum or the single-electrons states is symmetric
with respect to t:==O; if f/1, is the electron amplitude on site 11 of an eigenstate with
energy c, then the slate with :unplitudes (- )"f/1
is also an eigenstate, with energy -1:.
In particular, in the uniformly dimerizcd state, the gap between the empty conduction
and the completely filled valence banJs mnges from


The ground stale of a (sufficiently long) t:hain with an odd number of units,
N == 2 L+ I, and periodic boundary conditions, obviously, cannot be uniformly di-
merized and must contain a soliton (the same is true for an odd chain with open
boundary conditions). In this case, because of the symmclry of the density of
slates, the energy of one electron state is exactly zero. For a half-filled chain (one
electron per carbon atom) the solitonil: ground state is neutral. It has. however,
spin 1/2, which is the spin of the singly occupied zem-energy level (the L doubly
occupied valenl:e states have total spin 0). If we now add another electron to the
zero-energy levd, the solimn ch:trge will be - l' and its spin will be zero. Similar-
ly, by removing one electron from the zero-energy state, we create a spinless soli-
ton wilh charge +e. In the free del:tron model the charged and neutral solitons
have the same energy, as they diller only by the occupation of the zero energy
68 3 Disorder and Solitons in Tra11s-Polyacetyle11e
In Ref. [4], the soliton lattice configuration and within the SSH model
were found numerical ly. Analytical expressions for these quantities can be ob-
tained in the weak-coupl ing limit, when the gap

is much smaller than the
width of lhe n-clectron band 4t
. At this point it is useful to define the lattice cor-
relation length:
e _ VF _ 2ato
o- 6o- 6o.
In the weak-coupling limit eo becomes much larger than the length of the unit
cell a (<
-7 a for trans-polyacetylene) and the Peierls gap has a strong effect
only on the electron states close to the Fem1i energy F=O, i.e., states with wave
vectors close to The interaction of these electronic states with the lattice may
then be described by a continuum, model [5, 6]. In this description, the electron
Hamiltonian (Eq. (3.3)) takes the form:
where the real order parameter at x,=2na is defined by
= l2J,- 1,211 - l2n.2Jr+ l (3. 11 )
Furthermore, a
and a
are Pauli matrices and
'I' (x) = ('I' Ra(x))
o 'l'u(x)
is the fermionic field operator. The first tem1 in the Han1iltonian Eq. (3. 1 0) de-
scribes the free motion of the electrons and the two amplitudes 'I'
(x) and 'II L (x)
correspond to particles moving, respectively, to the right and to the left with the
Fcm1i velocity v,.. The second term in the Hamiltonian descri bes the backward
scallering of electrons from the lattice distortion wave.
Momentum conservation impl ies that the wave vectors of the phonons, intcmct ing
with the electrons close to the Fermi surface, are either small (forward scattering) or
close to 2k.F=nla (backward scattering). In Eq. (3. 10) forward scattering is ne-
glected, as the electron inter.lction with the acoustic phonons is weak. Neglecting
also the weak q-dependcnce of the optical phonon frequency, the lattice energy reads:
I I [ I )
H..,, = A.nvF dx Q 2 Dr '
where A.=

is the dimensionless electron-lattice coupling constant and

Q =

bare optical phonon frequency at q=nl1.

3.2 The /nswbility aud Solitons 69
The continuum model with the Hamiltonian equal to the sum of Eq. (3. 1 0) and
Eq. (3.12), describing the interaction of electrons close to the Fermi surface with
the optical phonons, is called the Takayama- Lin-Liu- Maki (TLM) model [5, 6].
1l1e Hamiltonian of the conti nuum mollcl retains the important symmetries of the
discrete Hamiltonian Eq. (3.2). In particular, the spi!Cttllm of the single-particle
states of the TLM model is a symmetric function of energy.
By minimizing the chain energy

one obtains the self-consistency equa-

tion for
.. " t
= -
- L.)'l'o(x) a, f11
(x)) ,
where ( ... ) denotes the average over the many-electron ground state for the lat-
tice configumtion (x).
The x-independent solution of Eq. (3. 13) for the uniformly dimerized chain

(3. 14)
Here, W is a cut-off of the order of the n-band width, illlroduccd because the
right-hand side of Eq. (3.13) is formally divergent. As in the discrete model, the
spectrum of eigenstates of H.,. for has a gap between


sepamting the empty conduction band from the completely filled valem:e band.
The inhomogeneous soliton solution with boundmy conditions Eq. (3. 1) has the
form of a hyperbol ic tangent [5, 6):
"()A (X-Xu)
u, x = <->t1 lauh ""T, . (3.1 5)
with eo as defined in Eq. (3.9). For the soliton configuration, the spectrum of the
single-electron states also contains, apart from the valence band with highest

and the conduct ion band with the lowest energy one state with
zeru energy (sec Fig. 3-4):
C/>u(x) = (Tu)
(3. 17)

70 3 Disorder and Solitons in Trans-Polyacetylene
---------- =0
Figure 3-4. nlC onJer par.unc1cr 6,, (x) for I he solilon soiUiion (lhick line) mKI lhc clccuvn
for 1hc in1r..1gap slaiC uccomp;.mying 1hc solilon (c.loucd line) arc :.hown 10 1hc lcll. To lhc
righ1 lhc spectrum of singlc-dcclron SI<IICS for lhc solilon lauicc configur.tlion is cJcpic1cu.
denote the eigenvectors of a
with eigenvalues I . This state is known as the
"midgap" state. Its wave function has the spatial extension

and is local ized
near the soliton position x
. The energy of the soliton is of the occu-
pation of the midgap state, i.e., charged and nculml solitons have identical ener-
gies, given by:
Es = - 6o.
(3. 19)
The single-electron spectrum for the antisol iton solution, is exactly
the same as for the soliton, except that now the wave function of the midgap state
is given by
'llo(x) = o(x)l+} (3.20)
The existence of a stale with zero energy depends only on the topology of (x),
i.e., on how (x) behaves at x-+ co, and not on its precise fonn (34 ). .
Up until now we have only discussed the situation where the Coulomb intemc-
tion between the electf?ns is neglected. As we mentioned in the Introduction, the
soliton concept does survive electron-electron imemctions, although the energetics
differ from the above. We will rclum to this in Section 3.4.
3.1 Dismrler: Tire F/uctullling Gt1p Model 71
3.3 Disorder: The Fluctuating Gap Model
So far, we discussed perfect trm1s-polyacetylene chains. In pr..tctice, however,
polymer materials sutler from various kinds of disorder: confom1ational defects,
cross-links, impurities, etc. 12). Within the SSH model (Eq. (3.2)), effects of disor-
der were studied by introducing randomness in the on-site puLcntials or in the
hopping amplitudes (see, e.g., L35, 361). It was noted in Ref. l37) that the effect
of non-magnetic impurities in Peierls systems is similar to that of magnet.ic impur-
ities in superconductors. Based on this analogy. the existence of a gapless dimer-
izcd stall! was predicted for sulliciently stmng disorder )37. 38). We note that,
though the eflect of disorder on the Pcicrls state is, indeed, titrong, the analogy is
not exact, since the scauering from impurities, apart from "pair-breaking" tenns,
also results in (r.mdom) "pairing" terms. Most importantly, however, the eflect of
disorder on the electron motion in 4uasi-onc-dimensional materials cannot be de-
scribed satisfactorily by the Abrili.usov-Gorkov theory of superconuuctors with
magnetic impurities [39). because of the strong electron localization. Strictly
speaking, even in superconductors the gap is tilled wi th electron states lor an arbi-
trarily weak conccntmtion of magnetic impurities l40). These states are localized
near the regions where the concentmlion of the impurities is high and the super-
conductivity is locally destroyed. In this section we show that the disordcr-in-
uuccd state1> that Jill the Pl!ierl s gap arc localized ncar the regions where the di-
meri zation changes sign. We also discuss the encct of these stales on the opt ical
properties of disordered Peierls chains.
If the random variations in the hopping a mplitudes and the on-site potentials
arc small compared to l u. the disonler may be deseribeu using the continuum
model. In this case, the density of slates can be found an:1lytical ly 127, 4 1). Here.
we concentmte on disorder in the electron hopping amplitudes (off-diagonal disor-
der). As the Peierls order parameter is related to the ahemating part of the hop-
ping amplitudes, off-diagonal disorder results in random lluctuations of the order
pammeter in the clcct.ron Hamiltonian (Eq. (3.10)) around some average
= 6o + 1/(x) , (3.21)
where '1 (x) is the fluctuating part, which is assumed to have a Gaussian corrclator,
{IJ(X)IJ(y)} = AJ(x - y) . (3.22)
This model, which is sometimes referred to as the Fluctuating Gap Model (FGM)
142]. has been used to study various aspects of quasi-one-di mensional systems.
Examples arc the thermodynamic properties of quasi-one-dimensional organic
compounds (NMP-TCNQ, TIF-TCNQ) 127), the effect of disorder on the Peicrls
tranl>ition 143. 441. and 1hc erti:c1 of quantum lallice llucluations on the oplical
of Pcicrls materials 141, 45, 46).
72 3 Disorder and Solitons i11 Trans-Polyacelylene
As we saw in Section 3.2, in the absence of disorder

the electron spec-

m has a gap between the energies and e=+6o. Disorder gives ri se to the
ppearance of electron states inside the gnp, although for weak disorder a pseudogap
till exists. Using the "phase fonnalism" (47], Ovchinnikov and Erikhman derived a
losed expression for the integrated average density of states p(c')dt!) of the
GM at arbitrary disorder strength [27]. The average density of states, p(c), that
y be obtained from their result, is plotted in Fig. 3-5 for three values of the dimen-
ionless disorder strength g = A/( vF6o). For small di sorder, one clearly observes
pseudogap. Close to the center of this pseudogap (lei the energy depen-
dence of the density of states is approximately given by [27]
ere and below we assume e to be positive, which is sufficient in view of the
ymmetry of p (e) for the Hamiltonian Eq. (3.1 0). For g < 2 the density of states
as a pseudogap (the Peierls gap filled with disorder-induced states). For g > 2 the
seudogap disappears and the density of states becomes divergent at c=O.
From Eq. (3.23) it is clear that at weak di sorder (g I) the density of states close
to the middle of the pseudogap is strongly suppressed. The reason for this is that a
large fluctuation of (x) is required in order to create an electron state with energy
This makes it possible to apply a "saddle-point" approach to study the typ-

Figure 3-S. Disordcr-avcrag!XI density of st:11cs p(1:) in the FGM for three of the dimcnsiunlc....s
disorder strength: g=O. i.e., no disorder (curve a). g=0.25 (curve b). g=4 (curve c). 1l1c fn:c <!lcctron
density Of SI:IICS was CI IU unity.
3.3 Di.wmler: The Flucllwting G11p Ma(/(/ 73
ical electron states occurring at these low energies and to calculate disorder averages.
This method, which gives much additional insight into the nature of the states deep
inside the pseudogap, was used in Ref. [48]. In that paper, we showed that the "sad-
dle-point" disorder fluctuation determining the most probable form of the low-en-
ef'_;y electron states, has the form l>f a soli ton-anti soliton pair, where the scpar..ttion
between the soliton and the antisoliton depends on the energy r. of the state. The
wavefunction of the electron state induced by this lluctuation contains two peaks,
whidl are localized near the two kinks of the fluctuation. Away from the kinks,
the electron wave function falls oiT exponentially on u length scale

In the remai n-
der of this section, we will describe these results in somewhat more detail and dis-
cuss the average density of states and the average optical absorption spectrum that
may be obtained in thi s way.
1l1e ''saddle-point" disorder fluctuation [49- 5 1] (also called the optimal fluctua-
tion) IJ(x) is the least suppressed one among the required large lluctuations. It can
be found by minimizing.
The first term in this equation describes the suppression of the probability of the
fluctuation with the corrclator Eq. (3.22) (the weight pl1l(x)J of the disorder con-
figuration is exp (- J d.nl (.x)) ). while the second term stems from the (:ondi-
tion that the energy c+[IJ(.x)J of the lowest positive-energy single-electron state for
the disorder realization IJ(X) equals 1:. 1l1e 11 is a Lagrange multiplier. It can
be shown that the disorder lluctuation 1/(X) that minimizes A [1J(x)J has the form
of the soliton-antisoli ton pair contigumtion described by [4H):
IJ(x) = -v,.K [tanh ( K (x- x0 (K (.x- , (3.25)
where x
describes the position of the disorder fluctuation in the chain, R is the
distance between the soliton and the antisoliton, and K is determi ned by
v,.K =

tanh (KR) . (3.26)
1l1c instanton is shown in Figure 3-6 by plotting = 6t
+ 1j(x) . The spectrum
of single-electron states for this is well-known fmm studies of polaron states
within the SSH H;unillonian 152, 531 and is also plotted iu Figure 3-6. lt consists
of a valence band (with highest energy - L1
), a conduction band (with lowest en-
ergy 6t1), and two localized intmgap states with energies (R), where
c (R) - 6tt
+ -cosh (KR)
Thus, the soliton-antisoliton scpamtion R is fixed by the condi tion c+(R)=c.
74 3 Disorder and Solitons in Trans-Polyacetylene
- - - - - - - - - - - - - - - - -
Figure 3-6. The sohlon-uuisolilon lauicc coofigurauon (lhick line) and 1hc clccuvn
= lrp_(x)J
li.lr lhc corrc!>ponding slate> (doucd line) are shown to 11..: lcfl . To lhc
righ1 Ill<! of singlc-clc.:rron si<IIC> for 1hc sol ilon.utlisolilon cunligumliun is dcpiclcd.
The two intragap states ll':a:(x) arc the symmetric and antisymmetric superposi-
tions of the midgap states localized ncar the soliton :.md the antisoliton:
I ( .fKl2 .fKl2 )
ll':t(x) = J2 cosh (K(x - cosh (K(x '
where 1} are defined by Eq. (3.18). :1: (x) is schematically plolled in Fig-
ure 3-6.
The energy splilling 2 between the intragap states decreases exponentially
with the soliton-antisoliton scpar..ttioo, so that for e 6o.

the correlation length dctincd in Eq. (3.9). The suppression factor
Eq. (3.24),
I 2 226o
A[17(x)] ::::: - (2.6o) R :::::-ln- ,
2A g I;
also depends logarithmically on energy, so that the weight of the saddle-point con-
figuration is
Comparing this result to Eq. (3.23), it is seen to give a good estimate for the
shape of the density of states inside the pseudogap at g I.
1.3 Di.wrclc:r: Tire Fluctuuting G11p Model 75
A more detailed calculation requires peri"om1ing the Gaussian integration over
the disorder realizations close to the "saddle-point" eonfigumtion Eq. (3.25). One
then finds the following expression for the average density of electron states per
unit length,
{p(c)} = _ e_ ( ec ) : -
ngvF 26o
For g I, this agrees with Eq. (3.23), confim1ing the validity of the "saddle-point" ;
approximation at small energies and weak disorder. The easiest way to get the result
Eq. (3.32) is to use the correspondence between the averaging over disorder realiza-
tions 17 (x) and the quantum-mechanical averaging over the ground slate for a certain
double-well potential I 54!. 1l1e .. saddle-point" disorder fl uctuation then corresponds
to the instanton tunneling the wells 155, 56).
The form Ey. (3.28) for the most probable disorder-induced electron states can
also used to calculate. in a relatively su-aightfurward way, the optical absorp-
tion cocllicient fur a half-filled chain at photon energy w 26
and g I .
Again, only a large disorder 11111.:tuation can make the energy uificrence between
the empty and tilled electron levels small. With the highest probability the photon
absorption will induce a tmnsition from the highest occupied to the lowest unoc-
cupied electron state. Due to the particle-hole symmetry, the energy of the lowest
unoccupiL'Ci state at half-tilling should equal +w/2, while the energy of the highest
doubly occupied state should equal - w/2. Hence, the saddle-point" disorder con-
figuration, whose probability largely detennines the absorption r.lle, is given by
Eqs. (3.25), (3.26), and (3.27) with r.+(R)=w/2.
Thus, in the saddle-point'' approximation, the absorpti on coefficient is the
product of the averaged density of states (which is essentially the probability to
find the necessary disorder fluctuation) and the osci ll ator strength of the optical
tr.msition between the two intr..tgap levels:
Here, d is the dcctric dipole operator, 111
(.r) arc the wave functions of the intmgap
states with energies w/2, and Cis an w-indepcndent coenicicnt (for small w, we
can neglect the weak w-dcpcndence of the real pan of the dielectric constant).
From Eq. (3.28), one finds that the oscillator strength is proportional to the
square of the soliton-antisoliton separation R. Using this, Eq. (3.33) reduces to the
tullowing lurm for the average absorption codlicicnt at low photon energy:
Altemative evaluations of the absorption spectrum (or the optical conductivity) of
Peicds systems within the FGM have been rcpo11ed in Refs. L451 and l46J. In those
76 3 Disorder tJnd Soli1011s in Tmlls-PolytJce/ylt'ne
papers, however, the factorization approximation, ( GG} = (G) (G). was used to eval-
uate the disorder average of the product of two Green functions. From the above, it is
clear that this approximation is not valid at low photon energies, as it results in the
optical conductivity (as well as the absorption coefficient) being proportional to the
second powcrofthc weight Eq. (3.31), ratherthan the lirstlcf. Eq. (3.33)1. Of course,
at weak disorder the absorption at photon energies w is small anyhow, but the
factorization approximation makes it even much smaller.
3.4 Disorder-Induced Kinks
In the previous section we a..o;sumcd that disorder results in random fluctuations of
the order parameter around some avemge value

Such an approach is, essen-

tially, a mean field treatment of the lattice. It re4uire:-. suflicicntly strong inter-
chain interactions, whose role is to establish a coherence between the phases of
the order pammeter in dilkrent chains.
In this section we consider the opposate case of very weak inkrchain interac-
tions .. In a first approximation, we neglect them entirely and study the effects of
disorder in isolated Pcierls chains. In this approach we no longer assume the
chain lattice to be uniformly dimcrized. Instead, for a given disorder realization,
we have to find the lattice configuration that minimizes the chain energy. In a
Peierls chain with a doubly degenerate ground state, even weak disorder can then
produce significant changes in the chain's lattice configuration. Numerical study
of the minimal energy lattice configumtion of a half-filled chain described by the
SSH model indicated that disorder in the electron hopping amplitudes can induce
kinks in the lattice dimerization l28, 29). In Ref. l30) we showed, independently
of the model of the Peierls chain, that the density of the disorder-induced kinks is
approximately proportional 10 the disorder strength. Furthcm1ore, if the Coulomb
interaction between the electrons is taken into account, the kinks are neutral and
For explicitness. let us assume that off-diagonal disorder is caused by chain
twists. which randomly diminish the overlap between the rr-orbitals of neighbor-
ing carbon atoms (see Fig. 3-7). The electron hopping amplitudes that depend
both on the interatomic distances and on the relative orientation of the electronic
orbitals on neighboring atoms can then be wriuen in the form:
1,,,H 1 = to+ a(u,.- u, ... . ) + c)r,,, +J . (3.35)
Here, the second term describes the change of the hopping amplitudes due to the
displacement of the atoms parallel to the chain [cf. Eq. (3.5)} and the third term is
a mndom contribution resulting from the conformational disorder (chain twists).
While the lattice displacements 11, arc dynamic variables, the lluctuations
due to disorder <lfe assumed to be frozen ( .. 4ucnched" disorder).
: <I> .
3.-1 Di.mnler-lndun:d Kinks 77
l.<' igurc 3-7. A simplifJC<.I pK:turc of a trcm.-polyacetylcnc chain with conformational <.lisor<.ler: the right
part uf the chain rotated with to its left over the angle "' The clcctron hopping ampli
tude on the twistc<.l bond is reduced by a factor of cos</'
The Peicrls order parameter is the alternating pa.1 of the hopping amplitudes
bee Eq. (3.11) I and now consists of two parts
The first part is the lauice dimerization,
which describes the alternating part of the hopping amplitude determined by the
shifts u, of the atoms and is the usual order parameter of the SSH model. The
second term in Eq. (3.36) describes the disorder
1J(2na) = Jt2, - 1.'211 - c512,.2, t l . (3.38)
Note that, while the mndom chain twists always decrease the hopping amplitudes
(all c5t,J,+I are negative), IJ(x) can be both positive and negative, as it is the alter-
nating part of the tluctuations. As in the FGM, we consider white noise disorder
with a correlation function given by Eq. (3.22). 1l1is corresponds to independent
random variations of the hopping amplitudes c5t on differclll bonds.
llte diflcrencc between Eq. (3.36) and Eq. (3.21) i:-. that in the FGM the lattice
was assumed to be uniformly dimerizcd, Llaa
{x) = wherea..o; now it has to be
found by minimizing the chain energy:
In the Hamiltonian Eq. (3.39) the first term is the harmonic lauice energy given
by Eq. (3. 12). It depends only on 6
;,., i.e., the part of the order parameter that de-
scribes the lattice disto11ions. On the other hand, the electron Hamiltonian Hc1 de-
pends on il(x), which includes the changes of the hopping amplitudes due to both
the lattice disto11ion and the disorder. llte free electron part of is given by
Ell. (3. 10), to which we ;Jlso add ;a term . .-. th;at describes the Coulomb interac-
78 3 Disorder and SCJiiiOilS in Trans-PCJlyacety/ene
tion between the electrons. Actually, the precise form of HcJ.cl will not be needed
for the following consideration, as long as the interaction between the electrons is
sh011-rangcd and does not destroy the dimerized state, i.e., we assume that in the
absence of disorder the (half-lilled) dl<lin reaches iL-; minimal energy in either one
of two unifom1ly dimerized configurations:

(x)=L\,. In particular, the on-site

Coulomb repulsion satisfies these criteria (17, 19, 20]. As we shall shortly see,
the existence of two degener.ttc ground states, which also implies the existence of
kink solutions, is crucial for the appearance of disorder-induced kinks, while the
precise form of flc
is only important to the extent that it determines the value
of Ao and the kink creation energy Es.
An important property of the dimeri zcd Peierls state is the existence of gaps in
the spectra of spin and charge excitations. For free electrons both gaps
are equal, while in the pre..'ience of Coulomb repulsion the spin gap is smaller
than the charge gap 123. 241. In what follows, we wi ll assume the temperature to
be much smaller than these two gaps, so that we can neglect electronic excitations
and replace flc.l6(x)] by its ground state expectation value.
Next, we argue that the minimal-energy lattice configuration in the presence of
disorder may contain kinks. At zero temperature the lattice conligumtion, i.e.,
6 1a1(x), has to be found by minimi zing the total chain energy (Eq. (3.39)) with re-
spect to

(x) at a given disorder realization 'I (x). This makes 6
., (x) implicitly
dependent on YJ (x).
In the absence of disorder the total energy of a half-filled chain ha<;, apart from
the two minima for 6(x)=6
(corresponding to the two degcnemte uniformly
dirnerized configurations), infinitely many nearly perfect extrema. These are the
multikink configur.ttions, in which a sequence of kinks and antikinks interpolate
between and +llo and vice versa (see Fig. 3-8). A kink is locally stable, i.e.,
the chain energy increases, when its form is perturbed. The energy of a multikink
configuration can be decreased only by changing the distances between the kinks.
However, when the sepamti on between neighboring kinks is large compared to
their size (which is of the order of the correlation length

= v,.-f the change
of the energy caused by shifts of the kinks is exponentially small, so that the en-
ergy of the configumtion with N kinks is approximately
- 6 :
Figure 3-8. A mullikink cunfigur.uiun.
1.4 Di.wrrler-lllduce(/ Kinks 79
Here, . is the kink creation energy and
is the chain energy in the absence of
kinks. As discussed in Section 3.2, kinks can be either charged and spinless or
neutral with spin In the SSH model

both types have the same en-

ergy Ill; if the repulsion hctwccn dc'-t mns is wkcn into account. the
neut r...l soliton has lower energy (25, 26(. In in the limit U 4tu (U is
the on-site Coulomb repulsion), the charge excitati ons have a gap U-4t
and the low-energy physics is described by the intcrJCtion between the Janice and
the spins of the electrons (the so-called spin-Peicrls model [57, 58]). In this case,
the energy of the neutral soliton is of the order of the gap in the dimcrized spin- .
Peierls chain, while the energy of the charged soliton U is much larger. Since
the on-site Coulomb repulsion in trtms-polyacetylene is appreciable [2), only neu-
tml kinks are induced by disorder in trans-polyacctylenc chains.
Let us now consider the change in the energy of a multikink configur.uion due
to weak di sorder. We will denote the lattice conli guration containing N kinks,
whose positions arc described by the N-dimensional vector z = (z
, z2, ... , ZN ), by
6N(xlz). To first order in fJ (x), the correction to the energy of the configuration
where the extremum condition for the con11guration 6N(xlz) at zero disorder was
For instance, the change in the energy of the uniformly dimerizcd configuration
(6(x) = llo) due to di sorder is
. 26o J (
c>Eo = - --
dXIJ x) ,
while for Lhe configuration with an antikink at ::
and a kink at z
, such that the
whole disorder fluctuation lies between ::
and z
, the change of energy equals
o2=-<5o. because between Z1 and Z2 6 2(xl::.,z2):::::: - 6o. We thus sec thal, in
the disordered chain, the conligumtion obtained by the perturbation of a kink-anti-
kink pair is energetically favorable to the perturbed uniform configur.ttion if
Here, we introduced
which for free electrons (SSH model) equals I [sec Eq. (3. 19)). Since the fluctua-
tions in d..n7(x) grow with the chain size L, for a suiTiciently long chain the in-
equality Eq. (3.43) can certainly be futritlcU, no maHer how small the disorder is.
80 3 Disorder cmd Solitons in Trans-Polyacetylene
The creation of kinks by off-diagonal disorder is illustrated in Figure 3-9. The
thick line is the ground state order parameter lln = 6(2an) = I2Jr- l ,2n - t
,,a+l for
a discrete chain of 160 carbon atoms. obtained by numerically minimizing the
total energy for one particular realization of the disorder. In this example, we ne-
glected the Coulomb repulsion and used standard SSH parameters [I]. It is dearly
seen that the order parameter fluctuates ncar a soliton-antisoliton pair configura-
tion. The disorder realization that was used ru; input is visualized by the thin line,
which gives The thin line in
fact directly represents the order parameter along the chain if we neglect the lat-
tice relaxation (the order parameter in the FGM model). In that case, no Janice
kinks are created.
It is not difficult to estimate the density of solitons induced in the chain by
weak disorder [30]. As for weak &-.order the distances between neighboring kinks
on the chain are large compared to the kink size c;
, the order parameter in a mul-
tikink configuration (Fig. 3-8) may be considered to take only two values:
6(x)=6o. This allows one to replace the order par.1meter by an Ising variable.
Then, Eqs. (3.40) and (3.41) describe the energy or (the continuum version ol) the
one-dimensional random-field Isi ng model. In this mapping, solitons take the role
of spin-flips, while the disorder IJ(x) is the analog or the random magnetic field.
As was first estimated by lmry and Ma (59], the balance between the cost
of spin-flips and the energy gain that may be obtained by orienting the spins par-
allel to the local magnetic field, lead to an average density of spin-flips (or soli-
tons in our case) given by:
n=-= 2
L (r.,A.v,.-)
This estimate, which is based on simple scaling arguments, may be substantiated
by calculating the free energy of a disordered Peierls chain, as we did in
Ref. [3 1]. Treating the lattice vibrations classically, the final result for the kink
density is

20 40
60 80
flgurc J.\1. The numerically obLainC\1 onlcr par.unctcr along a pulyacctylcnc chain of 80 pairs of car-
bon a1oms for one panicular (bul lypi.:al) realizalion of off-()iagonal disonlcr. 1l1C lhin lioc does not
account for lauic.:c relaxation, lhc 1hic.:k line (adaplc(] frotn Rcf. l 301}
3.4 Di.mrder-lncluCl'd Kinks 81
n(A, T) =
(y,J.vF) (I+
where T
is a temperature that is propot1ional to A
and which generally is much
smaller than E_ It can he argued and shown hy comparison to numerical simula-
tions [31 J, that the continuum model at T
behaves within a good
approximation as the discrete Ising model at zero temperature. Titus, (3.46)
gives corrections to the estimate by Imry and Ma that arc of the order A
If the
lattice vibmtions arc treated quantum-mcchaniclly, which prob<lbly is more
propri ate in view of the typical vibmtion frequencies of I o K, the result is very
similar in fom1 to Eq. (3.46); the lowest-order corrections then are of the order
A7ts [541.
Finally, we discuss the consequences of the disorder-i nduced solitons for the
optical and magnetic properties. In the absence of elcctron-clcctron interactions,
the finite density of kinks le<1ds to the appeamnce of a peak in the single-particle
densi ty uf st<1tes at t:=O, because each kink carries an electron state with zero en-
ergy (Section 3.2) [ IJ. At weak disorder this peak is sharp since the distances be-
tween the kinks arc large. so that the splitting of the energies of the electron
state.<> localized ncar diflcrent ki nks due to their mutual interaction is very small
( rv exp ( - t,)). The peak in the density of states should result in a midgap peak
in the optical absorption spectrum. In undoped trluls-polyacetylene, however, this
peak is not observed. This could be ascribed to a small magnitude of the di:;order,
but this is unlikely, because the: avcmge (presumably disorder limited) conjugation
length of trans-polyacetylene is known to be of the order of several tens of car-
bon atoms [60).
Because the on-site Coulomb repulsion decreases the neutral soliton energy
(25, 261 (y, < l ), it increases the kink density (Eq. (3.45)). At the :mme time, how-
ever, the Coulomb interaction shifts the absoavtion peak resulting from the neutml
kinks toward.'> higher cncr<.;ies [25, 261. where it may merge with the peak result-
ing from interband tmnsitions. This may explain the absence of a clear midgap
peak in the absorption spectrum, but it does not reconcile the theory with mag-
netic measurements. The neutral disorder-induced kinks have spin 1/2 and should
contribute to the magnetic susceptibility. However, the observed Curie susceptibi l-
ity for undoped trans-polyacctylcne corresponds to only one free spin per 3000
carbon atoms [ 14), which is much smaller than the avemge conjugation length.
These contradictions between theory and experiment indicate that the consid-
cr.Jtion of totally isolated chains of trans-polyacetylcne, which we restricted our-
selves to in this section. is too strong an approximation. Even if the interchain in-
temctions resulting from interchain electron hopping (611. Coulomb repulsion be-
tween electrons in different chains (62), and exchange by three-dimensional pho-
nons, arc not strong enough to bring us in the limit of the FGM (Section 3.3),
they still play a crucial role in suppressing the creati on of isolated kinks. The in-
terchain interactions tend to favor a coherence between neighboring chains, in
which, for instance, the double bonds on neighboring chains arc aligned. Thus, in-
terchain remove the degneri.lcy of the two uniformly dimcrizcd stales:
82 3 Disorder and Solitons ill Trans-Polyacetylene
The creation of kinks in one particular chain results in the appearance of a string
with the "wrong'' sign of the dimerization (as compared to the nei ghboring
chains) between the kink and the antikink. The energy cost of such a stri ng is pro-
portional to its length r, resulti ng in a linear potential.
V(r) = Kr, (3.47)
that tends to bind kinks to antikinks. The coefficient K measures the strength of
interchain interactions and may be called the string tension.
In order to create a kink-antikink pair in the presence of interchain interacti ons.
the disorder should not only compensate for the creation energy of the kink and anti-
kink, but also for the energy of the stri ng. Therefore, interchain intemctions suppress
the creation of disorder-induced kinks. The thermodynan1ics of interacti ng disor-
dered Peierl s chains and the dependence of the densi ty of kinks on the disorder
strength and the temperature were studied in Refs. 132, 63, 64]. Although. qualita-
ti vely, these models explain the above noted contmdictions between theory and ex-
periment, a quanti tati ve comparison is hard to make: estimates for the interchain in-
temctions have large error bars and, moreover, an independent measure for the dis-
order is not known. As in the above picture the Curie-like part of the magnetic sus-
ceptibility of trans-polyacetylene is given by the susl:eptibil ity of the disorder-in-
duced kink-antikink pairs, a calculation of this quantity and a comparison to experi-
ment may shed more light on the actual situation.
3.5 Concluding Remarks
In this contribution, we discussed effects of disorder on the electronic propet1ies
of quasi-one-dimensional Peierls systeJTL<;, like the conjugated polymer
acetylene. Since polymer materi<1 ls generally are mther disordered and the effect
of disorder on any quasi-one-dimensional system is strong, a proper descri ption of
these materials requires consideration of such effects.
As we have seen, disorder in the electron hopping amplitudes suppresses the di-
merized Peierls state. The mechanism of the suppression, however, depends on the
strength of the interchain interactions. For strong interactions, disorder decreases the
average value of the dimcrization by filling the Peierls gap with localized electron
states. We showed that the most probable fom1 of the wave function of the electron
states lying deep within the Peicrls pscudogap contains two peaks. The "saddle-
point" disorder lluctuation, which induces such a state, has the form of a solitou-
antisoliton pair and the peaks of the wave function are localized ncar the two kinks
of this fluctuation. The "saddle-point" approach allows for a relatively easy calcula-
tion of the low-energy density of states and the absorption coellicicnt.
While for strong interchain intemctions large deviations of the order pammcter
from its avcmge value arc unl ikely, for weak interactions the minimal-energy lat-
tice configumtion of disordered chai ns contains a linitc density of kinks and anti-
3.5 Cvucluding Remarks 83
kinks. These tend to destroy the long-range order of the Peierls state. The inter-
chain interactions bind nearest kinks and anti kinks into pairs and the transition
from the ordered into the disordered state occurs at the tempcmture at which the
pairs dissociate into free ki nks and antikinks. l11e disorder-induced kinks arc neu-
tml and have spin Even when they are bound, they strongly affect the optical
and magnetic propenies of disordered Peicrls systems.
We note that in this contribution, we have treated the lattice motion classically.
In lrtms-polyacetylene, however. the eflect of lattice quantum fluctuations is
rather important, because the CH units are relatively light l65]. In pat1icular, it is.
well-known that the quantum nature of the lattice adds a "subgap" absorption
wing to the low-energy side of the rigid-band absorption spectrum 166, 67]. Sev-
eral authors have modeled the eiTect of quantum Janice lluctuutions by static dis-
order. which was then tn:atcd wi thin the FGM H5. 461. 1l1e underl ying reason for
this view is the relative slowness uf the lallice motion. II should he noted. how-
ever. tl1<1t the strong dCJ1Cndem.:e of the lauice dynamics on the occupation of the
single-electron levels makes it impossible to descri be the quantum lauicc before
and after the absorption process hy one ;md the same static disorder. Incorporat-
ing the quantum lattice effects through disorder gives a fi nite absorption codll-
cient down to zero photon energy. A correct quantum treatment of the lattice,
however, should lead to a finite absotption threshold, given by the energy of a so-
liton-antisoliton pair (46.,/n wi thin the SSH mudd).
For long (infinite) uwu-polyacetylenc chains, the treatment of quantum lattice
fluctuations is very complicated, because many lattice degrees of freedom couple
in a non-linear way to the lowest electronic tr..Jnsitions. We have recently shown
that for chains of up to 70 CH uniL.;, the amount of relevant lauicc degrees of
freedom reduces to only one or two, which makes it possible to calculate the low-
energy part of the absorption spectrum in an essenti ally exact way [681. It re-
mains a challenge to study models in which both disorder and the lattice quantum
dynamics arc considered.
Note added in proof:
A recent theorctic;l analysis of the temperature dependence of the magnetic re-
sponse of neutral disorder-induced solitons 169], has revealed that these solitons
may explain the low-temperature deviation from Curie behavior that is observed
in experiments on Durham tran.v-polyacctylcne l70]. A more stringent test of the
theory would involve extending these experiments to even lower temperatures
(down to I K or lower).
A< k II (I, ,., ('{ lg {'1/1 ('Ill.\"
We would like to thank M. T. Figge and Professor D. I. Khomskii l(>r useful dis-
cussions. This work is pan of the resemch programs of the "Stiehting Scheikun-
dig Ondcr.wck in Nederland (SON)" and the .. Stil:hting vuor rundamcntccl On-
derwck der Materie (FOM)" which arc financially supported by the "Nedcrlandsc
Organisatic voor Wctenschappclijk Onder.wck (NWO)".
84 3 Disorder and Solito1zs ilz Truns-Polyucetylene
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38. K. Journ. Phys. C 19117. 2/, 5361.
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References 85
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4 Gas Phase to Solid State Evolution
of the Electronic and Optical Properties
of Conjugated Chains: A Theoretical Investigation
Jerome Comil, Donizetti A. dos Santos, David .Beljonne,
Zhigang Shuai, and Jean-Luc Bredas
4.1 Introduction
At the end of the seventies organic conjugated polymers emerged as very aUr.JC-
ti ve materials after the discovery that their electrical conductivity could be in-
creased by seveml orders of magnitude upon chemical or clcctrochemical treat-
ment referred to as doping in to the physics of semiconduc-
tors) [I j . Extensive theoretical and experimental studies initially addressed the
properties of trcms-polyacetylene [2] and then shifted towards more environmen-
tally stable conjugated chains such as poly(pam-phenylene) (PPP), poly(para-
phenylene vinylcne) (PPV), polythiophcne (PT), poly aniline (see Fig. 4-1 ),
which incorpomte aromatic rings into their backbone [3]. In 1990, the first report
of electroluminescencc from PPV [4} renewed the interest in conjugated polymers
and opened the way to the of electro-optic devices by exploiting their
semiconducting propea1ics and high luminescence yield. Ellicient organic light-
emitting diodes (LEOs) [5- 7] now available in the whole UV-VIS range [8-
1 0) and they are almost into the commercialization stage. Conjugated polymers
arc also used as acti ve clement in light-electrochemical cells I II], photodiodes
[12, 13], and solid-state lasers [ 14-16}.
In spite of outstanding achievements in the field of device fabrication, a full
understanding of the intrinsic electronic and optical properties of the conj ugated
chains is still far from being complete [1 7 j . This is partly due to the fact that the
experimental results strongly depend on the purity and/or morphology of the sam-
ples; hence, much caution h;.ts to be exercised when comparing different sets of
data. In this context, the theoretical techniques of quantum-chemistry can prove to
be useful in order to improve the understanding or the electronic and optical prop-
erties of the chains, for instance to chamclcrizc the nature of the excited states
playing an essential role in the electro-optic devices.
Accordi!lg to a large number of experimental studies, the most stable photogcn-
erated in the lowest excited states of conjugated chains are electron-hole
pairs bound by Coulomb attraction and associated to a local deformation of the
backbone, i.e., polaron-excuons [ I g j. A good insight into the properties of these
species be provided by quantum-chemical our rccen1 theoretical
88 4 Gas Phase to Solid State Evolt11io11 of the Electronic uud Optical Properties

Figure 4- 1. Chemical Slruclure of: (I) trwu-polyacclylcnc (II ) poly(paru-phcnylcnc vinylcnt:); (Ill)
poty(puru-pbcnytcnc); (IV) potylhiophcnc; uno (V) poly;milincs.
studies on the lowest excited state in PPV oligomers (i.e., the state acting as
source of light emission in LEOs ami lasers) have all owed us to describe the ab-
sorption [ 19] and photoluminescence (20) spcctm of various PPV oligomers and
to chamcterize the nature and chai n-size evolution of the relaxation processes tak-
ing place upon photoexcitation [21]. The choice of tinite-sire systems to mimic
the properties of actual polymer samples can be justi fied in many instances by the
reduced degree of delocalization o.1 long the chains, resulting from the presence of
physical or chemical impuriti es (22]. To further demonstrate the suitability of the
oligomer approach, we show in Section 4.3 that a detailed analysis of the wave-
function of those excited stales that are optically coupled to the ground state in a
long PPV oligomer, provides complementary information on the geometric and
electronic propenies of the electron-hole pairs. Furthcnnore, we demonstmte that
the photocurrenl action spectra measured for PPV and substituted derivatives can
be rationalized on the basis of the results of these calculations 1231.
We emphasize that some issues, such as the exciton bi nding energy, still remain
controversial; thi s pammeter, which we detinc as the difference between the energy
of a fully relaxed polaron-exciton and that of two separated polarons of opposite
sign, has been estimated in recent theoretical and experimental studies lo be in the
range of 0.0 to 1.0 eV 1241. Si nce the geometric relaxation effects are very similar
for an exciton and two separ.ued polarons l24J, the amplitude of the exciton binding
energy in the solid state results from a fine balance between: (i) the Coulomb aurae-
lion between the electron and hole and (ii) the polarization ell"ecLo; stabilizing the free
carriers (which have been largely overlookell in the past). A unitied picture explicitly
taking these two dominant contri butions into account is still lacking.
Calculations performed on isolated chains appear to be fully consistent with a
number of experimental data. However, many recent experimental studies have
clearly demonstmted that interchain effects can play an important role [25- 32). In
Section 4.4, we rcpon the results of COITclatcll calculations investigating the way
.J.2 Therm:tic:ul Methodology 89
effects modulate the absorption and emission characteristics with re-
spect to isolated PPV chains.
When the chains arc isolated (i n highly dilute solutions or in inert host ma-
trices), the luminescence (which originates from the lowest excited state, as stated
by Kasha's rule [33)) competes with seveml non-mdiative decay channels. In this
case, time-resolved studies reveal that the dynamics of the lumi nescence are iden-
tical to those of the picosecond photoinduced absorption features; this indicates
that intrachain excitons are the only photogenemted species (2&-29]. In the solid
state, various manifestations of interchain couplings have been observed, among
them: (i) a significant increase in the radiative lifetime without any substantial
los.'> in quantum efticiency (28j ; (i i) a lack of correlation between the dynamics of
the luminescence and those of the fast photoinduced peaks (25, 32j; and (iii) a
signilicant decrease in lluoresccnce quantum yield (26). These studies indicate
that intcrchain species present in conllcnsed media even though their nature
and origin is still unclear. Therefore by means of quantum-chemical calculations it
is of interest to try and uncover the nature of photogenerated species
and to mtionali re the somewhat contradictory experi mental observations. Deeper
understanding of the intcrchain ciTects in the licld of organic LEOs and solid-state
lasers should provide new guidelines towards the design of devices with enhanced
In Section 4.5, we discuss the optical pmpcnies of clusters formed by scxi-
thienyl molecules adopting the herringbone structure characteristic of their crystal
structure (34). The theoretical results arc compared to corresponding experi mental
mcasu remcnlo;.
4.2 Theo1etical Methodology
The ground-state geometry of isolated and intemcting PPVoligomcrs (denoted here-
after PPVn, where 11 is equal to the number of phenylene rings so that 11 = 2 corre-
sponds to the stilbene molecule) arc optimized by means of the semiempirical Har-
tree-Fock Austin Model I (AM I) technique (351. 1l1is met hod is known to provide
geometric parameters in very good agreement with experimental X-ray data 1361.
The chains arc set to be planar, in view of the weak torsions reponed in the solill
stale (371. Note that the grounll-state geometry of the unit cells constit uti ng the var-
ious complexes is found not to be affected by intermolecular interact ions. We deter-
mine the equilibrium geometry in the lowest excited state of isolated ;md interacting
PPV chai ns by coupling the AM I Hamiltonian to a limi tell Configun.llion lntemction
(AM 1/CI) scheme (38), as implementell in the AM PAC package (39). In the case of
scxithienyl molecules, the geometry used is that provided by X-ray data.
On the basis of the optimized grounll-state geometries, we simulate the absorption
spectra by combining the semiempirico.1l Ho.ulree-Fock Intermediate Neglect of Di f-
ferential Overlap (INDO) Hamiltonian lo a Single Conligurution Interaction
4 Gus Phase to Solid State Evolution of tlte Electronic a11d Ot11ical Properties
scheme. We use the INDO parametrization developed by Zemer and co-workers [40]
and express lhe electronic repulsion term via the Mataga-Nishimoto potential [41].
In order to avoid any size inconsistency, we systematically involve all the occupi ed
and unoccupied n-levels when generating the singly excited configumtions. The
emission spectra arc simulated on the basis of a very similar approach, except that
the starting geometry is the one opti mized for the lowest excited state in ito; rel axed
confom1ation [20]. It is important to stress that the excited states we refer to are sui -
tably described by the SCI approach; however, a much more elaborate treatment of
the correlation etTects would be required for a complete characterization of the ex-
cited states (including two-photon states) of a conjugated system [42, 431.
Excited-state wavefunction analyses are carried out in the framework of the Inter-
mediate Neglect of Diflcrential Overlap/Single Configumtion Interaction (INDO/
SCI) technique to chamcteri ze the properties of the photogenerated electron-hole
pairs. The SCI wavefunction writes:
cl>sct = r/>o + L C;' r/>i' (4. 1)
corresponds to the SCF solution, i' denotes the configuration formed by
promoting one electron from the occupied molecular orbital X; to the unoccupied
molecular orbital x.,; and C/ is the interaction expansion coefficient. For a given ex-
cited state k, we calculate = J ), which represents the probability amplitude in
finding an electron on a given site x,. assuming the hole is centered on the si te x11 = I.
Within the LCAO approximation, this probability is given by L45J:
= 1) = L C;'(k)Z;(l )z..(x .. )
where Z;(/) [z..(x.,)] is the LCAO coefficient associated to molecular orbital i [a]
on site l Lx .. ].
4.3 Wavefunction Analysis of the Excited States
in PPV Oligomers
The main goal of these calculations is to shed light on the intrinsic properties of
lhe electron-hole pairs generated in those excited states of PPV oligomers that arc
optically coupled to the ground state (i.e . observed in linear absorption spectra).
On that basis. we also aim ut rationalizing the lineshape of the experimental
photocurrent action spectra meu.o;ured by the Cambridge group for PPV and MEH-
PPV, poly(2-methoxy-5,-(2' -ethylhexyloxy-p:.mlphenylenc vinylene) [461. A typi-
cal plot of the frequency dispersion of the short-circuit photocurrcnt recorded in
air and conected for the incident photon tlux shows: (i) a one-to-one correspon-
4.3 Wuvefunctimt Anctlysis of tlte fcited Swus ill PPV 0/igomers 91
dence between the absorption features and the photocurrent peaks; and (ii) a large
increase in the photocurrent around the third absorption band that cannot be re-
lated to changes in the absmvtion coefficient [46].
In order to understand the origin of the large photocurrcnt mea<;ured at high
photon energies, we have simulated the absorption spectrum of a PPV oligomer
containing eleven rings, as shown in Fig. 4-2. We have also computed the wave-
function of excited states located in each of the absorption bands, assuming lhat
the hole is located near the middle or the oligomer backbone, i.e., on site x,,=34
(the sketches and the site labeling are reponed in Fig. 4-2). There is actually
manifold of similar excited states contributing to the total intensity of bands 111:
IV, and V but it suffices here to discuss the lowest in energy.
Figure 4-3 allows us to distinguish between two types of excitations. On the
one hand, we cakulate electronic distributions wi th a Gaussian lineshape that are
centered on the hole position and extend over a few repeat units. This is observed
for states involved in lhe first, second, and liflh absorption bands; there, the
photogcnemtcd electron and hole arc thus signilicantly bound by Coulomb attrac-
tion. These states arc mainly polarized along a direction parallel to the long chain
axis, in agreement with previous theoretical and cxperimcnial data [47, 48]. From
the results, we estimate the coherence length of the exciton in the lowest excited
state (peak I) to be on the order of 5 phenylene rings ( "' 30 A), as also reported


.e 60
' (jj
Il l
3 4 5 6 7
Energy (eV)
l; igure .a-2. INOO/SCI-simulalo:tl lim:m ahsorptiun Sl"li!O.: Irum ol' I he dcvcn-1i ng PI'V oligomer. 'lliC vcr
tk ;1l lines n:pl\:scm the uscillal<>r uf tho.: lr.m,iliuns lhal an: tk::.cril"ll!d; lhc silc labeling u:.c<l
for lhc wavcfun..:tiun analyses is 'huwn un lOp.
4 Cas Phase to Solid Stute EvoluJion of the Electrollic and Opricul Properties
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64
Carbon site number
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64
Carbon site number
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64
c C<!rt>on site number
,. 0.20
,. 0.20
4.3 Wuvefuncricm Analysis of rite Excirnl ill PPV 0/igomcrs
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64
Carbon site number
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64
c Carbon site number
Figure 4-3. AbSt>lute of the INOOISCI-cak;ulatco cle.:tron wavcfunctions IV'(x_,.K,, = 34)1 cal-
culated for lhc eleven-ring PJ>V uhgomcr as a funclion or cmoon site (hole fix cO on siLc 34) for the cx-
citcO stales corrcspontling LO: (a} the Cir..t Jlcak (3.0 eV}; (b) the set:ono absClrption peak
(3.1! cV); (c) tbc thiro.l absorption Jl<:ill. (5.h cV}; (til Jiurth Jl<:ilk (b.J cV}; u.O (c) the
fifth absorption peak (7.0 cV). The cnct'gies given parentheses rcli:r to the theoretical values.
by recent calculations based on U1e coupled electroni c oscill ator (CEO) representa-
tion (49]. The delocalization of the electronic wavefunction of the excitons is cal-
culated to be larger than the width or the lattice relaxations (on the order or 20 A
according to recent AM 1/CI calculations (20(): this is a typical feature in conj u-
gated chains. A detailed analysis of the configuration interaction expansion of the
excited states reveals that they originate from excitations between the same type
of molecular orbitals, i.e . either between fully delocalized levels (peaks I and II )
or between localized levels (peak IV). characteri:ocd by nodes on the pcmr carbon
atoms of the phcnylenc rings and hence cunlined on the armnatic cycles (50).
94 4 Gas Phase lo Solid Swle Evolution of the Elecltvnic and Oplicu/ Ptvperties
On the other hand, in the third and fi fth absorption peaks, we observe charge-
transfer states, for which there is a fi nite probability of finding the electron and
the hole separated by a few phenylene rings. Such states are polarized mostly per-
pendicular to the long chain axis and are described at the Cl level by a mixing of
excitations taking place between a delocaliz.ed level and a localized level. Recent
picosecond time-resolved measurements have shown that the decay of high-lying
excited states is extremely fast [5 1, 52]. 1l1e data indicate that the emission is es-
sentially from the lowest excited state within I ps; therefore, the probability of
charge tnltlsfer is intimately related to the ability of electron and hole to sepantte
at shoa1 ti mes. Under these conditions, the charge-tmnsfer character observed in
the absorption bands Ill and V is a favorable element for a fast dissociation of the
exciton. This dissociation, however, remains an extrinsic phenomenon since it is
believed to be linked to the presence of impurities; the external agents could for
instance be oxygen molecules giving rise to photo-oxidation of the samples and
the appeamnce of carbonyl groups along the conj ugated chains [53- 551, or water
molecules forming van dcr Waals complexes with the chains, as suggested by re-
cent high-level ab initio calculations !56).
To summari ze, wavefunction analyses allow us to distinguish cxt.:ited slates
where the electron and the hole arc significantly bound by Coulomb attmction
from those where the two carriers are loosely bound due to an dlicicnt charge
separation. We consider that such charge transfer states constitute the origin of the
large photocurrent yields experianentally observed at high energies [46).
4.4 lnterchain Interactions
4.4.1 Absorption Properties of Highly Symmetrical Complexes
In the following section, step by step a qualitati ve picture is formed describing
the impact of intermolecular interactions on the absorption and luminescence of
organic conj ugated chains. The present calculations do not distinguish between di-
mers and aggregates (for which the wavcfum:tions of adjacent chains interact in
the ground state, due to, for instance, solid-state ctTects) and cxcimers (where
overlap occurs only upon photoexcitation) 129].
Firstly, we focus on cofacial dimers formed by stilbene molecules; in such con-
formations, the amplitude of intcrchain interactions is expected to be maximized
157]. Table 4- 1 collects the INDO/SCI-calculated transi tion energies and intensi -
ties of the lowc.;t two excited stales or stilhcne dimers ror an inlerchain distunce
ranging from 30 to 3.5 A.
For large interchain separations (8 A ::-:;; R ::-:;; 30 A), the LCAO cocllicients of a
given molecular orbital ure localized on a single chai n, as intuitively expected.
The lowest exci ted state of these dimers results from a destructive interaction of
the two intrachain tr.1nsition dipole moments, wherea-; a constructive interaction
prevails for the second excited state. This result is fully t'Onsistcnt wi th the molcc-
4.4 lnlerc:lwin lnlemctions 95
Table 4-1. tmnsilion energies, intensities, and Cl of lhe lowest two
ellCitcd St.ates (S1 and 5:?. re.pe.:tively) of a cofacial c.limer forme<.! by Jwo stilbcoc molecules for
various imcn:hain dislilOCes.
lnt .. n:hain st,lle Transition Cl
oil>lance energy (eV) (arb. units)
30 A s. 4.097 0.0 -0.7 H-. L+ l--0.7 H- 1- L
s1 4. 1()(1 2.5 0.7H -. L+ I 0.7 H-l - L
t 5A s, 4.01!7 0.0 - 0.7 H-. L+ 1--0.7 H- 1 ..... L
s2 4. 112 2.5 0.7 H _, L+l -0.7 H- 1 L
10A s.
4.()()jj 0.0 - 0.7 H -+ Lt-1-0.7 H- 1-+ L
s2 4. Ul 2.5 0.7 11 - L+l--0.7 H- 1 _, L
7A s. 4.0:\4 0.0 0.67 H _, L+l -0.66 H-I -> L
Ii- I _. L+l i-{1.21 H _, L
s2 4. 1(>4 2.5 0.6911- 1 _. L+0.69 H _, L+l
6A s. 4.014 0.0 H _, L-0.67 H- 1 _, L+l
H _. L+ I +11. 17 H- 1 _, L
4. 1XJ 2.5 0.69 H- 1 _, L+O.C>IJ H _, L+ I
sA s, 3.91!5 (1.(1 --0.71 H _. L+ll.61l H- 1 -+ L+ l
s! 4.2111 2.4 11.6<J U - L+ H 1.61l H- 1 _, L
4A s, .U!70 0.0 0.!17 H _, L-0.47 H- 1 _, L+l
s! 4.235 2.3 0.77 11- L+l - 0.56 H- I -> L
3.5A s. 3.437 0.0 omH- L
4. 161 1. 8 0.93 H _, L+l
Note thai, at 3.5 A. the lowest imcnsc optical tr.msition involves the fifth excited state.
ular exciton model developed by Kasha 158, 59]. In this weak coupling regime
the calculated optical propea1ies can thus be mtionalizcd by a simple dipole-dipole
interaction model. The energy splitting calculated between the lowest two excited
slates increases when the chai n separation is lowered, despite the fact that the
LCAO cocllicients of a given molecular orbital arc still localized on a single
strand. In this mngc of interchain distances, the Cl description of the lowest ex-
cited state indicates that the probability or linding the exciton on one chai n is the
same for the two stil bene units. However, due to low energy tmnsfer r.11es be-
tween adjacent molecules. the exciton is localized at any given ti me on a single
chain. Consequently, the luminescence signal is chamctcristic of an isolated mole-
cule ;md is not quenched hy 1he intcrdtain cllccts.
In it regime of stnmg interact ion hctween the chai ns no optical coupli ng hc-
twceat ground stale and the lowe!\! cM:iao:d occurs. The absence or cou-
pling, however, has a dillcrent origin. Indeed, below 7 A, the LCAO codlicicnts
start to delocalize over the two chains and the wavefunctions become entirely
symmetric below 5 A Jue to an cflicient exchange of electrons between the
chains. This delocalization of the wavcfunction is not taken into account in the
molecular exciton model, which therefore becomes unreliable at short chain scpa-
r.Jtions. Analysis of the one-electron structure of the complexes indicate.-; that the
96 4 Gas Phase to Solid State Evolution of the E1ectronic and Opticttl Properties
HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied
Molecular Orbital) have the same parity, as is also the case for the HOMO-I and
LUMO+l levels (see Fig. 4-4). The lowest optical transition is described by a
mixing of the H -+ L and H- 1 -+ L+ I excitations, and is forbidden according to
the selection rules; the whole intensity becomes concentmted in the second ex-
cited state originating from the intemction between the H-+ L+I and H- 1 -+ L
transitions. The energy splitting calculated between the two excited states in-
creases continually when going from 30 A down to 3.5 A, as illuslr'clted in Figure
4-5. It should be noted that, at short distances, the splitting is not symmetric with
respect to the optical tmnsition calculated for the isolated stilbene molecule.
The one-electron structure of the cofacial dimer also reveals that the splitting of
the HOMO and LUMO levels arc not equal (0.31 cV and 0.16 cV at 4 A, respec-
tively). This explains the reason why the H-+ L+l and H- 1-+ L transitions have
different Cl weights in the description of the second excited state at short inten:hain
distances. n1e lack of electron-hole symmetry rcllects changes in the of the
overlap between the levels; the LUMO can be rationalized by the
fact that there arc more nodal surfaces in the LUMO wavcfunction than in the
HOMO. Indeed, the overlap of the molccubr orhiwls is made up of the sum of
many atomic overlaps with a product of LCAO coeflicients; the larger the number
of nodal surfaces, the larger the possibility of cancellation of terms, due to the signs
of the products of coellicicnK By extmpolation, in a one-dimensional stack of inter-
acting chains, the valence band can be expected to be wider than the conduction
band. The present results arc highly relevant with respect to charge tmnsport proper-
au--.---- L
bg _ _._ ___ II
bg - --.---- L+l
J0. 16<V bu _ _._ __ _
au - --.---
figure 4-4. S.:hcmaaic rcpreM:ntaliun of the onc-<:lcctron struclun: uf a single Milbcnc molecule and
thai uf a dinlCr funned by rwo sca>ar.lloo by 4 A. 1111: JNOO-calcularcJ CIK.'Jl!.Y split of
the HOMO and LUMO when suing from lhc isul:uctl mulcculc lu rhc <linter au: ilbo given.
4.4 lnterc:lwin lutemc:tious 97
4.5 -r------ - - ----- -----,



2 4 6 8 10 12 14 16 18 20
lnterohain distance
J."igurc 4-S. INOOISCIGlk:ul<lh.'tl lr.Jit\ilion encrgil!!> or lhc IOWC!ol two uptical or a .:of:JCial
di mer hy lwo muk-.:ulcs a funcl ion uf Tile horironlal line rdi:l'l>
lo lhc lr.lllsiriun energy nf lhe iMllarcJ molc.:ulc. Nure tllal the upper value a1 3.5 A
lo rhe tr.snsilion In the riflh excircd stale, which lhc lowesr intense abMlrplion f.:.tlurc.
ties in the solid stare, since they are consistent with the typical observation that in
conjugated polymers holes arc more mobile than electrons.
We now address the way the properties, calculated for highly symmetric con-
fomlations, arc affected by the size or the intem,ting unit To do so, we have
built complexe.-; formed by two PPV oligomers up to 7 phenylene rings
and separated by 4 and 6 A, respectively. In general, the trends prevailing for in-
teracting stilbenes hold true for the longer chains. However, two main differences
(i) The critical distance connecting the regime of weak and strong interaction
depends on chain length; this evolution agrees with earlier theoretical studies
which have shown that mcxlels b;L-;cd on the dipole-dipole approximation break
down when the interchain di st<tnce is than the size of the interacting unit
[60-62]. Interestingly, this cri tical distance saturates around 14 A; this value can
be reasonably associated to the average separation between the electron and the
hole in the excited state;
(ii) the second main dillcrcncc is that the spliuing between the two lowest ex-
cited states, calculated al a given separation distance, tends to decrease non-linear-
ly with chain length, <L'i shown in Figure 4-6. Note that this evolution contrasts
98 4 Gas Phase to Solid State Evolutio11 of tile Elec:tr<mic: and Opti,a/ PIVperties
with the molecular exciton model which predicts !he splitting to be proportional
to the oscillator strength (hence, to increase with chain length). These results can
be simply rationalized from perturbation theory by the fact that: (i) the nonnalized
n-LCAO coefficients decrease with the number of sites L (as L-
); (ii) the rele-
vant matrix elements arc constituted by a product of four coefficients (thus pro-
portional to L-
); and (iii) the dominant matrix tem1s are diagonal and their num-
ber is proportional to L. Therefore, the sum of the dominant terms describing the
strength of the interaction is proportional to L-
Though reduced, the amplitude
of the splitting is expected to be significant for chains having a size correspond-
ing to the typical effective conjugation lengths encountered in polymer samples.
However, for polymers that can be effectively described as an infinite chain, such
as MEH-PPV in highly drawn and oriented polyethylene [631. the splitting could
become extremely small. In such a case, the interaction would lead to a red-shift
of the lowest optical transition, as suggested by recent highly-correlated calcula-
tions perfonned on intcmcting polyenes [601. Accordingly, the luminescence
would not be quenched by the mechanism proposed for finite-size systems. We
have also to bear in mind that the shifts and splitting discussed above become
larger when increasing the number of neighboring chains, as discussed below.


--- -------------
111' /

0.02 0.04 0.06 o.ea 0.10 0.12
Figure 44). Evolution of lhc INDOISCJ-cakulalcc.l bclwccn lhc lowest Jwu optical
of l'Ofacial l.lintCr.> fomtct.l by Jwo PPV chains as a funcliun of lhc inverse numhcr or ( 1/u)
along rhc conjugated backbone of 1hc oligomer. The lhcon:tical results an: reponed for intcn:hain c.Jj,..
lance:. of 4 A (open circles) :mc.l (l A (lillct.l circles).
4 . .J /mere/will lntemctimrs 99
At this stage, we can draw seveml important conclusions regarding the absorp-
tion and emission properties of cofacial dimers formed by two identical PPV
(i) the lowest symmetry-allowed optical transition involves the second excited
state (or a higher-lying state at short interchain distances, as shown in Table 4-1 at
3.5 A) and is blue-shifted with respect to the isolated molecule. Such an evolution
has been observed experimentally for stilbene molecules [64] and for other conju-
gated systems It should also be noted that the blue-shift expected from
our calculations could be masked by additional c!Tccto; such as confom1ational
changes upon interaction; for instance, an increase in the planarity of the conju-
gated backbone characteristic of a gas/liquid to solid phase transition could result
in a red-shift of the lowest optical transition;
(ii) due to the absence of optical coupling between the ground and the lowest
excited states, interactions arc expected to strongly affect the lumi-
nescence efficiency, however, more so in molcculur m<tleri als than in polymers
since the amplitude of the interchain effect-; decreases with increasing chain
4.4.2 Photolumim.-sccncc Propeaties
of Highly Symmetrical Complexes
In the previous discussion, we have not considered Ulc possible influence of the
large electron-phonon coupling that is a trademark of conjugated systems; for in-
stance, the equilibrium geometry in the lowest exci ted state can differ signifi-
cantly from that in the ground state [20, 68, 69j. It is therefore of interest to in-
vestigate the role played by relaxation cll'ecLo; in the lowest excited state, assum-
ing there is enough time for them to occur.
As expected, the AM 1/Cl-optimizcd geometry of a cofacial dimer formed by
two largely sepamted stilbene molecules indicates that one chain possesses the
typical ground-state geometry of an isolated unit while the other strand presents
an equilibrium geometry characteristic of a si ngle stilbene molecule in its lowest
excited slate. When the imcrchain distance is lowered, the lanicc defomlations re-
main highly asymmetric; thi s is illustmted in Table 4-2 where we have collected
the C-C bond lengths in the two stilbene units at various separation distances.
Even though the chain, which is initially in the ground-state geometry, becomes
increasingly affected by the intermolecular inter.1ctions when the chain sepamtion
decreases, the major relaxation phenomena always take plat:e over a single chain.
The mostly intrachain ehamctcr of the exciton, also suggested by other theoretical
SlUdies [70, 71 ], can be understood as driven by the Coulomb anraction between
the electron and the hole, which is maximized when the two charge canicrs arc
on the same chain. Since there is an equal probability of finding the relaxed exci-
ton on each of the two ch<.tins, it is wm1h stressing that the most gencml solution
should be described beyond the Born-Oppenheimer approximation ao; a linear
combination of the asymmetric states ('f', = t/1
,.(R,.) and
100 4 Gas Plrase to Solid State Evolution of the Elect runic and Optical Pmperties
Table 4-2. Ground-stale and lowCSI-cxcitcd stale AM 1/CI-optimizcd C..{: bond lengths (in A) in a
cof:JCial dimer fonncd by two stilbene molccute.s separJJed by 3.5, 4.0, and 4.5 A, rcspa:livcly. Tite
geornctric-JI par.uncters for single molecules arc reponcc.l in the right-harld-snlc column.

3.5 A 4A 4.5A co
Ground stale
R l 1.397 1.396 1.396 1.395
R2 1.3!18 1.390 1.391 1.392
R3 1.415 1.410 1.409 1.407
R4 1.394 1.394 1.394 1.394
R5 1.391 1.392 1.393 1. 394
R6 1.411 1.406 1.404 1.402
R7 1.432 1.442 1.447 1.453
R8 1.366 1.355 1.350 1.344
Lowest excited stale
Rt 1.401 1.403 1.403 1.404
R2 1.3!!3 1.3!11 1.3!!1 I.] I!{)
RJ 1.424 1.427 1.429 1.4:10
R4 1.394 1.394 1 .. 193 1.:193
R5 1.3lll! 1.3lll! 1.31!!1 1.3!17
R6 1.420 1.424 1.425 1.426
R7 1.412 1.406 1.404 1.403
R8 1.388 1.395 1.398 1.400
tfozr(Rc), where we have explicilly noted that the equilibrium geometry of the two
molecules is di fferent. However, when the dimer is put in a condensed phase, dif-
ferent solvent shifts of the two stales can occur and the correct description is ex-
pected to be VJ, and '1/b and notlVJ, 'llh/.../2]1571.
The self-localization of the electron-hole pair is also supported by a detailed
analysis of the wavefunction of the lowest excited state of a cofacial uimer
formed by two live-ring PPV oligomer'S. In analogy to what we have previously
described, we have computed the probability amplitude lv(x.,,x
= 16, chain 1)1 of
finding the electron on a given site Xc when lixing the hole on site 16 in the mid-
dle of chain I of the dimer (sec Fig. 4-7). The corresponding wavefunction repre-
sents a Gaussian lineshapc centered on the position of the hole. The probability of
finding the electron on chain II, i.e., of creati ng .an interchain exciton, is only
6.7% when the two oligomers are separated by 4 A. This probability evotves ex-
ponentially with the intermolecular dis lance R going from 28. 1% at 3.5 A down
to 0.6% at 4.5 A (inset of Fig. 4-7). We emphasize that charge tmnslcr-excitcd
stales are observed at hiohcr energies, the lowest of those being 0.88 cV above
the lowest exci ted slate for the two chains sepamtctl by 4 A. In these states, there
is a large probability of finding the electron on chai n II when the hole is tixctl on
chain I, as illustmtcd in Figure 4-8.
::::: 0.3



:r 0.1
4.4 fiiiCtt'fWill ftlii!YCICtiOIIS
chain II

3.5 4.0 4.5
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Figure 4-7. INDO/SCI simulation uf the li o.a cx.:iloo J.tatc wavcfum:lion in a cufacial dimcr
funned by IWO fiv<.'-f"ing PPV oligumcrs. hv(x., .fA = I fl. chain 1)1. an intcnuulccular distance
o.f 4 A. l111(.r,.'.r = 16. d':'in hi rcpec!\Cnls the pmbahility ampliluc.lc of linding an ckctrun on a given
SJIC x, a.'i.-.ummg the hole 1s t:cntc":d lHl l(i of chain I of the dimcr (the Ulhcr chain hcing rcfem:d
IO c.:hain II). Tile site labeling is rcpn:-cntcd in the lup panel. TI1e inset the evolution of the
pruhability lo L'I'Calc an inlcn:hain Cllc.:ilon, fl rr. a function ur ll1e intcnnulccular dbtancc N. The H
arc given in A.
The above results indicate that the selection rules are relaxed when the geome-
try modifications taking place upon photOt::xcitation arc considered. Although the
tmnsition dipole moment between the grounu state and the lowest exci teu state re-
mains small, the luminescence is no longer entirely quenched by U1c inten:hain in-
102 4 Gus Phase to Solid Swte Evolution of the Electronic und Optical Properties
0.4 .,.------------------,
chain II
w 0.2

chain I

0.2 II

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Fagur-e 4-8. tNOO/SCt sinJUialion of lhc wavcfun..:lion = 16. Ill of loc
lransfer-excilcd Slalc in a cofacial dimct formed by lwo live- nng PJ>V ohgomcrs separollcd by 4A.
IIJI('<-Ail = 16, chain I)J lhe probabilily ampliludc in an eiCCiron on a given sil.e X..
assuming the hole is ccnlercd on 16 of I. 1lle site labchng s the same as Uta! rcp!lf'led on
lop of Figure 4-7.
Leractions and is red-shifted wilh respecl to the emission of the single molecule.
This is illustr..lted in Figure 4-9 where we have reported the
absorption and photoluminescence spectra of a cofacial dimer by two stil-
bene molecules separdled by a huge distance and by 4 A. In the reg1me of strong
interactions, the results also show that the shorter the interchain di stance is, the
larger the red-shift of the emission peak. The optical coupling between the ground
stale and the lowest excited state is simultaneously reduced due to the fact that
the wavefunctions become increasingly symmetric for low chain scpamtions. The
red-shift and the attenuation of the emission signal predicted by our calculations
appear to be fully consistent with recent experimental measuremcnls the
luminescence properties of PPV chains as a function of an external apphcd pres-
sure, i.e., more or less as a function of intcrchain distance [72[.
4.4. lntcrdwin lntemctiuns
3.0 3.3 3.6 3.9 4.2 4.5
Figure 4-9. INOO/SCI-simulaled absorplion :111d emission spcclra of 1wo stilbene molecules wilh a
huge inlen:hain (solid lines) and lho.o;c of a cofacial dimcr fonned by lwo slilbenc chams scp-
aralcd by 4 A (dolled lines) .
!he main of this section is that intcrchain couplings have not neces-
to be to a substantial decrease in the lumi nescence quantum
y1eld. As a mauer of fact, a decrease in the r..1dia1ive decay rate increases the rela-
tive importance of multiple non-radiative decay routes. In contmst, the effective-
ness of these channels can be greatly limiled by the confinement of the excitons
due to, for example, the fonnation of cxcimers or 10 1he migmtion of the photo-
generalcd species towards regions where the chains arc strongly intcmcting (i.e.,
!he low-energy domain of the samples), as suggested by recem experimental stud-
Ies [30, 3 1). The actual luminescence thus result-; from I he balance of these contri-
butions. In this context, the significant increase in the mdiative lifetime of the lu-
mi nescence in recent studies [28, 73 I can be altributed to the joint in!lu-
ence of a process and of the weak optical coupling between the
ground stale and the lowest excited slate.
4.4.3 The Influence of the Numbea and Relative Orientations
of the I ntea-acting Molecules
n1e next step in our study is go to beyond the mere consideration of two mole-
cules in a highl y symmetric configuration and to adJress the changes occurring in
the calculated oplical properties when increasing the number of interacting units
and when modulating the relative orientations of lhc chains. In this context, we
have lirst investigated the propc11ics of one-dimensional slacks conlaining up to 5
104 4 Gas Phase to Solid State Evolution of the Electronic and Optic:al Pro{Jerties
stilbene molecules at various separations. For large interchain distances, we ob-
serve that a cluster containing n units gives rise to a splitting of the lowest ex-
cited state of the isolated molecule into n non-degenerate states. This leads to the
formation of an exciton band for an infinite array of units, as elegantly discussed
by Kasha [58, 59). The entire oscillator strength is concentrated in the
between the ground state and the highest excited state of band, leadmg to
an hypsochromic shift of the lowest symmetry-allowed optacal tmns1t1on. ln con-
trast, the lowest excited state is not optically coupled to the ground state
found previously for the cofacial dimers) and is with respect to sm-
gle molecule. The width of the exciton band With the number of _mter-
acting units but tends to saturate mpidly; this evolut1on the
Hucke! calculations would describe the formation of bands m terms of mtmcham
or interchain transfer integrals. The same picture also prevails in the regime of
strong interactions except that in some instances sevcml high-lying excited states
are cakulatcd to be optically coupled to the ground state.
Regarding the emission properties, AM 1/CI cakulati!>ns. performed on ... clus-
ter containing three stilb\!ne molu:ulcs separ..ttl!d by 4 A. show tha_t the mam
tice deformations take place on the central uni t in the lowest cxctl!tl slillC. It s
therefore reasonable to assume that the wavcfunction of the relaxed electron-hole
pair extends at most over three intcr.u:ting chains. The results further demonst:..1tc
that the weak coupling calculated !>\!tween the ground state lowest exCi ted
state evolves in a way very similar to that reported for cofactal duncrs.
In order to address the possible inlluencc of positional disorder, we have cho-
sen to analyze the way basic operations such as translations and rotations affect
the properties calculated for highly symmet_ric _configumt_ions. This_ approach could
provide guidelines to prevent the loss of sJgmficant opt1cal couph_ng the
ground stale and the lowest exci ted state, and hence the quenchmg of lummes-
cence in the solid state.
We start from a cluster formed by two or three intemcting stilbene units sepa-
rated by 4 A. Small tmnslalions of any unit along the chain axis or in direction
tmnsverse to the chain axis (see Fig. 4-10) is a very inefficient process to recover
a significant optical coupli ng. to _the this is
explai ned by the fact that the rclat1ve onentatJOns ot the transtlton dtpolc mo-
ments (which arc polarized along the chai n axis) are not changed. In all CilSCS, the
lowest optical tmnsition is weakly coupled to the ground and the energy
splitting between the lowest two excited states is di rectl y related to the overlap
between the wavefunctions of the two units.
The second set of opemtions involves rotating the molecules. Starting from a
coracial dimer consisting of two stilbene units separ..1ted by 4 A. one molu:ulc
was rotated: (i) in the stacking plane an axis perpendicular to the molecu-
lilr planes and passing through the center of the vinylcnc linkage; and (ii) around
iL'i long axis, thus breaking the pamllclism between the In the
Iauer case. the calculated properties arc very similar to those obtilJOed lor the co-
facial dimer because the relative orientations of the tr..lflsition dipole moments arc
still not modi fied. In the first case, we observe that increasing the angle between
the chain axes leads to a reduction of the splilling between the lowest excited

4.4 lnterclrui11 lnteractio11S

/ ------7 /
-X I>

Figure 4-10. Skcldl of applictl tn a cufacal dimcr funned by two Sl ilbcnc moJ.c:QJ Jcs
SCpar.liCd by 4_ A whcu invt.-stigati ng the role ur Jisonler. The an: induuxl by:
(I) the nf unc molco.:ulc along Jhc chain-axis clin:clion; (II) 1hc 1r.1nslatiun of one molt.'t:ulc
along the transvcr.;c axis: (I ll) the mtation of one stilbene uniJ around its long axis; ancl (tV)
the n>talu.Jil ol one sulbcnc molecule around the ux1s while keeping 1hc p;
rallclism between
the molecular
states, due to a _decrease in overlap clliciency. In addition a tmnsrcr, from
the second state to the lowest one, of the electronic coupling with the
ground state ts also observed, as shown in Figure 4-11. In such confom1ations
the intemctio.n two chains thus leads not only to an intense
band _wtth to the single molecule but to the
of a _weak red-sh1fte<..l pcil k (t.e., a t'\!d tai l in highly disordered samples). The cal-
a supramolccular architecture chamcterizcd by a perpen-
dicular ol the long chain axes tums out to be an efficient confi guration
to J'\!ducc lummcsccnc.:c quenching in the solid state. This is due to the fact that
the lowest two excited states then degenerate and that the whole osdllator
involved in absorption is conserved in emission. Such pc
pcndicular ori-
entattons are encoumcred li>r instance in spiro-conj ugated molecules 1741.
In summary, _over a lm-gc r..1ngc or intcrchain distances, the most stable species
111 excited Still e of clusters formed by m<>lu:ulcs
arc mostly_ wtth :m The al so show that po-
laron-pmrs. ill so rclcncd to iiS mtcn:hatn cxcitons (con-csponding to .. positive
4 Gas Phase to Solid State Evolllticm of the Electrcmic and Optical Properties
4.25 -.::-------------,
--- --0-
--'() ......
> 4.15

Q) 4.05

0 10 20 30 40 50 60 70 80 90
Rotational angle (degrees)

:;) 1.5

c: 1.0

0 10 20 30 40 50 60 70 80 90
Rotational angle (degrees) . .
' .. I nnor "''rt ) an0 reJaJCd llltCru.l
4-ll INDCVSCI-calculatcd evolution ol the eucrg.cs ,u,.,- v- .
.... ol
agure 1 f ofacial Oimcr fom1cd by IWO .,.:nc

lies (bonum pan) of lowc.'l opufcahl "tx: lwccn the long molecular axes. when f l)-

. aralcO by 4 A a funcuon o I c uh...ur. o

, .. IV of
ocu cs scp I . . I . 0 the slacl>ing axis ;IIIJ keeping the muh:.:ular planes c ,ca>oe
aatmt: one 111\1 ccu e aruun . he S. s (S. _ s l tr.m,,llllll
4- 10). Open M!uafl:)o (doM.-d cir\:IC.\ ) to I .- 2 J I .
4.5 Clusters of Sexitltienyl Molecules 107
on on one chain in Coulomb aumction wilh a negative polaron on an adjacent chain)
can be generated in charge transfer-excited states. 1be latter are found at energies
higher than those of the lowest intr.1chain-cxcited smte. Since the average separation
between the electron and the hole in a polaron-pair is not expected to be significantly
different from that in an intrachain exciton, the polarization effects should not
strongly stabilize the energy of the charge transfer-excited stales with respect to that
of the lowest excited state. The fom1ation of polaron-pairs, observed in recent ex-
perimental studies [75 J, thus appears to have an extrinsic origin since it js related
to the presence of impurities giving rise to intcmctions between chains of different
nature and leading to a reversal in the ordering of intrachain versus interchain exci-
tations. Further theoretical and experimental studies :.u-e defi nitively required to un-
derstand the panu11eters governing the occurrence of charge and energy tmnsfer be-
tween intemcting chains in more detail. In actual samples, the decay in luminescence
is intimately to the concentmtion of intmchain excitons while the dy-
namics of the picosecond photoinduced absorption features results from the contri-
bution of both intmchain excitons and polaron-pairs; this rationalizes the fact that the
dynamics of the.'\c two processes is genemlly different. Depending on the nature of
the samples, the dominant photogenemtcd specie.-; could be either int r.1chain excitons
or polaron-pairs. 1l1is hus strong implications on the properties of the samples; as a
matter of fact, upon decreasing the interchain distance, the luminescence ctriciency
of chains supporting intrachain excitons is reduced whereas luminescence is ex-
pected to increase if polaron-pai rs arc mostly present since short distances would
favor their recombination.
Several strategies that could be followed to prevent a substantial decrease in lu-
minescence elliciency in condensed media emerge from the above results.
Approaches that can be suggested are: (i ) to minimize the splitting between the
optically-forbidden and optically-allowed excited states; this can be done either by
using long chains with highly dclocalized excitations or by separating the chains
with the help of bulky substituent-;; and (ii) to reduce the diffusivity of the exci-
tons to lumincl;Cence-qucnching traps, by fom1ing aggregation zones acting as
low-energy centers from which emission is allowed.
4.5 Clusters of Sexithienyl Molecules
We now turn to an investigation into the optical properties of dusters of u-scxi -
thicnyl molecules adopting the heJTingbone strut:ture. us determined by X-ray dif
fraction (sec Fig. 4- 12) 13ll. 1l1e theoretical results arc compared to relevant experi-
mental data, whit:h allows us to assess the reliability of our theoretical approach.
Various clusters comaining between 2 and 6 units are considered. We have tirst es-
timated the amplitude or the Davydov splitting as <1 function of configur:ation (this
splitting is dclined as the difference between the energy of the lowest excited state
and that or the higher-lying state strongly coupled to the ground state [761).
4 Cas Plrase w Solid State volr1tion of the Electrrmic wrd Optical Properties
Fi urc 4-l:Z. Sketch of the rclalivc orientatiuns of the scxithicnyl in the crystal and n:pre-
se!:taaion of the crystal axes a. b. and c discussed in the text. Note thai the layers arc Slacked along
the a
When consideri ng sexithienyl molecules located in the same layer no in-
temction between molecules aligned along the chain axis), the md1eate that
the Davydov splitting increases with the size of cluster but, m sys-
tems we have considered, tends to gel to 0.5 cV, as_
in Figure 4-13. For a cofacial dimer, the energy dtfterence IS _very scnstt1ve to the
interchain scpamtion; it evolves frotn 0.2 to 1.0 eV when gomg from 4 to 3.3 A.
In all cases, the lowest excited state is onl y weakly to the ground
due to the Jack of significant angles between the moments ol
units in the herringbone structure. Note that the amphtude ol the sph_t-
ting is largely dominated bj'
distances arc around 3.5-4 A) and 1s httle aflectcd by the mteract10ns_ between ad-
jacent layers, which are by A. We also obscr-.:e F!g, 4-1_3) that
the lowest charge transfer-excited state IS located the h1gh-lymg
state, as suggested by previous calculations and conlmncd by clcctroabsorpt ton
spectra rccordi!U on a scxithicnyl crystal 177].
4.5 Clusters of Sexithienyl Molecules



w 2.6
IT --
- e:, . .... .
[), ........... 6
2.2 -t---.-----.---r----r---.----!
2 3 4 5 6 7
Size of the aggtegate
folgurc 4-13. Evolution with the sit.c ul the scxithicnyl dust.: of the excitation cncrg1<.-s frum the
ground to the lowest exci ted laic (open cin:les}. lu the high-lying excited Slate stl'\lngly coupled
to the ground (open MJuan-). and lu the luwcst tnmsfcr-cx.: itcd stiltc (open triangles). In
all .:uses. unly intr-.tlaycr into.:ra.:1iom have l:x."Cn .:onsK.k:ro.:d.
The dominant features of the experimental optical spectrum of the scxithienyl
crystal is an absorption onset at 2.28 e V, pola1i:ocd along the b axis, and an in-
tense vibronic progression at higher energy wi th the 0-0 peak at 2.60 cV [76j, po-
larized along the c axis. We report in Figure 4- 14 the theoretical absorption spec-
trum of a complex containing six units on top of each other within the same
layer. The main goal of this simulation is to reproduce the overall shape and the
main absorption chamctcristics of the sexithienyl crystal; consequently, we have
not taken into account the HerLbcrg-Tcllcr coupli ng (i.e. , vibronic borrowing) pro-
viding intensity to the low-lying excited states. Our approach is based on the dis-
placed harmonic oscillator modd where the Fnmck-Condml factors fm a given
mode arc applied only to the states si:;nificantly coupled to the ground state and
expressed for cxcitons by [20, 781:
and for dtargc-transl'cr cxciaons by [791:
llO 4
Gas Phase to Solid Stute vol11tioll of the Electro/lie wtd Optical Properties
c polarization
b polarization
.!!. 2500
X 50
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
Energy (eV)
F. 4-1
. JNOOISCI-sintutalcd absorpt ion spcctrJ of a cunta.ming six top of
e!'h other within the same layer. for polarizations along the b (dOlled hnc) anc.l c lmc) axes.
In these expressions.
is the vibmtional quantum. number in the exci ted state,_ bu
represents the displacement parameter a'isociated wtth the mode for a neutral
f on (b"f/l = S is the corresponding Huang-Rhys factor); b+ and b_ the parameters
lor the positive and negative polarons fof1!ling the charge transfer :me
l . based on the usc of the single dommant mode at 0. 18 eV observl!d 10 Raman
(80}; the displacement are _taken a., adjustabl_:
chosen to match the experimental vibrontc (bu= 1.18, b+-:-b_- 0.55
. ) nd the line broadening is fitted to the expenmental rcsolutton. .
our case, a d F. 4- 14
The INDO/SCI-simulated absorption spectrum reportc m 1gure . s -
acteri:t.ed by a weak absorption at 2.24 eV polari:t.ed along the axts and a
tron vibronic prooression with the 0-0 feature at 2.58 eV, polanzed I c _c
s - gThese results
are in remarkable agreement with the correspondmg
data; they also provide a Davydov spliUing cV the
of the first band and the 0-0 peak of the mtcnse v1bromc progresston, wh1lc ,a
f 0 31 eY is obtained experimentally (761. Our rcsuiL'i cast doubt on other
va ue o .
- 1 v 11
recent experimental estimates of the Davydov sp attmg, > e -
4.6 Concl11sio11s u11d Outlook Ill
4.6 Conclusions and Outlook
In this chapter, we have tried to demonstrate that the computational methods of
quantum chemistry are useful tools to provide an understanding of the intrinsic
electronic and optical properties of isolated and interacting conjugated chains.
First, we chamcteri:t.ed the electronic properties of photogenerated electron-hole
pairs in isolated PPV oligomers, through a detailed analysis of the wavefunctions
in the excited states. This study gives access to how the electron distributes
around the hole in a given excited state.
In the second step, we went beyond the mere considemtion of isolated chains and
started investigating the properties in supramolecular architectures. We showed that
the changes occurring in the absorption and luminescence properties when going
from an isolated molecule to a duster containing several intemcting units can be
unmveled with the help of quantum-chemical cakulations. A geneml picture de-
scribing the inlluence of intennolecular inter:u.;tions was provided on the basis of
calculations by varying in a systematic way the sire, the number, and the relative
orientation of the conjugated chains; str.uegies were suggested in order to avoid a
substantial decrease in lluoresccncc quantum yield in condensed media. The reliabil-
ity of our thl.'Oretical approach was fut1hcr established by the remarkable agreement
observed between the calculated properties of clustl!rs torrned by sexithienyl mole-
cules and the corresponding experimental data. This reintorces the accuracy of our
melhod in using an INDO/SCI approach to shed light on the absorption prope11ies or
interacting systl!ms, provided that the relevant excited states arc suitably described
by single excitations (note that thl! interest or such calculations is rcinlorccd by
the fast satumtion of the I!Uiculatcd properties when increasing the size of the clm-
ters and their applicahility to a large class or compounds). We have also pointl!d out
that the chemical impurities are expected to play a major role in the dynamics of the
excited states, by inducing the formation of charge-transfer excitons. Although dis-
sociation processl!s ure highly desirable for the opcmtion of photodiodcs, much has
still to be learnt on the parameters governing the occu1Tence of charge transfer be-
tween adjacent chains. This is without any doubt a new challenge for futurl! joint
experi mental and theoretical studies.
This work has been partly suppmted by the Belgian Prime Minister Oflice or
Science Policy (SSTC) 'Pole d' Attmction lntcruniversitairc en Chimie Supr- .lluolc-
culaire el Catalyse Supramol&:ulairc (PAl 4/1 1 )', and the European Union Tmin-
ing and Mobility for Rl!scarchers (TMR) network program on Synthetic Electroac-
tive Organic Architectures (SELOA), the Belgian National Fund for Scicntitic Re-
search FNRS/FRFC, and an lBM Al:adcmic Joint Study. JC is Charge de Re-
cherches and DB is Olerchl!ur Qualilic or the FNRS. We ackMwlcdge stimulat-
ing discussions and collahomtions with R. H. Fril!nd, A.J. Hccgcr, A. Kohler, E.
Lunedci, M. Muccini, R. Silbey, and C. Taliani .
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5 Electronic Structure of Surfaces
and Interfaces in Conjugated Polymers
Michael LOgdlund and William R. Salaneck
5.1 Introduction
A description of the and chemical structure of pol ymeric and con-
densed molecular solid systems is an important ingredient in the field of organic
polymeric and molccuhtr materials in modern electronics applications. The investi-
gation of the interaction between conjugutcd polymer materials and various metals
has become an important issul.!, both for interfacial characteristics as well as for
doping-inclucecl effects. Studies on the interface characteristics arc of significant
importance in the connection with various device applications. Investigations of
initial stages of both metal-on-polymer and polymer-on-metal interface formation
are or importance in the context of how the interfaces may affect the actual de
vice performance. In other words, when a few isolated atoms of an active metal
are applied in some way to a polymer surface, they will react in a ve.ry different
way compared to the case where an isolated polymer chain is applied in some
way to the cle<.m surlace of an otherwise three dimensional metal substmte, with
or without the presence of an oxide layer (I). In this context, the single most use-
ful experi mental tool has turned out to be photoelectron spectroscopy (PES) (2).
Also, it has been shown that use of the results of appropriate quantum-chemical
calculations (3) in interpreting PES data in many cases provides a level of infor-
mation output which is larger than the sum of the two [4]. In this chapter, the
principles involved in the study of the electronic and chemical structure of conj u-
gated polymer surfaces and interfaces arc reviewed. Examples of materials system
arc included which demonstmtc information obtainable from photoelectron spec-
troscopy on both pristine and doped conj ugated polymers as well as the modifica-
tion of the electronic und chemical structure of conjugated systems induced upon
intcr..1ction with diflc rent metals such as aluminum and calcium. Also, the useful-
ness of the combinution of photoelectron spectroscopy und quantum-chemical cal-
culations is demonstr..tted with some examples. The theoretical models most com-
monly used arc only brielly outlined. More theoretical details are to be found in.
for example. Ref. (Jj .
This chapter is organi'l.Cd as follows: the experimental and theoretical tech-
niques are presented brielly in Sections 5.2 and 5.3. In Section 5.4 some materials
aspects and concepts arc introduced, where rnms-polyacetylcnc is used as an illus-
trative example.. A series of ill ustrative exampks on surfaces and intct1.uccs arc
116 5 Electmllic Structure of Surfa"e.\ cmtl lmerfcu:e.\ i11 Conjugutcd l'olynu:r.,
given in Section 5.5, including a brief discussion on some aspects of the ITO sur-
face and its interface with polyaniline, using indium-tin-oxide (ITO) as an elec-
trode in light-emitting devices. An up to date list of references are provided for
the interested reader to obtain further information. A basic knowledge of certain
principles of organic chemistry and solid state physics is presumed, but references
are also given here for more detailed information.
5.2 Photoelectron Spectroscopy
The use of soft X-my sources Jed to the development of X-my photoelectron
spectroscopy (XPS), originally known as Electron Spectroscopy for Chemical Ap-
plication (ESCA) [5}, indicating the applicabil ity of the method to surface chemi-
cal analysis. More or less simultaneous wi th the development of XPS, Ultmviolet
Photocle<.:tron Spectroscopy (UPS) 161. i.e., the usc of ultmviolct photon sources
in PES, was applied to studies of gases and bulk as well as electronic
structures of solids. The increasing use of the continuous spectral distribution of
synchrotron radiation [7, 81 as a photon source, however, has made the historical
terminology less meaningful. Today, PES has become a widely used tool for
studying the bulk and surface chemical and electronic structure of condensed m<tl-
ter, liquids, and gases. In particular, the method is very useful for studies of the
chemical and electronic structure of conjugated polymers and interfaces with poly-
mers because: (i) it provides a arutximum amount of chemical and electronic infor-
mation within a single technique, (ii) it is essentially non-destructive to most or-
ganic systems, and (iii) the method is extremely surface sensitive.
Although the purpose here is not to give a full undcrsl<mding of photoelectron
spectroscopy, it can be useful to discuss some of the specific features in a photo-
electron spectrum which can be helpful for the understanding of the diO'erent ex-
amples discussed in this chapter. The main emphasis in the background to PES
will be focused on the molecular solids aspect since this chapter deals with con-
densed conjugated systems. The interested reader can find a more in-depth discus-
sion on the technique, relative to organic polymeric systems, in Refs. [4, 9, IOj.
The fundamemal process in molecular photoionization is represented by
(5. 1)
where M
represents lhe isolated ncutml molecule, hv is the ionizing photon,
represents the positive molecular ion in the excited state, and e- is the photoelec-
tron which carries kinetic energy Ek- If Ek is sufficientl y large, then the escaping
electron and the molecular ion arc not strongly coupled. The energy balance ac-
cording to Eq. (5. I) is then given by
11 + /1 v = + E, , (5.2)
5.2 1'/wtol!ll!cflvll Spectm.n:opy
where Eo is the total energy of the neutral molecule in the ground state and *. is
the the molecular ion in an excited state. Thus, the b;;..,ic
equ ,' on used m mterprctmg photoelectron spcctrJ can be written as
photon '"' is known and the photoelectron kinetic energy distribution
IS measured m deduce the binding energy 1bc binding energy is thus
not equal to the bmdmg energy of the elect rons in the neutml ground state of the
molecule, bu.t corresponds to the energy diiTerencc between the initial ground
state and vanous final excited states. The electronic structures of M. and M are
usually. modeled in tenus of si ngle-electron st<lles, with as much ph
ysics buill in
as possible.
are possible single-electron molecular contigumtions, as shown
schem;all c<llly Ill Figure 5-l . In the neutral molecule in the ground state, repre-
sented as Mu. all of the electmns in the moh.."Culc ;arc occupying only the lowest
allowct.l energy levels { V,). while the V;' lcvds arc empty. The other panels illus-
v: wu

z .

u .....
-- -






M+m M *
- - -
- - ..
- -
-- . -
..... _
u. z
><wQ .....
a:>< OjS
sow :!:(f)


5 l;"'Jcc:trrmic: Structure? of Surfuces and llllcrfuc:el' in Conjuguted Polymcr.r
tmte the genemlized excited state of the (photo-ionized) molecular cation,
where an electron has been removed from the core-level, C;, but the remaining
electrons do not occupy the lowest possible single-electron states (the special case
of ionization from the HOMO level is illustmted as M .); and the optically excited
neutml molecule, Me; (where one elt:etron has been excited from the HOMO to
the LUMO in the illustration). The case of illustrates the phenomena of
shake-up, where an electron is excited across the band gap simultaneously with a
core-electron ionization event [5, 11- 13].
Most of the intensity in a photoelectron spectrum usually resides in one main
line, corresponding to a particular simple tinal excited state of the
which is fonned by the direct removal of a single electron from a spec1tic m1t1al
state of the molecule. However, all of the various possible final states, COITespond-
ing to a given initi al state, can in principle be observed, but usually they have
low intensities and can only be seen as weak satellites on the main line. In Figure
5-2. an idealized photoelectron spectrum, or energy distribution curve (EDC),
with the corresponding molecular levels is displayed. The most important feature
in thi s one-electron picture is that there is a one-to-one correspondence between
the peaks in a photoelectron spectrum and the one-electron molecular levels in the
neutral molecule. The small feature appearing on the low kinetic energy side of
the main peak, labeled C
in the idealized spectrum, COITcsponds to a _sa-
tellite; the escaping electron loses kinetic energy, 6 . a result of an
from an occupied level, V
. to an unoccupied level, V simultaneously wllh the
electron emission from a core-level, Cz.
During the photoelectron emission event there are electronic relaxation
occurring, which arc usually divided into it1tra- and inter-molccu_lar relaxatiOn ef-
fects. These effects can be mtionalized in a classical picture as lollows. An elcc-

I> !


<<< <
. c

r-() < r-c

:Z:m mg

o ;z:
U) o
\ ._,
! ,/
'! o
Jo'igun: S-2. An illcatizc<.l s pct:ll\llll wilh 1hc corrc.,puno.ling unl.O..Cil."t:lrun moh:cular levels.
5.2 P/totm!lectro/1 Spectroscopy 11 9

a photoelectron a molecule tXpically within about
I 0 s. The nuclear gcomctnc relaxation tune 1s around I o-
s (i.e., which corn:-
to _an optical phonoo frequency) while the corresponding electronic relaxa-
tion tune IS il!xlllt 10-
s 1141. Thus. the main line com:spontls 10 the binding en-
ergy of an electron in ;m ioni:t..ctl molecule where the electrons have hatl m
i.e.: the hole is fully scra!ned. but the nuclei are frozen during the process;
th1s 1s rekrrcd to as the adiabatic peak. The intra-molecular electronic-relaxation
effects occur in response to the creation of a hole-stutc in photoelectron spectros-
copy of an isolated molecule in the gas phase. In the solid state, there are also in-
ter-molecular relaxation etTects occurring due to electronic and atomic polarization
of the molecules surrounding the panicular molecule on which the hole-state is
created. The inter-molecular relaxation energy is given to the escaping electron
and thus the kinetic is increased, i.e., the corresponding peak in the photo-
spectra appcurs at a lower hinding energy compared to photoelectron
from the level in the gas phase. TI1is energy difference. i.e., the po-
larwttlon energy. 1s 111 the order of 1- 3 eV [15) throughout the valence renion.
The relaxation energy lor core-levels. however, can be much larger due to a hi"h-
er degree of localiL.ation of the core-holes 113, 14). b
5.2.1 X-Ray Photoelectron Spectroscopy
With XPS, as commonly carried out with Al(k,.) and Mg(k, ) labor-.atory sources, it is
possible to pcrfonn qualitative and even semi-quantitative anal ysis of chemical com-
posi tion in the ncar surface region of a solid sample. Changes in the valence electron
density will he rellected as small, but significant shifts in the core level bindino en-
ergies. so-called chemical shifts. although thc core electrons are not involved the
chemical bonds [51. Of course XPS can be (and has been extensively) used for stud-
ies of the valence band region, but the photoionization cross-section for the valence
photoelectrons in XPS arc approximately one ortlcr of magnitude lower than that for
the core which however IC<lds to more time-consuming experiments.
Also, the photo1onaz.at1on cross-sections are such that it is not very convenient to
study conJugated polymers, where interesl is in the states ncar the valence band
edge, which are very weak in XPS valence band spectrJ.
Another in PES spectra is the so-called shake-up structures, appeari ng
as weak satellites on the hi gh binding energy sitle of the main line. The shake-up
structure reflects the spectrum of the 1-clcctron-2-hole states "eneratcd in connec-
tion with photoionization, anti can give useful infonnation .iliout the valence TC-
elcctronic structure of a molecular ion.
The PES measurements arc pcrlonncd with reference to the Fermi level of the
photoelectron spectrometer, in solid as wi th here, by the way the
spectroscopy works. Thus, in case.<> when the Fcnni level shifts due to some
chemical of the sample, i.e . in the intercalation of gmphite or other
layered compound 1161 or in the doping of conjugated polymers [ 171. it is neces-
sa1y to account for the change in the Fermi energy level before interpreting spec-
5 Electronic Structure of Surfaces wul Interfaces in Coujugated Polymers
tra. This can be done, for example, by combining the XPS core-level spectra with
UPS valence band speclm . as described in more detail in the next section, or by
referencing to model compound (13].
5.2.2 Ultraviolet Photoelectron Spectroscopy
The most commonly used laboralory photon source for UPS is the_
lamp, although lhe use of synchrotron mdiation as a photon source 1s 111 extens1ve
use today. For valence band spectrOscopy, UPS has two over
First, the usual in-house photon sources have high energy resolutiOn, a full w1dlh
of half maximum (FWHM) of- 30 meV for the He lines, and second, the photo-
ionization cross-section for electrons is higher in the valence region for UPS.
However, the natur.tl line widths in condensed molecular solids, from both homo-
geneous and inhomogeneous broadening effects, can approach I eV at tem-
pemture ( 10, 1 g, 19 ). and a large fraction of the photon energy resol ut1on advan-
tage is not fully realized. . . .
As mentioned above, the PES measurements of sohd spccnnens arc pcrlormcd
relative to the Fermi level. ln some cases, however, it can be desirable to derive
the binding energies relative to the vacuum level from a photoelectron spectn:m
This is particularly important before interpreting ditTerent core-level ch_em1c:-'l
shifts induced upon, for example, doping or interaction with metals. In 111
some cases, the apparent binding energy shift can appear to be in the wrong d_lrec-
tion before the Fermi energy shift is taken into account [ 17, 20). en-
ergy shift can be deduced by measuring the position of kmettc energy
cut-off of the secondary electron distribution, as illustrated tn F1gure 5-3. The vac-
uum level can be located s imply by adding the photon energy to the secondary
electron cut-off energy; measuring down from the vacuum level energy to the.
known posi1ion of the Fcrrni energy (Ep) determines the work function (C/>.,) ol
the subst111te (21 j.
Au UPS Hel (hv:21.2 eV)


u. w

> w w


:< u 0 .....

z V) >

0 Ev
J;"igure S-3. UPS spectrum uf Au 1hc 10 obtain level rcli:rcnccd s[><!<:lra.
5.3 Tlwuretical Approaches 121
It is also wo11h pointing out that the determination of the reference level, i.e.,
the Fermi level of the spectrometer, is done by performi ng a UPS measuremenl
on a metallic specimen in equilibrium with the S(X-'Clrometer, laking for instance
Au as in the example here. Si1ll"e, in equilibrium, the position of the Fermi energy
is conslant throughout the cross-section of the thin films under discussion in this
chapter, the position of the Fcnni energy on the UPS spectrum is equal in analyz-
er voltage to lhe location of the Fermi level in the metallic subslrate, as observed
prior to the deposition of the organic overlaycr. This positioning of the Fermi lev-
el, coincident with that in lhe substr.1tc, has been observed in all UPS studics re-
viewed in lhis work, us well us in other molecular overlayer systems, on both me-
tals and semiconductor substr.lles (4, 22-25].
Valence band spectra provide information about the electronic and chemical slmc-
ture of the syslem, si nce many of lhe valence electrons participate directly in chem-
ical bonding. One way to evaluate cxpcrimental UPS spectra is by using a finger-
print method, i.e., a compari son with known standards. Another important approach
is to utilize wilh the results or appropriate model quantum-chemical cal-
culations [41. The combi nation with quantum-chemical calculations allow for an m;-
signment uf the diffcrem in the elccuonic structure in terms of atomic or
molecul<lf orbitals or in terms of band slructure. The experimental valence band
spcclm in some or the examples included in this chapter mc interpreted with the
help of quantum-chemical cakuhct ions. A brief outline and some basic considem-
tions on theon:ti cal approaches are outlined in the next secti on.
5.3 Themetical App1oaches
During the last decade. the progress in thcoretical methods and the access to
quantum-chemical c;clculations has become more available. Nowadays, lhc use of
quantum-chemical calculations in the interpretation of experimental UPS valence
band spectra is a common approach [26-29].
Usually the interpretation of UPS spectra of molecular systems relies on the
one-electron picture of the neutml molecules. In this ca'ic a one-to-one correspon-
dence between the m<yor peaks in the photoelectron spectrum and the one-elec-
tron molecular orbitals exists, as illustmtcd in Figure 5-2. This approximation is
assumed to be valid for large molecules. The numerical values of the calculated
binding energies of the peaks are usually set to the Hartree-Fock eigenvalues of
the molecular orbitals in lhe neutral ground :>late of lhe molecule, e.g., employing
the Koopman's theorem. When relying on quantum-chemical calculations, it is im-
portant to consider the various relaxation eflccts that occur during a photoelectron
emission event. The.'ie relaxut ion effects often make it necessary to apply correc-
tions that account for di llerences between the molecular orbitals of the neutml
molecule and the molecular ion. Usually the theoretical model calculations are
pcrfonncd on isolated i.e., not laking into account any illler-molecular
5 Electronic Structure uf Surfaces wrd Interfaces in Conjugated Polymers
imemction. This is justified by the observation that for organic molecules there is
a one-to-one correspondence between the UPS valence band spectra of the molec-
ular solid and molecules in the gas phase, caused by the genemlly weak inter-mo-
lecular van der Waals interaction between the molecular species in organic molec-
ular solids; there is a rigid shift throughout the valence region in the order of 1-
3 eV [15, 30]. The shift is due to polarization of the surrounding molecules which
stabilizes the final ion state and leads to a decrease in binding energy [13).
The systems discussed in this chapter give some examples using different theo-
retical models for the interpretation of, primarily, UPS valence band data, both for
pristine and doped systems as well as for the initial stag_es of interface for"':'ltion
between metals and conjugated systems. Among the vanous methods used m the
examples are the following: semiempirical Hartree-Fock methods as the
Modified Neglect of Diatomic Overlap (MNDO) [31, 321 and Ausun Model I
(AMI) (33): the non-empirical Valence Effective Hamiltonian tVEH) pscudopo-
temial mcthod[3, 34); and ab initio Hartrcc-Fock techniques.
A common strategy for calculating the density of valence states for large conju-
gated systems. both for pristine and charged (doped) systems, is to usc a two step
procedure. The ground state geometry is first optimized by applying a semi-em-
pirical method (for example AM I or MNDO). The optimized geometries then
serve as input for electronic structure calculations perfonncd with the VEH meth-
od. The AM 1 and MNDO methods arc known to yield reliable geometries for
large organic molecules. The appl icability of the VEH model in interpreting
photoelectron valence band spectm of conjugated systems is well estnblished
35- 37]; the VEH parameters have been determined by fitting to double-zeta-quali-
ty ab initio results on model molecules [3, 34). When using ab initio I:Ianrec-
Fock. the calculations on conjugated molecules has, of course, to be restnctcd to
relatively small systems due to the dmmatic<tlly increased computational clT011s.
In some cases. however, one can gain reliable detailed infomlation for a particular
material system by performing calculations on an adequate model system. More
details on the theoretical approaches are to be found in the references themselves,
or in other chapters of this book.
5.4 Materials
During the past decade, a large effort in improved synthesis of soluble conjugated
polymers has led to an in. the quality . of samples by
venl techniques, and thus made 11 poss1ble to obt:un more dcta1led mformat1on
about, for example, the electronic structure through the use of photoelectron spec-
troscopy. The high quality of substituted conjugated polymers with vurious side
gmups allows for detailed investigations or the inll uencc o.f the srdc groups o.n
the electronic structure, as demonstrated by Fahlman et a/. Ill the case of subsu-
tutcd poly(p-phcnylcnevinylene) L38J. In order to demonstrate the level of inlor-
5.4 Materials 123
obtainable ti'Om PES (mostly UPS), sorrie of the most commonly used
polymers are presented below. The subset of polymers chosen for dis-
arc poly(p-phenylenevinylene). polythiophene. and polyani-
hne. The bas1c chem1cal structures or these different conjugated polymers are dis-
in Figure 5-4 for subsequent reference. In order to introduce conccpl.., and
tenmnology, the electronic structure of tralls-polyacetylcne and the various types
of charge-bearing species in conjugated polymers arc discussed in the next two
5.4.1 Electronic Structure of trans-Polyacetylcne
1bc gcomctrica! structure of .. :ctylcm:: (see Fig. 5-4) is particularly sim-
ple; a. planar z1g-z:1g configuration with ultt:rnating single und double bonds of
1.44 A and 1.36 A 139). The band structure is very simple and well suited for
demonstrating the relationship between band structure, density or valence Slates
(DOVS), experimental valence band spectra. The:: culculatcd energy band
structure of trmn-polyucetylcnc, c<tlculatt!d using the Valence Effecti ve Hamilto-
nian method [3, 34), is compared with the measured UPS spectrum in Figure
5-5. The energy scale is detennincd experimentally, i.e., with respect to the Fenni
level in the UPS spectra. The input geometry for the VEH calculations has been
from AM I optimizations on an oligomer of trans-polyacetylene.
010erences wht:n usmg experimental values instead are small and are not found
to <tlfcct any of the results. Normally, a band structure is presented with the en-
ergy vertically and the momentum vector k horizontally. The band structure in the
figure is rotated by 90", to enable a more direct comparison with the experimen-
tal spectrum. To facil itate the comparison between the UPS data ;md the calcu-
lated band structure, the density-of-valence states, p() (or DOVS), is included.
The highest occupied energy band is the n-band, which can be seen clearly as the
,r{ /s,

y 1-y
5 ..... CtlCillll' ;Jt nr \tllllC uf lhc nmjugal.:l( 1>t.>lymcn. tli:.cuss.:J lll lhc .:haplcr
5 /ectromc Structure of Surfaces a11d brtcrftlces in Co11j11gated Polymers
-25 -20 -15 -10 -5

-25 -20 -15 -10 -5
Figure S-S. Valence baml spcclm of al
27 cV and 50 eV photoo energy, and the com:sponllmg DOVS llcnvcd from VEH cakulauuns. 1l1C
VEH band structure is shown in \he lower part of the figure (from Ref. )281).
band edge in the UPS spectra. The position of the n-band edge, changes
the electronic structure in the region of the edge, arc of central Importance m
studies of conjugated polymer surfaces and the early stages of formation of the
polymer-metal interface. Clearly, the UPS spectm, sensitive to only the top most
molecul es of the lilm, arc appropriate in such studies.
The electronic structure of trans-polyacetylene can be rationalizetl in the fol-
lowing manner (3). If the cartx>n-carhon bomls would be of et.JUUI in
the absence of dimerizmion, polyCJCetylenc would be a 'regular polyene , w1th a
unit cell consisting of a single (-CH-) group. At least within one-electron
three occupied valence bands would exist, corresponding, in localized bond orbi-
tal terminology, to approximately a C-C a-band, a C-H a -band and an-band, the
latter being derived from the remaining atomic orbital on each C-atom (the z-
axis being perpendicular to the molecular plane). occupied n-ba?d wo_uld be
only half filled, since there would be one eh.:ctron m each atom1c orbital
each C-atom, and the electronic structure of the polymer would have a mctalhc
5.4 Materials 125
character. However, due to a Peierls transition (or, equivalently in molecular ter-
minology, a Jahn-Teller distortion) and electron correlation effects, the system is
dimerized with altemating si ngle and double carbon-carbon bonds. This results in
a unit cell in trans-polyacetylene consisting of two carbon atoms, corresponding
to (-CH=CH-) units. Since the width of the one-dimensional Brillouin zone in the
unit cell wi th two C-atoms is onl y half of that for the regular polyene, each band
of the regular polyene is split into two bands, resulting in four occupied a -bands
and one occupied n-band. Due to the presence of dimerization, there energy
gaps at the Brillouin zone edge, ncar - 8 and - 15 eY in Figure 5-5, where each
pair of bands from the regular polyene structure is folded back to fonn the dimer-
ized-dmin band stmcture. 1l1e Peierls gap in the n-band, which occurs at the Bril-
louin zone edge, corresponds to the forbidden energy gap of approximately
1.5 eY in trcms-polyacetylene.
The details in the calculation allow for an assignment of the different peaks in
the UPS spcctr;.1 to dillcrenl calculated l>imds: Pe<tk A in the :spectra corresponds
to electrons from a band derived almost exclusivel y from C(2s) atomic orbitals.
i.e., the C-C' hackhune. Peak 13 is derived from the lhtt p011ion of a
band ne<tr
the zone center. Peaks (' ;uld 0 corrcspoml to from the ar ami a-'-bands
derived from cumbinalit)ns of C- C and C- H bands at points in the Brillouin zone
where there is u high density of states, i.e., at the zone center ncar - 9 e V and at
the zone edge ne.tr - 8 e Y. The broad peak E has its origin in the strongly dis-
persed n-band, which also contributes to peak D. The valence band edge corre-
sponds to the highest pot1ion of the occupied n-band, at the zone edge.
It can be instructive to follow the evolution of the a-bands when going from
the unit cell with one carbon atom to that wi th two carbon atoms. As mentioned
above. the a-bands can loosely be to as C-C and C- H. In polyethylene,
the upper bands arc essentially C-H and the lower C- C {3J. Because of the large
dispersion in polyacetylene, however, this separation in energy does not occur.
This is demonstmted in Figure 5-6 where the evolution of the two a-bands is
shown. The two a-bands cross at about - 15 eV, m; seen in Figure 5-6a. Upon
folding the bands into the tina Brillouin zone Figure 5-6b another band crossing
at about - 18 eY occurs. At the points where two a-bands of like symmetry intend
to cross, there is an band-crossing. In addition, energy gaps occur at the
Brillouin zone edges. When taking into account the avoided band crossings and
the energy spliuing <tt the Brillouin zone edges (Figure 5-6c), the actual a-band
structure of can be fully rationalized.
5.4.2 Charge Storage States in Conjugated Polymers
The intrinsic low dimensional geometrical nature of linear polymer chains, as well
as the general property of conjugated organic molt.."Cules that the geometric struc-
ture is dependent upon the ionic slate of the molecule (strong clcctron(hole)-lat-
Lice interactions), leads to the cxistem:c of unusual charge can-ying These
manifest themselves through either optical absoq>tion in the neutral
5 Electro11ic Structure vf Surfaces w1d Interfaces ill Co11jugated Polymers
0,0 0,5 1,0
0,0 0.5

/ I
I '
I '-..

-15 / I
..... .,
/,. ___
0,0 0,5 1,0
tigure 54;. Illustration of the evolution of lhc two u-bands in mms -polyacctylenc.
tern or charge transfer doping, as self-localized elecu-onic states with energy
within the otherwise forbidden electron energy gap {40-44]. For m n-
type doping, although the very first single electron on the (any) lt"CliiS-
polyacetylene polymer chain goes in as a polaron {42, 431. po_larons rcad1ly
bine to form a lower energy state, that of the soliton, named alter the
which describes its behavior [40, 4 11. Although solitons must be funned m pmrs
[45j, usually a single species is sketched for <.-onvenicnce. An isolated
containi ng an excess electron, leads to the of a electromc stat_e
within the energy gap .. The schematic rcprcsentat1?ns of a pos1t1vely c ha'?ed soh-
ton (left), a neutral soliton (middle), and a negattvely charged sohton (nght) arc
shown in Figure 5-7 [43, 451. . . .
Some photoelectron spectroscopy studies of tram-po_lyacctylene m _the
t28, 46], p -type doped [47- 521 and doped l_52J lorms, can be lo_und m
literature. Although no new well del med sulJcture IS detected. dop111g, wh1ch
would correspond to doping induced soliton levels, the dens1ty ol state.<; close to
s+ -----

so - t-

'/1// /// / / //1
':'\ \ \\\\\.

Figu.rc S-7 .. Oanu dia&:lm of solilons with pol>llivdy n<.'"tltral, and negatively charged sys-
from lcl'l 111 right.
5.4 Materic1/s 127
-14 -12 -10 -8 -6 -4 -2
Figure S-8. UPS valcm:c himd spct:lra or llupcu muu -pulyacctylcnc for K-uupcu, neutral, and CI0
<lopc<l fmm top lo holtonl (a<laptt..'tl rrum Ref. 1521).
the Fermi energy levd hilvc hcen reported for both 11-typc 1521 and p-lypc 151.
521 doped tra/1.\-polyilcetylcnc. It shoultl he kept in mind here th:..tt only tH ypc
doped spct;ies would he directly detectable in PES. As illustmtions of the cll.'c-
tronic structural changes induced upon doping, are UPS spectra shown in Figure
5-8 in the cases of potassium-doped (top) and perchlorate (CIO;j)-doped (bottom)
/ra/ls-polyacetylcne {521. The spectrum corresponding to the pristine polymer is
shown in the middle as a reference for the doped situations.
The evolution upon doping is cxpl:..tined as li.>llows: new mid gllp states arc
formed immediately at the initial stage of doping, with Fermi energy level shifts
towards higher binding ener<.;y in the case of pcrchlor.tte and to lower binding e n-
ergy in the case of potassium doping. These shifts arc in agreement with the re-
of electrons fmnllto the /ra/1.\-polyacetylcne chains upon the 1'-
typc/n-typc doping.. A filled mid gap band is expected for the 11-type doping
while the mid gap band is expected to he empty for a p-type doped situation.
Upon further doping, density of states appc<tr close to the Fenni level, as shown
magnified in Figure 5-8 .. This evolution is explained here a:; the of a
mew/lie state. The mechanism behind this fonnation of a metallic state is, how-
ever, not fully understood.
Also in the case of non-degenerate ground state polymers, the very first single
electron on the (any) isolated polymer chain goes in as a polaron .. However, the
individual polarons interact (combine) to form spinless bipolarons, which is a
lower energy configuration. Thus, in general, depending upon the symmetry of
the ground st;tte, the charge-carrying species arc charged polarons, spinless
chargl.-d solitons. or spinless charged bipolarons 140-43, 45. 531 .. The negatively
charged hipolitrun slalcs for poly(p-phcnylcncvinylenc), or PPV, <t
128 5 Electronic Struc:ture of Surface.v and lmcrfates in Conjugmed Polymers

Figure S-9. Band diagram of ncgalivcly charged bipolarons (BP--) in PPV.
conjugated polymer, arc sketched in Figure 5-9. These species. solitons, polarons
and bipolarons, represent the lowest energy eigcnstatcs of the l:oupled electron
(hole)-lattice systems (54), <tnd arc responsible for the unusual electrical, magnetic
and optical properties of conjugated polymers.
5.5 Polymer Surfaces and Interfaces
In the following sections, results from various photoelectron spectroscopy studies
of poly(p-phenylenevinylenc), polythiophcne, and polyaniline, ar1d their intentc-
tion with ditferem metals will be discussed. The intention is not to cover the
whole existing Iitcmture, but still give a relatively extensive overview, and, where
appropriate, give references for further reat.ling.
5.5.1 Poly(p-phenylenevinylene)
In Figure 5-l 0, the experimenwl UPS Hcl and Hell valence band spectr.t of PPV are
compared with 1he results of a calculation of the band structure based on the VEH
modei[2H). The chemical structure of PPV is displayed in Figure 5-4. 1l1c excellent
agreement between experiment ant.! theory may be seen, there three
reasons that the experiment and theory might not agree al all bmdmg encrgacs: (I)
photo-ionization energies arc not included in the thcon:tical (2)
many-body effects, inherent in photo-electron spectroscopy, whach appear 111 the lO-
ner valence region ponion of the valence band in hydro-carbons; ant.! (3) the VEH
-25 -20
-15 - 10
-15 -10
5.5 Polyma Surjllas ami lnterji.Jccs
5 0
5-JO. _l-Ie I and II UPS valence band 'flllo:lra uf PI'V with DOVS derived from
VEH COJk:ulaiiOtl'>- Tile VEH band slruciUrc in lhc luwcr ll'lrl uf 1hc liguc (from Ref. 12!1J).
models have not been properly parameterized for states in the inner valence band
regi?n. _On the ot_her especially good agreement is expected and found, at low-
er bmdmg 111 the so-called frontier electronic slructurc region.
den_slly valence states, shown in direct comparison wi th the UPS spcc-
tm, IS lrom the band s_tructure which is shown al the bouom or Figure 5-
10. The port1on of the electronic structure which is of most interest the so-called
elccbonic structure, is at the low binding energy region, . to the right
ot the figure. at higher binding energies, peaks A, B and C, 01iginate
electrons _m d1ftercnt a-band'> while pe<tk 0 is built up from contributions
the four a-bands, the lowest n-band, and a small portion from tbc re-
latively tlat part ol the_ n-band. The two peaks at lowest binding energies,
peaks E and F, arc denvcd from the three topmllst n-bands. Pc;tk E is dominated
by next h_ighcst n-bmuJ, which is extremely llat, since it corresponds to elec-
levels lully localized on the bonds between onho carbons within the phenyl
nngs. In general, a llal band results 'in a high illlcnsity peak in the DOVS, since
there arc many slates per unit energy just ill the llat hanll. The larger dispersion of
130 5 Electronic Structure of Surfaces 011tl lnte1j'iKes i11 Coujugatetl Polymers
the top n-band results in a lower intensity in the UPS In studying
moms on the surfaces of the PPVs, the low energy electromc structure, as seen m
UPS, changes in particular ways, depending upon the nature of the interactions or
the metal atoms with the surface of the polymer. Also, this energy region is sensi-
ti ve to substituents as demonstrated by Fahlman et al. [38], where the fine details
in the low binding energy part of UPS spectra have been compared with VEH
calculations in a series of PPVs with different substituents such as alkyl chai ns,
me.thoxy groups, and cyano groups. Details such as the splitting between lhe two
topmost peaks (E and F in Fig. 5- l 0) and the position of the valence band
relative to the Fermi energy arc affected. The latter is consequence of a change m
the size of the optical band gap.
In the many reports on photoelectron spectroscopy, studies on the interface for-
mation between PPVs and metals, focus mainly on the two most commonly used
top electrode metals in polymer light emitti ng device structures, namely aluminum
[55-62] and calcium [62-67). Other metals studi<Xl include chromium [55, 68],
gold (69J, nickel [69], sodium [70, 71 ), and rubidium (72]. For of n_ick-
el, gold, and chromium deposited on LOp of the polymer surfaces, mtemct1ons
with the polymers arc reported [55, 68]. In the case of the between PPV
on top of metallic chromium, however, no interaction with the was
lected [55]. The results conceming the interaction between chronuum and PPV m-
dicates two different effects, namely the polymer-on-metal versus the metal-on-
polymer intertace formation. Next, the PPV inte1face lormation with aluminum
and calcium wi ll be discussed in more detail. Interface Formation Between Aluminum and PPV
In connection with the progress made in the fabrication of light emitting diodes
(LEOs) from conjugated polymers, some of the most promisi ng results have
obtained with poly(p-phenylenevinylene) as the light emission medium, With
(hole-injecting) ITO-glass as the transparent substr.tte and with a calcium or alu-
minum electrode as the (electron-injecting) metall ic contact.
There are two more or Jess equivalent approaches when studying the chemistry
at an interface with the help of PES. One way is to build up a metal ovcrlayer on
top of the polymer using physical vapor with a full set. of
data recording between the vanous steps. Another posstbthty ts to grow a th1ck
metallic overlayer on top of the polymer and then, in a stepwise fa..-;hion, etch
away layer by layer using ion (e.g. Ar) bombardment. The latter been
by Nguyen et al. 155]. A set of XPS core level spectra, recorded dunng stepw1se
removal of the aluminum top electrode, are shown in Figure 5- 11 . Note the re-
verse order of the set of spectra in the case of the C(l s) peak (middle).
In Figure 5-12 is a set of core level spectra shown, which have been recorded
between successive steps during the growth of an aluminum metallic overlayer on
top of PPV [59]. The thickness o{ the aluminum layer for the lowest and highest
coverage correspond to 2 and 20 A, respectively.
In both of the above cases, the PPV lilms were prepared from precursor poly-
mers and converted at elevated tcmper ..uures wi th a minute amount of oxygen
5.5 Polymer Surfaces a/Ill lntetjaces
u.... ............. 1 ----.1 ......... ""- . _ ... ...........
536 532 528 288 284 280 76 72 68
Jolgure S-11. XI>S L' Ofl: lcvd S(X'\:Ir.. rc.:ot\k:d during n:mnvals olthc aluminum layer on
PPV (;nlaptcd from (S5J).
r- - ,- - I --. -
Q(1S)A C(ls)

534 532 530 288 286 284 76 7 4 72
5-12. Xl>s cure level rL'<.'ortlcd during dcpu,itiun of aluminum on PPV
(a<.laptet.l from IS9J). HJC Al(2p) spce1ro1 have lx-cn numlali,.._'<.l In L'l(ll:ll IIICI<II mmpuncnt intensity (at
abuol 72.5 eV).
contamination present on the polymer surtitccs (Konstildinidis reports slightly
more than 4 at.% of oxygen).
Some comm?n be seen in the (I) oxygen is present
thn>.ughout the mterractal rcgnm. extending <Jil the way to the outcnnost metalli c
surface; (2) two comtxmcms can be detected in the case of the aluminum signal;
and (3) the carbon peak shape remains essentially unchanged and the bindino en-
. . . b
posnto? c_onstant. The source of the relat ively high oxygen concen-
trations are m the uuerlace and in the metallic layer itself. The two component in
the Al(2p) spectra, at about 72.5 and 74.5 eV, originates from oxidized and metal-
lic aluminum, respectively. As can be seen in both cases, the feature related to
_uluminum has a relatively large intensity in the ncar polymer surface re-
gion, would expected in the case of oxygen-contaminated surfaces; oxy-
spcctes as carbonyl groups would be the primary reaction
sne for the vapor-deposited aluminum [591. In connection with point 3 above, it
_menti oned in similar work out by Ettedgui et ul. a succes-
SIVe shtlt, m the order ol 112 cV. was dclcctcd for the C( l s) peak, which has been
5 Electronic StruclUre of Surfaces cmd Interfaces in Colljugclled Polymers
b d be u1
at the ,ntcrface [57 58]. 1l1e core level shifts can,
d1scussed as a an '
. '
however, be explained in different tenns [73]. . . . h-
. . d b Dannetun et al . [561. using the same alummum lee
. In a stu y y d" .d. t I [59] i e UPS and XPS the fine detmls m Jhc va _ lence
mque as Konsta 101 IS e a . . . . t
and ed e of the UPS spectra, together wi th the evoluuon_of ur:
? h Cg( 1 ) XPS core level spectr.t. shows that Jhe imeracuon wllh alummum atoms
m t e s . tal ults are supported
strongly affects the frontier orbitals of PPV. The ex_penme? res PPY . d AI
b results obtained from theoretical studies of the mteracllon _between_ an .
y h . fi nd that AI preferentially w1th the vmylene mol-
atoms, w ere 1t was ou . . d . 1 odifies
eties, which have large contri butions to the frontier orbitals, an. yh ":, "d" -
the geometrical structure by the fonnation bonds and sp Y n za
lion, which leads to interruption of the 7t-eOnJugallon [74, 75). Interface Formation Between Calcium and PPV
The low binding energy parts of the UPS He I (21.2 cY photons) valence band
spectm of poly(2,5-diheptyl-p-phenylenevinylene) recorded
different stages of deposition of calcium, are shown Ill Fgu.rc 5-1_3. !f1el cfty
. d hains on the phenyl groups do not contribute to the mtcnslY m l 1e
energy part, e.g., below eY 1661. The spectrum at the bollom corrc-
0 J


<!) (j)
Ui w
.... c(


-10 -8 6 4 -2 0
1 1 . H 1 UPS spectr.1 of DHJ>I>V rcl.'t>n.ku during succcsstvc
5-13. Low bmdutg .P'1
" rt

.. , (one Ca awm per munumcr) OIIPt>v with u

, . 1 of calctum 1l1c HlSCI s 1uw:. I lc u I""" . . .- .. . . (fm u
ucpust ton . . . I . b. k u to emphasize the calctum-ltluu..:u '
simplccstimah: of th.: c cctmn 'IC gmuu . .
Ret. (66J).
5.5 Polymer Surftlt'es wtd lmerfaces
sponds to pristine DHPPV. while the upper-most curve corresponds to the pres-
ence of about one Ca-atom per DHPPV monomer unit, as detennined from the
relative intensities of the XPS Ca(2p) and C(l s) core-levels. The energy scale is
relat ive to the vacuum level, determi ned <L'i described above, and the Fenni en-
ergy lor C<tch spectrum is indicated by black bars. The XPS bindi ng energy of the
Ca(2p) level indicates that the Ca atoms are in the ionic lonn. At the first stages
of Ca deposition onto the polymer surface, a complete doping of the top layer oc-
curs, as probed by UPS. and upon addi tional deposi tion satur.ttion doping is at-
tained in the surface region. The excess Ca <ttoms in the surface region :then dif-
fuse somewhat into the bulk. Finally, the C(l s) spectrum broadens and shifts
s lightly towards a lower binding energy as the deposit ion of calcium continues,
indicating charge tmnsler from the calcium to the carbon atoms. As a result of the
deposition of Ca, the work function of the sample changes from 4.0 (0. 1) to
3.0 eY, which is close to that of metallic calcium.
In the low binding energy parts of a UPS spectra, signatures of charge tr-clllsfcr
(doping) versus covalent chemical bonding can be distinguished. New features ap-
pear in the previous empty energy gap, which is more clearly shown in the inset
of Figure 5-13, where a simple subtmction of the inelastic electron background
signal has been carried out in order to the interpretation of the new in-
duced states in DHPPY. It can be seen that two new electronic states above the a-
band edge of the pistinc polymer. near -4.0 eV and - 5.8 eV relati ve to the vacu-
um k vd . arc induced upon doping. Details such as the position wi thin the other-
wise ' " ' dden energy gap, and the relative spliuing of the two new states, arc
similar to those in the case of sodium on PPV 1701 and sodium on cyano-substi-
tuted PPV 171), where two new (bipolaron) stales wi thin the gap were observed.
In both calcium and sodium doping of PPV, features corresponding to doubl y
charged species arc detected even al the lirst very low doping steps (66, 70. 7 1).
In the case of rubidium doping or PPV, however, an evolution from singly
charged species at very low doping levels to doubly charged species, correspond-
ing to a polaron to bipolaron tmnsition, can be detected as the doping level in-
crea'ics 172].
Some results from XPS studies of the interface formation between calcium and
PPVs have been reported by Gao and co-workers. The studies have been focused
mainly on the interface fonnalion with the lctmhydrothiophenium precursor PPV
162-65. 671. but <tlso on an oligomer of PPV containing six phenyl groups (761 as
well as some PPVs substituted with phenyl groups on the vinylene moieties (771.
A general result from these studies is that binding energy shins arc detected li.1r
both the C(ls) and Ca(2p) (as well as in the O( ls) when oxygen is present in the
sample:;), as the ovcrlayer grows. In the polymer C(lscs 162-65, 67. 771. the sur-
races showed an oxygen conlitmin;Hiun r.mging from 4 up lo 17 at.%, and in
some cases sulfur impurities remaining from the precursor, which are most
likely to act as re<tction sites for the vapor-deposi ted calcium. The shift in the
C( Is) peaks in the samples has been allributcJ lo a band bt'llding in the
C<tsc l(>r the polymers 162-(>5, 67
771 and to molemlar eua1:y h!l'el b<'nding in
the case of the PPV oligomer deposited onto a calcium surface 176). This is the
same inlerpl\!lation as in the: case of dc:pusilcd 0 1110 PPY as
5 kclronic Structure of SurftJces wullnterfaces ill Conjugated
above, where also a shift in the C( l s) peak was the same [57,
58). It is important to repeal here, that the core level sh&tts can be explamed m al-
ternati ve terminology [73].
5.5.2 Polythiophene
Polythiophene [78} is a promising .rr:ateriaJ for applica-
tions, due to its relatively high stabthty and. m the form
[79-81]. Upon substitution, with e.g. alkyl stde-chams [79, 80], ex-
hbt properties such as solvatochromism [82} and thennochromtsm [83j.
a large variety of substituted polythiophenes with various band gaps extsts
(for example sec Ref. 1811). .
Two Hc11 UPS spcctr.t of poly(3-hcxylthiophenc), or P3HT, compared_ the
DOVS derived from VEH band structure llBI. shown 111
5- 14. n
e geneml chemical structure.: of IS sketched. tn Flg_-
ure 5-4. The two UPS spectra, were rcconlcd at two_ dtlfc_rcnt
+190C and -60"C, respectively, and the DOVS wm. dcnved VEH
t" ons on a planar confom1ation of P3HT. Compared to unsubsut utcd polythto-
the main inOuence in the UPS spcdm due to the prcsence of the hexyl
.. . : .
-60 c .. _.
-20 -15
. . ..-... .. .
,.. .,.
. . ....
. . , .
: .
. . .
. .
_ ..
. .
. .......
., .___
lo' igun: 5-14. He 11 UPS o f poly(J.Iw.:xyllhiuphcne). r.xuruc<l at ami +190"C, <. -ontpan:c.l
with DOVS derived from VHI calculattons (lrom Ref. 11131).
5.5 Polymer Suifaces ami l11teifaces 135
side-chains, is additional intensity in the energy region from about - 5 to - 12 eV,
as deduced by comparison with the fine details in the YEH calculations. The en-
ergy region below - 5 eY is derived entirely from electrons in the uppermost n-
bands. Thus, the frontier orbitals which are important in, for example, metal/poly-
mer intemctions, are unaffected by the hexyl-chai ns. From a spectroscopic point
of view, however, one problem with the side-chains is that the XPS C( l s) core-
level signal from electrons in atoms in the thiophene units will be obscured by
the signal from the carbon atoms of the side-chains. This effect will be discussed
in more details later in connection with the interaction between and
polythiophene. When comparing the fine details in the low binding energy part of
the UPS spectra with the calculated DOVS, it can be concluded that the spectrum
recorded Cit -60' 'C corresponds to " more planar situation than that recorded at
+190"C. This is in agreement with optical absorption spectroscopy. where it was
founll that the optical hand gap increases with increasing tcmpemturc [H2J. I nterface Forma tion Between Aluminum and Polythiophene
The evolution of the XPS C(l s), S(2p). and Al(2p) core level lines, upon AI de-
position onto poly(3-octylthiophcnc) films (PJOT), is shown in Figure S- IS ll$41.
The S(2p) spt.-ctrum for the pristine polymer consists of two components. S(2p
and S(2p_v::! ). tlue tu spin-orbit coupling.
The main clkct upon AI deposition C<UJ be seen in the S(2p) core level, where
a new component is gradmtlly growing on the low binding energy side of the
peak. Also in the C( Is) spectrum, a small shoulder can be seen on the low bind-
ing energy side. However, for most of the samples, no shoulder was found on the
C(l s) level, and only a very weak shoulder could be found in some of the sam-
ples at the highest AI coverage, as seen in the C( Is) spectrum (to the left) in Fig-
ure 5-15. Since aluminum is expected to intemct preferentially with the carbon
S(2p).A Al(2p)
c 0
I ll.
I w



w <



290288-286284282-280 170168166164162160 80 -78 -76 14 12 70 -68
lo' illurc 5-15. XI'S C( Is). S(::!p). :Uitl Al(2pJ SI><XII"a of the AVP.lOT for AI ' :over-
age. ntc C( Is) anu S(::!p) spe<:tr.t of lhc pristine system is al lhc lx>llom and inc reas ing AI cuvcragc
(frnm Ref. 111-i iJ.
5 Electrollic Structure of Sutfuc:es and lllletfuc:es in Conjugated Polymers
atoms of the conjugated backbone [85), and the C(ls) spectrum of P30T is
nated by the aliphatic carbon :lloms of the side chains, . any _new carbon spectes
might be small in numbers, because not only do the ahphattc carbons
the major contribution to the C(ls) line, but also because a pru1 aro-
matic carbons are expected to be affected by the AI deposttlon. '!'he mrun hne . of
the Al(2p) shifts slowly towards a lower binding energy as the thackness of AI an-
creases which is consistent with cluster-like growth of AI on the surface. The
energy of the Al(2p) is - 74.0 eV at the lirst . AI and shifts
slowly to - 73.3 eV for an AI layer equivalent to a few A, _as stall somewhat
different from the bulk metal value of - 72.7 cV. A low mtensaty component ts
present on the high binding energy side of the Al(2p) peak (corresponding to AI
atoms where the electron densities arc lower relative to unaffected atoms). A small
amount of oxygen was detected in the P30T films, about one per ten thio-
phene rings, indicating that this component might conespond oxadazed
A complementary study of the inter.JCtion between alumanu_m and tht?phene
was carried out by using a model system consisting of a polythaophene oligomer,
namely a-sexi thienylcne (a-6T). The lack of aliphatic side chains that
the C( 1 s) signal from the carbon atoms in the bockbone, and the possabahty m
situ prepamtion of films, i.e., obtaining contamination (oxygen) free samples from
a-6T, allows for more detailed information. The C(Js), S(2p), and Al(2p) core lev-
els upon AI deposition onto a-6T arc shown in Figure 5-16 For AI on a-6!,
a shoulder apperu'S more clearly on the low binding energy sade the mam
line upon AI deposition. The evolution of the S(2p) line as to
the evolution of the S(2p) observed for the case of alummum deposated ont_o
P30T. The evolution of binding energy for the Al(2p) line is similar to what as
observed for AIIP30T, except for the fact that no high binding energy component
is detected, indicating that this feature seen in AI/P30T, indeed. is related to the
formation of AlO,. species.
C(1s) 0
'iii en


.. z
z <(

... w

290288 286284 282260 170 168166 164 162 160 80 78 -76 74 72 -70 68
Figure 5-16. XPS C( ts). S(2p), and Al(2p) spcclm of the Allu.-6T inlcrfucc for incn:a.,ing AI cover
age. The C( Is) and S(2p) sp.:clra uf lhc prislinc syslcm is al lhc tx1IIUIII ant! AI ..:ovcr.,gc
(fmm Kef. 11141).
5.5 Polymer Swfaces am/ llllerfuus
From the experimental data presented above, the conclusion would be that AI
reacts with both the sulfur atoms and the carbon atoms in the backbone of the
thiophene units. However. the result') from both semi-empirical MNDO calcula-
tions on a aluminum/a-6T system, and ab initio quantum-chemical calculations on
a aluminum/a-trithienylene (a-3T), shows that the aluminum atoms preferentially
fom1 bonds wi th the a-carbons of the thiophene rings (86 J. The AI-C bond leads
to a redistribution of the charge density in the Al-oligothiophene complex relative
to the sepamte . pa11ners. The aluminum atoms become strongly positive, as ex-
peeled, and electron density is tmnsferred to the a-carbons and the adjace.nt sulfur
atoms, while the atomic charge of the fJ-carbons remains unaffected together with
the charges on the thiophene units without aluminum. Although the amount of
negative charge transferred from the AI to the C ru1d S atoms diffe.rs somewhat
depending upon the computational level, <til of the calculations point to a charge
lhl! AI 10 the a-carbon and the adjacent S, and only to U1cse sites.
On lonnallon of a bond AI and a a-carbon, the hybridisation of that car-
bon atom changes from sp
to sp:\ i.e . the conjugation is broken at these si tes.
1l1is selective bonding of the AI atoms to the a-carbons can be explained in terms
of the electronic structure of the lowest unoccupied states of the pristine mole-
cule. These states are lound to hybridize with the AI valence levels to lorm the
occupied states of the complex. Since these states obtain a large contribu-
llon lrom the a-cruixm. it is expected that the bonding ptdercntially takes place at
these si tes. Reaction of the AI, which is an electron donor. directly with the sulfur
atoms. is less likely, due to the inherently high electron density on those sites.
Thus. the combined expeaimental and theoretical results indicate that U1e chemi -
cal shift observed for the S(2p) core level, of about 1.6 eV, should be due to a
secondary effect from the allachmcnt of AI atoms to the adjacent carbon atoms.
Indeed, this is fully consistent with ab iuitio Hartree-Fock llSCF calculations of
chemical shifts in aluminum-oligothiophene complexes (87). From culcula-
hons on a Al2/a-JT complex, where the two AI atoms arc attached to the a-car-
bons on the ccntml thiophene unit, the chemical shift of the S(2p) level for the
sulfur atom is found to be 1.65 eV. which is in close agreement with the
value about 1.6 eV (84). It should be pointed out that although
seveml dtflerenl Al-thaophene complexes were tested in the llSCF calculations, no
stable structure, where a11 AI atom binds directly to a S atom, was found [87 j.
The spectra (not shown here) recorded upon AI deposition onto the conju-
gated thaophene systems shows only small visible changes in the positions of the
in the spectra [84]. 1l1e main ciTcct is a rapid decrease in intensity, which
mdacates that a metallic overlayer is formed since the cross-sections for the
Al(3p) or AJ(3s) are much lower than for the C(2p) or S(3p) orbitals. This is con-
sistent with the Al(2p) XPS spectm discussed above . Interface Formation Between Copper and l)olylhiophcnc
The XPS S(2p) core level spectra recorded duaing the stepwise deposition of cop-
per onto poly(3 hcxylthiophcnc), or PJHT (S8J arc shuwn in Figure 5- 17. The
S(2p) spectrum at the top correspond to the pristine system. On increasinl' l'tlJlfX'r
138 5 Elearonic Structure of Surfaces tuul Jmerfaces in Conjugate'/ Polymers
168 166 164 162 160
Figure 5-17. XPS S(2p) spcc1ro1 of the Cu/PJ HT interface fa Cu covcmge. The S(2p) spcc-
uum of the pristine system ;11 the top and Cu downwards (adapted from Rcr.
covemge, a new feature is growing up on the low binding energy side of the
S(2p). The new feature has a binding energy shift of about 2 eV towards lower
binding energy, indicating an increase of electronic charge on the sulfur atoms
due to the interaction with the copper atoms. As in the case of P30T discussed
above, the C( Is) spectrum of P3HT has a large contribution from the alkyl side-
chain. However, in the case of AVP30T, a weak signal on the low binding energy
side could be detected at a high level of aluminum coverage, while no visible
changes in the C(ls) signal occurs in the case of copper deposited on P3HT [88].
Thus, the results indicate a direct intemction between the copper atoms and the
sulfur atoms in the thiophene units.
This interpretation is supp011ed by the results from a combined experimental
and theoretical study by Ghijsen et a/. [89]; the copper on P3HT interface was in-
vestigated by photoelectron spectroscopy, using synchrotron mdiation as the
photon source, and combined with the rcsullc; from quantum-chemical calculations
performed using a density functional technique. The valence band spectra, re-
corded with 40 eV photons, shows no significant change in the low binding en-
ergy part of the spectra upon copper deposition, i.e., the frontier orbitals seem to
be unaffected by the copper atoms; the highest occupied n-band is delocalizcd
along the carbon backbone in the case of polythiophene. The calculations resulted
in a optimized Cu-S bond of about 2.2 A, indicating that a strong bond has taken
place between these atoms. Also, the geometric structure of the carbon backbone
is not significantly changed by the Cu-S bond, in agreement with the lacJ... of ob-
servable changes in the low binding ene1-gy pan of the experimental spectm (89J.
In addition to the Cu/P3HT system discussed above, Lachkar et ul. have re-
ported results from studies on the intemction between P3HT and Cr, V, Ti, Ag,
and Au [88, 90]. From the expe1imcntal results it was concluded that Ag, as in
the case of Cu discussed above, interacts exclusively with the sulfur atoms; Cr. V,
and Ti inteJ<tCI with both the carbon and sulfur atoms; Au does not interucl al all
5.5 Polymer Surfaces and Interfaces
with P3HT. In a separate theoretical investigarion of the interaction between thiu-
ph.ene. and the V, Cr . Cu. and Au, using a density functional technique, the
the. resul ts .ror the cases of copper and gold [91 ).
J..e., no .nh.:r.JdJon was found lor gold whrk copper was found to intemcl exclu-
WJih the atom:-; in the thiophene unils. However, in the cases of vano.t-
dJum and chrom1um. it was found that strong covalent bonds arc fonned between
the V the a-cart>ons in the thiophene unit, and similar, but weaker.
covalent occur between Cr and all the conjugated atoms in the
phcne umt (91 ). Thus, the changes in the S(2p) signal, detected upon deposition
of':' and Cr, could be attributed to a secondary effect, as in the case of the inter-
acLJon between AI and P30T discussed above.
5.5.3 Polyaniline
has past few ycaJ'!\ been considered for a number of applica-
such as optical tracers, COJTOsion inhibitors, and anti-
films texllles .. Pulyamhne has outstanding redox prope
1ies and a divcrs-
. through substitution. The geneml fonnula of polyani-

dtsplaycd m. F1gure 5-4. Three base (neutral) forms of polyaniline have

been the fully reduced leucoemeraldinc lorm (Y= I), the half oxidiz.cd
emeraldmc lonn 1/2): and the full y oxidized pemigraniline fom
the m the literature photoelectron spectroscopic studies of pol _
anthne can be found: (1) polyaniline in different oxidation states
the dopmg mechantsm [92- 971; (ii) the inte1face formation with metals or semi-
conductors and (iii) corrosion protection [102- 104).
The spectm of the ememldine base fom1 of polyaniline is
compared wJth VEH-dcnved OOVS in Figure 5- 18 J97 j. The DOVS were derived
from the VEH band structure cakulations shown at the botlom of Figure 5-18.
agreement between the experimental and theoretical rcsull-; in
par1tcular m the low binding energy region extending from - 10 to - 5 eV which
to the n-band region. allows for a detailed assignment of the differem
f'?'tures Ill the spec.trum. TI1e feature at - 5.5 eV 01iginates from the highest occu-
pied molec:ular orbual (HOMO) which corresponds to electronic states localized
on the ammo groups and the aromatic rings they sunound. The small feature at
eV. to electrons in the second and third highest occupied rnolec-
_.orbttal, HOMO-I a.nd respecti vely. The HOMO- I orbital is mainly
over the amme umts and the phenyl ri ng while the HOM0-2 is dclo-
cahzcd all. rings and units. The peak at - 8 eV originates from
m several llat ?ands whtch coiTcsponds to. electronic states completely
l?cahzed. on. the nngs. In the next section, the interaction between polyani-
hne and Jndum-tm oxtde will be discussed.
5 Electronic Structure of Surfaces and Jmerfuces ill Co11jugatcd


- 15 -14 - t3 -12 -11 - 10 -9 -8 -7 -6 -5 -4
-15 -14 - 13 - 12 -11 -10 -9 -8 -7 -6 -5 -4
Flgure 5-18. UPS speclnlm of the emcr.lldinc ba.o;c form of polyanilinc is compared with the VEH cal
culaled band strudure (bouom) and lhc VEH DOVS. Polyanilinc on Indium-Tin-Oxide
Concerning studies of metal/conjugated polymer interfaces, the main focus has so
far been on the interface fonnation between conjugated polymers and metals of
interest for electron injecting electrodes in polymer light emitting devices.
Although other transparent, high work function, _ exist,
(ITO) is so far the most commonly used hole mJectmg contact m LEOs. Cml?-
pared to metal-on-polymer interface formation, as discussed above_, muc_h ts
known abo ut the intcmction at the polymer-on-ITO interface. Befor-e dtscussmg
the actual interface formation between polyaniline and ITO, some aspects of the
ITO surface itself are outlined. .
One of the most important parameters of ITO, apat1 from the transparency,
the relati vely high work function. In a compamti vc photoelectron _
study of ITO from different sources, atld prepared hy diiTcrent tcchmques, a varm-
tion in the chemical composition and work functions are reported ( I 0 I, I 051. For
three carefully chosen types of ITO, the chemical composition and wort- functions
5.5 Polymer Surfaces und lllterfuces 141
were determined, using XPS and UPS, a.-; a function of sample-cleaning proce-
dures. After cleaning with acetone and isopropanol in an ultra-sonic bath, the
work functions vatied. by some tens of an eV, between the different ITO samples,
whilst treating the samples with hydrogen peroxide r"l:sulled in about the same
work function (4.60. 1 cV). In the Iauer case, it is interesting to note that both
the chemical composition (ln/Sn r.uios ranging from 7 to 9) and the morpholooy
varies between the different ITO sampl es [I 0 I]; the surface roughness, as
by atomic force microscopy (AFM), vatics over the range of 25 to 100 nm [101).
Also, when using the ITO substrates in LED devices the influence of the substr.uc
precleaning on the device pcd"om1ance ha.o; been studied (I 0 I, I 05). The hydrogen
peroxide treatment clearly improves the device perfonnance, which could be at-
uibuted to the increased ITO-workfunction. Most interesting is the fact that,
although an improvement in the device performance was found for the hydrogen
peroxide-treated ITO surfaces and that the work functions are the same, the pcr-
fonnancc varies. This demonstrates that both surface roughness and work function
have primary inllucnce in the hole-injection characteristics at the polymer-on-ITO
Although polyani line has not been used as the acti ve polymer itself in LEOs, it
has been used as an additional layer to improve the device performance. For ex-
ample, by usi ng a combination of doped polyat1iline atld ITO as the tmnsparcnt
anode of a polymer LED with MEH-PPV ao; the active layer, the volt-
age was lowered and the quantum eOiciency increased si!,'Tlificantly, compared to
devices using ITO alone as the hole-injecting atlOdc [106, 107). 1l1is effect was
attributed to a higher electronegativity of doped polyaniline as compared to ITO.
which then provides a lower batTier to hole injection into MEH-PPV ( I 08 J. In
multilayer LED devices based on poly(2,5-dihexadccanoxy phcnylene vinylene
pyridyl vinylcne), undopcd emer..tldine ba'ie has been used as an insulating layer
between the emissive polymer layer and the electrodes, resulting in a decrease in
the total resistance as the number of insulating polymer layers increases (109).
Thus the nature of the electrode/polymer interface plays a critical role in dctcnnin-
ing the device
Also, failure modes in LEOs due to the ITO substmtc, such as indium cJiO"usion
into the active polymer (IIOJ and oxidation (degmda tion) of the emissive poly-
mer, where the ITO acts as a source of oxygen f i ll, 1121. have been repor1ed. In
this context, coating the ITO-anode with polyaniline, ao; used in MEH-PPV-bascd
LEOs, was reported to stabilize the chemistry of the electrode-polymer interface.
In addition to a higher c urrent and brighter emission, the polyanilinc injection
layer lowered the rate of degradation ao; compared to uncoated ITO. This was <tt-
tributed to a reduced oxidation or the emissive polymer as the polyanil inc layer
pmvidcs a barrier for the passage of oxygen out of the ITO. In addition. an im-
provement in microscopic shot1 fonnation indicated a planati:t.ation of the anode
interface by the polyanilinc film f l l:! 1.
Ultra-thi n lilms of polyaniline may be spin-coated onto the ITO substmtcs. By
studying thick lilms, spct:tm of the polymer itself arc obtained. As the thickness
of the polymer overl;tycr is some of the subtle details of the intcrf;tcc be-
tween the very thinnest possible polymer l;tycr (essentially a mono-layer, in the
142 5 Elec1ro11ic Slruclure of Sutfaces a11d buerfac:es u1 Ccmjugaled Polymers
best case) and the substrate (ITO) may appear. In the best case, enough detail can
be seen to infer infonnation about the nature of the intemction of the polymer
with the ITO. Emeraldine base films of ditTerent thicknesses have been studied by
XPS, with particular attention made to the N(ls) core level spectra. One such se-
ries of spectra is shown in Figure 5-19. In the case of the thickest film (at the bot-
tom), the N( I s)-emission contains two components with spectral peaks at binding
energies of about 400.2 and 399. 1 eV, corresponding to the amino- and imino-ni-
trogens in the emcraldine base. Decreasing the film-thickness leads to a decrease
in the intensity of the main amino-component in the N(ls) spectrum, while a new
shoulder appears at higher binding energy. From an analysis of the data it may be
inferred that there is an imcraction between the amino-groups in emeraldine base
and the ITO-surface [101(. One complication with the interpretation of the N(ls)
spectra is that the commonly used solvent NMP, which can ditlicult .to remo.ve
from the emcrakline base, contains ni trogen. The N( Is) s1gnal assoc1atcd w1th
NMP would appear al the high binding energy side of the amino-component, at
about the same binding energy as the new feature appearing in the spectrum at
the top in Figure 5- 19, and adding intensity to this region. Thus, the dcacaM: in
intensity for the amino-nitrogen contti bution still indicates a reaction between ITO
and the amino-nitrogens.
In a complementary study of the intcmction between polyaniline and ITO, oli-
gomeric polyaniline model compounds, namely phenyl-cappc.d amino (PC2) .and
imino (PC20X) dimers [1 13, 114) have been used. The chem1cal shuctures of
polyanil ine oligomers arc displayed in Figure 5-20. Both substances arc soluble m
408 406 404 402 400 398 396 394 392 390
J'igure S-19. N(ls) XPS cmc lc"d spcc1r:1 uf cmcmlllinc_ ;ltl:""il. .. -d on ITO. The hlfl must
lrum corrcspum.ls hi uhr.Hhi n lihn (in 1hc munu layer rcgnnc) wlulc rho.: houum spccuum cum:SfXMIOs
to lhick film.
5.5 Polymer su,faces Gild llllerfaces

I - I -
uf lho.: pulyanilinc mudd .:umpuunlls I'C2 pltenyl...:app..-d
an1lmc tluncr: illlllllO cumpnulltl) anti i'C20X (uxidi1.<--d phcnyl ...:oopf".'<i aniline lluncr. imino , -.,
chlorofunn, thus avoiding the problem of residual Films of vatious thick-
nesses were prepmcd fi't>m solutions with dill'crcnt concentrations of the oli .. o-
mcrs in chloroform by spin-coating onto ITO-samples. The ITO surfaces
prcdcaned by ozone treat ment over a period of 5 min.
A. of XPS N(ls) core level spectra, recorded for different thicknesses of
the muno compound, arc displayed in Figure 5-2 1. In the case of the thick
PC20X-Iilm, the N( I contains a main component at a binding energy
of 397.8 eV, together wuh nunor peak components at 3'J'J.4. 401.6, atld 405.1 eY.
1l1e Iauer peaks arc auributed to shake-up tmnsitions and wi ll not be discussed
further. thickness decreases, a bmadcning of the N( 1 s)-emission to-
h1gher bmdmg occurs. This evolution is completed when only the
chen.llsorbcd 1s present on the ITO-surface, result ing in a broad, sym-
metnc N( I s)-emtss1on composed of the 01iginal component (slightly shifted to
eY) and an additional, high binding energy component at 399.3 eY. This
sphllmg of the N( l s)-emission indicates that there is an intemction between one
of the two imino-nitmgens in the model compound and the ITO-surface whereas
the imino-nitrogen docs not interact with the [I 14].
However, 111 the correspondmg scncs of spcctr.t for the! amino model compound
(not shown here), the N( I s)-emission cssemially remains unchanged at a bindino
energy of 9 .e Y, except for a small incrC<.Jse of the width of the peak. o
The low energy parts of the UPS-spectra for increasingly thinner layers
of both the compound (PC2) and the imino compound (PC20X) on ITO
me shown m 5-2:!. the case of the thick PC2-li lm, the low binding
energy electromc sllucture d1splays well resolved peaks at - 5.8, -6.9, -8. 1, and
- 9. 1 A, B, C atld D). Decreasing the film thickness in a gradual
ol peaks and B, until a broad, unstructured shoulder is observed in the
hmal ol the chcnusorbed monolayer. Tl1us, although the XPS-rcsults did not re-
veal any of the atnino-gmups with the ITO-surface, such interactions
111d1cated by _the UPS-spectra. Even more dramatic changes of the low-
bmdmg energy clcctromc structure occur for the imino-compound, upon mlcrac-
144 5 Electronic Structure of Surfaces and lnterfuces in Conjugated Polymers


--405 --400 -395
BINDING ENERGY ret. to fF (eV)
lligure 5-21. N(ls) wrc level spectra of the iminu llllxlel mmtxuolll 1'<:20X alhurhcu out ITO. The
upper curve to a thick lilm, lhc ..:entral curve tu an imcnncuiatc thick lilm, and th..: luwer
curve to an ultr.s thin lilm, csscnJi:tlly a mono-layer in thidncss. The bold solid lines art.: the liued
curves and the thin solid and lines al\: the Gaussian peak L-omponcnlS for physisorbcd and che-
misorbcd PC20X, rcspeclively.
tion with ITO. As seen on the right in Figure 5-22, three resolved peaks appear in
the low binding energy region at about -7.8, and -8.6 eY (labeled A, Band
C) for the thick PC20X-Ii lm. As the film thickness decreases towards the limit of
the chemisorbed monolayer, the three peaks coalesce into a broad peak :.tl -8.2
eV, with a shoulder tailing towards low binding energy. Together with the split-
ting of the N Is-emission observed in XPS, these results clearly indicate a strong
interaction of the imino-groups with the ITO-surface.
In summary, the results for the case of the polymer indicate that only the arnino-
nitrogens interacts with the ITO surface while the model studies demonstr.Jlcs that
both amino- and imino-groups reacts with ITO. Thus, ful1her investigations arc ne-
cessary in order to obtain a complete picture. Studies using model systems that con-
tain the whole cmemldinc base SCC.Jucnce have been ini tiated [ 114[.
5.6 Summary
Some del:.tils of the electronic structure of :.t specific metal-on-polymer interface
h:.tve been presented to illustnuc the importance of sut.:h interfaces in dctennining
5.6 Summary 145

Ci) 1-
z CJ Ci)

<( 1-


-15 -10 -5 -15 -10 -5
F1gure 5-22. UPS ' l"-'t."Jr r lh
, a n C <lllllllll molt)d Clllll'" >UIId J'C2 (I I\) I .
I C20X <rHII). ;>liM>oi><:d nn ITO l l . . ,.. " <10< 1111111u mtlllcl cnmpuunu
.. "" tIJCmnM curves arc the I tell pl.'\: f 1 k "I
an: I he dtllen:nce SIIC<:tm (Bell) hctwcen in.-rco.sin I
. . _ s o tue lo mhcr curves
Tile lower t:urv.:s CUITCSjllllld to tlllr.s-thin y ,,IIIIICI lolms llll I ro uno a clean ITO Stufac.:.
s. cs.-.cnu.o Y a mono-layer 111 lhickncss.
device performance in polymer LEOs ln evet . .
some chemistry that occurs at the inteliace Th:' there always
ere IS no such thmg :.ts an Ideal
l -po without interfaci:.tl chemistry of one SOI1 o . h Th me-
conclusiOn :.tpphes
.,., . 1 anot cr. e same
. f
po ymer-on-( , 0 IIUeface, a.c; demonstmted by the 11
ac 10n o 1e emerald, b d h .
und . . I a'>e an . c two oligomeric polyanilinc model com-
po s With ITO. In this context, ll IS clear that the ult' . I .
face will be one of the m . . . . . . llll:.tle contro of the mtcr-
lymer-b .. electro . d aJ_Or dctemunmg steps m the exploitation of reliable
... -..ou niC eVICCS.
.. th_e and t.:oopcr.Jtion of :.til of their collea-
R be ... .. Y_ pet alive ICscut-ch projects, but I.!Speci:.tlly Jean-Luc B .

Eymard Reboun,
a TMR Network

Hoc I t A B ,, .
S well .ts by a contr;u.:t Wtlh
t.: ls . . ,escaL-ch on conJU":.tlcd polymen; in L" k.. . . .
end by grant f. h S . . o .
opmg Is suppo11ed m gen-
. . . s tOm l e . Natural Scaenccs Resc:.trch Council (NFR lh,
Counc1l lor Engineering Scient;es (TFR) and
, S . . ), . e
llonal Bo:.trd tor and Technicul Development (NuTt:K). l lc wcdtsh N:.t-
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wtl Neluted 1'/aelllllllt'IIU I""" '

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114. T. Kugler, unpublished.
6 Electronic Structure and Energy Transfer
in Solid a-Sexithienyl
Carlo Taliani, Fabio Biscarini, and Michele Muccini
6.1 Introduction
Semiconducting conjugated polymer.; have been widely studied over the last
twenty years for their unique electronic and optical which fundamen-
tally reside on the delocalized n-clectron structure. In the early stages of the siudy
of conjugated polymers it was thought that the n-':=onjugated backbone would pro-
vide Ihc pathway for coherent elcctmnic tr.msport within the macmmolccular unit.
Fut1hcr studies showed, however, that real polymers have a finile distribulion of
conjugated chain lenglhs and it became clear that electron transp011 would ulli-
mately be limited by inten:hain hopping. Oiher !rapping centers for electron trans-
port arc chemical defects of the macromolecular ensemble as well as morphologi-
cal disorder of the material. II was at lhis stage that the use of oligomers had the
fin;t impulse and was widely considered a valuable rouie to the underslmlding of
the inirinsic properties of conjug<lled polymers. In the early nineiies the develop-
ment of organic field ellect transistors (FET), based on u-sexilhienyl (T
) by Gar-
nier eta/. fl , 2] and conlirmcd soon afler by Osloja eta/. (3] and Dodabalapur
et a/. f41. clearly indicated lhat lhe availabili ty of chemically pure <llld ordcrcJ
solid-. was the requisite 10 achieve reasonable working conditions for the FET op-
eration. This finding opened the avenue for the developmeni of lhe so-called plas-
tic: elec:t mnics. Disorder moreover is dettime111al not only to electric 1r.mspo11 but
also, to a lesser extent, energy transport. Both charge and energy transp011 are
among the basic steps in the oper ..llion of the organic light emiuing diodes
(OLEO) 15. 6]. Recombination is followed by energy lransfcr within the manifold
of lhe excited electronic slales leading ullimatcly to an exciton. The notion of ex-
citons as lowest in conjugated solids is now univen;ally accepted since
the emission of OLEO is molecular in char.lCter as opposed to band-to-band mdia-
Iive electron-hole recombination. Exciions in molecular crystals were extensively
studied over the Ja.-.t decades (7, 8J. Anisotropic intennolecular intemctions in the
ordered molecular solids were shown to allow the fonna1ion of collective Bloch
electronic excil<llions (Frenkel excitons) in which the excitation is strongly bound
to the mol ecular enli ty and therefore is called tight bound excilon as opposed to
the weakly bound exciton (Wannier exciion) in inorganic semiconductor.;. Never-
theless, the exci tonic band sl11Jcturc of conjugated oligomers is not known and the
rclaiive energy of the lowest singlet Frenkel exciiPn with respect to lhe conduc-
6 Electronic Structure and Energy Transfer in Solid u-Sexithicmyl
tion band (the exciton binding energy) is still a matter of controversy. In this con-
text oligomers of polythiophene, and in particular u-sexithienyl (Tt.).
vidcd the basis for a deeper understanding of the nature of the electromc e.xclta-
tions in conjugated systems. Although solid T
is the focus of the work
in this article, many considerations drawn here arc of more general apphcat1on to
the conjugated organic materials. . . .
The oligomer approach to the investigation of. properties of matcn-
ab offers several advantages: the starting matenal has a well-del mcd molecular
composition, it can be purified by high vacuum (HV) and/or. rec?s-
tallization, and processed as a thin film by clean techmques such as
in ultra high-vacuum (UHV) in the absence of both an.d cc:>ntammants. It
allows the comparison of film and single crystal properties, wh1ch IS useful wh.en
the con-elation between molecular ordering and intrinsic response of the conJU-
gated material is sought. In Section 6.2 we describe the experimental
for the growth of Tt. thin films in HV and UHV, and the1r by
means of optical techniques and sc.:anning force microscopy. The
ture and the optical properties of T, thin lilms have discussed 111
two recent reviews [9, 10]. We first discuss the electromc structure ol ISOlated T<,
in Section 6.3, then in Section 6.4 we explain how the molecular levels form
Frenkel exciton bands. The spectroscopic investigation of Th single crystal shows
indeed that the lowest crystalli ne level (Davydov component) is accidentally for-
bidden as a consequence of molecular packing and that the splitting. of
levels (Davydov splitting) is as much as 2600 em- . Since the relat1ve
of molecules is the cause of the forbidden of the lowest cxc1ted sohd
level from which radiative emission (fluorescence) eventually occurs, it is clear
that molecular packing is a very impo1tant aspect that controls the photophysics
of molecular solids. The weak fluorescence quantum yield in solid T6. as opposed
to the free molecule, is due precisely to this solid state effect and not, as original-
ly thought, to the crossing of molecular gerade and .ungerude states [II). Sec-
tion 6.5 we will cover the fundamental aspects of thm film growth mechamsm as
a preliminary step towards the control in the way in grow
fonn complex morphological structures. We will show that 1t 1s to delib-
erately achieve various morphologies depending on the For
first time it is pointed out that the film morphology has a selj-qffine t.e.
the film arises from a recurrent building unit on a broad range of spaual scales
which establish a spatial correlation. This result is paJticularly relevant since
charge and energy transpo1t are both affected by disorder, although
the spati al scale at which these processes occur may d1tlerent. In f:U:t charge
transport is a process which explores the few neouest
while energy transport is a dipole-dipole (F6rstcr)med1ated lntcJ-actJon wh1ch ex-
plores a wider spatial range. Regardless of the scale of both charge and
energy transport may be govcmed by the same morphologcal In
Section 6.6 we will present our results on the clfcct of molecular d1sorder on the
electronic properties and on the photophysics ofT 6 both in single crystal and
in thin films and how this affects the polarization charactenst1cs of lluorescence
and dcctrolu,minescencc. In Section 6.7 we summarize our main lindings.
6.2 EA71erimental 151
6.2 Experimental
films grown high vacuum (HV) (base pressure 10-
mbar) by sublima-
tiOn of punficd matenal from a Knudsen cell in a moditicd commercial
Auto306). The configuration of the system is constant for all samples,
With the substmte placed 10 em above the quilrt: crucible containing T and nor-
mal . . T (>
. to Jls ax1s. he is heated on its back side by contacting with a resis-
ti ve plate and the effechvc tcmpcmture is calibrated by means of a thennistor
the_ mica surface wi th silver paste. A qumtz microbalance placed in the
proxumty . ol t.he moni tors the amount of the deposited mate1ial. The
qu.artz 1s earned ou.t using AFM by measuring the thickness of pat-
temed Til IJims .. an:_ obtamcd by growth onto a 3 mm diameter copper gid
(2000 mesh pcnodJclty) IJxed to mica and then -cmoved. The deposition mte is
lvs: and the llow of material and heat is when the desired nominal
th1ckness 1s
A second M:t of .was grown in UHV from a Knudsen cell in an organic
depos1110n (OMBD) appamtus (Rial Vacuum, Panna, Italy),
wh1ch was specifically devoted to the growth of molecular materials. The nrowth
chamber . base is 3xl0-
mbar. The lilm thickness is monitored by a
quartz momt.or, near the sample holder, which had a sensitivity
of 0.1 Als. The mte ot dcposu1on of Til was 0.2 Als. During growth the tempcm-
ture the sample was detected with a thenuocouple touchinn the back side of
the. nuca which is rcsisti vely heated on the s<Jmc side. The s:.ne procedure de-
scnbed for HV growth was applied to the calibmtion of both the thickness moni-
and the effective temperature. AFM topographical images have been obtained
m contact mode_ 1- 10 Hz scan J<ltes. In order to work with low setpoint
forces and to mmumze the contact area, soli cantilevers (sp1ing constant 0.03-
0:06 were used aJld 1-clativc humidity was kept below 20% by flushing dry
mtrogcn m the measurement chamber.
of matc1ial deposited aJld the I!ITcctivc of the substr.tte
dunng we1-c systematically varied, while deposition mte was held con-
s.taJll. A set ol about 50 samples has been gcnera1cd. T
tihns arc stable over
tune, due to the barriers for surface relaxation and
and the topographical features remain unaltered over a time span of sevcr.tl
Til sin1e e1ystals were grown l>y under an argon atmosphere wi th
an expc111.11ental appar.ttus described in details elsewhere (12]. Single crystals
were obcamed after. days of growth as self-sustaining plates a few mi lli-
meters long aJld w1U1 thicknesses of the order of 10 J.l . X-ray analysis indicates
[ 121 that surface o_r the single CJystals currcsponds to the be plane. All the
san.lples (thm hlms aJI? smgle were mounted in the sample holder of a
hehum . bath cyoslat lor spectrosCOpiC measuJ-cments. The single crystals were
first a microscope, anJ the mea.'iUI"CillCnls were pcr-
fomled WJt h the hght prupagatmg along the crystal axis. For the Jluorcsccncc
nk!asurcmcnts of single crystals aJld thin films, was provided altcma-
152 6 Electronic Structure a/ICJ Energy Transfer in Solid u-Sexithienyl
lively by the 488 nm line of an Argon ion laser, and by a Nd-YAG-pumped dye
la.scr. The optical emission was collected either by an optical multichannel analyz-
er fitted with a ceo army, or by a photomultiplier coupled to a monochromator.
In the latter case, the signal was processed by a lock-in and the output was fed di-
rectly into a personal computer. Fluorescence excitation measurements were per-
formed by scanning the excitation energy of the dye laser and monitoring selected
fluorescence bands.
6.3 Excited Electronic States in Isolated T6
The molecular structure of T
is given in Figure 6- l. The structure is calculated
to be slightly non-planar [13) in the free molecule while it is planar in the solid
[ 12J. Since we mostly dl.al with propenies of the solid. we will consider T
planar in the following .ton. The electronic states arc classilied according to
the symmetry of the irTl.u .. representations of the molecular point group C
which are illustrated in Table 6- 1. It can be seen that only two ditrcrcnt excited
state symmetaies are optically allowed, namely A, and B., . The fonner transforms
like a tr.tnslation perpendicular to the molecular plane while the Iauer transfom1s
as translations in the long and in the shon molecular in-plane axes, respecti vely.
In planar aromatic molecules, B., states are expected to be responsible for the opti-
cal tmnsitions at low energies involving 1C electrons while the A,. states, which
have hydrogenoid chameter (Rydberg states). are accessible by high-energy excita-
tions. Long and shor1 axes polarized transitions have different energies but might
have the same symmetry. In order to distinguish between them, we will label
them B,.(L) and B,(M) respectively. In addition to the 'aJiowcd' u11gerade states,
there are A
and 8
gerade states which will not be accessible by ordinary optical
spectroscopy since they arc optically 'forbidden' according to the pa1ity selection
rule. Nevea1heless, these levels may be optically reached by two-photon spectros-
copy, i.e. the simultaneous absorption of two photons.

n 0 ()
e - . e e .. e e - - -)-- B,ll.l
() I. f J I)

l<lgure 6-1. Molecular stnk:turc of u-sexill1icnyl lllC in-plane king()'). short (x) and normal (:)
mok:t:ular axes arc in<lk:.uoo a.s well a:. tbc nf the A. and lJ. slaiClt. s .. -e rcxt for
<li!>(;USJ>ion (Section 6.3 ).
6.3 Excited Electronic States in lso/uted T
6 153
Table _6-1. Cv. molecular poinl group. The ck:clrOnic slates of lhc flat T
molecule arc classified
lo ll.lC lwo. foltl axis (C2). invcr..ioo (i). antl gli<lc pl:u1e reflection (a,,) symmetry
111.: A, antl II, cxc1tt:tl slalC.'> lmnslonn hkc ("/) a long lhe molecular axes an<l
are opl_cally alk1wc.J. 1h.! A., slalcs arc wi1h rhe polariwbility ICJL\Ur coenponcnL'
(u). bcmg lbcu:furc onc-phutun lorb1<ltkn an<ltwo-phutun allow.:d.
c21o E

A.o: I I
I H,
u.(,l't <ly_.,. au uxy
- I I - I
I -I
u,.,. Cl:
- I
- I - I
I T,, T,.
The nature of lo":'csl electronic transition in thiophene oligomers T,, has
been a . matter of fo_r some lime in the context of the expected cross-
over of_ states. as functton of the conjugation chain length [Il l. Since electron
allccts more the lowest lJ, than the A.o: state, which in shon oligomers
1s at lugl_ter cner<tiY th<m the 8,, the increase in the number of thiophene unils (i.e.
length) a crossover of making the the lowest.
Calcul<tllons by Kohler tnthcatcd lh;tl the crossover may occur at about II = CJ unit
Ill_ 1. including multiple excitations and
mter.u:uon 114, 151 indicate, however, that the lowest excited state
m Tc, .s 8,. oscillator strength of the tmnsition in solution increases
Wtlh cham-length as shown in Figure 6-2 forT,,. 1!=2 to 5. The di-
rect conhnnation of the assignment of the lowest excited states as B,(L) was first
by Laz:zaroni et at: I from the simultaneous observation of the polari-
of the op11cal absorption 111 the UV-VIS as well as in the IR of a minuscule
s_ngle crystal gro":'n from the melt. Fut1her confirmation of the a.o;signmcnt wa.o;
gtven by the polanzcd spectroscopy of Tc-. in stretch oriented fi lms of polyethy-
lene [ 171: A 8, (M) state has been observed at higher enel"'.;ies ( 16, 171. At
the localton ol the lowest 1\.o: state, the two-photon spectroscopy of thin films
showed a resonance at 18 350 em- 1181. which was originall y eaToneously inter-
preted as the location of the lowest nmlccular 1\.o: state. Later studies on the exci-
band structure in the Tt. single crystal (sec Section 6.4) al lowed us to assign
th1s geraciC! t_o a_ of the exci ton band. The two-photon resonance,
than_ bem? mtnnstcally molecular in is the result of intermolecu-
lar anter.u:llons m that split the lowest B,(L) exciton into four compo-
nents, one of whrch ts aw The location of the second 2A state at about
500(} - I bo . K '
em . a ve the smglct, has been assigned by Nunzi et a/. by means
of Kerr ellipsometry (191. Fmally, the lowest triplet level has been located by Pm1
et a/. at 12 200 em- . from I he dependence of the delayed fluorescence excitation
spectrum ?f solid_ T,,. f(>r In 5 1::!01. n,e din:l.t h:alion of the triph:t iudit:alcs
that the smglcHnplet sphttmg, which in turn is a mca.o;urc of the effect of elec-
tron-electron cotTclations, is as high as 6000 em- .
6 Electronic Structure ancl &wrgy Tra11sjer ;, Solid u-Scxithienyl



350 400
figure 6-2. Abs01p1inn uf T n uligudu.:nyh l/1 =:! Ill 5) 111 Jiuxanc
6.4 Single Crystal Electronic Structure
The electronic excitations of the free molecule discussed in the previous sc_ction
stricdy apply to the molecule in the vapor in embc<klcd m an
amorphous matrix. The scenario changes dnunaucally 111 sohd where the
Jecular packing is the result of the balance between opposite the_ attracung
Van der Waals forces and the repulsive ste1ic intcmcuons. The mtcr..1ctron of the
molecular levels causes a spread of the excitations into a band which depends
the intennolecular distance, the relati ve orientation of the molecules, and the oscil-
lator strength of the transition. The resulting collective excitation is
ized onto the molecular entity and is tenned "tight-bound Frenkel exc1ton . Opti-
cal excitations, as a consequence of momentum conservation, probe only
levels of the exciton band which correspond to the null wave vector k. In drfl er-
ent directions of the crystal , the k=O resonance depends on the dispersion of the
exciton band in k-space. The spread of the exciton band is also known a'i the Da-
vydov splitting [1:!, 211. In the weak coupling limit 12_1 l each mo_Jecular level, fl!-
gardless of the electronic or vibronic spreads an e_xc1ton band
width is modulated by the rooistribution ul the ell:ctromc oscrllator strength 11110
Fmnck-Coudon vibronic components. These excitonic bands lonn therefore. a
dense manifold of states, which mpidly become a continuum at higher cnergrcs
within the spread of cncrgic.'i of each individual electronic transition: In t.urn, cad1
independent electronic tmnsition fonns an excilou band w1dth m
depends on the intensity of the molecular transUIOil. Also
might fonn localized Frenkel cxcitons. In the solid, in addition to localized
tions, there arc delocalii'.ed excitations in which an electron is pmmoteJ lrorn a
6.4 Single c,:vswl EleciiVIIiC Structure 155
molecule to a neighboring molecule and eventually into the continuum of the con-
duction band. These new states, which are peculiar of the molecular solid state,
are known as charge-transfer excitons (CTE) and remind of the Wannier excitons
known in inorganic scmiconductoP.> in their hydrogenoid character and their ener-
gies converge ao;ymptotically towards the energy of the conduction band. lbese
excitations, in the tcnninology of conjugated polymers, are otherwise called (in-
terchain) polatvn pairs. The reduced Coulomb interaction of the CTE makes it a
preliminary step _for the separation of the excitons into separate charges . . This pro-
cess has been w1dely discussed in conjugated polymers by Bassler and co-work-
ers r221. Indeed inter-layer CfE have been located in the energy range of 2.7-3. 1
eV by elcctroabsorption spectroscopy (23j. Since the CTE marks the lower limit
of the conduction band, towards which the CfE levels converge, we assume that
the conduction band is around 3.0 eV, consistent with the steady increase of
photoconductivity (24). On the other hand, the photoconductivity at the optical
band edge is due to exciton dissociation.
The crystal structure of the vacuum flux grown single crystals is shown in Fig-
ure 6-3 together wilh the direction cosines between the molecular and crystal
axes. The crystal system is monoclinic and the space group is P2
/u with four
molecules in the unit cell. By arbitnuily choosing molecule I, the application of
the symmetry opcmtions of the factor group (C
,), which is isomorphic with the
space group, generates the other three molecules in the unit cell: molecule 2 is ob-
by applyin? the inversion symmetry (i); molecule 3 is gener .lled by the
ghdc plane reflecllon (a); and molecule 4 is the resull of the two-fold screw axis
rotation (C2). The crystal wavefunctions (w(o;) arc linear combinations of the mo-
lecular wfs within the unit cell and fonn a basis for the ineducible representations
of the factor group (8). Molecular and crystal electronic states are correlated 1ia
site group which is fo_m1ed by the symmetry of the factor group re-
tamed by the molecules rn the crystal. In the cao;c of T
, the molecules sit in a
gcneml position and therefore only the identity symmetry operation () is com-
mon to both the molecular and the factor groups. The site group is C
and U1c
corrdation is given in Table 6-2. As a result, each electronic level of the mole-
cule, rcgardlc.-..o; of its parity, spli ts into the four dillerent components of the factor
It has been experimentall y shown I I 6, 17, 25, 261 that the lowest singlet ex-
ci ted electronic state of the isolated mok'(:ule (I
8,) is polarized along the L axis.
The crystal fi eJJ splits the L polarized molecular state into four crystal states of
which a, and b, arc accessible by one-photon spectroscopy. We usc capital
letter-s lor lrce-molcl:ulc states anJ lower ca...e symbols for crystal states . 1l1e crys-
tal levels b.: and b, Jepcnc.J on the photon wavl!vcctor k allll the con"l!-
l!nertdics are obtained by linear combination of the intemction cxchangl!
1ntcgmls between thl! molecules. Out.! to the conservation of momcmum. only
k=O levels arc optically accessible I:! I 1. For k = O the energy values arc the fol-
6 Electrunic Structure aud Energy Transfer ill Sulit! u-Sexithienyl
a' b c
0.9163 -0.0008 0.4004
-0.3440 0.5200 0.7819
-0.2051 -0.8542 0.4778
Fagure 6-J. Top: Structure of !he T
single cryst.al unit cell. The a, b. and c axes arc
indicated. Molecule I is arbitr.lrily chosen. whilst the numbering of the other molet.-ules follows the
of the factor group symmetry opetations as in the text_ Bottom: direction cosines
between the mulecular axes L. M. N and the onhugonal crystal coordinate system a' , b, c.
is orthogonal to the b monoclinic axis.
) =Eo+ D -Ht, t + 1t .2 + 1, ,3 + 1t ,4
E(au) =Eo+ D + /1, t - l t ,2 - 1t,3 + h,4
) =
+ D + lt , t + lt ;l- lt,J -1,,4
) = Eo+ D + l,, t - lt .2 + 1, ,3 - 1, ,4
(6. la)
(6. lb)
(6. l c)
(6. ld)
is the energy of the free-molecule-excited stale (<P*), and Dis the differ-
ence between the electrostatic energies in the ground and excited stales. /1 .t is the
interaction exchange integral between trunslationally equivalent molecules
.t =

where the operator Vt . l is the intennolecular potential

energy), while lt.
, lu. and /
.4 arc the interaction exchange integrals between
molecules. 1l1e excitonic molecule model
[271 prcdtcted a sphHmg as large as I eY of the I B, molecular level 128, 29, 301.
6.4 Sillgle Ct}'Stal Ele<tmuic Stmclllre 157
Table 6-2. Correlation diagram of !he C
point group of the T., molecule (left column) with
clll factor .group for solid T,, (right column) ,.;, the site symmetry c, group (CCllt<.T). L. M. ano.J N
mc.bcatc thc pnnc.:apal molocular tr.msition dipole anon\Cnl,, whilc a. b. and c arc tl\C crystalline axes_
Molecular symmetry
A ..
Site .. ymmctry
Factor group symmetry
A more refined approach uses the t wo-centers potential expansion, which consid-
ers the intemction between point muhipoles located at the centers of the two
charge distributions. Since the exchange integml interactions vary as l/r
and the
numbers of interactions increase as 1''. one has to choose spherical shapes for the
convergence or the sum to be guaranteed (Ewald sumo; melho<.l) 1311. This proce-
dure has been successfully used, e.g., the anthracene crystal [32j. The funda-
mental requisites for the point-dipole approximation [8) to be valid are: i) the
pole must be than shortest intem1olecular distance, and ii) high--
er m. the mulllpole expansion can be neglected due to the strength of tbe
transtllon dtpole moment We point out that the fonner conditi on does not hold in
the case of T
and therefore the ab::.olute energy values of the four factor group
cannot. be correctly predictccJ. However, we expect that the energy
level ordenng obtained by the calculation still holds. The qualitative scheme for
the crystal enero,;y levels corresponding to the 1
8, (//L) molecular level, a.o; de-
rived from the Ewald dipole sums, is reported in Figure 6-4. The calculated val-
ues of the


exch:mge interaction integmls arc negligible as a conse-
of the essentially two-dimensional character of crystalline Tc, (see Fig. 6-
3). Thts leads I( sec Eq. (6. 1 a)-(6. 1 d)l to the deucneracy of the a and b crystal 0 If . ,,
components with a); and b):, respectively. We note that the lowest component (a,)
is formally allowed. However it is c:.kulaled, within the oriented gas model
(OGM), to be vanishing :ts " consequence of the relative orientation or the lransi -
6 ElcLmmic Stmcwrc and Energy Transfer in Solid u-Sexitllicnyl
tion dipole moments and of their orientation with to the crystallographic
axes. The a, component is therefore a 'dark' leveL Htgher order effects
the oriented gas model (OGM) may allow some intensity in the au component, tn
which case we would expect it to be completely along the b crystal
axis. 1l1e upper b., component is instead a 'bright' level (optically allowed) and is
polarized in the ac crystal plane. Emission is expected to take .place the
est Oavydov component for the efficient non-radiative rclaxauon wtlhtn the exct-
ton band [7]. In order to predict the energies of the Oavydov levels, one to
take into account the total molecular wavefunctions. Correlated quantum-chenucal
calculations have been performed [33) to describe the nature of electronic excita-
tions in crystalline T
. Since the interlayer interactions are negligible (vide supra)
we consider clusters of T
molecules by taking the relative coordinates from the
crystal structure within the be layer. A single contiguration
al ism has been used in combination with the Hartree-Fock semtemptncal mter-
mediate neglect of differential overl ap (INDO) technique (34}, t? t.he
singlet excited states. The evolution with cluster size of exctlatton energtes
from the ground state to the two Davydov components <.wtth a, and b,
tries) is displayed in Figure 6-5. When the cluster szc. the dtffcrence
between the a., (b-polarized) and b, (ac-polarizcd) transtllons mcreases and satu-
rates for about six molecules (sec Fig. 6-5).
b.(ac); b
B.(L) ----.._
a.. (b); a.
Free Crystal
l' igure 6-4. Qualitative energy level diagram of the 1
B. exciton b;md stroaure of Tc. _at K=O derived
by lhe Ewald dipole-dipole sums for excilalion light propagatmg along the a cry!.1.al :IAIS.
6.4 Single Crystal Electrcmic St111cture
3.4 .----------- ----- -,
-o- low-energy OavidOII compooent (a)
-o- . high-energy Davickw compooenl (b.)
3.2 -
6 CT excited Slate (b.,)

"' <:
-o--- -o

2.2 + --.-- -.---.---.._:;.--.:;_.--1
2 3 4 5 6 7
Scu of the aggregate
l' igurc t ... S. Ex..:llUun ..:ncrgie frn111 lhc 1!-ruond state tu the twu [}.IVyduv (aH and h.J ;L'
a function uf the T" du,tcr sit..:. TI1c du,tcr.; arc built with the <.T)'Sial structure considering T
, mole-
cub lying within 1hc san..: b.: layer.
6.4.1 Davydov Splitting
The b- and c-polarized absorpti ( spectra of aT
single crystal at 4.2 K are reported
in Figure 6-6a and b. The lowest energy resonance is completely b-polarizcd and lies
at 18 360 em- . At 20 945 cm-
in the b direction there is a very intense and broad
peak followed by the typi..:al spectml shape of a vibronic progression. At the same
energy the c-polarized spectrum saturates because the light is completely absorbed.
The detailed vibronic assignment in b and c polarization is reported in Table 6-3.
We assign the b-polarizcd transition at 18360 em- to the lowest au Oavydov
level. We recall that the lirst sharp resonance in the two-photon excitation spec-
trum of a polycrystalline lihn wa.'i found at the same energy of the one-photon
resonance of the single crystal I 18 I and was originally interpreted a.-; an intrinsic
molecular gerttdt! level

In view of the exciton structure obtained from the

single crystal we conclude that the two-photon resonance is due to the Davy-
dov component of the 1
B, lowest si nglet instead. 1l1is is indeed in agreement
with the expectation of a degenemcy of the and a, Davydov levels. The b,
component is polarized in the ac crystal plane and should not be observed in b di-
rection. For this transition to be obseaved directly we should be able to mea.-.ure
the absorption in the c direction for energies higher than 21 ()()() em- . However.
the c-polarizcd absorption spectrum saturates due to the thickness of the sampl e
under investigation, which is in the mder of 10 J.lm. The b, Davydov levd is ob-
served in the b-polarizcd spccoum a1 20945 cm-
a.'i a consequence of opti..:al
6 Electronic Structure and Energy Trwufer iu Solid u.-Sexithicnyl

--; 1.4
19000 19500 20000 20500
Wavenumbers (em.
. 6-6a b- and c "'>larizcd absorption spcctr.t of T
single crystal a1 4.2 K. f?' :md o: arc_ two
tgun: r . . the (c--. 6 4 1) The moM mtcnsc vtbr.lltonal
Hert.berg-Tellef false origins as dtscusscd m text .,..-._tton
ntOlles are indicated.
misalignment of the sample. The energy between two Davydov
components leads to a measured Davydov sphttmg of 2600 em . . .
In the polarized absorption spectra (see 6-6a) the actlvtty of
false origins is ea!;ily recognized . . The false are by the_
of the electronic origin with totally symmetnc (TS) Nevertheless, the
tensity of the polarized vibronic bands is obviously from that tf
h I
ld be due to the Franck-Condon mcchamsm. A conststent mter-
t e coup mg w u . . ,
pretation of the experimental spcctr..1 involves the Herzberg-Teller vtbromc cou-
6.4.2 Her.tberg-Teller Vibronic Coupling
The tr.tnsition moment Jl between the llPN(P,)
and (II are the electronic and vibr.ttional wavetuncttons rcspectt vely, ts delincd as.
ci 2.28

6.4 Siugle Cty:;t11 Elertnmic Stroctun: 161
(b.)+ 1275
20000 22000 24000 26000 28000 30000 32000
Wavenumbers (em )
Figun: 6-6 b. b- and cpolarw:d absorption spco.:tm or T
single crystal at 4.2 K extended to higher en-
ergy. Above 21 UUO o.:m ' the b-polarizcd S[l<.-o.:trum shows bmad which are discussed and as-
signed in the text (Section 6.4. 1), while in o.: the light is <- 'Ontplo.:tely :tbsubcd.
By expanding the electronic transition moment operator p(Q) as a Taylor series in
the nuclear normal coordinates about the equilibrium configuration Q
, one obtains:
Substitution of Eq. (6.3) into Eq. (6.2) leads to the following expression for the
vibronic transition moment
J.l = (cJ>N(P,(Q)!Jt(Qu)!4'>c(Pj(Q)} + )QoQdcPc(Pj( Q)) + ...
The tirst tcm1 of Eq. (6.4) represents the Fr..1nck-Condon coupli ng in which the
electronic transition moment JL(Q) is independent of the nuclear coordinates and
the polarization of the transition is that of the electronic origin !lPN}- 1l1e second
term of Eq. (6.4) represents the Her.tberg-Tellcr (H-T) vibronic coupling. 1l1e in-
dex k runs on the normal coordinates of the molecule, hence when the Condon
approximation is relaxed, the electronic transition moment acquires a dependence
on the nuclear coordinates. Within the HerLbcrg-Tellcr mechanism. two electronic
excited states couple via a molecular vibmtion which induces a 'borrowing of os-
cillator strength from the higher electronic excited slate to the vibronic level of
162 6 Electronic Structure w1d Energy Trtmsfer i11 Solid u.-Sexitllienyl
Table 6-3. Vibr:uional assignmem of the b- and c-polarizcd absorption .or T6 single crySlal at
4.2 K The proposed assignment is in ugrcemem lhe lllOSt VJbrdllonal modes found by
Birnbaum et ul. 1641 in Lhe excitmion spcclra of nkllnx ISOlated tctrath1ophene (T4) al low temper.u.urc.
em ' c Polarizal ion b Pol;:uizaJion
l\v (cm-
) l\v (cm-
18360 Uu-0
18486 0'
18657 0 "
18700 0+340 (0)
18832 0'+340 (+6)
19 015 0 +660 (- 5)
19017 0 " +340 (+20)
19318 0 " +660 (+I)
19635 0+1275 (0)
19646 0 " +660+340 (- I I)
19817 0 ' + 1275 (+56)
19945 0+ 1590 (- 5)
19952 0 " + 1275 (+20)
20077 o + t590 <+ 1>
20252 0 "+1590 (+5)
20945 h,
21450 0 +2X 1590 (- 90)
22250 bu+ 1275 (+)0)
23535 1275 (+40)
the lower eleclronic excited state. In fact, the matri x f?r H-T-induced
transitions from the zero-phonon ground state lwc} to the v1bromc state of
t he excited electronic state jQ>N} can be expressed as:
= LMjN8M((<I>MIJli<Pc})/(E((J>M) - E(cJJN) - {6.5)
F s are the unperturbed energies of the electronic and vibr..ttional respec-
t" 1 and 8 is a constant energy factor which depends on the state.
r:.n E
. (6.5) that of (/>M is 111 th1s case
and that the correction decrease.'> with the mvcrse energy m1smatch between the
relevant levels. . . . 1 . . . d . 1
In the case of T
the lowest excited smglet state 1s I 8,. and 1s pola'2ze a ong
L (vide supru). A second intense electroni c. state. at about 36<}00 em

signed to 8, (liM) (1 6, 30]. Therefore, the v1bromc
tween 1
8, (IlL) and the higher 2
8, (liM) onl y be totall?'
vibmtions (s<.:e Fig. 6-7). The transua? n as rotated
polarization direction of the lendmg. 2 (liM) Wllhlll
the oriented ga.o; model. is c-polanzed w1th, a polar1zaton of .. .
We a.o;sign the peaks at 184g6 em- (0 ) and I H657 em (0 ) ol F1gU1 c 6-6.1
10 vi bronic Ievell., acting as false origi ns which mc generated by Herzberg-Teller
6.4 Single Crystul Elel:lrVItic Structure
Figure 6-7. llcrzbcrg.Td l.:r vibmnk coupling scheme in lhe
case of T..,. Tite two lowe:-t singlet excited (lB. :md
211,.) cuualk in 1111ally synunclrio.: (11
) inducing oscilla-
- --'-------- Q tur stre ngth honuwi ng from the 28. clectroni.: st.atc 10 tho.:
Ill. "il>mnio.: st:uo.:.
coupling of the 1
8 , and 2
8, electronic excited states via a modes at 126 em-
and 297 em- , respectively. Yibronic progressions whose description is
reported in Table 6-3 arc built on both false origins. The activity of totally sym-
metric modes at frequencies 340 em- , 660 em- , 1275 em- , and 1590 em- is
observed. This assignment is confirmed by the observation Utat the same Herz-
berg- mechanism is acti ve in emission. Figure 6-8 shows the high energy
pan of the fluorescence spectrum and the low energy pan of the absorption in b-
and c-polarizations. We a.o;s ign the emis.-;ion false origin A, 165 em- below the
origin of fluorescence, to H-T coupl ing with the ground state totally symmetJic
phonon mode, which in absorption gives rise to the 0' 11-T false origin (promot-
ing mode 126 em- in the excited state). The false origi n C is due to the ground
state totall y symmetric mode at 306 em- associated with the absorption 0 ' H-T
false origin (promoting mode 297 em- in the excited state).
1l1e room tempemturc Raman spectrum excited in pre-resonance cdnditions
[35] indeed shows bands at 169 em- ' and 306 em -. which arc in agreement with
the modes observed in the lluoresccncc spectrum and that have been assigned by
ab initio calculations to tmally symmetri c vibrations 11 31.
The b-polarized absorption bands (sec Fig. 6-3b) at 20 945 em- , 22 250 em-
and 23535 em- arc assigned to a vibronic progression built on the b, Oavydov
component with the totally symmetric mode at 1275 em- .
6 Elcctrouic Structure and Energy Trwufer iu Solid u-Se.xitllienyl
' ..
:: ;: ::
. . - ..
.. ...
._.,: .::
. .
: :
297 0"
: ..
; .
18250 18500
- 1
..... ...
0.8 g:
Wavenumber {em l
6-8. b- and c-polariCd absorJ
tion and nuon:sccncc spcclr.l in. the
cnc. The nuorcsccn.:c A and C currcspond w the 1"1:-c ungns 0 :IIIli 0 dcnhhcd
in absorplioo.
6.5 Thin Films
6.5.1 Growth in High Vacuum
In molecular Ulin films the structure and hence the
f ons differ substantially from their counterpart m a crystal. a smgle .crystal
' . t table thermodynamic phase of tht: molecular matenal, the thm
represen s a s
h tl of thm
can be regarded as a metastable or kinetic fom1 of aggregation. n t . e .
films by high-vacuum sublimation a nux of hot gas molec.ules a
colder substrate surface so that condensation takes place betorc the thcnnahzauon
of the molecules is achieved. The resulting morpholog.Y. depends not .only on the
. olecular propcrties and coopemtivc eiTccts ansmg from the
mtnnslc m b 1 1 t , a uons and
t r. tons but also on the nature of the su strate-mo ecu c Ill cr. c
ar me ac 1 . d. IT .
e.-;pecially on the kinetics of growth (e.g. impinging mte, nucleatiOn.' 1 us1on, coa-
lescence reorganization desorption). 'fbe latter is controll ed by the mtcrplay among
ex such as deposition rate . t.empemture and
of deposited material, viz. ti me of or
it is important to understand and control the k111ellc.:s ul . growth Ill to

the ba.;ic relations between (ilm structure, molecular ordenng. and the rclcv.mt clcc-
6.5 TIIi11 Films 165
and optical properties, as well as to obtain films of reproducible quality. It was
found by X-ray diffraction (XRD) that T
films grown at room deposition tempem-
ture (RT) possess long-r.mge molecular order [3, 36, 37) and therefore there is a
spontaneous tendency towards ordered aggregation. Upon changes of the deposi-
ti on temperature, enhanced anisotropy in the electrical properties was observed, as
correlated to structural (XRD) and morphological (SEM) changes [38). These obser-
vations led to the conviction that T
films on silicon consist of stacked layers of T
molecules wiUt a more or less enhanced molecular order within each layer. Evidence
that layered growth in oligothicnyls on silicon starts from the early stages was in-
ferred from AFM observations on quinquethicnyl (T
) [39), albeit an extensive in-
vestigation at larger thickness was not carried out. It was shown by optical linea
dichroism [301 that the ordered growth ofT(, decrcast:s and eventually fades out
at increa.-;ing thickness. Furthcnnorc, the dominant growth direction, i.e. the molec-
ular orienlation with rt:sped to the substr..tte being either planar or homeotropic, de-
pends on the nature and structure of the substmte [40). Thus, it is important to carry
out growth studies with well-defined and characterized surfaces, which has not been
the case in the majority of spectroscopy and electrical investigations and device aj>
plications. The extensive defects (structural, chemical, morphological) present on
surfaces such as glass, oxidized silicon, 4uartz, and ITO-coated glass oflen hinder
the intrinsic feature of the growing film. such as surface roughness and gmin bound-
aries. In U1is context, metal surfaces are excellent substrates which can be chamcter-
izcd i 11 situ by a wealth of surface science techniques. Extensive work on quartcrthic-
nyl ('f4) and end-cappro oligothicnyls grown OntO noble metal low-index surfaces
[41-451 has demonstrated that the resulting films exhibit planar orientation, and thilt
the structure of the tirst molecular ad layer can be commensurate with the underlying
metal surface mesh. Growth onto noble mt:tal surfaces is a suitable template route for
ordered planar growUl, and ordered lilms several monolayers thick with strong in-
plane anisotropy (46, 47} have been obtained by exploiting the intrinsic anisotropy
of Au( II 0) missing row reconstructions.
Another approach is to start with atomically smooth and clean surface.<> such as
mica, highly oriented pyrolitic graphite, and metal dichakogenides, as substrate.'>
for thin tilm growth. Mica oiTers the advantage that its hydrophilic surface might
be a reasonable model for the growth on the technologically mor.e relevant silicon
wafers, lTO, and glass. n1us, we unde11ook an extensive work study on T
fil m
growth on freshly cleaved ruby mica aimed to elucidate the quantitati ve aspects
as well as the ba.o;ic kinet ics of Tt, li lm growth.
6.5.2 Thin Film Morphology
llte morphol ogy of Tt, thin films is very sensi tive to the growth conditions
501. Most of the earl ier optical studies have been canicd out on granular lilms,
whose typical morphology is shown in Figure 6-9. However. a hmad morphologi-
cal diversity, rang,ing from islands (sec Fig. 6- 10) to layers and lamellae (sec Fig.
6- 11) can he ohtaincll varying experimental parameters. Such a complexity <triscs
166 6 /cctrvnic Struc:wre and Em:rgy Trcm.ifer in Solid u-Sexitltienyl
from the dominance or suppression of one or more intervening mechanisms of
growth because the diffusion of molecules on the fonning film is changed by the
deposition temperature, the amount of material, and the time of growth.
The early stages of growU1 involve nucleation and formation of islands (Fig. 6-
10). Density of nuclei, lateml size, height, and molecular order within the islands
depend upon the deposition temperature. At RT the islands (::::::500 nm diameter)
exhibit regular features like sharp comers and multiple peaks in the distribution of
the topogr..tphical height, which are integer multiple of 2.4 nm viz. T
length 150).
By comparison, the islands at 150"C are much larger and exhibit mono-
molecular temce steps but their edges are branched rather than regular, as in the
growth of diffusion-limited aggregates [51 ].
At increasing thickness, the film morphology at RT becomes granular. Small
gmins (few tens of nm in diameter) fonn upon completion or the film. then the
gmin size increases with the amount of material. This tmnsition from 20 islands
to a 3D film is similar to a Stranski-Krastanov [51) growth lmnsition. although
owing to the non-equilibrium conditions, this simple scheme should not strictly
apply. It is interesting to comparc the evolution with thickness described above
with that of a film grown at high temperatures (150"C) and depicted in Figure 6-
11. At 150C nucleation of a few tens nanometer-wide protrusions takes place
after an almost complete fi rst monolayer has been formed. This tirst monolayer
exhibi ts a considerable degree of order, which is apparent from the sharp edges
around the voids. 1l1e average step height of this monolayer with respect to the
bottom of the voids is 0.6 nm, which suggests that molecules in this layer lie
tlat mther than homeotropic on mica. The nature of the imemction driving the for-
mation of such a fi rst monolayer. where the molecules lie probably sideways, is
not clear, but might be an electrostatic attraction between a partial positive charge
localized on the S atoms of T
, and the negatively charged mica surface. Around
the outgrowths protruding from the tina monolayer (whose hei ght from the mono-
layer is twice T
molecular axis) the islands grow layer-by-layer. The terr..tee
height 2.30.4 nm corresponds to T
van <ler Waals length, i.e. the molecules in
the film are oriented homeotropically with respect to the surface. At about 50 nm
a prolifemtion of elongated nuclei occurs [50], which at larger thickness evolves
into a network of oriented lamellae. Lamellae are the result of a change in the di-
rection of growth or simply a recrystallization phenomenon. Such type of growth
tr.msitions might be specific to anisotropic materials and cannot be modeled
strictly by canonical growth modes (Frank-van der Merwe, Stmnski-Krastanov,
Volmer-Weber) [5 11 of atomistic growth prot:esses.
The growth mode for 300 nm thick tilms was analyzed hy means or the evolution
of the grain size with the deposition temperature l4gl. The mean grain size (A)
grows according to an Ani1cnius behavior with an activation energy
, =0.360.04 eV. This value is in good agreement with our model calculations
(481 based on independent experimental parameters. which yield 0.27 eY for tnms-
lational and 0.5 cY for the rotational barriers experienced by a single T
moh:cul e on
the van der Waals surface potential generated by stacked layers ofTb molecules (sec
Fig. 6-1 2). The corresponding grain size distribution is skewed on the large sizes and
is invariant with the deposition temperature. This suggests that grain growth lakes
6.5 Thiu Films
(,..9. Typic;! granular 111orphology or
T,: gmwn at <lcpositiun T=25 C ;md
II = 10() nm. Height r;mgc is 41 um
(lmlll hlm:k tu white).
Flj;Urc 6-10. bland grnwth al: (a)
dcpu!>ilillfl C. fl =5 11111: lhl
1'= 150 c. ft = Jt\1\1
(1- ll. Evnlulinu nf lht: 111<111Jhulu!!Y with
III' J'I!;"JIIg nf (rc-
(}lltlc<l :t' lhc unlllin;al li hu Jhid .ncss) at .tq
linn 'I'= ISO C.
168 6 Electronic Strucwrc wuJ 1!/wrgy in Solid cz-Sexithienyl
rr rT '.).'
Ftgun: 6-12. Model for the calculation of the van tier Waals potential experienced by a single T
ecule on a T6 ordered surfoce. Eoch molecule is modeled as a chain of 6 polariwblc spherical uniL'I.
and the surfaL'C as slab, layer containing molecules (only part of the cluster is
shown). TIIC niO<lel is ba;;cd on X-r.ty di ll'roction and dielectric constant experimental data. TilC two
configur,llions used for evaluating the COrrllgation of the surface potential are shown. Adapted with
pennis:.ion from Ref. )48).
place by coalescence at expenses of the smaller grains, as a consequence of mndom
diffusion in two dimensions. Since the standard deviat ion increases linearly with the
mean size, growth in high-vacuum is not suitable to yield homogeneous grain size.
This might be a limitation when the aim is to tailor properties with gmin size (e.g.
peak in the photoluminescence) or for nanofabricution.
For a given thickness and increasing deposit ion tempemturc, the film morphol-
ogy changes gmdually, mther than abruptly, from gmins to lamellae. This behav-
ior is similar to the order-disorder pha.-.c tmnsitions of the second order, although
here the more ordered 'phase' is obtained ut higher temperatures [49). A conve-
nient way to locate the transition is to observe the evolution of the orientational
order of the domains. Since lamellae (see Fig. 6-16) stretch along prclerential di-
rections (related to crystallogmphic directions of the mica surface), we proposed
an experimental procedure to construct an angular tensorial property from AFM
images simil ar to the measurement of the angular order tensor, which is used to
locate the director in scattering experiments on oriented nematics. The relevant
'order parameter ' here is the mean second Chebyschev polynomial (l:os 2u},
where a is the azimuth of the long axis of a lamella wi th respect to the preferen-
tial al ignment direction. Details of the method are given in Ref. [49J. At the onset
of lamellar growth, the second Chebyschev polynomial undergoes an abrupt in-
crease of slope, which all ows us to locate accurately the temperature of the tmnsi-
tion (Fig. 6- 13). In this fashion we have been able to construct a 'kineti c'
diagram of the different morphologies of T
as a function of deposition tempem-
ture and thickness, which is shown in Figure 6- 14. The kinetic nature of the
growth process is evident when the temperature evolution of the mean size versus
I rr is ploucd for diiTcrcnt film thicknesses (sec Fig. 6-15). The curves are parallel
in the semi-log plot, as the mean grain size decreases with thickness at a given
tempemturc while the activation energy is the same, being the process governed
by self-diffusion. Furthermore, the transit ion from gr.tins to lamel lae with tem-
6.5 Tlti11 Films 169
fo'igurc 6 13. Oricntational oruer parameter vs de

ten . , . , . . . .
and lantellac. rcspc.:tivcly. Str.ti .. Ju lines reprcsc I I be . r f 'Jtalurc. Clrdcs and S<ju;trcs arc
gmin <lat:t. respc.:tivdy. Affitptc<l fmm t{cr. H.Jr." Sl tl or t tc lamellae dat;t aud mean value or the
at _d<X:reasing temperature as the film thickness is decreased
. nee . 1> can be obtained also at lower deposition tern
(lew tens C) lor a suttablc decrease of thicknc.-.s TJ

s v
, , ,
the I . r . . . . . Ul: ICC IS conststent With
cvo ulton o molecular order momtorcd by optical dichroism [ 26J.
Scaling Behavior of Surface Roughness
of sh<tpc <llld anisotropy in T
, films Slii!"Csts thatth re . . . . ..
rncrca.-;c Ill tht.: mok:cular ordt.:rin" ami hictarlly . 1.: 1 ts a plugtcssrvc
d . . "' r "tea structures a th
tempcra_ru_rc This suggests that at higher t;.n eratures and s o e

ttor_l. progressrvely approach the crystal phase. Therefore b
postliOn tcmpct'Uturc at a thickne and a tc l'o . . l t . g de-
. ,, ,, I II S a nee II IS po 'b) t
a contmuous set of metastable hascs between th . . '. . . sst e_ o
him up to the crystal. It is then to ask whyc atsgot.lvrOeJn>t c polyhcrlyslalhne
pears a d h . e. morp o ogy ap
. . ' . n ow II would be possthle to change it to another. This is the very I" " I
unpotant step towards a real .

. . . . . . . con m o llc spatial <trr..mgemcnt of molecules in a
fi_lm. and the unphcattons for controlling the optical <IIIli clcc.: llical pnpc
, ..
1 Vtously 1 J tcs arc o )-
170 6 Electronic Struc:ture and Energy Transfer in Solid a-Se.xitllienyl

0 .01
2.2 2.4 2.6
0 IOOnm
.a. 50 nm
2.8 3.0
3 .2
Figure 6-14. Avcrdge domain vs. inverse temper.uurc for diiTercnt film lhickncsses. Er-
ror bars represent the mean absolute error and stmight lines the be.st lit for each film Dotted
line is the locus of the lransition from gr.tins to lamellae. Data for 50-nm films arc from the
correlation length of the topogr.tphy lluctuations. Adapted from Ref. (50(.
In order to answer these questions, we analyzed the film morphol ogy quantita-
tively by means of the scaling behavior of the surface roughness q [51 , 52),
which is detined as the root-mean square (r.m.s.) fluctuation of the topogmphy.
The basic ideas of this approach can be ill ustmted by means of some general con-
cepts. In general, the morphology of real surfaces depends on the length scale of
observation r. However, for some surfaces termed self-aftine, the morphology is
scale-invariant after the vertical dimension is anisotropically rescaled relatively to
the length/scale. Self-affinity implies that the surface roughness obeys a power
law o(r) :=:::. r" where u is the roughnc.'>s exponent which identifies the universality
class of growth 153 J. Sclf-aflinity implies that there is a spatial com:lation of the
Jluctuating interface on scales of length r r..tnging from the dimen!'>ion of the smal-
lest structural unit to a correlation length beyond which the value of a satumtes.
Thus, a self-affine interface (which is the analog in nature of a mathematical frac-
tal object) is gencr..tted by propagation on larger scales of some elementary motif.
The ba..o,;ic mechanism which leads to the organization of smaller structures onto
the resulting architecture can be inferred by measuring the exponent a. ThercJ'ore,
this framework yield-; important information on dynamic processes occurring on
lamellae (2D-3D)
terraces (2D)
50 100
grains (3D)
200 250
6.5 Tlti11 Films 171
Then of high-vacuum-sublimed T6 fil ms as a fu!ll:tion of,._._,;_
ma l>U r.ttc t rc ness h. """fAT."
scale can be extmcted from data obtained on the more easily
access e mesoscoptc scale.
in adopted for measuring the scaling behavior from AFM

The power spectral density (PSO) of the Fast Four-

. . . I : l . c.: . pogmp lY '(x, y) is estimated [54), then averaged over the
azunut 1a angle f1J to yteld the radial PSO (/) as detailed in [55 J:
PSDU') =

j df1Jil;(f cos fiJ.! sin fiJ) j

From the Wicner-Kinchine -theorem the inte!!mted PS
ness vs the length/scale': , D yields the r.m.s. rough-
a() [ ]' I'SD(f)/ilj] {
l / r
Here, the mean height (It) - 0 Ec: (6 1)
I h L . . . . . - , . ts calculated on an image with scan
. J ts the spattal lrcqucncy (i.e. the inverse di stance) and f. . 1 , N
qutst lrcqu 1c n
"''"' ts t1e y-
. et y. lC ana ysts lor the relevant scalt.tl

( 1
1 u 1 o ''" es vtz. corrc ' Ilion
roug lllcss exponent, etc.) tun he catTicd out either on the roul!htwss ;h-7)
6 /ectro11iC Stntcture and Energy Truusfer in Solid u-Sexitllicnyl
or on its reciprocal space analogue (6-6). We found th<tt the former is more robust
with respect to fitting procedures. . .
In Figure 6- 16 we compare two images of the same san1ple at d1fferent magm-
fications. lf the image side is taken as a ruler, then the length of lamel_lilC
turns out to be invariant. Furthermore. as more details arc resolved at mcrcasmg
magnification, it is apparent that the fi lm texture is made increasingly
lamellae. The existence of such recursive pattern emerges from the companson of
the corresponding radial PSD, shown in Figure 6- l 6c [56}. appear to be
the continuation of each other, revealing respectively more deta1ls at larger
(see Fig. 6- l6a) or at higher resolution (see Fig. 6- 16b). With these concepts m
mind, we have analyzed the morphological transition in T6 fil ms from grams to
..... .. - ...-.. _.

3 4S6ll9 l 456 119
,. Cun) . .
Figure 6-16.. (a) and (b) Morphulllgy url",,lilm (lr= IO(lnm. T= 1_50 'C) at I\YU dill'en:nt
(c) the corrcspornling angularly <IVeragcd fnlln E41. (6.7) (empty and full
tivcly). Line is bc,t-lit accortling to the phcnomcnolugK:al n (r)= a,. .... ll-cxp(- r/c,) l 1561.
6.5 Thill Films 173
lan1ellae [57]. ll1e former exhibit a modest self-affi nity over just one order of
of the spatial length scales. while the latter display a self-afline behav-
IOr more than 2.5 decades. which is unusually large in natuml systems. The
tmns1llon corresponds to a continuous change in the dominant mechanism of
growth from purely diffusional (a= I) (581, in the case of granular films, to mo-
lecular beam epitaxy (MBE)-typc of growth (a=0.66) [59] for lamellae (see Fig.
6- 17 a). In the latter case. molecular diffusion is fast and the growth of the inter-
face takes place. by anchori ng at tetTace edges. We also showed that a strajghtfor-
wanl way to the mean gr.1in is by means of the correlation length of
the surface fluctuations rather than usmg the conventional approach of area mea-
1.4 f
grai ns
----I--L _,_ ------__
0 .8
1 ,, I I
___ ____ ____ ____ __ ____ ______ ___ ____ ____ ____ _ ! ___ _

100 150 200

2 .0 2.5 3 .0 3.5
l' lgur c 6- 17. (;I) Rnughn.:"-' ' "'I"'IICIII iu.-.,..,.. arc
proolctll>ll.' .f purely dinu,iunill ttlut-da.,hed) 1!1111 anll MUE growth (!191; (b) length vs
mversc tlcjiOSitlon T. Wcghtcu !Jc,t-lit Anhcuius CI(Uatun is plnllctl a.' the line. Adaptctl fmm
Rd. j!\71.
174 6 Electronic Structure cmd Energy Transfer i11 Solid u-Sexitltienyl
suring, which is rather arbitmry in the case of compact grains. TI1c square of the
correlation length seems, in fact, related to approximately the mean gmin size,
and hao; a comparable activation energy (see Fig. 6- 17 b). Furthermore, a mini-
mum saturation roughness can be achieved in T
films just below the transition
from grains to lamellae (in the case analyzed for films at 150C), which together
with the large domain size and the increased molecular order {48-50j suggests
that an optimal morphology for seveml investigations and applications can be ob-
tained. Such analysis is also useful to monitor the effectiveness of processes
aimed to control the roughness of thin film interf.tces, such ao; thermal annealing
Experiments on transport, injection, electroluminescence, and fluorescence
probe the spatial correlation within the film, therefore we expect that their re-
sponse will be sensitive to the self-affinity of the film. This approach. which we
proved useful in the analysis or AFM data of conjugated molecular thin lilms
grown in high vacuum, has never been applied to optical and electrical
on these systems and might be an interesting route to explore. We have started to
assess the influence of differe m spatial correlations in thin films on the optical
and the electro-optical properties, as it will be described in the next set: tion.
6.6 Disorder Effect on Energy Transfer
6.6.1 Single Crystal Fluorescence
The fluorescence spectm of il T
single crystal at 4.2 K polarized along the b and
c crystal axes arc shown in Figure 6- 18. In both polarizations there is a sharp
component superimposed on a broad background. It has been shown that the
sharp emission occurs in less than <l ps after excitation, while the broad emission
takes place at longer delay times as a consequence of energy tmnsfer into Imp-
ping species below the exciton band {61]. Previous experiments showed that the
relative intensity of the unstructured emission increases when the structural order
of the sample decreases, as is the case of more defected crystals [61 J. Absorption
of up to 1000 em- below the bulk electronic origin has been by fluo-
rescence excitation spectroscopy [611. It is clear that the structuml quality of the
sample is reflected by the concentration and depth of the defect states. Defect
slates may arise from T
molecules which experience a local molecular environ-
ment different from the bulk. A crystal defect (vacancy, dislocation, etc.) or a
chemical impurity may modify the molecular environment leading to a lowering
of the energy of the excited electronic state which, at low temperatures. causes an
efficient exciton energy tmpping. These slates, which act as cflicicnt emiHing cen-
ters, are quite common in crystals [7J.
The origin of fluorescence is at I H 332 cm-
and is b-polarizcd. Comparing the
origin of Ouorescence and absorption (sec Fig. 6-H) we notice that, although both
6.6 Di.wrtler Ejfe<t 1111 Ellet:r:y Tm11.y(er
c polarization
b polarization
15000 16000
Wavenumber [em']
Figure 6-IH. T., .:rystalpularit.cd lluorcS<.'CIICC , 'CI 2 .
on the origin and on the A. 13. a lid C tal . , . .t . .'t. K. ll1e matn v?ro111c lxin<ls built
6.6. 1 ). ""' :lfc llldK.Ih:d. Sec text fur d1scuss10n (St-ctiun
arc b-polarized as expected ro D d
_ , . . . . .
"" . ov component, there is a shift of 28
?ledl .dTfilus mdtcates tlJat the optical emtsslon originates from a molecularly local
tz e eet state {X-trap) w f -
. d b .s a consequence
energy tm.nsfcr from the exciton
an su sequent trappmg We th
k at I H 332 - . . . . asstgn . htghest energy emission
: bo - . em to. a shallow X-trap whtch mamtams lhc same polarization of
orig, n in
Th . . . . . . ' ms rumcnta resolutton
e mtnnstc absorphon ongm hnewidth, detcnnined with by the . ,
sct-up used to tncas
. .
. ure Je emtsSton, ts 12 em- (full width of h If .
f:Vhm) _to_ the 8 em- (fwhm) of lhc tluorescencc ori in a2
;he X-tr.tp is a well dclined localized

L S u . bthe crystal is alfcctcd by a residual inhomogeneous
evcra -po an zed sharp bands are assigned as ro d . .
vibmtions at 699, 738, 10
56 1169 1460
. d g totally symmetnc
, (' ' - an l504 em but It on the fluorescence
fl sec F:g. These modes are in excellent agreement with those ob-
crystal Raman spectra thai we measured exciting at 1064
Except for the strong C==C stretching mode at 1460 c - 1 .
h .
show a sho
1 p . . 1 - Ill a t esc modes
. rogesston lllltled to the hrst vibronic conlJ>Onetlt . d. . I
tivcl w ,. k d. Ill tcatmo a re a-
y ca . ts1?111on along these normal coon.Jinates in the excit d . TI
complete a.o;signmcnl or b- and c-polarizcd spcctr<t is
blc 6-4. Uy gomg to htghcr energtes the vibronic h<tnds huih nn lhl'g nri .. in " .;,.,
6 Electronic Suucture a/Ul Ellergy Trallsfer in Solie/ a-Sexitlrienyl
. . . f lhe b ant! c-polarizcd fluorescence spectra of T" at 4.2 K.
Table 6-4. Vibr.!IJOnal assgnment o
b Polarize()
l:iv (em-
699 broad
731! sh
1383 2 vw
1460 s
1504 w
1793. 1 s
2148.3 w
2 195.0 w
2502.9 broad
2828.9 broad
2924 w
2961.9 vw
3252.8 w
e Polarized
t::.v (em-
165.4 vw
247.6 w
265.6 vw
306.3 m
355 vw
416.3 Ill
521 .7 vw
861!.8 vw
903.8 vw
952.3 w
1009.6 m
1047 m
1217.2 w
1301.8 w
1358.2 m
1537.9 w
1570.3 w
1614.7 sh
1633.2 m
1670.5 w
1686.1 m
1723.5 s
1754.7 l>h
1774.3 vs
1809.9 s
11!79.2 w
2474.3 broatl
3234.8 w
3278.9 w
Origin. 11!332 em
Fulsc origin A. a"
False origin B. al<
A - 107 (+6.8), ""
False origin C. ""
B - 107 Hl.4), (IJ(
c - 107 {- 3.0), "
c - 2xl07 (- 1.4). a,.
(0..(}}-699 (0.0), UN
(0-0}-731! (0.0), a"
A - 699 (-4.4). ""
A - 738 a"
B - W9 (- 5.7), u"
c - (-4.3). ""
c - 731! (- 2.7). til<
(0-0}-1 056 { +9), :Ia!
A - 1056 (+4.2), a
13 - 1056 (+1.1!), a,.
c - 1056 (+4.1 ). til<
(().()) - 1369 {- 14.2), l ll<
(0-0) - 14()() (0.0), (I"
(0-0) - 1504 (0.0). (II<
A - 13W (- 3.5). a"
A- 2Xf!J9 (-6.9), a
B - 1369 {+1.9), u"
A - 1460 (- 7.8), ""
c - 1369 {+4.8). (IJ(
A - 1504 {- 16.7). al<
B - 1460 {- 15.9). u,.
B - 1504 (- 3.1), ""
C - 1460 a,.
(0..0) - 1056- 738 (+0.9), tl"
C- 1504 (+0.4). a,.
c - 1460- 107 (-5.9), " "
(0..0) - 1460- 699 (+10.7). ""
(().0) - 1460- 738 (+3.0), (II<
c - 1460- 699 (- 9.0). ll"
(0-0)- 14W- 1056 (+13. 1), " "
(0-0) - 1460- 1369 (+0.1), al<
(0-0) - 2x 1460 (-4.0 ). ""
(0-0) _ 1460- 1504 (+2.1). a"
C - 2xl 460 (-8.5), a.
(0-0) - 1460- 105<> - 731! (+1.2), til<
C - 1504- 1460 (-8.6), (II<
6.6 Disorder Effect 011 E11ergy Tm11sjer 177
1llblc 6-5. CompariS(>n of the a" vibr.1tioual nnb in the ground and excited states. 1lle totally sym-
metric vibro1tions nf tbc gmund state in the R:unan sp<..-ctrum excited in prc-n:sonancc coldi-
(351 and in the ll uun:sccncc )62( arc compatctl with the of t1b i11ilio calculations
(131. The cnm:spmk.ling vihmtnns in the xcik'<.l late arc IIJCOIMII'I:d in tlJC absurptiun spectrum.
Ground late
Raman Auorescence
) (em '>
169 165
306 306
699 699
1460 1460
1504 1504
Ex<.itc<.l state

sec bcocling
(39), esc beocling
a. (38), esc bending
a .. (33). esc bending
(II), CaCa, CfJCP stretching
a.(IO). OJ.CfJ stretchi ng
totally symmetric (TS) moues acquire substantial c polariwtion intensity. 1bis ef-
fect is due to a tmnsition moment 'rotation' as a consequence of Herzberg-Teller
mixing of the lowest 1
8., (IlL) to the higher i B, (liM} via totally symmetric
modes. This effect is particularly evident for the 1460 and 1504 em- modes. The
increasing intensity of these modes could be due to the vibronic coupling becom-
ing more elficient the lower the energy difference is between the vibronic band
and the lending slate. We notice thai the vibronic band at 16872 em- , which is
assigned as the C=C stretching vibmtion built on the origin, gives rise to stimulat-
ed emission when pumped with energy as high as 35

While the origin is almost completely polarized along b, the c-polarized spec-
trum is twice as illlcnse at lower energies starting at about 18000 em- in corre-
spondence with sharp c-polarized bands at (A) 18 167, (B) 18084, anti (C) 18026
em- . At the same energies the spa:trum starts 10 show a broad background.
The A, B, and C bands, are origins of vibronic progressions with totally sym-
metric vibrations at 107. 699, 738, 1056, 1369, 1460, and 1504 em- as shown in
Figure 6- 18.
The comparison of the vibr,llional modes energies, determined by i) Raman
scattering, ii ) 11uoresceJK'C, iii) ttb initio calculation, and iv) absorption, is reported
in Table 6-5. We note that, as in the case of T
[64). the C=C stretching mode of
1460 em- in the ground stale tlecreases its frequency significantly (1275 em- ) in
lhe first excited electronic
6.6.2 Thin Films Fluorescence
It has been shown in Section 6.4 that thin films grown by sublimation on insulat-
ing substmles possess a high degree of order, which is rellected in the dichroic
behavior of the optical absorption [ 17, 40. 65, 66). Since the long molecular axis
forms an angle of 32" with respect to the film normal, the molecular arnmgement
is similar to that of the single: ctystal on a he fucc. Til..: low temperature ah-.urtl-
178 6 Eleclrrmic Slruclure ami Energy Transfer in Solid a-Sexilhienyl
tion (L6 K) of the thin film is compared with the polarized absorption of the be
single crystal at 4.2 K in Figure 6- 19. The low energy spectrum of the tilm shows
sharp bands, which have a linewidth that is of the same order of the low tempera-
ture absorption of the single crystal, indicating that the film indeed possesses a
high degree of ordering. Remarkably the a,. origin is also observed in the film as
a shoulder together with the 0' and 0" Henberg-Teller false origins. At contr.LSt
wi th the sharp absorption, the tluorest:ence is quite broad and, moreover, totally
different from the fluorescence of the single crystal. The additional and more in-
triguing observation is that the fluorescence spectrum varies from film to film de-
pending on the preparation conditi ons. This difference may be quire large a.-. in
the case shown in Figure 6-20.
In retrospect, by inspecting the lirer.llure, we find a confirmation of this vari-
ance (see for instance Ref. [67]). Peak intensities of bands originally assigned to
Franck-Condon components of the excitonic emission have r.tndom relative inten-
sities. This would not be possible if the bands were intrinsically vibronic.
we know that the excitonic emission, as ir is observed in single crystals, is r..tther
sharp at low temperatures, we were forced 10 reconsider the assignment of the flu-
orescence of thin films. From the temperature dependence of the fl uorescence effi-
Sil1gJe Crystal
Wavenumber (em')
4.2 K
F1gure 6-IY. Ollnparison of the b- anc.l c-polari/.cd s ingle crystal absorption sp<.'Ctra al 4.2 K with the
absorption of a polycryslallinc thin lilm al 1.6 K. Note thai the a,. origin is also
ob:.crvcd in the lihn.


6.6 Disvnler Effec:l 011 Energy li-tmsfer
wavenumbers [em"' ]

. lcmpcr.uun: (4 K) lluorc.-.ccncc l>pcclm of lwn uiiTcrcnt films of 1: prepore' u----

1 en:nl COuuiiiOOS. " - "

ciency we have shown that rudiative emission is consistent with an Arrhenius- ct"-
vated process and the exislence of two indepcJldent decay channels [68j TI a
solved n . . me, re
. . . uorescence m the_ ps rime scale reveals tha1, at short times after
the spectrum 1s predommantly cxcitonic. AI delay times longer than 50
lhe spec.trum becomes broader and broader acquiring the spectral characteris-
tics of the cw and ar longer times it is totally dominated by the bro d
features l?l , 68j. _Th1s 1s a clear indication that excitation relaxes quickly into
of band diffuses in space, during the lifetime of the excita-
tion, explon ng an area defined by the diffusion length If dun
g th' . . d
walk th . IS 1an om
e VISlls a s1te whose characteri stic electronic energy 1
than th, ex t b d d . . . IS ower
. c c1 _on an an 111 add1t1on rhe tempcrmurc is lower rhan rhat required
to exit from 1t, then rhe excitation is eventually t11pped 1'he b
th fi ... , . . . ' r a emiSSIOn IS
ass1gncd etlcct. Smcc rhc emission is broad rhc trap is not
on a spcctfJc sue wil h characreristk energy, otherwise rhe emis-
s_tOn_ he shaq_> :1s m lhc of X-uaps (1itlt: .\'llflra). The broad
tJCS are mstcad of an mhomogcncous cner"y d'tstrlbur
bl , f 1 , 1 . co an enscm-
e o mo ccu es thai have a packmg which diflcrs from the predominantly or-
180 6 Electrouic: Structure ami Euergy Tnmsfer in Solid u.-Sexithienyl
dered packing of the bulk. We call this ensemble an aggregate. Even a small num-
ber of aggregates is sufficient to act as an efficient trapping agent. The trapping
efficiency is determined by the relative weight of the exciton diffusion length and
the density of aggregates. An independent confirmation of the aggregate nature of
the emission is given by the comparison of the spectrc1 obtained by exciting at dif-
ferent energies, above and below the bottom of the exciton band. The site-selec-
tive fluorescence experiment is shown in Figure 6-2 1. The spectrum is indepen-
dent on the excitation energy until it reaches about 17 700 em- . At excitation en-
ergies lower than about 17 260 em- , in the last two curves at the bouom of the
figure, the fi rst peak of the emission at 17 300 em- disappears and the rest of the
spectrum becomes broad. This indicates that the first peak is due to a different
species from those which arc responsible for the rest of the spectrum. This obser-
vation suggests that there arc at least two different sets of aggregate states in the
film. 1l1e relative density of these states may be different from sample to sample.
There arc aggregates which arc stable in the grounll stales and aggregates which
are only stable in the excited stale. The Jailers are also called excimcrs 171. We
may distinguish between these two possibilities by looking at the fluorescence ex-
citation spectrum. This is reported in Figure 6-22. A clear peak is observed at
17 700 em - I. At thi s energy the absorption spectrum shows only a smooth tail.
The peak at 17 700 em - I locates therefore the energy of the aggregate and shows
that the aggregate is stable in the ground stare [68j.
Wavelength (nm)
600 700 800 900
20000 18000 16000 14000 12000
Wavenumber (cm'
Figure 6-21. Sile-selcctive fluorescence me.JsurcnlCnls of a T., lhin 111m. Starting from Jhc lop spec-
trum the exciJalion energies were al 17tl60. 17700, 17390, 17240. 17095, an<.l 16950 cm'
, rcspcc
lively. Tile reminiscence of the exciJing laser lines is shown by lhc sharp peak on Jhe lcf1.
6.6 Disorder Effect Ull Euergy Trcmsfer
Wavelength (nm)
550 600
1.2 650
w q
fl! 0


20000 18000
Wavenumber (em' ')
Jo'igurc 6-22. Auorcsccncc cxciJaJ
f .
15 380 to 17 3()() em- . In lhis energy fi:m dcrccted al energies spanning from
m s unc Jangcc.l.
Morphology-Dependent Polarization of Fluorcsct!
and Electroluminesccnce nee
As we discussed in Section 6.5 the mo holo f . - .
to the growth co


. If gy
T6 lhJn h lms s very sensitive
ns. we now restnct the t d fl
lure we have shown that dur, ng de o .:t. h s u. y ' ms wuh granular srruc-
. . P s1 1on t e gr.un SJ'"' and d , h.
gr.uns mcreascs rapidly h . . . . . . "" Ol' enng WJt 1n the
cases, the height f lh _mcrea:; mg substrate temperature [29, 37, 69]. In all
o c steps of the films morphology measured b AFM
that, whatever the dimensions of rh . . T . Y show
mutely upright on the We 6 ap_Proxi-
to aggregates Aggregar. .
0 1
at emJssJon 111 thm lllms 1s due
cs may or may nor have
prefe . t'. 1 .
granular structure. If they do ' t h ld . . . ren a onenrauon m the
to check this effect we havd result m a pol<tnzcd tluoresccncc. In order
thin films. Moreover, we lluorcsccnce on
phology allecrs the degree of lluorcse p I t>: of _chcckmg If and how the mor-
. cncc po anzaron. For this p h
stud1cd the fluorescence polarization . . . . we ave
age gmin diameters, in the range <.hiTerent aver-
text we have rc a d . . . . . an . nm, and 111 the same con-
p r II: a scncs of one l.tyer Tb-bascd hght cmiuing diodes (ITO/
182 6 Electronic Structure and Energy Tra11sjer in Sulitl Cl-Sexitllienyl
T&'Al) having the same range of avemge gmin sizes (200-1500 nm). On these
LED devices we have also measured the polarization degree of electrolumines-
cence. Measurements were made in a plane perpendicular to the substmte with the
viewing angle changing from 0, along the normal to the substrate, to (90),
perpendicular to the normal, as shown in the Figure 6-23. Within an amorphous
film, emission of light is isotropic. but the measured angular dependence of emis-
sion varies approximately with the cosine of the viewing angle because of refmc-
ti on and reflection at the fi lm surface [70]. The angular dependence of externally
detected light is determined by a competition between the emission distribution
within the film and the effects of refmction and refl<.'Ction described above. In our
experimental contigumtion, the relative intensities and angular dependence of ver-
tically (V) and horizontally (H) polarized light arc detennined by the components
of the transiti on dipole moment of the aggregate with respect to the direction of
observation. If the transition dipole moment is oriented parallel to the long molec-
ular axis we expect the vertically polaril.Cd intensity to vary approxi mately as the
cosi ne of the viewing angle, and the horizontally polarized intensity to peak at
some angle to the normal. However. the intensity of both polariations is equal at
the ov viewing angle since there is rotational :.ymmctry about the normal to the
film. We note that interference and microeavity ell"ccts can also make U1e emis-
sion peak at non-zero viewing angles. These effects. however, arc easily tlistin-
guishable from those of molecular orientation because the intensity of the vertical
anti horizontal polariwtion:. is approximately U1c same for the fonner but quite
tliffcrent for the Iauer. Simi larl y, if any of the light that is waveguidcd in the film
is scattered into the forward direction we expect it to be isotropically distributed,
and therefore not to contribute to the polarized emission.
Figure 6-24 a shows the angular dependence of the fluorescence anisotropy (H-V)
in fi lms made at temperatures of 22 "C (ca. 200 nm gmin diameter - case A), I 04 oc
T6 (-ve contract)
normal to
the film
Figure 6-23. Sketch 11f the expcrimcnt:tl armngcmcnt for mc;t,unng the angular llcpcndcncc of Ouorcs-
cenc.: and clc.:trulumincsccm:c. The viewing angle U is van!.lll between - 90 " <lllcJ +90v.
6.6 Disvrtler Effect un Energy Trcm:.fer
1.5 c

u::: 0.5
3 v

1 5
v 1
b) 0
6-24. a) Pular l'l:Jln.""<:ntatrun ( from - 90 . '" +'XI I t II . .
arusutrullY (I I-V l in T,, fi lm,. walh rai n ,,z . ( I c(l() ur l< .angular dcpcru.kn<.-.: uf lluun.""<:cncc
200 . o ' .1.-,; 0 ' IIIII (un.n MjU'U"C ' ) '"'" (1"11 .
nm (open can:lc') b) n1c .
,. ul r . .. f .-- vvv nm a ctl ''rclcs) ant.l
. o il uCJ)CI!uCilCe 0 clc.:trul 1 . , '
rom th.: LEO cuntactcd part
1 th , .

anc,.,cncc anasutropy (H-V)
c 1oa111e 1oamp cs.
(ca. 600 nm diameter - CCJSe B) and 155 oc . I .
from the film grown .:t rootn re (ca. nm dtameter - case C). Flu-
mperature s completely u I . ed
t _ ough X-ray measuremenrs show that . h til . npo anz even
. sue t ms are well ordered Ani ot . b
S<..'en, however, Ill the fluorescence of the film "th . .. , . . : . s can e
and the degree of polariwtion h_lgheL r
Ill I e polar plot are in fact clearl . . . . gmms. OU<;S
First of all we notice that the are more in case C.
the long molecular axis. Secondly the de rec of t_ Is mdeed parallel to
the average grain size. Fluorescence as . r h . b. IS dependent on
the result of energy rmnsiCr which i;l d ely discussed m this section, is
spati al scale of morphology. which are

the exciton diflusion len nth of the most pct"f-.... r y I ,liS higher than
d . d o ...... mo ecu ar smgle cry ral . ("
ecu es nm). Tile grai n size dependence dl.>t:s not rcllect th. f h s s J.e .. _ew
of the diffusion len nth und poltr
., .,
011 1
. ere ore t e compctliJon
o .... nemoy loss at the r 1 b
observed by AFM. The self-similar ro rt rh . . . . , .. . :' c ua oundaries
in_ undcn;tanding this apparent In help
Wi ll be a series of hieran:hil:al structures th . orp ?_ogy IS there
space. Groin bo d . . .
. . at arc smular at d11lerent scales of
by AFM arc ower. from those directly observed
y to be responsible ol the polariwtion memorv loss.
184 6 Electronic Structure and Energy Tmnsfer ill Solid u-sexithienyl
We assume that at the grain boundaries aggregates, that are responsible of the radiative
emission, are randomly oriented and therefore giving rise to isotropic emission.
Figure 6-24 b shows the angular dependence of elcctroluminescence anisotropy
(H-V) measured on the same samples as were used for the fl uorescence experi-
ments, making proper contacts. The electroluminescence is isotropic in the film
with average grain diameter of 200 nm and is more and more anisotropic at high-
er avemge grain diameters. Moreover, the anisotropy is larger in the case of elcc-
troluminescence than in fluorescence. This indicates that, in addition to the energy
tmnsfer govem<.'d polariu ui on memory, there is another effect which is affected by
morphology and is contributing constructively to the polarization memory. We ar-
gue that this effect is charge recombi nation. Charges have a better chance to re-
combine and form excitons within the ordered bulk than at the grain boundaries
in the case of larger gmins than in the smaller ones. Once the exciton is formed,
it dilfuses wit hin the ordered bulk and eventually emits from the ordered bulk
rather than bclllg trapped at boundaries.
6.'6.2.2 Morphology-Dependent Energy Transfer
In the previous subsection we showed how the morphology of vacuum-sublimed
polycrystalline films affects the polarization properties of lluorcscencc and electro-
luminescence. Here we show that, by controlling the film morphology, the energy
lntnsfer within the film can also be controlled, thus allowing l11e modification of
the spectral properties of the emission. We consider four representati ve film
morphologies (sub-monolayer, islands, layers, and grains) which have already been
discussed in Section 6.5. The variation of the low temperature fluorescence spectra
and its relati on to film morphology is shown in Figure 6-25. For sub-monolayer ar-
chitectures the fluorescence spectrum shows the sharp excitonic features observed in
the single crystal, and the residual contribution from molecular aggregates results in
a broad background. The cxcitonic electronic origin and the 1460 em- vibronic
Franck-Condon progression built on it, are clearly identified. In U1e fihn morphol-
ogy characterized by non-inter.tcting islands, the molecular aggregation is still unfa-
vorable and the mdiati ve emission retains a strong excitonic chamcter. The layered
morphology leads to an increased relative weight of aggregates emission which
smears out most or the excitonic sharp components. The gmin-likc morphology
gives rise to the typical broad bands fluorescence spectrum that we discussed
above. II is entirely due to emission from molecular aggregate states !61] and none
of the excitonic features persist. The energy level of the first aggregate (A in Fig. 6-
25) is located at about 700 em- below the boHom of the exciton band. A progres-
sion of the intense C=C stretching mode ( 1460 cm-
) genemtes the low energy fea-
tures of the aggregate spectrum. Since this aggregate acts like an cfTi cicntlr..tp for the
excitation, any excitonic (sharp) feat ure is smeared out from the fluorescence spec-
trum. From the optical behavior of the different molecular architectures it ".tppears
that molecular aggregates arc funned due to Lhe coalescence of different gr.tins of
material. At the gmin boundaries, ensembles of molecules ean indeed be tom1ed
with intem1olccular intemc.:ti ons diiTerent from the bulk, lt;ading lo low cnergy-local-
il..cd electronic states.
6. 7 Cullclusions
Wavenumber 1 em 1
Figure 6-25. '11<:\:lr.t m 4.2 K of T I . . . .
grams; b) island.,; d) sub-nwnolaycr wuh. morphology by: a)
layer architecture O.Xrc;L'i(:s the cncnov tr.
. lli . wcr nslly of aggregate stales in the sub-mono-
. . . cv uiL\ Cr C ICICII<:y IO low cncr, t 1. . tJ
qwrcs donunant cxcitonic (sec Sc ( ,_
gy ' a c' an the lluon:!>CCJI<:C ac-
" lOll n .. . ) .
. possibility of controlling the morphological and strucrur I d . h
td ts a fundamental requirement for the . d a t. sol-

emrOsston properties of a lumincscem material within an ,. uhcttbth!Y. of

t e ( LED) device. tg emtttmg
6.7 Conclusions
In article we have reviewed the results of a oint " . . . .
logtcal invc.'>tigottion of a-scxithicn I T J and morpho-
whil'h is assi .. netl to I 8 s,)l.t . . yl ( The sml::lct ckx:trunic lcvd,
o ,. . t s 111 lle smglc crystal tnt f 1
1l1e SltlJClurc of the exciton hand is by the ltne. lcvclsd.
u a sorptwn an
186 6 Electronic Sttucture ami Energy Transfer in Solid a-Sexitllienyl
fluorescence-polarized low temperature spectra. The Davydov splitting between
the lower opticall y allowed a., crystalline level and the higher bu level is mea-
sured to be 2600 cm-
giving the first piece of clear evidence of the extent of the
intermolecular interactions in a model-conjugated oligomer. The large energy im-
plied in the splitting could be an important factor in determining the sequence of
the excited states and the photophysics in real conjugated polymers in general. In
this case the lowest Davydov component is acc:idemally forbidden as a conse-
quence of the peculiar molecular arrangement within the unit cell. This fi nding
explains the dramatic reduction of the fluorescence quantum yield in the solid as
compared to solution. Most of the vibronic intensity is via the Herzberg-
Teller coupling. We show that the energy transfer in the solid state is highly sensi-
tive to the morphological structure and to the molecular ordering. Fluorescence is
mostly excitonic in the single crystal while it is dominantly due to aggregates in
the case of ordinary thin films. Thin film growth in high-vacuum has been exten-
sively investigated by atomic force microscopy. The effect of two relevant growth
pammetcrs (deposition temperature and film thickness) on the morphology has
been quantitatively analyzed to obtain growth relations. The large variety of mor-
phology in T
fil ms, grown by high-vacuum sublimation, ari ses from the kinetic
control of the growth process. Films of reproducible quality and features can be
obtained by controlling the growth conditions. The growth relations of T
were inferred by measuring the evolution of morphological properties from AFM
images using statistical methods. In particular, we showed, using topogmphy scal-
ing arguments, how morphological tmnsitions can be monitored by meru1s of the
roughness scaling exponent and the correlation length of the topogmphical fluc-
tuations and interpreted in terms of changes in the controlling mechanism of
growth. The fact that in T
films a self-affinity in the topographical features eK-
ists, should also imply that those phenomena (such as charge injection, transport,
recombination, and eKci ton diffusion) related to the spatial conelation of molecu-
lar sites, to the extent of short-range intermolecular interactions, and to the local
ordering, are sensitive to the morphology ru1d could be used as probes for the
morphological changes. We reconcile in this way the different optical behavior of
the single crystals as well as of the polycrystalline films grown under dilferent
conditions. Excitonic emission is indeed shown also by thin films with a high de-
gree of ordering. Fluorescence <md elcctroluminescence of different thin film
LEOs with different morphologies are strongly inlluenced by the grai n sizes and
we show that films with average grain size of more than 600 nm manifest a polar-
ized LED emission. Finally, by controll ing the early srage of the growth. we show
that energy tmnsfer is strongly aiTected by the development of aggregates at the
gmin boundaries where individual coalesce into one another.
R. Danieli, W. Gebuuer, 0 . Greco, E. Lunedei, R. Mahrt, R.N. Marks, R. Michel,
P. Morelli, M. Murgia, P. Ostoja, G. Ruani, P. Samorf, T. Virgi li, R. Zamboni, D.
Bcljonne, J. Cornil , P. Vivi lle, R. Lazzaroni, J.-L. Bredas. H. Bas.-;lcr, F. Gamier,
G. Horowitz, and A. 13rcc have participated to the work which is reviewed here.
Rt!ferem:es 187
thank Beatrice Stefanelli for help in the prepamtion of this manuscript. We ac-
knowledge support from the EU-TMR Prognrnunc SELOA FMRX-Cf960083
and CNR-PF-MSTA II Progeui Coordinati DEMO and FREMO. '
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7 Spectroscopy of Photoexcitations
in Conjugated Polymers
Paul A. Lane, Sergey Y. Frolov, and Zev Y. Vardeny
7.1 Introduction
The combination of cllicienl phololuminescencc (PL) and ease of processing ha-;
gener..tted much interest in conjugated polyml!rs with respcl:l to their usc in light
emitting diodes (LEOs) and other optoclcctronil: devices [1-5]. 11tis interest h:l!;,
in lum, led lll ex1ensivc investigations imo the nature and dynamics of photoex-
ciled states. Phmoexcilalion dynamics in conjugated polymers span a wide r.mgc
of timescales. Singlet excitons self-lrap and migrate on a subpicosecond timescale
and decay within approximately one nanosecond. Long-lived photocxcilations
such a-; polarons. bipolarons, and triplet excitons arc formed by the non-radialive
decay of singlet excitons and have lifetimes exceeding a millisecond at low tem-
peratures. As a consequence, multiple spectroscopic techniques are required to un-
dersrand the photophysics of these novel materials.
We have investigated the photophysic.-; of conjugated polymers using a varie1y
of linear and non-linear spectroscopies. Photomodulation spectroscopy (PM) uses
two light sources whereby absorption of a pump beam modulates lhe transmission
or reflcclance of a probe beam incident on lhe sample. PM spectroscopy can de-
tect a variety of phenomena, depending upon the ti mescale of the me:l!;uremenL
Transient PM sLUdies with nanosecond or better resolution have detected slimulat-
cd emission (SE) and phmoinduced absorpti on (PA). also known as excited state
absorption. Continuous wave (CW) PM spectra include contributions from PA.
photoluminescence (PL) from spontaneous emission, and electroabsorption. The
Iauer signal is caused by electric fields <arising from photogenerJted charged exci-
lations. As photocxcitatilm Jynamics in conj ugated polymers span a wide range
of timc.-;calcs, we have employed both tmnsienl anJ CW PM spcctrosl:opies lo Jc-
tect photoexcitations and measure their relaxation dynamics. Optically detected
magnelic resonance (ODMR) has also been employed lo delennine the spin of
long-li ved photoexcitations.
Conjuguted polymers ure centrosymmeuic systems where excited states have
definite purity of even (A
:) or odd (B,) and electric dipole lr.msitions are allowed
only between slates of opposi te pmity. The grounJ stale of conjugated polymers
is an even parity singlet slale, wri llcn <L" the PM speclroscopy is a linear
technique probing dipole allowed onc-t>holon trJnsitions. Non-linear spcclrosco-
pics complement these ml!asuremcnts as they can couple to dipole-forbidden Iran-
190 7 Speclro.Kopy vf Plwtocxcitatio11s in Conjugated Pvlymers
sitions and reveal the existence of even parity states not detectable by li near spec-
troscopy. We report studies on the two-photon absorption (fPA) and clectroab-
sorption (EA) spectra of conjugated polymers. By measuring the two-photon ab-
sorption spectra, it is possible to clarify and enhance our understanding of U1e
physical states of these polymers. Employing ilie Z-scan technique enables accu-
rate identification of TPA bands, since it measures real as well as imaginary x
EA probes change in ilie absorption spectrum due to an applied electric field and
are sensitive to both even- and odd-parity states.
7.2 Experimental Techniques
7.2.1 CW Photomodulation Spectroscopy
In the continuous wave (CW) experimental setup a sample is constantly ill umi -
nated by a probe beam and the steady state change in the transmission is detected
(see Fig. 7- 1). An argon ion laser has been used to genemte the pump beam and
the probe beam was from an incandescent lamp (tungsten or others), pr<XIucing a
broad spectrum (0.5 to "'5 J.lm) l6 ]. Both pump and probe beams arc directed
onto the sample film and the tmnsmiued probe light is collected, filtered Uuough
a monochromator, and detected by a photodctcctor. Both the pump and the probe
Arlaser --- 7\
prObe ,
c /)

( .----h
7-1. diagmm of the
CW PA spectrometer.
7.2 EJ.pelimental Tedmiques
'"':'ere di spersed across the sample; the probe is assumed to have a uniform inten-
sity and the pump a Gaussian di stribution.
the 6.T in .the sample T is very small (6. TIT
-:= I 0 a phase-scnstttve (lock-Ill) detection technique has been used. TI1c pump
ltght ts a. a rclcrcncc frequency (usually in the audible frequency
mngc), therefore !:. T ts modulated at thi s frequency too. The modulated t:. Tis de-
tected a lock-in amplifier referenced at the same frequency. By simul taneously
mea-;un ng !:. T_ and ! and the wavelength of the probe light, ilic spectrum
of 6. TfT stgnal ts obtamcd. Tile tmnsmitted probe light f(tl) through the sam-
ple ts represented by:
I (cl) = 1(0) e-"'
( I - R)
(7. 1)
!(0) is the probe light incident on the film, a is the absorption
c?cfltctent, cl the film ilitckncss, R the rctlectivity, and reflections from the back-
the film neglected. 1l1e absorption coefficient is equal to the density of
excuattons multtphed by the absorption cross-section (a= na). The pump beam in-
duces changes in both u. and R:
t:.I(d) = I(il)( I - R)(e- llwt - I ) - t:.R . /(O)e- <nllul' (7.2)
6. / is in '.ransmission with the pump on and the pump off.
Alter normalwng the equatton by l (cl) and assuming t:,.(.({/ 1 it follows that:
6.T t:.R
- = - 6.u.d - -- .
T 1- R
In all our conjugated polymer samples R is less than 0. 1 and 6. R!R < 10-6 [7 j . Be-
cause!:. TIT typica!ly in the range of 10-
- 10-
, the second tenn in (3) c-.tn be
neglected. Thts rclatton holds onl y in the small signal li mit (!:.ad 1) for iliin
films, where the pump light is absorbed uniformly, creating an equal di stribution
of t:.a across the film.
For. lock-in amplification ilie pump is modulated m a reference frequency w
(sec Ftg. 7_- I), whtch means that t:.T is not constam over time. Rather, its magni-
tude (and tls phase) depends on the modulation frequency [81. In order to find the
t:.T_(w), u.s assume that the recombination dynamics Hre
monomolecular wtth a smgle hletunc T. Then we can write for the number den-
sity of excitations N at time t :
c/N(t) = G(t) _ N(1)
dt T
where G(t) is genemtion mte and N(I)/T describes the monomolecular decay
rate. The rate G(t)= yP(f)/luv, where P(l) is the pump power, ftcu the
energy of a smgle pump photon, and )' the quantum clli cicncy of the photl>cX(' ita-
192 7 Spec/lvscupy uf Plw10excitaticms in umjugatecl Polymers
tion. We take into account only the fundament411 Fourier component, neglecting
the higher orders:
G(t) = G(w)e- ;"". (7.5)
Assuming N(t) has the same form and substituting into (4), we find:
N(w) - -t
- I + (w-rl l + (wti
Relating N(t) to the absorption cross-section a(lla=Na)
/1T [ I WT ]
--= - i G(w)rad.
T I + (wr)
I + (wrf
The first term in Eq. (7.7) is the in-phase signal, which has the same pha_se as
that of the pump, and the second term is a quadmture or out-of-phase s1gnal,
which has a 90 phase relative to that of the pump. Their resr<:ctive de-
pendencies are shown in Figure 7-2. The normalized change_ m trans_m1ss1on can
be related to the excitation cross-section and quantum y1cld of genemllon:
11T S liw
a(.'.)= - ---
T yrPabs
where a(.'.) is the photoinduced absorption (PA) cross-section at the probe wave-
length .'., and Sis the illuminat(:d area of the sample [9]. .
The decay of photogenerawd charged exciwtions _as p<>larons and btpolar-
ons should be bimolecular. In this case, the rate equauon IS wntten:
dN(t) = G(t)- R(N(t) )
The dependence of the in-phase and quadrature lock-in detected signals on the
modulation frequency is considerably more complicated than for the case of
monomolecular recombination. The steady swte solution to this equation is
straightforward, dN fdt = 0 => Ns.'i = JG/i?. but there is not a geneml
N(t) to the inhomogeneous differential equation. Furthermore, the
will vary throughout the sample due to the Gaussian distribution ot the pump Ill-
tensity and absorption by the sample
where r is the distance from the center of the pump beam. z is the penetration
into the sampl e, a is related to the beam width, and u. is the
cient. If one fUJ1her int:orpor.ues diffusion, the rc:-.ulting problem ts non-tnvml.
7.2 EJ.]Jerimentul Techniques
0. 1
--In phase
- - Quadrature
100 1000
Frequency (Hz)
Figure 7-2. Frcqucnc:y dependence of lhc in-pha:,c anti ljU<Illr.uun: PA sit:nals.
1 o
Whi le it is possible: to simulate the modulation frequency dependence, this must
be dune on a case by case basis.
7.2.2 Optically Detected Magnetic Resonance
Optically detected magnetic resonance (00MR) has yielded val uable information
a?<>ut of long-li ved photocxcitations of conjugated polymers. The tech-
mq_ue rehes upon the intemction of exci tations with an applied mag-
For a patt1clc wuh non-zero spin, placed in a magnetic field, the Ha-
miltOnian 1s:
(7.11 )
is the spin of 'if a tensor defining the intemction of the par-
!lcle the field, and f! 1s the apphed magnetic ticld. The g-tensor is diagonal
m_ a ?asls set Ill the symmetry of the molecule and possesses three
A-; there 1s only a very slight in the g-valuc for conju-
polymers [IOJ. the tensor can be replaced wtth a constant and the Hamilto-
man reduces to
(7. 12)
For spin resonance <ESR) measurements, the sample is placed in a rcso-
between the pieces of an electromagnet. The mag-
netiC lldd 1s mcrcascd. wh1ch Jndutcs a Zeeman splill ing of the exdta-
194 7 Spectroscopy of Plzotoexcitwions in Conjugatetl Polymers
tion energy levels. Resonant absorption or emission of microwaves occurs when
the splitting of the energy levels matches the energy of the microwave photons
H). Magnetic resonance also has an effect on photoexcitation dynamics
as the absorption of microwaves will equalize the populations of the two coupled
spin sublevels. Consider two triplet sublevels X and Y with sublevel populations
11;. generation rates G;, and recombination rates R;;::= 1/r;. Under steady state condi-
tions dll;ldt=O and from Eq. (7.4) we can write
n; = G;/R;. (7. 13)
At the resonant field, the two sublevels are coupled and have generation and
recor!lbiJlation rates G = (Gx + Gr)/2 and R = (Rx +Rr)/2, and populations
iz = G/R. The difference in the total triplet population at resonance and under
satur.Jtion by microwaves is:
- Rx- R\.
Jn = nx + lly - 211 = (111' - llx)
(7. 14)
Population redistribution among magnetic sublevels produces a change in either
the absorbed or emitted light associated with the excitation. 1l1Us, magnetic reso-
nance can be optically detected, replacing direct observation of microwave absorp-
tion by the pammagnetic species. This scali ng up from the microwave to infrared
or visible frequencies makes ODMR extremely sensiti ve: up to I 0
times more
sensitive than conventional ESR.
For spin- 1/2 excitations such as electrons and holes in nomml semiconductors or
polarons in conjugated polymers. a single resonance is found centered at the field
Ho = lzvfgp (7. 15)
where p is the Bohr magneton. Magnetic dipole intemctions between the unpaired
spins composing triplet excitons add additional tem1s to the spin Hamiltonian:
- - 2 tn2 2 n2
J/ s- s= gJluH S + D(Sz- 3.)-) + E(S .. - .)_):) . (7.16)
The zero field splitting (ZFS) pammeters D and of the triplet exciton are:
(7. 17)
E =--IJ ---
3iJi (l -x
4 ,.s
(7. 18)
AI I (b)
! ! j
Magnetic Field
7.2 Experimemal Techniques
Zeeman 'Piiuing nf triplet exciton sublevels
Ol thc_a[lphcd magnetic field. (b) Change in PL in-
tensity at magnc!K: resonance.
;;;ere_ X, y, T _r are co-ordinates of the spins in the triplet state
e ues o_t ttu: spm Hamrhonian depend upon both the ma nitude . . .
leld and tls dtrcction relative to the principal axes of the I ot ..;::e
onentatron of the molecule relative to ii determines the ener ies of th e. e
levels hence, the reson. fields Figure 7 3 show . fe tnplel su.b-
. r fi - s a ragram o energy e
app :d lor the applied tield aligned along the z princi al a:i
to the_ applied is unaffected by
downwards. . e s are mtxcd, wrth one spltt upwards and the other split
A single triplet has three resonant fields, two due to 11m -1 t . . . .
one due to Ill =+'> . . . s- ransll tons and
. "s -- tmnsrtt ons. For amorphous or polycrystalline sam les
are formed due to conrri butions from <til ossibl: : two
ol wrth to applied field. The full-field
o ns=l transrltons ts centered about H, and has th , 1 II ,
cal potnts: u c o owmg cntt-
singularities at 11 = H
(D _ 3E)/
shoulders at 11 = Ho (D + 3E)/
and steps at H = Ho Dfg{J
The lwlf:field triplet powder pauem due to A.,, -2 tra .
= s- nst ons as a
singularity at
and a shoul der at
II = V(llo/2l- ([)2 + 3&)jg2p2
H = {Ho/2){ I - H<D - )/Ho]
} .
(7.2 1)
. The ODMR spectrometer resembles the PA spectrometer h F
Wtth the sample placed in a microwave cavity between the 11.1. .7-1,
The sample _is constantly ill uminated by the
mrcrowaves arc coupled into Lhe .. t
h ns.
gurde Changes J/ PL cavt Y 11roug a wave-
. tn or r, m probe tr.msmission arc
tectcd b 1 k
y oc - 111 am-
196 7 Spectroscopy of Photoexcilalicms in Conjugated Polymers
plification of the photodiode signal, with the lock-in refe.rcnced to the microwave
modulation frequency. We describe the two different kinds of measurements as
PL- and PA-detected magnetic resonance (PLDMR and PADMR, respectively).
Two kinds of PADMR spectra can be measured: H-PADMR spectra in which {JT
is measured at a fixed probe wavelength A while sweeping the magnetic field /1,
and A-PADMR where fJT is measured at fixed // on resonance, while A is varied.
PADMR spectroscopy is especially valuable in deconstructing PA spectra with
contributions from multiple photoexci tations with differing spin signatures.
7.2.3 Transient Photomodulation Spectroscopy
In many respects the time-resolved pump-probe technique is similar to the CW
counterpart. The use of pulsed laser light permits direct probing of both the mag-
nitude of the PA and its dynamics. n1e experimental arrangement is practically
the same as for the CW version, i.e., both pump and probe beams are focused
and overlapped onto same spot on a sample. In addition, the pump and probe
pulses are synchronized so that the time interval 1 between them is constant and
confined to a certain time r.mge (in our case up to 3 ns).
A critical difference between the tmnsient and CW measurements is that while
the CW probe source unifomdy illuminates the sample, both the tr.msient pump
and probe beams have Gaussian distributions. Equation (7.7) can be rewritten for
the transient case as:
IJ.T y Eabs
- -T = -, (r'! 2) a(A)f(t)
+ r
where Eab is the absorbed pump energy per pulse,f(t) is the rc.o;ponse function of
the material, and r
and r
are the diameters of the two light beams. Two impor-
tant functions, a (A) and f(t), determine the magnitude and dynamics of f).Tff.
However, the above fommlas are good only when the time delay t is sufficiently
greater than the pulse duration of the pump and the probe light pulses. In order to
find a more gener.sl expression we have to use a slightly different approach. We
take into account that the pulses are not infinitesimally short. Their time depen-
dencies are given by the intensity functions l prubc(t) and lpump(l) and shown in
Figure 7-4, where the time dependence is considered on very short time scales in
the order of femtoseconds. The material response function j(t) is assumed to be
instantaneous with some relaxation time r.
Seveml laser systems have been used in our time-resolved PM measurements.
For the measurements, a colliding pulse mode-locked (CPM) dye laser
was employed lll ]. Its characteristic pulsewidth is about 70 fs, however, its wave-
length is fixed at 625 nm (or 2.0 eY). For ps measurements at various wave-
lengths two synchronously pumped dye lasers were used ( 12). Although their
time resolution was not better than 5 ps, they allowed us to probe in the probe
photon energy mnge from 1.25 eY to 2.2 eV. In addition, a color center lao;er
7.2 Experimentul Techniques
0 tot t
Fagure_ 74. Excilalion anti probe alon ' with nit< . . . .
trdllSmtsston ill> fun\:tions uf lh.: punln..p be _,_
. S tlcnsny anti ..:hanc in
,. ro "" ay tunc. c
(CCL) can be easily incorpor t d h' - .
a e mto t s configuration It gives us the . d"' t' I
Spectf'd range of 0 17 1 0 86 y . . il ul IOna
CCL is 20 ps.' be .the mode-locked
A gennaniUm detector has been used lor tl1 , d t . y ufsmg a saturable absorber.
. c c ect1on o the CCL . n
e ex pen mental setup for th 1 . ,-. . lA,;

CPM laser is shown . F 1 u ;;.a ast (lemtosecond) measurements using the
One of the is

coming out .or the. CPM.
autocorrelation analysis. The other bea pulse duratiOn usmg an
pump and probe beamo; Af , . . m a common source for both
pump portion is directed.. t ths beam spht mto two ponions (30nO) the
10 o an acousto-opllc rnodul
(AOM . . '
modulate the pump intensity with SUPers . fi a ), whch able to
ponent of the AOM . . . . . o uc re_quences 1131. In the mam com-
MHz) . t Pczo-ele_ctnc crystal, a la.o;t oscillating electric field (I 00
'' es a San Ill" aCOUStiC w h' J d' 'fi
magnitude of ta d.<> . . ave, w c 1 Jt mcts the incident li<>lll The
c s n mn wave Js modul t <.1 1 11 c
MHz the result being th; modula;ion of genemtor .at 4
the zeroth or the first order in the diffraction at , . . cam. We use ether
surements we have chosen the ;wroth d . p . as a pump, and 10 our mea-
tude of the modulated pum wer Our. cr, so. the magni-
crystal, the femtosecond d1sperson
feet a set of four prisms hao; been used . . . . .' _o compens?tc cl-
sion, which nullilics the posi ivc a hnc<rr negat ive dspcr-
7 Spectroscopy of Photoexcilalicms in Conjugated Polymers
ao modulator
delay stage
"0 "0
0 c
CT 3
Cl> "0

7-5. Schcmalic diagr.1m of lhe
PM spcclmmctcr.
The probe ponion of beam, on the other


th and Probe P
ulses The t1me delay can van
tween e pump
with. the resolution of less than I fs. . d . . 11 1 . nd focused with a single lens
11 d probe beams are ma e p.lra e a .
e pump an . th .' le is placed with its substmte in front of Jt (t?-
onto a sample. Usually: . e. sa';;:' !Teet of hotooxidation. Visually, with the md
wards the beams) to mmnnze e e . . an overla d. The magnitude of
of a _the (Eq. (23)). A_fter the
the sgnal f!.T cntccdally detpehe loc'-,n final adjustments optimizmg the
n 1 has on "" ' 1 h tod
sg a . . . . .t 1' he probe light is detected by a SJ con p o e-
erlap are made to maxumze ' . 4 MH I
with a build-in filtering that inn
der to avoid the scattered pump h gh_L. whctcdh 'b with a JJ2 plate_ Then the
th polari;wtion of the pump IS rota y I he
setup: . . ti t f the detector is set in such a way that on y t
polanzallon analyzer m ron . . . rture is used to block
probe light passes through ln addton, a small sze ape .
off the remaining hght. . . . l'ficd and sent to a fast lock-in
The electrical signal from the detector IS preamp ' I data
. computer which can take one or severa
amplifier. Jt dgoesl tTho ae delay is by the computer through a
nts for a gven urne e ay. d the
po . II UNIDEX ll (Aerotech). The translation stage movements an
stage . er . . th ne or seveml points are recorded for
data acqustJon arc synchromzed, so at o . I . . t' o (S/N) sev-
. . d I ) 11 . rove the -to-nOJse m '
each stage posillon (tunc cay .d d With this PM system, normalized
eml time scans can be run an average .
changes as small as 5x I o-o can be measured.
7. 2 E.l:perimental Teclmiques
7.2.4 Non-Linear Optical Spt.'Ctroscopy
We employed two non-linear spectroscopies to probe even parity A
states in lu-
minescent conjugated polymers, Z-scan for two photon absorption (TPA), and
electroabsorption (EA). Various experiments that probe the two-photon-allowed A
states have shown that, for luminescent conjugated polymers, a single, strong
two-photon-allowed transition is observed above the 18,. state. By measuring the
TPA spectra over a wide spectml mnge, it is possible to clarify and enhance the
understanding of the physical mechanisms involved in the observed properties of
conjugated polymers. Employing the Z-scan technique to measure TPA spectr.l en-
ables accurate identification of actual absorption peaks, since it measures real as
well as imaginary i
This allows the of dispersion in the real pan of
'. which must accompany TPA bands. Furthermore. since the Z-scan can direct-
ly detect signs of the complex l l components, it avoids the misidentification
of one-photon satumtion as two-photon spectral 1151.
The index of refraction in a non-linear optil:al material can be written:
where E is the electric field of the incident photons. Self-focusing occurs as a
combination of a positive n2 and a spatial variation of the laser intensity in which
the beam is more intense at the center than at the edges. The result is that the re-
fmctive index of the non-linear medium in the center of the beam is larger than
that at the edges and the medium acts as a positive lens focusing the beam. Self-
defocusing occurs if u2 is negative. The experimental apparatus used to measure a
reduced-aperture Z-scan is shown in Figure 7-6 inset. A Gaussian beam is tightly
focused by a lens and passed through the non-linear medium, where z is the dis-
tance between the sample and the focal plane. Consider the case of a sample wi th
negative 112 As the sample is moved towards the locus, the im:rcased power den-
sity results in a negative lensing etTcct with a net result of collimating the beam
and consequently increasing the detector signal. As the sample moves to the +z
side of the focus, the negative lensing eflcct diverges the beam and reduces the
detector signal. For an open apenure Z-scan, the aperture is removed and two-
photon absorption will decrease the ligh transmitted through the sample. Exam-
ples of open and reduced-aperture Z-scans perfonncd on a cumulene containing
oonjugated polymer are shown in Figure 7-6 1161.
Open and reduccd-apenure Z-scans were conducted on polymer solutions to
eliminate anomalous etlccL-; associated with optical damage and surface inhomo-
geneities. cs2 was used a-; a reference material to dctennine the peak on-axis in-
tensities at each wavelength, since it has good optic;.JI quality. a large, fust. dispcr-
sionless n2, and has been previously wcll-dmracteri zed by absolute Z-scan mea-
surements. To obtain the high peak powers required for Z-scan experiments, a re-
generatively-pumped dye amplifier system wa-; employed. A Qu:.mtronix fre-
quency-doubled Nd : YAG lser provides excitation for a synchronously pumped
dye la.-;cr. A dye amplifier was built to amplify the 76 Mllz dye la..,er

c .98
"' c


7 Spectroscopy of Plrotoexcitatiuns in Ctmju8ated Plllymers

Z (mm)
Z (mm)
- 10
. d. . (b) Open a" ... '"rc Z-sc01n.
__ _. r\ , z.scan Inset z -sc01n schematiC aJ;rJJn. 1!'""-
F"igure 7-6. (a) Redu""" ape urc
. h" h peak powers at the desired wave-
pulses at a reduced mte_, _thereby were thus amplified up to 50000
lengths. The_ rcpelltlo25n mOtHe ie pulses at up to 300 GW/cm2 peak in-
times, resultmg m lO ps, z

tensity. . z . rocedure whcrl!in we pcrfonn a reduced-
We employed a comparatlvc ed by reduced and open-aperture Z-
aperture Z-scan Oil cs2 y ?. . elcngth The pcak on-axis inten-
h I mer solution at a part leU ar wav . . . . . '
scans t e po y . . h CS peak to valley transmiSSIOn change usmg
sity, _Jo. IS then axis of refmction. Based on the
previously measur va u . . . by ll7}
work of Sheik-Bahae et al., the equation tor /o IS given

W jcm2 (7.26)
- 5.6 x 10
7.2 Experimemal Techniques 201
where is the maximum transmission change observed in the reduced-aperture
scan and OD is the optical density of the neutral density filter. This equation
takes into consideration losses as a result of reflection from the glass cuvette.
Z-scan measurements were conducted over the spectral mnge of 576 to 846 nm
using various laser dyes in the three-stage dye amplifier system. TPA measure-
ments at 770 to 790 nm were obtained by employing a regeneratively amplified
titani um: sapphire laser system. A pulse repetition rate of I kHz and lock-in detec-
tion was employed to reduce noise. Z-scan data were saved and analyzed gtaphi-
cally to acquire the tmnsmission changes. The non-linear index of refraction, 11
was then directly calculated from the tmnsmission change [ 17). The non-linear ab-
sorption, a
, was calculated at the z=O position (the point of highest intensity) by
itemtively solving the e4uation
dl (r)
= - ttuf -
where I (r) is the Gaussian-distributed intensity and Clo is the linear absorption.
Electroabsorption (EA) spectroscopy, measured using an electric field to modu-
late the absorption, enhances the ji11e structure in a material's optical absorption
spectrum. An electric field perturbation applied to the material under investigation
creates small changes in the electron wave functions accompanied by small
changes in the electronic e nergy levels that can consequently be measured as
changes in the <tbsmvtion. In principle, EA spcct1-:1 be analyzed by compari -
son with Lhe lirst deri v<tli vc of the linear absorption since the lB., Stark-shift leads
to a derivative-like feature. Disorder in most polymer films, however, leads to a
distribution of polarizabi lities and energies of the I Bu exciton, so that a first deri-
vati ve analysis of the EA spectrum is not possible. Although the EA spectrum
can be modeled by a series expansion of the absorption spectrum
= 'cnd"(ad)/dE"). such a phenomenological approach often lead<; to un-
realistic interpretations. In this paper, we will show a model for calculating the
EA spectrum, which also accounts for the TPA and transient PA features.
The experimental setup for the EA measurements is shown in Figure 7-7. A
small sine-wave source was connected to a custom-built step-up transformer, the
output of which was connected to the electrodes. Electrodes for the application of
an electric field were deposited on a sapphire disk in an interlocking finger geom-
etry, as shown in Figure 7-7 inset. The gap between electrodes was 20 J.un, which
pem1itted a lield of the orde r 10
V/cm. The films then cast on these electrodes
were from polymer solutions. TI1e samples were contained inside a cryosl<1t for
measureme nt-; at low tcmpcmturcs. A mcchanically-dmppcd light source (typic<tl-
ly a xenon lamp) was focused on the ent rance slit of a computer-controlled mono-
chromator. The light was tihered to eliminate second-order scattering ctfects and
prevent detector suturation. The light was refocused on Lhe sample with a mi rror,
and detected by a UV-cnhanccd silicon photo<.liodc operated in the photovoltaic
mode. This configumtion mini mized any and heating of lhc
polymer films. TI1e photodiode clect1ical output was directed to a com-
puter-controlled lock-i n amplilicr. 202 7 Spectroscopy of Photoexcitations in Conjugated Polymers
l'igurc 7-7. Schcma1ic of the EA
spectrometer. Inset: Silmple geometry with
interlocked metall ic stnps.
For each EA spectrum, the transmission T was measured with the mechanical
chopper in place and the electric field off. Tite differential tmnsmission /H' was
subsequently measured without the chopper, with the electric field on, and with
the lock-in amplifier set to detect signals at twice the electric-field modulation fre-
quency. The 2/ dependency of the EA signal is due to the quadratic nature of EA
in materials with definite parity. I:J.T was then nonnalized to I:J.Tff, which was free
of the spectral response function. 1o a good approximation {1 8], the EA signal is
relmed to the imaginary part of the optical third-order suscepti bility:
4nw 2
- I:J.T j T = I:J.a.d =-1m (x(
l( -w; (.u, 0, 0)) x F d
where d is the film thickness and n is the refmctive index. The zero-frequency
components in Eq. (7 .27) are from the low modulation tield frequency electrodes,
which are negligible compared to the frequency of the optical field.
7.3 Poly(para-phenylene vinylene)
7 .3.1 Absorption and Photoluminescence
The absorption spec1rum of poly(2-methoxy-5-(2'-ethyl-hexyloxy)-para-phenylene
vinylene) (MEH-PPV) is shown in Figure 7-8a. Phenylcne-based conducting poly-
mers such as MEI I-PPV exhibit multiple absorpt ion features extending well into
a. 0.5
:J 0.4

Po/y(para-phenylene viny/ene)
Energy (eV)
( b)
1.8 2
Energy (eV)
Figure 7-8. (a) Abso t ' d
unit. rp IOn an (b) photolunuuc.'il:cocc spectrum of 000-PPV l . .
nsct. polylfk:r rcpc:ll
the ultraviolet. The absorption spect.rum . . . .
band !hat peaks at 2 4 eV (I) t . dd' IS composed of four bands: a low-eneroy
4 7
wo tltonal weak b d . h o
. cV (II and Ill) and a broa-' b d an s wu peaks at 3.7 and
o u an centered l 5 9 V (
works by mult iple groups 119
. a e peak IV). Recent
entire absorption spectrum or' PPV

the of lilting the

tmnsition and is most probably tite IS the mam dclocali zcd n-n*
tmnsition followed by seve I h ol an_ mhomogcneously broadened
bands are no! well resolved due th ra onon The phonon side-
distri bulion in this fi lm. In _u n:lattvcly broad conjugation
vbrallonal satellites were well rcsotv I : . ( dtson.lcrcd MEH-PPV lilms,
. C( Ill a w) II. The origin of hatul I I
204 7 Spectroscopy of Plwtoexcitativns iJ1 Conjugated Polymers
been a matter of controversy, assigned either to charge conjugation symmetry
breaking caused by the substitution, or to the existence of short PPY chains in the
film [20, 22]. No such controversy exists for the remaining bands. Bands HI and
IV are due to transitions between localized and dclocalized states.
1be PL spectrum and onset of the absorption spectrum of poly(2,5-dioctyloxy-
para-phenylene vinylene) (000-PPY) are shown in Figure 7-8b. The PL spec-
trum exhibits several phonon replica at - 1.8. I. 98. and 2. 15 e Y. The PL spec-
trum is not corrected for the system spectral response or selt:.absorption. These
corrections would affect the relative intensities of the peaks, but not their posi-
tions. The hi ghest energy peak is taken as the zero-phonon (0-0) transition and
the two lower peaks correspond to one- and two-phonon transitions (1-0 and 2-0,
respectively). 1be 2-0 tmnsition is significantly broader than the 0-0 tr.msition.
This could be explained by the existence of several unresolved phonon modes
which couple to dcctronic transitions. In this section we concentmte on films and
di lute solutions of 000-PPV, though si milar measurement!'. have been carried out
on MEH-PPV 123}. Fresh 000-PPV thin lilms were cast from chloroform solu-
tions of -5% molar concentration onto quartz substrate:.; the fi lms were kept un-
der constant vacuum.
7 .3.2 Transient Photomodulation
The tr.msient PM spectr..a of 000-PPV films at 300 K, measured from 0.75 to
2.2 eV, are shown in Figure 7-9 for time delays t =O ps and 1.2 ns. The PM spec-
trum at t=O ps can be divided into two spectral regions. Above liw= 1.7 eV we mea-
sured llT>O. 1be close resemblance of the llT>O band to the CW PL spectrum leads
us to assign this band to stimulated emission (SE) [24, 25]. The contribution of the
steady state PL to the delay time-dependent SE signal was small (<5%) and could be
easily subtracted since it did not depend on the tmnslation stage position. Below
nw= 1.7 eY we observed two PA bands peaking at 0.9 eV (PA
) 1101 and 1.5 eV
(PAz). The decay dynamics of theSE, PA., and PA
bands arc compared to those
of the PL band in the inset of Figure 7-9. Except for PA
, all show a single exponen-
tial decay dynamics with lifetime r..,.:::::240 ps. which is equivalent to the decay of the
photogencr..atcd excitons <.lcnsity. PA
initially follows the 1-.ame exponential decay
dynamics up to -300 ps, then it <.leviates and becomes much slower dominati ng
the PM spectrum at longer times. As seen in Figure 7-9, the PM spectrum at
t = 1.2 ns contains only a single asymmetric PA band, which is slightly blue-shifted
from PA2o whi le PAt an<.l SE are barely detectable at 1.2 ns.
We observed similar PM spectra in 000-PPV dilute solutions, shown in Fig-
ure 7-10. PAt. PAz and SE can be again identifie<.l at the same probe photon ener-
gies as those in films. r., in solutions, however, longer ( - 440 ps, see Fig. 7- 10 in-
set), and PA
deviates from a single exponential dynamics at times longer than
I ns. The primary excitations in 000-PPV dilute solutions must be singlet exci-
tons, since the polymer chains are isolated and hence, the possibility of exciton
dissociation into polaron pairs is greatly reduced. Then from the similarity of the

7.J Po/y(paru-pheny/ene vinylene)

0.8 1
1.2 1.4 1.6 1.8
Photon Energy( eV)
\0 ff
\ 2
. d Q)
2 2.2
Figure 7-9. PM of 000-PPV Iii . .
dcc<!y dynami.:s of I' A and SE. ' Ill at pump-probe delay limes of 0 and I ns. Inset:
' ' I
2 2.2
1.2 1.4 1.6 1.8
Photon Energy(eV)
rrgurc 7-10. PM S(X:Cirum of 000-PPV . I .
Inset: decay dynamil-li of J>A barTds and Sii. so utron at pump.pmbe dchly times of 0 and I us.
206 7 Spectroscopy of Pho10excitalio11s in Conjugated Polymers
PM spectra and their decays in 000-PPV films and dilute solutions, we conclude
that the primary excitations in 000-PPV films are also singlet excitons [26]. The
long excitonic lifetime and a corresponding high PL quantum efficiency [27] indi-
cates that 000-PPV is a high quality polymer material, which is very suitable for
electrooptics and laser action applications [28].
The two transient PA bands discovered by ps PM can be directly associated
with singlet excitons via a measurement utilizing three pulsed laser beams, as
shown in Figure 7-11 inset. In essence, the singlet excitons are used as an optical
switch. The switch is turned on by photogeneration of singlet excitons by a pump
beam at t=O ps and turned off by stimulated emission induced by a dump beam
at t=t
The dump beam fluence was in the order of 10
llle pump beam
is tuned within the absorption spectrum and the dump beam is tuned where there
is stimulated emission, but no absorption or PA. The effects of this switching are
measured by a probe beam at 1=1
, which is tuned within PAa (0.8 eV) or PA
(1.5 eV) spectral r.mges. Any changes in the PA dynamics due to SE require that
the PA band is related to singlet excitons.
figure 7-lla compares the respective transient decays of PA
with and without
the dump pulse at 1
= 150 ps; the difference in the PA decays is also shown. It is
seen that the PA magnitude is reduced (or switched off) at t
by about 20%. llle
magnitude of PA reduction is linear with the dump beam intensity up to a 30% re-
duction in llT. This switching eflect is caused by the decrease in the singlet exci-
ton population, 6N, due to SE induced by the dump pulse at 1
The reduced PA
at t>t
continues to follow the same exponential decay as for t<t
, since the re-
combination process is monomolecular in origin with no correlation among the
photogenerated excitons and thus N(t) is not affected by 6N at Ia. As seen in fig-
ure 7- ll a this also leads to an exponential dynamics for c5T(t). We also tried vary-
ing the delay time Ia between the pump and dump beams [29] and found that
c5T(t) decays follow the same exponential fom1 with lifetime Ts, independent of t

This simple decay form can be readily explained by a SE process at t-ta. Since
) is proportional to N(l
), where 6N(1
) is the number density of dumped ex-
citons, the decay dynamics of c5T will follow those of llT.
In Figure 7-11 b we also demonstr.tte the excitonic switch for PA
. In this case
we kept the pump at 2.3 eV, the dump at 2.0 eV, and tuned the probe to 1.5 eV.
Again we show PA
decays with and without the dump pulse at Ia = 200 ps. It is
seen that c5T is formed at t=t
, providing di rect evidence that both PAa and PA
are due to singlet excitons. In contmst to the switch at PA
, 6T decay in the PA
spectml range depends on t
At ta =0 ps 6T(t) decays exactly as llT(t). However,
lo r 1
>0, ()T(t) deviates from llT(I) and the deviation increases with the switch-off
time, Ia. as seen in Figure 7- ll b for oT at ta = O and 200 ps. The rea.-;on for this
more complex behavior of PA
is the mixed contributions to PA
at t>O ps
from both singlet excitons and longer-lived species. We shall now show that the
long-lived species arc triplet excitons, to rmed by intersystem crossing of excitons
from the singlet to triplet manifolds. ()Tis caused by singlet exciton alone, since
triplet excitons do not mdiate and therefore cannot be influenced by the dump
pulse via SE at 2.0 cV. Then. since the contribution of triplet excitons
with ta. the deviation of 5T( I) from !J.T(t) becomes more apparent at longer 1

7.3 Poly([>ara-phenylene vinylene)
to -
' ""
I s:: " -
uTff ...
I -w ....
I " :. .
.,,, ... .._. - .:,. .. -
1 ()-5 - """";:
0 400
800 1200

Figure 7-11 (a) D.:cay
. r ., .
ynamtcs o r'At wnh without the 1 J
. .
pump. dump, and prob.: pulses. (b) <lyn;unics r P. . l ump pu sc. nsct: tune profiles of the
for ' = 0 and ' = 200 ps. . o 'A2 wnh and Wtlhoua the dump pulse. Shown
of singlet consisting of two PA bands and an SE
urn, amed. esse.ntaal states diagram shown in Figure 7-12. The
P. eam tnduces transttaons from the ground state (lA ) t lh fi . II
c t te (IB ) c
o e rrst a owed ex-
a 11 r O owmg a relat ively samail relaxation ( - 0 1 V) ..
occurs hum the relaxed I B to the lA I . du . S . . c emassron
. . . 11 .c n ;a llaon to E. PA from IB 1 1 .,,
energy cvcls as anduccd lor the even-pari ty mA and kA . . . II o u.,. lCr
cent elegant theoretical calculations h;ave assign;d the nAo: We note .. that
tons and the kA . b. .
g o c arge tr.tnster exca-
th . to a aexcuon, a bound sto.atc of two cxcitons [30] Ho
err exact character cannot be inferred fr.,..,tn our PM . wever,
v measurements.
ill 0.6
7 Spectroscopy of Phowexcitatio11s ;, Co11jugated Polymers
F.gure 712. Configur.!lion coordinate diagram o(
the foor essential states s.howing the photophysical
processes. Also shown is the calculated PA spec-
trum based on level energies from EA spectroscopy.
7.3.3 Non-linear Spectroscopy (TPA and EA)
The existence of even parity states lying above the IBu have been identified by
two-photon absorption (TPA), two-photon tluoresccnce excitation [311. and clec-
troabsorption (EA) spectroscopy. We measured the TPA spectrum of 000-PPV
by Z-scan [32] showing both the rea] and imaginary components of X(3) Figure 7-
13 compares the linear absorption spectrum of 000-PPV to the spectra of the
real and imaginary molecular second hyperpolarizability. The imaginary compo-
nent, y", is proportional to the TPA coefficient a
, while the real component, y',
corresponds to the non-linear dispersion, 11
The y" spectrum shows a clear peak
at eV, 0.5 eV above the peak of the IB, absorption band, and a shoulder at
eV, which may cotTespond to a second TPA band. They' spectrum clearly
indicates dispersion near the two y" peaks, as expected from Kramers-Kronig
analysis, and permits us to identify two distinct TPA bands.
Figure 7-14 shows the EA spectrum of 000-PPV up to 5.0 eV, measured at 80
K with an ac electric field F= 1.4xl0
V/cm. The intensity of the EA signal
, showing the dominance of the quadratic field term in EA of conju-
gated polymers. The EA spectrum is composed of strong features in the spectral
range of band 1 in a(w}, followed by weak features in the region of bands 11 and
Ill. Since it is known that localized states have a weak contribution to the EA
spectra due to their low polarizability [33), the EA result indicates that localized
states are indeed involved in bands II and lll. This, however, cannot resolve the
controversy of the origin of band 11, since band II in the leading models is par-
tially due to localized states.
1nere are three main EA spectral features in the energy range of band 1: a deri-
vative-like feature with 7-Cro-crossing at 2.29 eY, followed by vibrational features,
and an inducctl absorption band between 2.9 and 3.2 cV. 111e features below
2.5 eY are the results of a redshifted IB, exciton energy, and its phonon side-
bands (Stark shift). These features are more easily observed in EA than in absorp-
.... -
.iii c:
c :J


<;J 4
X 3
- ;.- I
cf) 2

::J 0
-->- - 1
3 :13
Erergy (eV)
3 J.Z 3.4
7.3 Poly(p(lra-pflellylene vi11ylelle)
Jo' igun: 7-13. (a) Linear absol]>lion
of 000-PPV, (b) part
of )' In two-photon
aoo (c) real p;m of )'
(propoo1ooruol lo lhe nonlinc:or in-
dex of rcfrm:oion. 11!>
lion because of the dependence of the exciton polarizability on th . . .
length. These samples arc disordered and show '1 )I )0 . , e
galion lengths (211 s .. . b . . . I 'CI. ndcr.mcc ol shorlcr COIIJII-
f h h . sorpllon probes all conjugation lengths, the domi-
nance o t e s orter chams leads to a mostly featureless abs .
Elcctroabsorption, on the olhcr hand, is a x(3) prn.ess 'lttd.therc. o, . rphon
'"" ore pre crcnlt<sll y
210 7 Spearoscopy of PhutoexcitaJions in Conjugated Polymers

.... 0
1.5 2 2.5 3 3.5 4 4.5 5
Energy (eV)
Ji'igurc 7-14. Measured (bold line) and cakulaletl (lhin line) EA spcc1r.1 of [)()()..PPV.
probes the remaining longer conjugation lengths. This gives rise to the sharper
spectral features and also explains the emergence of the phonon side bands.
The induced absorption band at 3 eV does not have any corresponding spectral
feature in u(w), indicating. that it is most probably due to an even parity state.
Such a state would not show up in u(w) since the optical transition IA
-> ntA
dipole forbidden. We relate the induced absorption bands to tmnsfer of oscillator
strength from the allowed lAg ..... lB., (absorption band I) to the forbidden
-> mA
tmnsition, caused by the symmetry-breaking external electric field. A
similar, smaller band is seen in EA at 3.5 eV, which is attributed to the kA
The kA
state has a weaker polari:zability than the ntA
, related to a weaker cou-
pling to the lower l Bu state.
We successfully simulated the EA spectrum by calculating the imaginary part
of the third order optical non-linear susceptibility [35]. The sum over stales (SOS)
model developed b6 Orr and Ward [34 J was used to calculate the third-order opti-
cal susceptibility X

and simulate the transient PM and EA spec-

tra reported here [35]. This particular model is useful because its formulation is
not affected by singularities as are some other common fom1Uiations [36]. This
model includes the four essential states, shown in Figure 7- 12, namely the IA.o:
(the ground state), lB.., the mAg. and the kA
, four phonon replicas and a chain
length distribution function. Calculations were carried out using summation over
the stales shown in Figure 7-12, and their strongly coupled vibrations using ap-
propriate Frank-Condon overlap integrals (see above). The fitting parameters were
energies of the IBu, mA
, and kA
states, their dipole couplings and relative con-
figumtion coordinate displacements, &]; whereas the frequency of the strongest
coupled C;::C stretching mode (1600 cm-
) was directly detennined by Raman
7.3 Pu(\tJXJrttphellylene 11inylene)
, The EA shown as a dashed line in Figure 7- 14, is in good
agreement wtth the measured EA spectrum. Using the fitting pammeters of the
EA spectrum, we were also able to calculate the PA from the relaxed l B exc
to the utA and kA 1 1 . h "
PA .r( .o: usmg t e Huang-Rhys approximation. The calculated
. shown

Ftgure 7- 12, agrees very well with the experimental PA

_at 1-0 ps (see Ftg. 7-9 and 7-10) and thus validates our nodel The
Lion ot th . post-
- e even state ts also tn good agreement with the TPA ba 1d t
-3.5 eV shown m F1gure 7- 13.
7.3.4 CW Photomodulation
As noted above,_ the decay dynamics of PA
deviate from the respecti ve SE d
PAt Whtle the two latter features are due to singlet excitons PA co
contnbuttons from longer-lived species. We probed these spe cies by. 'cw2P'At . ams
Lroscopy. The 300 K PA . . spec-
lh . spectrum of a 000-PPV film ts shown in Figure 7-15
e pump beam was modulated at 700 HL. and the PA spectrum is dom t d b '
peak e the r.llio of the in-phase and quadrature si na:;,a :c
ma!e excttatton hl etune of about r:::::O. J ms. Above 2.0 eV th . . .
denvattve linesh h. h . e spectrum has a
. . . ape, w c resembles the EA spectrum shown in Fi ure 7- 14
ThtS StgnaJ IS due 10 a COmbination Of bleaching of the ground state
and EA due to photogener...tcd charged excitations. An additional PA band
surcd at 80 K _shown below, has a peak at :::::: 0.4 e v. The bands at 0 4 d
eV dtlfercnt modulation fre4uency dependency and are d
dtslmct excttauons. t; uc o
1.5 2
Probe Energy (eV)
Figure 7-15. In-phase :1110 tju:tdr.uun: I'A of 000-PPV.
7 Spet:lroscopy uf Plwluexcilllliuns i11 Cunjuguled Polymers
The spin signature related to the CW PA spectrum can be readily at
low temperatures by PADMR [37]. The PADMR n:easurements were earned out
at 10 K on a 000-PPY film utilizing S-band microwaves at 3 GHz. The H-
PADMR spectrum of a 000-PPY film, measured with the probe wav_elength set
to 800 nm, is shown in Figure 7- 16. The H-PADMR consisted
asymmetric band with a peak at 390 and symmetnc band _at
1065 Gauss. Both bands are negati ve wh1ch means that magnetiC Ieso-
nance increases the recombination rJte of excitations and thus reduces the as-
sociated with the.-re excitations. The low-field signal is due to flm. = 2 transitions
of triplet excitons, i.e., it is a half-field triplet powder pattern. We were unable to
detect the full-tield triplet powder pauem. It has, however, been measured at X-
0 .....

350 400 450 500
Magnetic Field (Gauss)
ro -4

1040 1060 1080 1100
Magnetic Field (Gauss)
l' il,!un: 7-16. (a) Half-fi clll and (b) H-PADMR spcclm uf DO().PPV.
7.3 Poly(para-phenylene vinylene) 2 13
band (9.35 GHz) and to be 1000 Gauss wide centered about [3H].
1be band at I 065 Gauss IS due to spin- 112 excitations, i.e., polarons.
F1gurc 7-17 compares the ).-PADMR spectra at 390 and 1065 Gauss to the PA
spectrum measured at HO K. The triplet A.-PADMR spectrum tits very well both
the PAz band measured by tmnsiem PM spectroscopy (see Figs. 7.9 and 7. 10> and
the CW PA spectrum (sec f-ig. 7- 15). We therefore condudc U1at the slower PA.,
arc due to inten;ystem crossing (ISC) from singlet to triplet
havmg a much longer lifetime than singlet cxcitons. The lSC rate in n-conj ugated
polymen; has been generally assumed to be low. However, it can be enhanced in
fi lms due the presence of paramagnetic (spin I) 0
molecules (39j.
Assummg that PA2 1s composed of contributions from both singlet and triplet ex-
citons, we calculate for flT(t) atluv= 1.45 eV:
where a and constants. In Eq. (7.32), a is given by a,-r./asr
sc. where as and
a, are optical cross-sections of PA at 1.45 eV for singlet and triplet excitons,
and L-.c is the intersystem cros!>ing time. From the PA
(see Ftgurc 7-12.b) we found a==0.06. Then from <_..=240 ps we calculate
sc-4 ns, _assummg as and nl" are comparable at 1.45 cY. The same analysis for
PA2 decay m DOO-PPV solutions gives

20 ns. The slower ISC mte in solu-

tions is consistent with the lower dissolved 0
Analysis of the spin- 1/2 A-PADMR spcctnnn is more complicated as it contains
two .rcat_ures with. increased and decreased transmission. As the photoexcitation
density IS propOI1IOnal to - fiT, we describe these as PA-qucnching (!5n<0) and
_(ou >0) bands. We defer detailed discussion of the spcctnnn to the
tollowmg section, where we compare the dopi ng, PA, and PADMR studies of u.-
sexithiophene (cL-61) and polyU1iophcne. Magnetic resonance is found to enhance
/ x4
0.8 1.2 1.6
Probe Energy (eV)
.... ,.,.,.
2. 0
.l'igure 7-t7. Spin- 112 (MJiilllinc) lripk:l (d;o,.hc"\.1 hnc) ..1-PADMR "fll.."\:lr:l nf DOO-I'I'V.
214 7 Spectroscopy of Photoe.xcitations in Conjugated Polymers
the recombination rate of spin-1/2 polarons. As like-charged polarons can com-
bine to form bipolarons, magnetic resonance can increase bipolaron populations
and yield a PA-enhancing signal. Our results thus indicate that polarons in 000-
PPV have two absorption bands, P
at 0.4 eV and P
at 1.4 eV, and bipolarons
have one absorption band, BP
at 1.1 eV. Comparison of the spin-1 /2 ).-PAOMR
spectrum to the 80 K PA spectrum leads us to assign the low energy PA band to
photogenerated polarons. The existence of charged photoexcitations explains the
photoinduced EA signal above 2.2 eV.
In summary, we found that photogenerated singlet excitons in 000-PPV films
arJd dilute solutions have a strong SE in the visible, and two associated PA bands
in the NIR spectral ranges. These bands can be used to fom1 an ultrafast excitonic
switch with variable switching times, providing direct evidence of the primary ex-
citations in 000-PPV. In addition, we detem1ined the ISC time into the triplet
manifold to be of the order of 5 ns and solved the puzzle regarding PA2 at 1.5 eV;
we found that both singlet and triplet excitons strongly contribute to PA at 1.5 eV.
7.4 Polythiophcnc
7.4.1 Linear and Non-Linear Absorption
Figure 7-18a displays the linear absorption of a P3BT film and the polymer re-
peat unit. The absorption spectrum is broadened by a combined effect of phonon
side bands and inhomogeneous broadening caused by the conjugation length di s-
tribution and impurities in the films (40, 41 ]. The onset of linear absorption char-
acterizes the energy of the lowest lying exciton, which corresponds to the pump
photon energy of 2.2 eV used in the ps measurements. The TPA spectrum is
shown coincidentally with the absorption spectrum and has a clear peak at 3.2 eV,
about 0.5 eV above the 18" peak (32]. There is a shoulder about 0.3 eV above the
first TPA band, though the dispersion data in this case is not as clear as for 000-
The EA spectrum in Figure 7- 18b shows that the Stark shift or the lowest lying
exciton produces a characteristic derivative-like feature (uajDw) around 2.5 eV
[40]. 1his energy corresponds to the vertical 0-1 transition in the conligur.1tion co-
ordinate diagr.un (see Fig. 7- 12). The lowest exciton energy level is Stokes-shifted
with respect to the absorption maximum and is located at approximately 2.2 eV.
However, there is considerable residual absorption below 2.2 eV extending into
the near IR region. 1his is extrinsic to the polymer film and may be associated
with the presence of defects and impurities. As with 000-PPV, even parity states
couple to the ground state via the intermediate level of 18" exciton. They are not
observed in the linear absorption spectrum, but can be detected by TPA and EA
spectroscopies (291. As discussed above, the electric ticld mixes states of different
parities, which can allow one-photon transitions between I A
(ground stme) and
7.4 Polythiopheue 215
2 2.5
3 3.5 4 4.5
Energy (eV)
t.5 2 2.5
3 3.5
Energy (eV)
Fib)guEnA 7-11!. (a) One- an<l two-photon an<! absorption of PJBT
spt!Clrum uf PJBT
(401. Indeed, the EA in Figure 7-18b shows two posi-
tiVe b.mus at -3.3 eV and -4.2 eV, wh1ch have been associated with the mA
and kA
states L40J. 11
7.4.2 Transient Photomodulation
Figure 7- 19 the ps transient PM spcctm for time 1=0 and t= 1 ns
where - 11T/T IS ploued versus the pruhe photon energy. The PM spectrum .. ;
.1 0
7 Spectroscopy of Phoroexcitations in Conjugated Polymers


0.8 1.2 1.4 1.6 1.8 2 2.2
Photon Energy(eV)
Figure 7-19. Transient PM spectra of P3BT films at (a) ps and (b) 1 ns.
t=O ps (see Fig. 7.19a) consists of increased transmission (f.T>_O) above 1.7 eV
and PA (f.T <0) below J .7 eV. The PA consists of two bands, whtch label PA,
and PA
The similarities between Figure 7-12 and 7-22 lead us to asstgn the PA
to tmnsitions from the I 8" state to the mAK and k.AK states. The f.T>O spectrum
is quite similar to the CW PL spectrum (see Fig. 7-19 inset) and we therefore
sign this signal to SE from IBu to JAK induced by the probe beam. The SE_ ts
shorter-lived than the PA as is seen in Figure 7-19b. At t= I ns there rcmams
only a bmad, long-lived PA band (PA
) with a shoulder extending into
hw> 1.7 cV region; no SE is observed and we also note that PA
has almost dts-
appeared from the PM spectrum. These results bear a striking to
those shown above on DOO-PPV, although the shape of the longcr-hvcd PA spec-
trum is quite diflerent. We return to this result in the following section. _
Because of the similarity between the ps spectra of DOO-PPV and P3BT hlms,
it is reasonable to assume that the PM at r=O ps in the latter films is also mostly
due to the photogencrated intrachain excitons. In order to confirm this assump-
7.4 Polyilziophene
tion, we have compared the photoresponse dynamics of the SE, PL. and the two
PA bands in P3BT. The region of long-lived PA overlaps with the short-lived SE
region and this makes it difficult to measure the co&:recl SE decay. Nevertheless,
the PA contribution to the SE signal is minimized when the SE decay dynamics is
measured at probe energies near 2.2 eV. Figure 7-20a compares the SE decay at
580 nm (2. 14 eV) and the PL dynamics in P3BT; it is seen that the two transients
follow each other. As can be seen from Figure 7-20b, there is also a correspon-
dence between the SE and PA1 decays, showing that PA
is also due to the emis-
intntchain Since both SE and PA
decays are due in part to non-ra-
dmttve recombinatton (or exciton dissociation), which may differently affect the
SE and PA
optical tnmsitions, some discrepancy is observed in their respective
decay time const<mts (see Fig. 7-20b).
0 100
- - Pl{700nm)

}/ 1\vv
200 300 400 500 600
"-. PAt= 94 cxp( 11162ps) + 2J cKp ( -lilns)
...._ .._.. PA
FiJ!urc 7-20. Comparison bcawccn lr.msicnt decays of (il) Pl. and SE and (b) PA
and SE in lihns of
7 Spet.:truscopy uf Plwtoexc:iWtion.v in Coujugated Polymers
We note that for all transients (SE, PL, and PA
) the photoresponse decay is
non-exponential, which is an indication of a broad distribution of typi-
cal of slrongly disordered materials [9]. However, the PA2 decay dynam1cs
in figure 7-2l a is markedly different those of _SE . PL, or PAa .. fast m-
tial decay of PA
can still be associated wuh the excllomc decay: wh1ch demon-
strated by fitting both PA
and PA
decays with biexponenllal (see
fig. 7-19 and 7-20). In both cases there is a fast decay component w1th about a
150 ps time constant which conesponds well to the SE The much
lived PA component (PA
) must therefore be due to other than regular
singlet excitons. Figure 7-21 b illustrates this fact, showang the at
the isosbestic point (J..=770 nm, see Fig. 7-19), theSE 1s ex-
actly compensated by the excitonic PA
. The rcmaanmg response. charactenzes th_e
secondary photoexcited species associated with PA
. These spec1es are non-lum1-
500 1000 1500 2000
500 1000 1500 2000
Jolgure 7-21. Photorcspon.'IC a1 (a) 1.5 eV (PAz? and (b) lhe is_o:,bcstic poinl in t>3BT lilms
ahc crossover from s&imululoo .:mbsion 10 phutomduccll .Wwrpuun.
7.4 Polytliiopliene 219
nescem and have very little observable PA companion in the IR region (the PA
region). We also note that PA
is photogenemted within the time resolution of our
apparatus ( -5 ps) [25, 42). We show below that both polarons and triplet exci-
tons have PA in this spectral region, giving two possible origins of the long-lived
SE is present only in sufficiently thick films of P3BT. If the sample is too thin,
i.e., its OD at 625 nm is less than 0.6, then SE is not observed and only PA is
present in_ this case. Figure 7-22 illustrates this situation, depicting two normal-
Ized tmns1ent PM decays measured at exactly the same experimental conditions,
except for the samples thickness. Gain can be observed in the thicker film (sec
Fig. 7-22a), but no gain is present in the thinner film (see Fig. 7-22b).
Oased on this experiment, we come to the conclusion that the photoexcited
states in the bulk of the sample and those dose to its surface are different The
pr-obe beam may ei ther reexcite photocxcitations. detecting PA, or induce transi-
tions back to the ground state, resulting in photon emission or SE. For surface
states in P3BT lilms, the probability of the first process (PA) could be greater
than that for the second (SE). Such states may not contribute to PL either, which
has been conlinned by a lower PL quantum yield of thinner !ilms [43]. These sur-
face photoexcitations may be associated with defects created as a result of poly-
mer oxidation. Their concentrmion in the is higher than ahat in the bulk
of the film. The PA from these excitations can inacrfcrc with the otherwise observ-
able SE and cancel it out. Even when a P30T film exhibits absolute gain at
t=O ps, the photoresponse consists of the excitonic SE combined with the PA
which can be due to the same excitons, or a Y other excitations present at
same time (see Fig. 7-22). This observation is similar to the previous reports
of PPV-based polymer fi lms [25. 42), where intrachain excitons have been fom1ed
with low quantum yield, probably due to poor films quality.
0 .,

I \
--PA(Ihinner film)
- - SE+PA(1h1cker film)
I- 40
0.5 0 0.5 15 2
igun: 7-22. Oplical gain in PJBT lilms: nonnulizcd 011 Ul .:V in a &bin film (l>Oiid
line) and a lluc.:k rilm (brukcn line).
220 7 Spectroscopy of Pltotocxcitatiuns in Cuujugated Polymers
7 .4.3 CW PhotomoduJation
There has been much controversy regarding the nature of excitations in
conjugated polymers. This controversy bears on the of elec-
tron correlation effects. Adding a charge to a cham causes a
neous distortion of the chain. Thus, the proper descnpuon of the excita-
tions in polymers with non-degenerate ground states arc polarons w1th .spm S= 1/2
and bipolarons with spin S=O. Figure. 7.-23 sho":'s an energy level
conjugated molecule in its neutral, ox1d1zed (cali on), and .
lion) states. Upon removal of charge from cham by .chem1cal
or photoexcitation, a structural relaxation the h1ghest
bital (HOMO) and the now singly-occup1ed (SOMO) mtrudcs the gap.
For luminescent oligomers, the parity of the molecular orb1tals
even and odd. Thus. a positive will .hav_e two
and p as the third possible trJns1t1on (P
) 1s d1pole forbidden. a
live wi ll have two similar transitions, though P1 may be slightly_
due to differences between positive and negative charges (charge conJugatiOn
synunetry violation). Upon removal of a second charge the same
is a further structural relaxation, resulting in the energy dmgrum on the nght s1de
of Figure 7-23 for a positive bipolaron. . . _ .
The point at issue is whether or not the molecular p1cture w1th
acting n-electrons is applicable to conjugated po!ymers. The alternaove
tion is one with weak Coulomb intemctions. In th1s case, the molecular orbtta_l de-
scription is inappropriate and none of the above are_
forbidden. we explore this issue by companng the spccm1 _of_ excitations
of polythiophene and a-conj ugated sexithiophene (a-6T). Slmllanlles the
PA of polarons in a-6T and polythiophcne lead to adopt the p1cture
for charged excitations and, hence, the electromc of conJugru_ed poly-
mers. We show below that PADMR spectroscopy d1stmgU1sh the absorption spec-
tra of polarons and bipolarons.
The absorption and photoluminescence (PL) _spectra a-6T at 80 K
are shown in Figure 7-24. There is an onset of absorptJOn at. 2.1 eV,
sharp peaks and a maximum a.t eV. A band .'s seen at
4.5 eV and is due to direct exc1tallon of the nng . We take the first
peak as the 0-0 transition and calculate an opt1cal gap Eg=2.4 eV. The PL spec-
. l

l'igurc 7-23. Schematic tliagmm of en-
ergy and optical mmsicnts of
II sp2+
ncutr.tl molecule, polaron W'") and bi
7.4 Polytltioplrene 221
1.0 1.0
$' 0.8 0.8
0.6 0.6


ll. 0.2 0.2
0.0 0.0
1 1.5 2 2.5 3 3.5 4 4.5 5
Energy (eV)
Figure 7-24. PL anti abM>rption
of u-6T film.
llllm has a well-defined vibronic structure and is a mi1ror image of the abso1-ption
spectrum close to the absorpti on onset.
The doping-induced absorption (DIA) spectrum of a-6T doped by FeCI] in
solution is shown at light and heavy dopant concentrations in Figure
7-25. for light doping. the spcct1ll m consists of two absorption bands (P
and P
which arc the signature of polarons. At higher doping concentrations. another
band (BP
) appears at the midgap and the two polaron bands diminish. ESR stud-
ies have reported a sharp increase in spi n density for light doping followed by a
decline at higher <.loping. These results indicate the formation of spin- 1/2, singly-
chmged polarons at low doping. TI1is is followed by a second oxidation step.
which results in the formation or spinlcss. bipolarons al high dop-
ing. We note the formation or an absorption band at 2.4 eV in the most heavily
doped sample. This can he explained by Lmnsitions from the HOMO to the
LUM0+2 or the HOM0-2 to LUMO (441.
The in-phase and quadrature PA spectra of a-6T measured at 80 K with a mod-
ulation frequency of 200 Hz arc shown in Figure 7-26 l44J. TI1c spectrum exhi-
bits three bands at 0.80, 1. 1, and 1.54 eV, respecti vely; each of which is accompa-
nied by a high-energy phonon replica. TI1e bleaching of Lhe in-phase PA above
1.7 eV is due to thermal modulation of the PL due to heating of the sample by
the probe. The rcl;tti ve positions of the PA bands com:spond to the DIA bands
shown in Figure 7-25. The red-shift of the PA bands relative to the DIA bands is
due to differences between solution and fi lm properties. Hence, the bands at 0.80
and 1.54 eV are tentatively assigned to polarons and labeled P
and P
; the band
at 1.10 eV is assigned to bipolarons and labeled 13P
. As can be seen in Figure
7-31, BP
almost completely disappears in the quadrature specll-um, proving that
trapped bipolarons are shorter lived than tmpped polarons .
Figure 7-27 shows the frequency dependency of the in-phase PA bands in a-
6T, measured at the maxima of the various PA bands. As expected, the two polar-
on bands are correlated with one another, having vi rtually the same dynamics. In
contrJSt, the bipolaron PA hand al 1.1 eV is Vil1Ually nat from 10 to 1000Hz, in-
dicating that trapped pol. 1s arc longer li ved than tr..tppcd bipolarons in u-6T
The excitation lifetime), moJcled by comparing the data in Figure 7-27 to
- "iii
: 0.6
iii 0.4
0 0.2
7 Spet.:lroscopy of PlwtoexciltJtions in Conjugated Polymers
0.4 0.8
( 1 BP
! 0
! I
I i
! '
l \
I \
I '
! \
; \
i \
1.2 1.6
hv (eV)
2.0 2.4
Figure 7-25. Doping induced absorption uf u-6T at low (solid lin.:) and bigh (dolled line) doping con-
0 2
1.2 1.6 2.0
hv (eV)
Figure 7-26. In-phase and quadr.uure PA spectra of u-6T film.
the prediction of Eq. (7.7). In order to model the frequency dependence of the P
band, lifeti mes of between 20 !lS and I ms were required. In there is re-
latively little variation in bipolaron lifetimes. The fit to the BP
band required
only lifetimes of 10 and 50 llS. Polarons and bipolarons have been shown to be
tmppcd by defects [45]. Hence, these results suggest an extremely broad distribu-
tion of polaron trap energies and a relatively narrow distribution of bipolaron trap
energies. We should note that tl1e intensity of the BP, slightly decre;:tses as vc is
varied from 10 to 1000 Hz. This may indicate that a smart fulClion (Jf bipob:roos
are relatively long-lived to I ms) or due to a slight of a vjbro-
nic sideband of Pt to the PA at 1.1 eV.

7.4 Po/ytlriopltene 223

........... .........
hr 1()3 104 10S
Modulation Frequency (Hz)
d.:pcndcn..:c uf lhc PA of u-6T li lm, <II the p.:al..s uf the

300 400 500 1000 1150
Field (Gauss)

7-21t (u)
11-I'ADMR and !b) )..
0.4 0.8 1.2 1.6 2.0 2 .4
I'AOMH spectra of 11 -6T film. The
Probe Energy (eV)
Hf pularuns, und lriplct cxd-
tuns arc labeled.
224 7 Spectroscopy of Photoexcituticms in Conj11guted Polymers
The H-PADMR spectrum, shown in Figure 7-28a, includes both a narrow reso-
nance at g:::::2 due to spin- 1/2 polarons and a half-field powder pattern due to
spin-1 triplet excitons. The .A.-PADMR of t riplet excitons, shown in Figure 7-28b,
consists of a single, broad band centered at 1.5 eV with a peaks at 1.4 and
1.55 eV. As observed for 000-PPV, the spin- 1/2 .A.-PADMR contains both nega-
tive (On<O) and positi ve (On>O) bands. The energy of the two negative PADMR
bands coincides with the two polaron PA bands P
and P
This is consistent with
the concept that these two bands are due to spin-1/2 polarons and further indi-
cates that magnetic resonance reduces the steady-state population of polarons. The
presence of a broad, PA-cnhancing PADMR between 1.0 and 1.45 eV suggests
that magnetic resonance results in higher populations of bipolarons. In order to
explain this result, we consider bipolaron generation and recombination processes:
Generation : p J: + pi - np2
Recombination : np2.t. + pT- -+ p.l. (7.3 1)
where So is the ground state. As bipolarons arc spinless, they can be formed only
from like-charged polarons with antipamllel spins. Hence, this is a spin-dependent
process which may be enhanced by magnetic resonance. While the recombination
process in Eq. (7.30) is not spin-dependent, magnetic resonance reduces polaron
populations, which may in tum reduce the recombination r.ue of bipolarons. We
conclude that microwave absorption, due to magnetic resonance, leads to in-
creased steady-state bipolaron populations by either increasing their generation
rate or reducing their recombination mte.
With the above results from a -6T in mind, we consider the CW PA and u-
PADMR spectra of P313T. The PA spectrum of P3BT at 80 K, measured with a
modulation frequency of 20 Hz, is shown in Figure 7-29a. Both of these spectra
have peaks at 0.55 and ::::: 1.5 eV, though the relative peak intensities arc not the
same in the in-phase and quadmture spectra. The in-phase and PA sig-
nals are equal at 1.5 eV, whereas the in-phase signal at 0.55 eV is much weaker
N 0.6 L1TouT). Thus, even though the li neshapes appear to be the same,
one of the peaks must contain contributions from two different excitations. The
apparent discrepancy was resolved by measuring the in-phase PA spectrum wi th a
modulation frequency of 20 kHz, as shown in Figure 7-29b. The spcctllJm is
dominated by a PA band at 1.56 cV. We thus conclude that there are two di stinct
types of long-li ved photoexcitations; the first has a single PA band at 1.56 cV and
the other has PA bands at 0.55 and 1.5 cV. Comparison of the in-phase and quad-
mture signals at 0.55 cV results in a rough lifetime of r::::: 13 ns. As for the Iauer,
both excitations contribute to the PA at 1.5 eV, and from this we can deduce that
the first excita tion must be much shorter-lived than the second excitation.
A deeper insight into the nature of the CW PA is provided by PADMR spectros-
copy. The .A.-PADMR OJcasurcmcnts were perfonned at 10 K with the magnetic


0 .4 0.8 1.2 1.6
Probe Energy (eV)
0.4 0.6 0.8 I 1.2 1.4 1.6
0.4 0.6 0.8 1.2 1.4 1.6
Probe Energy (eV)
20 Hz
1.8 2
1.8 2
7.4 Polythiophene 225
.. igurc 7-29. PA spcclra or P3BT tilm,
mc.Jsurcd with a modulaJion fn.-quen<:y
of (a) 20 Hz and (b) 20 kHz.
7-30. A-PADMR SJ><.'dra or
P]BT liims, a1 lhc rcSlmanl
fields fur spin-II:! species (solid line)
und lriJ!lcl cxcilons (dashed line).
fie_ld set ,to th:, of the powder or the peak of the spin- 1/2
resonance (st:c Ftg. 7-30). The tnpleti,-PADMR spectrum contains a single ne"ative
at 1.5 eV we therefore conclude that triplet excitons arc the
The spm-112 J.-PADMR contains both negative and posi tive bands, as ob-
served for both 000-PPV and c.t-6T. Based on the PA and J.-PADMR spectra of
226 7 Spectroscopy of PlzotoeJ:citatiolls i11 Co11jugatcd Polymers
a-6T, we attribute the two negative bands (On<O) to polarons and the positive band
(On>O) to bipolarons. We thus conclude that dipole selection hold for both conju-
gated oligomers and polymers. This result is of fundamental importance to conju-
gated polymer photophysics. These are molecular materials, where the charged
photoexcitations reside in molecular orbitals rather than free cruTiers in bands.
Photon absorption in P3BT films primarily leads to the fonnation of intrachai n
singlet excitons, which can be identified by their characteristic tr.lOsient PM spec-
trum consisting of a SE band and two PA bands. These excitons are short-lived
(150 ps) due to both radiative and non-radiative decay channels. The latter in-
cludes the fonnation of triplet excitons and dissociation into polaron pairs. We
have also detennined that P3BT films are very susceptible to photooxidation; the
defects created on the film surface during the film deposition actually prevent SE.
Thus, the photophysics of fi lm surfaces differs significantly from that of the bulk
P3BT films. Multiple CW spectroscopies have been applied to study long-lived
photoexcitations in u-6T and P3BT. We have detennined that polarons have two
subgap PA bands and bipolarons have one. These result-; indicate thm dipole se-
lection rules hold for charged photoexcitations and that these charged photoexcita-
tions reside in molecular orbitals.
7.5 Fullerene-Doped DOO-PPV
Photoinduced metastable charge transfer from a n-conjugated polymer onto C60
has stirred widespread interest due to implications for the photochemistry of var-
ious organic and biological systems [46-48). Persistent photoconductivity in ful-
lerene-doperl polymers has drawn particular attention due to possible applications
as low-cost photovoltaic devices L49, 50]. Fullerene/polymer blends have been
studied by CW PL and PA spectroscopy [5 1, 52], photoconductivity [53], and
light-induced ESR (LESR). Doping both quenches the PL and decreases the emis-
sive lifetime, depending on the dopant concentr.uion. This behavior is consistent
with ultrafast charge Lr.tnsfer tO C60 and attributed to non-mdiative quenching of
singlet 1
B., excitons by positive polarons injected onto the polymer chain. It is
similar to the effects of photoinduced oxidation, which also quenches the PL. In
the case of carbonyl (C=O) formation by photoinduced oxidation of PPVs, the
lifetime of the remnant emission is also sharply reduced [54).
7.5.1 Transient Photomodulation
Both the spectrum and dynamics of the transient PM change m<lrkedly upon Coo
doping. The doping concentration is given in mol%, where I mol% doping is
CtJUal to one c60 molecule per hundred polymer repeat units. The PM spectrum of
pristine 000-PPV film, measured at t=O, 100, and 1200 ns, arc shown in Fig-
,......_ -10

(a) pristine
0 4
1.2 1.4 1.6 1.8 2.0
Photon Energy (eV)
7.5 Fullereuc-Doped DOO-PPV
Figure 7-31. Transienl PM spcclm of
(a) pristine 000-PPV anc.l (b)
10 mol% Coo: 000-PPV. measured
2.2 wiah c.lclay limes of 0 ps (circles).
:!00 ps (SI.juarcs). anc.l 1.2 ns (dia-
ure a. The SE spectrum (!J.T/T>O) is the same as the PL spectrum, which is
by phonon Fig. 7- 11 b), whereas the photoinduced absorp-
tion (PA; !J..T/1 <0) comams a sangle PA band peaking at 1.5 eV. This band was
shown above to be due to photoexcitcd singlet excitons [25]. The PA not
change up to 1.2 ns, when the SE signal has diminished, showing that there is no
PA above 1.8 eV at t=O ps. 1l1c PA at t = 1.2 ns has been attaibutcd above to a
combination of and t.riplct cxcitons. The PA onset and peak arc similar at
l.Oanol%. <;l.cl dopang (see Fag. 7-3 1 b), but the PA spectrum above 1.5 eV is en-
urdy daflcrcnt, extending to above 2.0 cV. Whereas the SE of 10 mol%
Coo: 000-PPV is quite shoat-lived ps), the PA decay at 1.5 eV is much
Hence, PA _in Cc-111-doped 000-PPV appears to be due to a photo-
fonncd wathm ...... 5 ps and with a lifetime r >I ns. We note that the tran-
saent SE and CW PL spcctr... arc essentially unchan<>ed 0 and 10 mol%
doping, which indicates that the l""<tdiativc species is :he same in both pristine and
doped films.
The transient SE dynamics of C611 : 000-PPV fi lms at doping concentmtions bc-
t:ovcen 0 and I 0 mol% arc shown .in Figure 7-32a. 1l1e SE decay is roughly exponen-
tial and can be lit to ot an exponential and a long tail f=/u cxp (-t/
(53). The SE hktamc 'sE gradually decreases as the c(J() concentrat ion in-
7 Spectroscopy of Plrotoexcitaticm.1 in Conjugated Polymers
100 200 300400500
1 (ps)
600 700



80 '
______ ___ _120
4 6
7-32. PL dc.:ay ur 1)()().
PJ>V lluping cuoh:cnlr.sliuns.
(b) Chungc in PL inlcnsuy. curl\!lalcll
lu lhc llcli:cl Spi!Cing. ht'iel: PL spcclra
vs doping conccnlrJlinn.
creases, from 200 ps in undoped, pristine 000-PPV to 30 ps at 10 mol % doping.
This change is correlated with changes in the integmted PL intensity (see
Fig. 7.32b), which is proportional to the quantum yield 'I These results are strik-
ingly remi niscent of the effects of photooxidation on PL observed by Yan et ul.
[25}, who demonstrated that as the density of carbonyl bonds increases, both rsE
and the PL intensity decrease. Our results therefore suggest that the observed elfects
of C
doping are due to exciton diffusion and subsequent dissociation at photoin-
duced defects injected onto the PPV backbone. The PL spectrum (see Fig. 7-32 b
inset) is unchanged by doping, indicating that the same singlet excitons are respon-
sible for SE in both the pristine and heavily doped samples.
For a 30 diffusion process of excitons towards defect centers with spacing r, the
relation ?trvL=cD.,,.c should hold, where Dcxc is the diiTusion coelf ident and
10, depending upon the distribution of defects [56]. Tite spacing betwel!n de-
fects r
is given by = n
and the total defect density n
, where 11
the density of native defecLo; in the pristine 000-PPVand llc>U is the dl!nsity of phmo-
gencmted defects. For a native defect density equivalent to 0.5 mol% doping, we
found that at various Coo doping concentr.ltions ?otrvL=const. From the 30 rela-
tion, we estimate that, for excitons in 000-PPV, 10-4 cm
/s, fairly
close to 2xl0 -
/s, which was previously obtained for excitons in MEH-PPV
fi lms from photooxidation PL quenching dynamics [531.
In order to determi ne the nature of these novel photocxcitations, we compared
the PLOMR of both C
-doped and pristine 000-PPV, shown in Figure 7-33.
The PLOMR of I 0 mol% C(.cJ: 000-PPV is roughly 10 times as intense as that of
7.5 1-'ullln m-Dot)('<IDOO-PPV
1.4,------ --- .-------
...J 1.0
!e 0.6
0 0.4
the undopcd sample and also contains a doublet resonance at 1072 G. The most
striking difference between the two spl!ctra, however, is the appearance of a
"'200 G wide resonance about g 2 with clearly resolved shoulders at 1045 and
_1095 G. In addition, a weak half-field accompanying signal appears at G
m doped 000-PPV, shown in Figure 7-33 inset. The half-field triplet resonances
that are seen at 390 and 400 G in pristine and doped PPV, respectively, are due to
PPV triplet cxcitons.
We can refute several explanations for the observed broad resonant spectrum
(BRS) around g::::: 2 and its accompanying half-field resonance in C
: 000-PPV.
It cannot _be due to PPV triplet excitons as the spectrum is too narrow L57].
Although ats width is similar to that of C
triplets eCoo) [58}, there is no evi-
dence of fu!lerene PL in any of our samples. Moreover, magnetic resonant en-
hancement of
Cfl<J decay would lead to the creation of more ppy+/Cffl defect
cente.rs, yielding a PL-quenching resonance, not an enhancing one. We therefore
suggest that spin intemct ions between charged polarons may explai n the BRS fea-
an? its half-field companion in Cc.o: 000-PPV. The two possibilities are
antcractmg polarons on the polymer chains or Ci.c,JPPV+ complexes. We refer to
both as polaron pairs, taking into account that the negative polaron
be_ cathcr on the polymer chain or the fullercnc molecule. Tite spin Hamilto-
man ( // s.s) of such pairs consislo; of Zeeman terms and an exchange tenn:
// s-s= tfil :if,. + fJH If,, s,, + s, .. 1' . s,, (7.33)
V: ere li"!' and 1 are the exchange-coupling tensors, respcc-
ttvely, H ts the magnetic field, und S,. and S
, arc the spin-1/2 electron and hole
respectively, the pair. If we assume the g-tensors are isotrop-
IC, d1fl enng only 111 thetr pnnctpal value, and have the same principal axis as the
! -tcnso_r, then th_e first _term reduces to g.fJHm..,,.+g
We may separate the
tsotropac and amsotroptc poations of the exchange tensor in Eq. (7. 1) by defining
l o = (1_, + 1,. + J:) and J , = J: + 111 etc. For the cusc Ct:2 - g
,)fJ/1 J, s s is
C4uivalcnt tO that Of a of idcntkal ions 159j and Cilll OC wri tten as:
230 7 Spectroscopy of PlwtoexciUJtions i11 Conjugated Polymers
where S =S,. + S
and s; = S
xS2.r etc. Eq. (7.37) is equivalent in form to that of
a spin-spin Hamiltonian with an even (singlet) solution at Es = - l o and three
odd (triplet) sublevels centered at Er = lo.
As 1; + 1; + = 0, Jl s-S can be rewritten in terms of two independent param-
where [)' and E are the ZFS parameters of the exchange triplet. The triplet form
of 11 s-s for the odd solutions now reads:
Comparing the BRS in figure 1-.:n to the predictions of &js. (7.19) lo (7.2 1).' we
determined D' = 115 G and E = 22 G. These exchange ZFS parameters predact a
lw/f-jicld resonance at 530.5 G I Eq. (7 .22) 1. in good agreement with the weak
half-field signal seen in Figure 7-:n.
The full-lield 1-1-PAOMR of the 10% c, .. ,: 000-PPV sample taken at 1.3 eV (sec
Fig. 7-34 inset), has roughly the same lineshape as the PLDMR (see Fig. 7-33) en-
abling us to sepamtely measure the absorption spc.ctr.1 of isolated polarons. at
H= 1072 G and the pair species at H= 1050 G. The polaron il-PAOMR consists
of two bands with maxima at 0.45 and 1.4 eV, in good agreement with the previous
results on pristine 000-PPV. We note that no signal attributed to bipolarons could
be detected. This suggests that photoexcitations resulting from dissociation of singlet
excitons remain paired, in agreement with the BRS. We further note that this is a
confimtation that the bn>O band detected in 000-PPV, a-6T, and P3BT is not
due to a defect species or unintentional doping. Otherwise, this signal, if any-
thing, should be stronger in the fullerene-doped sample. The pair A.-PAOMR al.so
contains two bands, but the high energy band is blue-shifted by about 0.4 eV wath
respect to P
of isolated polarons. We label these bands PP
and PP2. The similarity
between the PP
band and the broad ps transient PA spectrum of 10% 000-
PPV film (see Fig. 7-3 1 b) enables us to identify the latter spectrum as mainly due
to polaron pairs gcner.1ted in less than 5 ps. . .
Our results also shed light on the long-lived PA_
band detected an trJnsaem PM
measurements of P3BT (sec fig. 7- 19) and can explain changes in the PA spectra
observed in scveml ps transient measurements of films of PPV derivatives at ener-
gies around 1.8 eV (9, 25, 60). In good PPV films tr.1nsicnt PA spectrum
shows a PA band of excitons at 1.5 eV whose dynamacs match those ol the PL
and stimulated emission (SE) (9]. However, in measurements of oxidized [251 or
-doped fi lms 1601, there appeat'S a new PA band at about 1.8 eV whose dy-
namics are not cotTelated with those of the PL and SE. Based on our il-PADMR
results here, we aurihute the new PA band at 1.8 eV to polaron pair excitations.
These may be created tia exciton dissociation at extrinsic defects such as carbo-
7.5 Fullerene-Doped DOO-PPV

0.4 0.8 1.2 1.6 2.0
Probe Energy (eV)
Figure .i-PADMR Ill mol% C,., : DOO PPV, llle<lsurcd :lllhc peak uf Jhc spin-1/2 sig-
nal (pohtmns) or the broad spectrum (polaron pairs). The 11-PADMR spectrum is inset.
7-35. uf the energy levels and optical
lr.msallnn of oppu,.atcly-chargcd pulurons and polaron
nyls or complexes. TI1is solves a puzzle in the field of
photophysacs Ill PPV whach has recently been extensively debated.
Our a:esults on polaron pairs are summarized in Figure 7-35, a schematic dia-
gram of the energy levels and_ optical tmnsitions of polarons and polaron pairs.
polarons and polaron_ paars have two optical transi tions; the polaron pair
PP2 at a hagher energy than the P
tmnsition and the pair tmnsi-
tJon as rclatavely weak. The shift of the energy levels is due to the Coulomb
allractwn between the oppositely-charged polarons composing the pair. Mizes and
shown that a Coulomb interaction between polarons compos-
mg the paar, shafts the energy level positions. Due to their mutual attraction the
energy of the negati_ve polaron shift upwards and those of the po-
laron down.wards. and Conwell predict three transitions; the highest
(PP2>. 1s with res1x.>ct to the high energy P
suaon. II the transumn, whtch translcrs :111 electron between the purtially occupied
232 7 Spectroscopy of Pholoexdlations in Conjugated Polymers
levels of the two polarons, is weak or forbidden, lheir calculations are in agree-
ment with our experimental results.
Using a variety of transient and CW spectroscopies spanning lhe time domains
from ps to ms, we have identified the dominant intrachain photoexcitaLions in
Coo-doped PPV films. These are spin-correlated polaron pairs, which are formed
within picoseconds following exciton diffusion and subsequent dissociation at
photoinduced PPV .. /Ct;
defect centers. We found that the higher-energy PA band
of polaron pairs is blue-shifted by about 0.4 eV compared to that of isolated po-
larons in PPV.
7.6 Summary
We have demonstrated the power of combining a variety of spectroscopies in
studying the photophysics of conjugated polymers. Photoexcitation generates
singlet excitons with lifetimes of approximately I ns. Singlet excitons are chamc-
terized by one stimulated emission band and two photoi nduced absorption bands.
The PAis due to absorption from the lowest odd-panty I Bu state to the even par-
ity mA
and kA
states, which have also been detected by two-photon absorption
and electroabsorption spectroscopy. These results are summarized in Figure 7-12.
Triplet excitons arc formed by intersystem crossing of singlet excitons and have a
single PA band. The dominant charged species arc singly-charged polarons having
two PA bands and doubly-charged bipolarons having one. These results arc sum-
marized in Figure 7-23. In fullercne-dopcd 000-PPV, we have detected the polar-
on pair species, consisting of two oppositely-charged polarons bound by Coulomb
attraction. The absorption spectm of polarons and polaron pairs are compared in
Figure 7-35. Fullercne doping of 000-PPV quenches lhc PL efticicncy by injec-
tion of positive polarons on the polymer chain, leading to the fom1ation of long-
lived polaron pairs.
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8 Photophysics of Methyl-Substituted
Poly(para-Phenylene)-'I)'pe Ladder Polymers
Guglielmo Lanzani, Sandro De Silvestri, Giulio Cerullo,
Salvatore Stagira, Mauro Nisoli, Willi Graupner,
Gunther Leising, Ulrich Scherf, and Klaus Mullen
8.1 Introduction
Conj ugated polymers arc essentially chains of carbon atoms having in common n-
clectrons dclocali zed along the backbone. The nature of the primary photocxcita-
lions in conj ugated polymers is a long-standing question, which has been
addressed both and expc!rimentally. The tightly-bound exciton pic-
lure, assuming strong electron correlation, seems now the most appropriate de-
scription of the electronic structure, in contrast to the initially proposed band-like
theory. However, this model cannot fully account for the charge photogeneration
mechanism in such systems given the relatively small energy required to ionize
the initial exciton state. In this contribution we discuss the photophysics of a pro-
totypical n-conjugated polymeric semiconductor, namely a methyl-substituted
poly(para-phcnylenc)-type ladder polymer (m-LPPP) II), as investigated by sub-
picosecond time-resolved spccuoscopy. m-LPPP is a good model system for in-
vestigati ng fundamental physics of conjugated polymers due to the narrow inho-
mogeneous broadening that allows a clear resolve of its features and distinction
between intr.1-chain and inter-chain properties. Our investigation provides a rather
complete picture of the photocxcitations scenario in m-LPPP, which has general
validity in the class of polymeric semiconductors. In addition the results contrib-
ute to the basic understanding of the phenomena involved in the applications of
m-LPPP, which is used as the active layer in blue light-emitting electrolumines-
cent devices l2J and lasers [3, 4}.
The chapter is organized as follows: in Section 8.2 a brief overview or ultrafast
optical dynamics in polymers is given; in Section 8.3 we present m-LPPP and
give a summary of optical prope11ics; in Section K4 the laser source and the mea-
suring techniques are described; in Section 8.5 we discuss the fundamental photo-
excitations of m-LPPP; Section 8.6 is dedicated to r..tdiative recombination under
several excitation conditions and describes in some detail amplified spontaneous
emission (ASE); Section 8.7 discusses the charge generation process and the
photoexcitation dynamics in the presence of an extemal dcctric field; conclusions
are reported in the last section. 236 8 of Methyi-Substilllted PPP-Type Ladder Polymers
8.2 An Overview of Previous Results
Pioneering work on ullr.tfast optical dynamics in conjugated polymer:; (CP) was
carried out by C. V. Shank and Z. V. Vardeny on polyacetylene (CHx) (5, 6]. CHx
is the first synthesized CP and probably even now it remains the most extensively
investigated, both theoretically and experimentally. These early works showed that
CPs have ultntfast optical response with non-exponential recovery dynamics.
Most of the population decays in the mnge of l ps, with a tail in the ground state
recovery that extends to the ns time domain and longec. Quasi steady state photo-
modulation spectroscopy has shown that a fraction of photoexcitations is trapped
at defects, and survives up to the ms time range. The non-exponential decay of
the transient tmnsmission change (described by a power law -r'") was ascribed
lO geminate recombination of the photoexcitations, assigned to charged topologi-
cal kinks (Solitons) of the dimerization pattern (7}, after mndom walk along the
one-dimensional chain. Deviation from the inverse square root depcmlence ex-
pected for ideal infinite chains was explained by chai n Lenninations, i.e. the very
same defects that cause conj ugation length distri bution. The photoiU<.Im:ed trans-
mission spectrum, containing two intmgap absorption bands, was r..tlionalized
within the one-dimensional band-like picture for Peicrls semiconductors (7). The
early imerprelation was entirely based on intr.t-chain properties, even if inter-
chain energy mi gmtion was known to occur. For instance tr.msient Raman experi-
ments with ps resolution showed that this process is quite eflicienl in mixtures of
high and low gap conjugated segments (8].
The trans isomer of CHx is non-luminescent, while the cis isomer emits light
TI1is observation drew the auention to emitting polymers with cis-like carbon
structures, opening the route towards appl ications. Among luminescent and elec-
troluminescent materials poly(p-phenylenevinylene) (PPV) is by and large the
most studied. The ps transient transmission di tTerence spectrum of PPV contains
stimulated emission (SE) and a broad unstructured photoinduced absorpt ion (PA).
TI1e two compete because of substantial spectral overlap and PA kills SE in a
few ps. This finding was initially discouraging for lasing applications of PPV {9).
A consequence of PA and SE having different dynamics is that at least two differ-
ent photoexcitations should be considered. The emiuing state, responsible for SE,
with general agreement is assigned to singlet exci tons, whereas the assignment of
the dark state is under debate. L. J. Rothberg and co-worker:; have proposed this
PA to be due to polaron-pair, i.e. a pair of coulombically bound charged states lo-
cated on adj acent chains ll 0 J. The key point of this model is that n overlap be-
tween adjacent chains may reduce the energy gap between neutral and charged
states, thus allowing for spontaneous genemtion of interchain p<tirs or correlated
charges. This assignment has been, however, t-'Ontrastcd by seveml groups whose
results were explained by only considering imrachain tightly bound exci tations
[ 11, 12] or extrinsic effects related to oxygen { 13). Nevertheless polaron-pairs re-
main an important concept which can be used to mtionalize a number of experi-
mental results, such as optical detected magnetic reslmance and ullmfasl photo-
conductivity [ 14].
8.3 Optical Properties 237
The role of disorder in the photo h . , . f .
tensively described by lhe wo k p o. conJugated polymer:; has been ex-
worker:;. Based on ultrafast cam l . out In Marburg by H. Bassler and co-
o ummescence (PL) (15 1 ti ld d ed
cence quenching ll6J and site-selective PL . . . . Je -m uc lumines-
Siale thermalization was proposed h' h I 17], a model for excited
w' tJ . h . . w c consden; mtcrcha . . .
. ' 1111 t e mhomogcnousty broadened de . . . . . . m_ excllon mgmtJOn
mterpretation of our results in m-LPPP ol states. 'Vt!e base part of the
some in Secti ons 8.4 and 8.6. on t s model, which WJIJ be discussed in
While the importance of inter-chai f . , . . . . .
photo-excited state is now generally n k e Ill dctennuung the late of the
(CPG) mechanism is still a lll<tller of l_he_ charge phorogenemlion
slates (polarons) are formed b . the molecular picture
dsorder I 18j in this case the fl . y _mtelc am excton breaking assisted by
fer charJcter, (pol:tron-pair) . ?m1aktodn of an intermediate slate with charge tmns-
. . s nvo e A second 1 d I h. h .
mer-ltke description of the int -a h . . .: n o e, w Jc mducles a Wan-
be . ' c am excllon propose . h . d. .
responsible for charae generatio 119! . . . s on-e aan ssoc.ation to
This mechanism docs tl:< uire f l , . has :1 secondary role.
based un phohx:onducti.VIty 1111'' . . < llll.ltlun ul an Hllcrmcdiiile state. Fin:.lly
l:U.'iUICillenls ('>Of d ' '
and hole exdtation Was sun nested El t . . ill .I band-to-band electron
ments on m-LPPP l EDs r . d : cl,; Je s assisted pump-probe ex peri-
. p cscnte m Secti on 8.6, are ai med to clarify CPG.
8.3 Optical Properties
In 8- 1 we show the chemical structure f . .
gallon and the reduction of dcf . _o .. !he in conju-
porate a poly(p-phenylene)(PPP) b kbo wa..., the mam moll vatJOn to incor-
D I h . ac nc mto a ladder poly ,
ue o I e sJde groups auached to th PPP . . mer slllJclure [21!
polar solvents is Th' . . . the . ch_am excellent solubilit y in
. . IS IS e prereqUISite f od
1gh Opi icaJ quality. A detailed present t' f I or pr polymer films of
a JOn o 11e synthesis, sample preparation,
R:.C,.,H, R'=C6H,, Y=CH
l' igure H- 1. Chcllli.:al
238 8 Pltotophysics uf Metltyi-Substitwed PPP-Type Ladder Polymers
and cw optical properties of m-LPPP films is reported in Ref. [22]. Here basic
properties arc mentioned, such as absorption and photoluminescence, which are
strictly connected with the following discussion.
Time-integrated photoluminescence spectrum of m-LPPP film, for low excita-
tion fluence (0.3 m.J/cm
) at 3. 18 eV with a circular pump area is reponed in Fig-
ure 8-2a as a solid line. It displays a well-resolved vibronic structure wilh 0-0
transition at 2.67 eV (465 nm). In a previous study on m-LPPP [23], a strong PL
band in the yellow region was observed and attributed to aggregate emission. The
absence of this component in the sample under study indicates that no such aggre-
gation is taking place. The 0-0 transition is partially re-absorbed due to the small
Stokes shirt between emission and absorption. Ground state absorption is reponed
in the inset of Figure 8-2a and shows clear mirror symmetry with the emission
spectrum. Absorption in the sub-gap region is very low (< 12 cm-
) with a steep
onset leading to a maximum value c.Lm:u. 1.1 x I OS cm-
and the fluorescence
quantum yield is about 30% (24].
At high excitation lluence (2.4 mJ/cm
) the emission spectrum collapses into a
narrow line located at 2.53 eV (see Fig. 8-2a. dashed line), slightly blue-shifted
with respect to the low intensit y emission. TI1e process strongly dcpenus on the
shape of the excitation area. For a rectangular spot, li ne narrowing occurs at

i.e. 45 times a lower lluence than for a small circular spot, whi le the
2. 1
. .., 2
2.4 mJ/cm
" II


0-2 0-1
0.055 mJ/cm
40 Jll1l
2.2 2.3 VI 2.5 2.6 2.7 2.8
Energy (eV)
Figure 1!-2. (a) Normalil.co PL spec-
tra of m-LPI'P films ;II 1'= 77 K for
cxcitalioo at 3.2.:V (39() om) wilh a
circular al 1w.1 cJiOi:rcm Ou-
eoces: 0.3 mJ/cm
(solid line) and
2.4 mJ/cm
line). The insel
shows lhc room lcmpcritlurc absorp-
tion spect rum of m-LPPP. (b) Nor-
malized PL spectrum for cxcilalioo
wilh a rectangular spol at a nucnce
of O.OSS mJ/cm
(from Ref. 1251
with pcnnbsion).
8.4 Experimemal 239
spectral position of the nanow pe k .
prctation of such peculiar (see Fig. 8-2b). The inter-
tO eCtlOn 8.6.
8.4 Experimental
8.4.1 Conventional Pump-probe
of the experimental set-up is shown in Fi u -
Tt. sapphire lru;cr system with chi ed . . . re_ 8 3. Th_e laser source was a
pulses at 7HO nm and 700 Jl] cnc7 .. Which provided 140 fs
pulses at 390 nm were generated b ot I kHz. The excitation
in a 1-nuu-thick LiBlO crystal Thy c harmonic of the fundamental beam
and the exci tation dfoc
scd to a.,spot size of 80 J.im
c n an m.J/cm- per pulse. Pump-
probe beam
Pump beam

140 fs
Figure M-3. of lhc cxpcrimcnlal M!l-
up for pump-probe experi-
ment,. SJ IG: MX(lno gcncrJiion
PO: pholudiocJ.:; OMA: opli<:ill noul-
240 8 Photophysics of Methyl-Substituted PPP-Type Luddrr Polymer:.
probe experiments were carried out in the visible and near infrared spectral range
using the white light supercontinuum genemted in a thin sapphire plate. Mirrors
were used to collect the supercontinuum pulse and to focus it onto the sample in
order to minimize frequency chirp effects. The following measurements were car-
ried out: i) the whole white light pulse was spectrally analyzed after passing through
the sample using a spectrometer and a silicon diode array. Transmission dill'erence
spectra are plotted as f!.Tfl', where f!.T is the pump-induced transmission change, ob-
tained by subtracting pump-on and pump-off data, and Tis the sample transmission.
In the small signal limit where !!.a is the absorbance change associated
to the excited state population N (f!.u. =uN, where u is the transition cross section)
and d is the sample thickness (for very thick samples dis replaced by the pump pen-
etration depth). f!.T>O is associated to photobleaching (PB) or SE, f!.T<O to PA.
Averaging over about 10
data acquisitions allows a sensitivity of about 10-
6.Tn; due to a small chirp of the pulse the overall time resolution in this experiment
is 500 fs; ii) the evolution in time of the is measured in a narrow spectral
window of I 0 nm using interference filters in front of the Jctector. In this case
we use a pre-amplified photodiode and the standard lo<:k-in technique. This allows a
higher sensiti vity of about 10-1 in a beucr time-resolution, which is limited
by the experimental cross-com:lation to about 200 fs . In both experiments the pump
beam was linearly polarized at the magic angle with the probe; iii) photoinduced
anisotropy decay was measured by setting the pump beam at 45 o with respect to
the probe and collecting two sets of data with an analyzer placed in front of the de-
tector pamllel or perpendicular to the pump polari7-Lttion; iv) cw photoluminescence
spectra, collecting the light emitted in a direction perpendicular to the film, were
recorded using an optical multichannel analyzer and aver..tging over 100 to 1000
laser pulses.
8.4.2 Field-Assisted Pump-Probe
In these experiments we used single layer LEOs prepared by spincoating m-LPPP
from a toluene solution onto indium tin oxide (ITO)-coated glass substrates. After
annealing approximately 100-nm-thick m-LPPP layers for 24 h at 70''C, alumi-
num electrodes were applied by vacuum evaporation. l11e layout of the experi-
mental set-up is shown in Figure 8-4. The pump and probe beams pass the glass.
ITO, and polymer to be reflected by the aluminum. With no voltage applied lo
the LED, we measured conventional tr.msient pump/probe spectr..t, as previously
described. With the device biased we measured the total dynamic.:s in the presence
of the electric field (6.TI7)F In order to detect small field-induced changes of llT.
we applied a modulated voltage to the device and referenced our detection at the
field modulation (MF) frequency. In this way we detected only field-induced
changes in the spectra. which we call Following our nomenclature
In this spcctm a fie!ld-induced increase has the same
sign as that of the photoinduced transmission signal, whilst field-induced reduc-
tion has the opposite l>ign.
8.5 Tht Prillltll)' Plwto(.tdtutions in m-LPPP

Pump beam
OMA [?J--;,
.Figur,c 8-J. Layout of the cxpcrimenJal :.CI-up for ficld-
asststcd SfJL"Ciroscopy. PO: pholooiodc
OMA: oplrcal mullrchanncl analycr.
. We estimated that the characteristic lime f, . . . .. .
With a mobility of 10-J em:! v- s- d OJ tJaveltng to the electrodes,
em, is 10 ns for a 100-nm-thick _maxunum field of I MV/
movement of lhe charge caniers are _cttccts caused by the
surements and can be neglected o fti h er than the tunescale of our mea-
the time-behavior. In be identified looking at
elcctnc fieiJ etlects on the transition --u Mf . flu includes
molecular levels, and is expected to . strength, u, and Stark shifts of the
they not depend on pump-probe state trans!tions
they tncrcase with time l(lllowi" the ly. hcrcas fm excucd state tr.msJtions
A.,.. . ., pu sc cross-<:orrclat' N
ul Mf' sgnals arc ascribed to field

d d h . on. on-mstantaneous
. - uce c anges m the po I .
ynanucs of the photogencrated species. pu allon densty and
The Primary Photocxcitations in m-LPPP
In this experimental result-; are described w . .
pump-probe technique to m-LPPP by applying the
_of hqUtd nitrogen 1251. These results all !n at the tempera-
Citations of m-LPPP and the tna,n rei . ohw the JdentJlJcatJOn of the primary ex-
. . axat1on c annels h . .
excJtatJon density re<>imes rc invest'g t d . d . 1 part Jcu ar, the low and high
. "' ' a e 111 or cr to get n . 1 .
processes associated with the emission r . . . a JllsJg II mto the physcal
mc-narruwmg phenomenon.
242 8 Plwtophysics of Methyl-Substituted PPP-Type uulder Polymers
8.5.1 Overview of the Experimental Results
6.Tff spectra for excitation intensity of 0.3 mJ/cm
and different pump-probe de-
lays (r
) are shown in Figure 8-5. Positive 6.T for probe energies higher than
2.3 eV were measured, and negative 6.T for lower energies. Since there is no
ground stale absorption in the positive 6.T region, we assigned it to stimulated
emission of the 0-1 and 0-2 lines. In the PA region a sharp band at 1.4H eV can
be seen, which decays on the same timescale of SE and a weak PA band at
1.9 eV. Following the time evolution of the 6.Tff spectrum up to r
=400 ps the
decay of the main features can be seen and finally two PA bands are left in the
spectrum, at 1.9 and 1.3 eV (see inset of Fig. 8-5). Upon increasing
the excitation densities, up to 12 mJ/cm , the shape of the 6.Tff spectrum changes
dramatically in the positive signal region. This is shown in the upper panel of Fig-
ure 8-6: a dip in the SE spectrum develops around 2.64 eV (470 nm) and at very
high excitation density SE changes sign turning into PA. The lower panel of Fig-
ure 8-6 shows that this intensity-dependent PA has disappeared within about 4 ps.
The dynamics of the SE peak at 2.53 eV is strongly affected by the excitation
density, as shown in Figure 8-7, where SE decay for three different excitation
-rd=400 ps
-rd=40 ps
-rd=4 ps
-rd= o ps
1.4 1.6 1.8 2.0 2.2 2.4 2.6
Energy (cV)
Figure 1!-5. Transmission difference spcclm of m-LPPP a1 7=77 K excited al 3.2 cV for various
pump-probe delays. The inscl worns oul the low encrsy region for 0 ps (solid line) and 400 ps
(dashed line) delay. Doping induced :1bwrp1ion (DIA) data an: also fur comparison (from Ref.
(251 wilh pcnuission).

Tlte Prinwry Plwtoe.xcitations in m-LPPP
2.4 2.5 2.6
Energy ( e V)

SE of m-LPPP films
ill K: (aJ al 0.6 ps pump-probe de-
lay for mcn:asins pump (b) for
7.2 nt.J/cm
Cltl"italion at two
delays (from Ref. 1251 witlJ
conditions is reported Th
. . e decay timescale be . h . . . . .
denstltes, reaching about 2 ps for the highest comes s ortet fot htgher exctlatJOn
A Model for m-LPPP Electronic Structure
We assume that standard Coulomb-correla d
[I J] properly described the intrachain etc .le . models for luminescent polymers
immchain photocxcitation generate sin of In this case
(Bu). which are responsible for the s;ont .odd _panty
the pump energy in our cxpcrilllcnL-; is Since
e latgcr lhan the Onlt<"al ll ;on
8 Photophysics of Methyl-Substituted PPP-Type Ladda Polymers
2.53 eV
0. 12
2 4
time delay (ps)
obc delay at three differ-
" 7 SE '- ty at 2.53 cV in m-LPPP at T=77 K vcr.;us pomp-pr
Figure o ""'-'
. t' on fluences (from Ref 125) with pcnmsston .
cnl CXCil<l I
. d t be hot states. lntrachain thermalization may,
the initial excttons are expecte
o the pump pulse dumt1on.
however, occur WI _un 0 I .b . transition is initially centered at2.5 I eV,
The SE band asstgned to the -h romcl .... ated PL spectrum at low energy den-
. d m tto t e lime tn cg.. .
t.e. blue-shtlte wt respcc V F I err a red-shift of the decaytng SE spcc-
sity, which is located_ at 2.48: . h or

in time-integr..tted PL
trum can be seen. which rcac t 8-8 Spectral relaxation of SE can be ac-
within about 10 ps: as tn energy sites. such as longer l:Onju-
counted fo_r by . 26 This is a collective thermalization pro-
galion chams wtth a smallet gap [ ]. redistribution and it is typical of

the intmchatn excess energy .
cess that may o ow . . .
LPPP films containing aggregates, the rot-
disorder molecular nin' of the phntoexcitations. In this case
gration process to a qutck. lr..typ,. g PA band which is assigned to intcrchatn
spectrum contatns a broad . . . ked [261 and the PA of
A . . It the tntnnstc dynamtcs ts mas . .
species l23_. 2 }. s a resu_ T d I order to exclude intrachain
singlet excttons cannot be tdenll .. n hown that oligomers with no conJuga-
as [ IS]. Transient photoinduced
tion length do

wfth ump polariz.ation parallel and

anisotropy. obtatncd by cfdt'onal more direct information supp01tmg
dicular to the probe, provt es a t t
1.2 I 494
c: 8.496
:J Ul
..ci 0,8 en
<! 0,4
8.5 The Primary Phowexcitatious ill m-LPPP
Energy (eV)
2,5 2,6
Figur e 8-H. SE spectra of m-LJ>J>P lilnt.'< at T: 77 K for pump-proi)C delay:> 0 lsulid line) und 12 ps
(dal.hcd line). rditx<ttion: the inset shows the position of the SE peak a function of
the interchain thennaliz.ation. In general, photoexcitation with linearly polarized
pulses induce optical anisotropy in the film. Titc initial dichroism is lost because
exciton diffuse to chains with different orientation. This process is extremely fast
in amorphous regions where a single hop to the adjacent chain is enough to change
ll1e initial geometry of Ute excitations. The experimental evidence of polarization
memory loss in m-LPPP lilms [2SJ, to be discussed later in more detai l, demon-
strates that energy diffusion is actually taking place within the photoexcited vol-
ume. We understand polarization memory loss and spectral relaxation as experimen-
tal signatures of the same phenomenon, namely the thennalization of the excited
state through interchain migration.
SE dynamics versus excitation intensity, shown in rigure 8-7, points out the
presence of a fast exciton depopulation process. For low excitation densities the
SE decay is nearly exponential with a time constant of 25 ps, while for higher ex-
citation densities it becomes increasingly non-exponential and the fast component
of the decay is complete in less than 2 ps. We conjecture that the observed deple-
tion of exciton population at high densities is due to ASE along the 111m plane.
ASE, which is a process which has no threshold, acts as an intensity depeudeut
mechanism of population depletion. Note that the probe interacts with the exciton
populatio11 stimulating emission perpendicularly to the lilm For this rca-
son, upon increasing the cxcilatiun power. we tine of the spcmtct-
''emts emission but not of .\tiuwlated emission.
PA at 1.48 eV instantaneously, shows spectral relaxation to the red, and
decays on the same timescale of SE, a.-. shown in Figure 8-9. We assign the ob-
served PA to singlet Bu exdton transitions towards higher lying even parity (A..:)
states. We can speculate on the nature of this state within the proposed model. A
pos.-;ihle candiuatc for the final stale is the illtrac:lwill biexcitun. However, its en-
ergy level is located below the two-exciton state by an amount equal to the hind-
8 Photopllysics of Methyl-Substituted PPP-Type wdder Polymers
0.0 1---.-Uo
- 10 0 10 20 30 40
time delay (ps)
Figure 89. Modulus of 6T versus pump-probe delay at 1.41S cV and 2.53 cV (from Ref. (25) with per-
ing energy. Since this cannot be larger than the exciton binding energy, estimated
to be about 0.5 eV [27], the biexciton level is expected to be 5 .ey._
exciton to biexciton transition would then appear at 2.3 eV and thts ts
thus ruled out. A second candidate is the continuum state, but electromodulatton
spectroscopy shows that this is located at 3.3 eV [27), implying a _transiti?n en-
ergy of 0.5 eV. The remaining possibility is the so called mA
state, t. e. a htgh ly-
ing even parity state with a large dipole coupling. with I Bu state [II], and that
is expected to play an important role in the rcspo?se.
shoulder seen at higher energy (around 1.55 eV) ts asstgned to a vtbromc repltca
of the singlet exciton transition. The shift of 0.07 eV corresponds to energy of
a vibr.ttional mode which is observed in absorption and electro-absorptton [27].
The PA bands 1.3 eV (950 nm) and 1.9 eV (650 nm) present ditrerent dy-
namics and a longer lifetime with respect to the singlet They should
therefore be assigned to different photoexcitations. Let us first dtscuss the. PA at
1.3 eV. The same PA band has been detected by steady state 6.TIT
(cwPA) on m-LPPP films 128). In these measurements bean:'
chanically modulated cw laser and the observed_ have ltfetunes tn
the ms time domain. Based on temperature, exctlatton mtenstty, an_d frcquenc7 de-
pendence, it has been assigned to triplet-triplet tr.tnsitions. We that as-
signment is also true for our time domain. Due to spcdr.tl wtth the
PA band we cannot di stinguish between slow gcneratton vw
and ul trafast generation via non-geminate electron-hol e or
fission. However, the latter is unlikely because the energy lor gencraun!? a tnplet
pair is expected to be larger than the pump photon enei'6Y The lowest smglet
cited state in m-LPPP is located at 2.7 eV. Exciton fission from 3.2 cV would nn-
8.5 The Primary Phoroexcitutious in m-LPPP
ply a huge singlet-triplet energy separation > l.l eV, a value that seems to be
rather unlikely.
The PA at 1.9 eV and its vibronic replica at 2. 14 eV have been observed in m-
f!PP films . by various cw techniques: doping induced absorption, charge injec-
spectroscopy, and (29]. these reasons they can be unambiguously
asstgned to charged spectes. the mset of Fig. 8-5 we show for comparison the
match of the data obtamed by chemical doping of m-LPPP films with our
transient results. that the_ occurrence of the same absorption spectrum for dif-
ferent and u:-clnstent tcchmques strongly suggest the assignment to isolated or
weakly mteractmg polarons, in contrast to polaron pairs. We conclude that
stales are phmogeneratcd within 500 fs, since the PA at 1.9 eV is already
tn the 6.TIT spectrum at rv=O. and does not decay within our experimen-
tal _time range, . up to 400 ps. The process can be either intrinsic or extrinsic, i.e.
asststed_ by an tmpurity such as oxygen. A conclusive statement on the generation
can not be a! this Additional infonuation on the CPG pro-
1s extmcted by electnc ltcld-asststed experiments that are presented in Sec-
lion 8.6.
8.5.3 High Excitation Density Scenario
The spectral of SE upon increasi ng excitation intensity is shown in
Fig: 8-_6. V.:e tt as superposition of SE and a new PA band with diiTercnt
Transient photoinduced anisotropy provides use-
mformatt on lor the of the transi tion moment of the species respon-
for The m-LPPP him ts a uniform distribution of randomly oriented
chams wluch docs not display macroscopic dichroic properties. If the transition
of the excited and the ground slate are parallel, the initial polarization
ralto p*=PAu/PA.t. is [30]. lf _lhe transitions moments are tilted with respect
to one ;not her the p* ts given by p* = (I +0.8 a)/( 1-0.4 a), where
a =(3 cos. C/J-! )12 and q, .' s the angle
between the transition moments. The resull'i
tn Ftgurc 8-10 lor 6 m.Jicm excitation intensity show that there is com-
and PA an.J that PA is proportionally stronger in the perpen-
The maxt.mum reduction of SE occurs at ro= 1 ps, indicat-
mg a_ ume constant lor PA of 200- 300 Is. In order to evaluate the PA
ratto we should know how the SE behaves. We assume that the ini-
llaJ. SE ratio is 3 becau:o;e no substantial exciton migration is going to
dunng overlap tunc. At rn= I ps. p* for SE is reum:cd by the
same observed lor PA at 6!)0 nm. bcc;Iusc the faller describes the ell ect of
the singl_et exci ton polarization free of ;my uther competing ellccts.
Based thts 1.1ave been able Ill that p*( 1 ps) lor PA at
470 nm ts .. 1. 1. 8. Tlus 111 ytdcls an of the tilt ing angle ur appruxi-
50 unccr1at nty by the inuin:ct evaluation of p. Thi s result
s: however, stgntltcant because tt tndtcato::s that the PA tmnsition moment is tilteu
With respect to the chain axis. l11e cllect can not be assigned to ultrafast exciton
248 8 Photophysics of Methyl-Substiwted PPP-Type Ladder Polymers
0 I 2 3
time delay (ps)
Fi uri! ti-10. 6Tal 1.112 eV (a) and 2.64 eV (b) in m-LPPP lilmsal 7"=77 !< for polariza-
parJIIcl (solid line) and j)i:rpendicular (clashed line) (from Ref. 125) w11h penmss10n).
diffusion because this process can at most lead to p* = 1 . and it
th . f AT '"e propose assignment of the PA to mtercham exclUJIIOits
change e Sign 0 L.l YY' r
whose skewed transition dipole moment reflects the local
uy The anisotropy decay data indicate that the state ts fonned w1thm I ps
in about 3 ps. Note that the of a high PA on
a very short timescale is common to other conJugated polymers, as for_ mstanc_e
ppy 1 13] but it has never been discussed._ Due the spectral w1th SE, tt
is not easy to infer information on the 1ntens1ty dependence can only
s ulate on the nature of this species: One poss1bl11ty IS
reactions take place at high den_s1ty, _to.
of excitonic molecules or other by-products ot exc1ton fus1on, such as polamn
pairs (i.e. pair of Coulomb-oorrclatc<.l charges).
8.6 The Emission Process in m-LPPP
In the revious section we have shown that for an excitation above the
PL lin:-narrowing threshold, the shape SE_ spc:ctrum
This demonstrates that the spontaneous em1ss1on sp1ke IS not due to a nov_ twns;
lion existing in the photoexdted material, as would be the case for exc1tomc mo -
8.6 Tire l:./uissio11 Process i11 m-LPPP
ecules. The conclusion is further substantiated by the observation that exciton
condensation depends only on the density of the excited species and not on the
shape of the spot, in contrast to the results in m-LPPP. Collective or co-
opemtive emission processes are instead to be considered. An experiment of exci-
lation cross-correlation PL in m-LPPP films above threshold have shown that the
characteristic time associated with the emission phenomena is about 2 ps [31j, i.e.
much longer than the expected de phasing time (I 00 fs) . This argues against super-
fluorescence, leaving ASE as the most favored mechanism to account for PL line
narrowing iri m-LPPP. G.J. Denton et aL have reached the same conclusions for
PPV [32].
It has been demonslr.tted that the whole photoexcitation dynamics in m-LPPP
can be described considering the role of ASE in the population depletion process
(33). Due to the collective stimulated emission associated with the propagation of
spontaneous PL through the excited material, the exciton population decays faster
than the natuml lifetime, while the electronic structure of the photoexcited materi-
al remains unchanged. Based on the observation that time-integrated PL indicates
the presence of ASE while SE decay corresponds to population dynamics, a nu-
merical simulation was used to obtain a COITClation of SE and PL at different exci-
tation densities and to support the ASE model !33). The excited state population
N(R,t) at position R and time t within the photoexcited material is worked out
based on the following equation:
--:- 0.6

<l 0.4
0.2 -
0 2 4
6 8
Time delay (ps)
Figure 11-11. Sui ill line: l!J.T ill . .'i3 .:V lir llilfcn:nt CM:ilallun Oucncc,, o.,,hc<l lines: lining oil-
lamed frum lhc rhcurcrical 11111dcl in rho: l.:xt (frmu Rd. f.l:ll with pcnnb,lun).
8 Plwtophysics of Methyl-Substiltlled PPP-Type Ladder Polymers
where Wp is the genemtion rate due to the pump pulse, T the
cay, y the bi-molecular recombination constant (related to exci_l<?n-exciton
lation), J
ot is the photon rate crossing the volume dV at pos1t10n R and ume t,
and G is the spectrally integrated local gain for photons the dV.
Note that the model contains two intensity-dependent recombmat1on mcchamsms:
ASE and exciton annihilation. Both are active in the photocxcitcd volume and
should be simultaneously taken into account. From comparison of the
simulated results with the experiments (see Fig. 8- 11) we extract the peak gam
cross-section Up. relevant for lasing application, up-::::::5.15x 10-
and the bi-
. . 5 104 3 - 1
molecular recombmauon constant y-:::::: x em s .
8.7 Charge Photogeneration in m-LPPP
In systems. sudt as quantum-conlincd and conju-
gated polymers, the first step of optical absorpt ion is the creati?n of bound elec-
tron-hole pairs, known as excitons 1341. Charge photogenerauon occurs
when excitons break into positive and negative This process 1s of essen-
tial importance both for the understanding of the fundamental physics of
materials and for applicati ons in photovoltaic devices and . S1nce
exciton di ssociation can be affected by an external clectru.: held, hcld-mduced
spectroscopy is a powerful tool for studying CPG. . .
In inorganic low-dimensional systems, weakly bound exc1tons show. Stark sh1ft
of the optical absorption and fully dissociate in the presence relatively. small
tields (10
V/cm) parallel to the confining barriers [35). The t1me evolut1on of
these phenomena has been measured by transient experiments t!'c of
an electric field which determined a strong dependence of the Iomzatlon t1me on
the tield [36). In conjugated polymers, there is an extensi_vc of litera-
ture on electric field-induced CPG in the stationary regime [16), wh1lc only few
experiments have been carried out in the time The evolution of
CPG was investigated either via transient quenchmg of photolummescencc [16.
37] or photobleaching [3S 1. or via photocurrent measurements [39]. The. photolu-
minescence and photobleaching quenching are indirect probes of CPG, smce they
cannot monitor the product of exciton dissociation, and in photocurrent measure-
ments only mobile chargl!S can be detected with a limited time resolution of a few
tens of ps 139}. . .
We have studied Lhe temporal dynamics of CPG in m-LPPP _by
field-assisted pump-probe experiments on LED structures, as m_Sccuon
S.3.2. The narrow line-width PA assigned to polarons (see Section S.5.2) 1s a fin-
gerprint of charge generation in m-LPPP. Monitoring the dynamics PA
band enables us, for the first time, to directly observe the CPG dynamics m a con-
jugated polymer with sub-picosecond time resoluti<?n. [401: . .
In Figure 8-12 we !>how the field-induced transm1ss1on spectra
(11T!T),.,.. for negatively biased LED at 13 V and at d1flcrent pump-probe delays.
8. 7 Chaf1:e PlwtfJgent.'rtllicm in m-LPPP 251
I .H 2.0 2.2 2.4 2.6
Probe Energy (eV)
1-!gur c 8-12. Ficld-imluccd diffcrcnliat spoclm (6TmAII' fur a positive bias of 13 V ami
drflcn:m pump-probe delays (from Ref. (40( with permission).
We. a 11T,.,F signal for energies hi gher than 1.8 eV, and a weak
pos1t1ve s1gnal lor lower energies. By applying an electric fi eld to the polymer,
we_ expect to sec quenching of the singlet exciton population due to dissociation.
sh?uld lead to the observation of a decrease in singlet exciton features, re-
sultmg m negauve 11T MF in the SE region and positive 11TM,.. in the PA region. If
polarons arc generated, !1T11w should also contain a corresponding increase in the
polaron PA. (l:l.Tfl)MF signal at Tv=5 ps displays all these features; we ob-
serve t":'o negat1ve bands, at 2.5? and 2.35 cV, which correspond to a quenching
of the smglet and negat1ve bands, at 1.91 and 2.1 e V respectively, which
are due lo mcrease m the polaron PA spectrum (and its vibronic replica). For
probe lowc_r than 1.8 eV, we observe positive 6.T
u:. corresponding to a
quenchmg of smglet exciton PA. Note that for probe energies larger than
2.65 there 1s a strong negative (11TIT)M,.. signal; this feature is present also at
ncgat1ve_ pump-probe delays and is due to static clectromodulation, caused by
Stark sh1ft of the slate op_tical Lmnsition. At longer pump-probe delays, be-
cause of the dec-.ty of smglct cxc1ton population, both field-induced changes in SE
and PA arc very small. At T0 =400 ps the remaining PA is due to the long-li ved
polarons !!Cncmtcd by the electric li dd at earlier times. We can thus conclude that
8 Plwtoplaysics of Methyl-Substituted PPP-Type Ladder Polymu.\
2 3 4


10 20 30
Figure 8-13. Field-induced diiTeren-
lial trans mission (- 6Tfl),.,r at 1.91
(solid line) and 2.53 eV (dots} as a
function of pump-probe delay. In
the upper panel we also show. as a
line. the pump-pulse aulo-
0 t OO 200 300 400
correlation (from Ref. [40) with per-
Time Delay (ps) mission).
the (l:lTrnMF spectra provide direct evidence of field-induced exciton dissociation
into charged slates.
More detailed infonnation on the kinetics of field-induced phenomena can be
obtained by studying the (l:lTrnM,.. signal at selected probe as a
of pump-probe delay. We monitored field-induced exciton at the sm-
glet SE (2.53 eV) and at il<> PA ( 1.5 I eV), and that of CPG at the
polaron PA (1.9 1 eV). At rv=Ops (see r-ig. _(llTrn,.w arc zero;
this means that there is no sig11ijicant exciton dtssuc:wtum on rite twu:sc:ale of the
pulse duratiun. Thus, we can rule ou_t a licld-induc_ed reduction of
strength as the main quenching mechanasm. The PA at 1._9 1 eV has
an initial fast rise, growing to of its ti na! value wttlun 2 ps (Ftg. 8- 13a).
followed by a slower increase on the 40 ps timescale (sec Fig. 8- 13b) pla-
teau on the 400 ps timescale (see Fig. 8- 13 c). The field-induced SE quenchmg at
2.53 eV also shows an initial fast rise, reaching its maximum value by ro=2
foll owed by a slow decay; for ionger time delays. the signal vanishes, due to_ cxca-
ton recombi nation. The field-induced signal at 1.5 I eV has the same behavaor as
that at 2.53 eV, but with opposite sign, being a PA quenching.
-1 0 0
8. 7 Clwrge Phntogeneratima in m-LPPP

Neg. bias

' ..
10 20 30
Time Delay (ps)
Figure 8-14. (a) versus pump-probe dch1y at 1.91 eV for V,...=- 16 V and pump excitation
intensi ties 1.2 m.l/cm
lin.:) and 0.24 m.l /em! (da..;IK.-..1 line). l11e inset shows (- 6Tfl)m a1
1.91 eV ;md 20 ps versus cxcit:uinn inlcnsity. (h) same as (a) pu1H(l excitation intensity 1.2 nt.l/cm
With V.,...,. =-16 V (solid line) a nd V.,,,=-8 V (dashed line). 11lC inet shows (- 6T//)Mf" at 1.91 cV
and 20 vcr.;us field: open squan:s=positivc bia."; filled circles= negative bias (adaplcd from Ref. [40J).
We investi gated the dependence of CPG on both exci tation density and applied
voltage. Figure 8-14a shows that the kinetics of polaron fonnation docs not
change upon lowering the pump fl uence by a faclor of 5. This is in contrast to
the possibility of CPG through bi-molecular exciton fusion and subsequent auto-
ionization (411. A plot of the fidd-induccd polaron population at 20 ps versus ex-
citation density (see inset of Fig. shows a strong saturation, which sets in at
the threshold value for ASE. We explain this as bei ng due to depletion of the
singlet slate caused by ASE and by bi-molecular excitt>n-exciton annihilat ion.
Both proCl..--sscs occur on a timescale that hccomcs faster than charge separ .ui on at
moderate excitation inlensilies, thus competing wi th CPG.
Polaron ki netics is also unaffected by variations in the applied voltage, as
shown in Figure 8- 14 b. 1l1c inset of Figure H- 14 b shows CI'G eflicicncy as a
function of the applied dectric licld. Symmeli)' wi th respect to the LED bias volt-
age rules t)Ut space cnccls and cxciloll-C<!Il"ier interactions. In addition. we
note that (/lT/fhw has a 'lu;adratic tkpcndencc on thc electric field, similarly to
8 Plwtophysics of Methyl-Substituted PPP-Type Ladder Polymers
E=2.53 ev
s 10 15
Time Delay (ps)
lo"igure 8-15. Fichl-induccd exciton breaking r:ue y(t). calculated from Eq. (8.2). inset shows the
experimental field-induced S 4ucn..:hing aJ 2.53 eV the cx..:rton 4ucochmg M st-11' (I) cal-
culated using Eq. (8.2) (solid line) (from Ref. 1401 wrth pcnmssson).
PL quenching data f 16, 37}. The characteristic energt supplied by the F
be esti mated as cF (eV), where F is ;:bout 10 and
exciton delocalization length, is about 10 A [27). obtam _eY_. whtc:h
provides the order of magnitude of the exciton energy 1f gen-
emtes non-correlated polarons. It will become clear m the followmg sect1ons that
this estimate refers to interclwin-lwt cxcitons.
The interpretation of our CPG data is compl icated by the o_f compa_ra-
tively fast mdiati ve and nonradiative decay channels for the wh1ch
compete with the field-induced dissociation. ln order to a ptcture of
the observed mechanism and disentangle it from the smglet exc1ton dcl.'ay dy-
namics, we define the following phenomenological time-dependent parameter:
y(r) = ---= - - - -
NsF dt Up SEF dt
where NsF=SE
.1us is the singlet exciton population in presence an electric
field, N
,M...-=PAMJJCTp is the field-induced populallon, CTs(CTp) IS the cross-
section for stimulated emission (polaron absorptiOn). SEF=(ll.Tf'Dr measured
2.53 eV and PAMp= (ll.Tfl)

F measured at 1.91 eV. In this calculation th_e contn-
bution of singlet PA at l.9 1 eV was correctly subtracted. A plot of 1s
in Figure 8- 15. If singlet exciton breaking in the an electnc field IS a
first-order process that directly results into polaron !onnallon, y represents the
8.7 Charge Plwwgeueration in m-LPPP 255
field-induced exciton-breaking r.1te. To check the validity of this hypothes is, we
to demonstrate that we can reproduce the measufC?d singlet exciton popula-
tion quenching using the following equation:
SEMF(t) = SE(t) ( exp [- J y(t')dt'] -I)
in which the only free parameter is the ratio uiu,.. The result of this calculation,
using y(t) as obtained from Eq. (8.2) and u!/a
.=2, is shown in the inset of Fig-
ure 8-15. 1l1e good agreement between the experimental and the calculated field-
induced SE quenching signal strongly supports our conjecture of exciton dissocia-
tion into polarons, without intenncdiatc charge-transfer states. Thi s is further
strengthened by the ohserved quadmtic field of the polaron genera-
Lion (sec inset rig. tS- I 4 h), which, as recently proposed, indkates a neutral precur-
sor stme for ch;u-ge generati on t42).
The plot of )'(/) suggests that CPG occurs on two separate time regimes. One
is highly dispersive and Lakes place within the fi rst 2- 3 ps. The other is only
weakly time-dependent and persists for longer delays. The initial rate can be as-
signed to CPG driven by exciton migration towmds lower energy sites within the
disorder-induced density of state COOS) 125). During such thermaliwtion, hot ex-
citons reach dis.wciatiou sites, whereby charge generation takes place either by an
on-chain LI9J or inter-chain process I 16]. Note, however, that only the fanner
model predict-. exciton separati on into uncorrelated carriers. In section 8.5 we ob-
served that thennalization to the bottom of the DOS occurs in a few ps, in agree-
ment with the measured timescale for dispersive y(r). The lack of electric-field de-
pendence of the CPG kinetics can be considered as further evidence for the diJTu-
sion-limited nature of the proposed dissociation process. Wi thin this model CPG
becomes negligible once the exci tons have reached the bollum of the DOS. where
their mobility is dmstically reduced 143].
The small and weakly time-dependent CPG that persist<> at longer delays can
be explained by the slower diffusion of excitons approaching the localization edge
fl 5]. An alternative and intriguing explanation is, however, field-induced on-chain
dissociation, a process that docs not depend on the local environment but on the
nature of the intrachain state. The one-dimensional Wannier exciton model de-
scribes the excited state [44). Dissociation occurs because the electric field re-
Coulomb barrier, thus enhancing the escape probability. 1l1is picture is
mterestmg, but so far we do not have any clear proof of its validity.
256 8 Plrotoplrysics of Metlryl-Substiluted PPP-Typc Ladder Polymers
8.8 Conclusions
Based on sub-picosecond time-resolved spectroscopy we obtained a picture,
sketched in Figure 8-16, of the photoexcitation scenario in m-LPPP films. Absorp-
tion of photons with energies larger than the optical gap_ an
excited state (l), which loses excess energy by intra-cham vtbr.llJOnal redtstnbu-
tion (2) and by interchain energy migration {3). The timescale for the former
mechanism is not known, but it is reasonable to assume it is short. of the order of
100 fs. Interchain cooling, which is identified by spectral relaxation of the SE
band and by memory loss, occurs on the I 0 ps timescale. Note that
the two mechanisms are strictly correlated because accepting chains acquire an en-
ergy larger than their own gap. This excess energy is however fairly small, mak-
ing a cold-exciton mignuion picture plausible. As long as the excited slate can
propagate there is a finite prubabilily of dissociation (5). Elcctrit: field
this process, and this is uctually how it was possible to d_irectly_ detc:ct. 11, deter-
mining the timcscule und the dynumics. We find thut dtssocauo_n
becomes dominant, even for fields exceeding I MY/em. Th1s unphes a fimte exci-
ton binding energy of the order of w- eV. The absorption spectrum of the disso-
ciution product indicates that non-correlated polarons ure formeJ. This finding is
better explained by the on-chain dissociation model, while the sample geometry,
in whi ch the electric field is perpendicular to the substrate, is more natumlly asso-
ciated to an interchain hopping. A conclusive statement on this complex subj ect
could not be reached. Thennalized singlet excitons are associated to a PA transi-
tion at about 1.5 eV (6), which displays a vibronic replica at 1.57 eV, and a SEat
2.5 eV {4). The characteristic PA band at 1.3 eY, assigned to triplet excited states,
is observed in the PA spectrum for 400 ps pump-probe delay, pointing out the
presence of radiationless decays, which selection rules (7). .
In the case of a high excitation density, amphficauon of the spontaneously
photons can take place, the emitted light being guided _through film. ASE
depletes the exci ted state and results into a peculiar hne narrowmg of the emtss1on
spectrum, which Fks at the gain At very high excitation ex-
ceeding 10
em- , a new species appears mthe PA spectrum. We propose 1Lo;
rnent to interchain excitations, either neutrdl (bi-exciton) or charged (polaron-pair).
l<' igurc 8-16. A picture uf lhe photocxcitalion !iCC
nario in m-LPPP. see lcxt for a discussion. p+ is a
pos lltvcly charged chain (polaron), whih: x- can
be either a ncgalivcly charged chain or an electron
su..:h as oxygen.
This PA is in a direction with respect to the main optical
transttton, and partmlly overlaps wuh SE, causing optical losses .
. The proposed scenario is mainly based on the molecular approach, which con-
stders polymer as an ensemble of short (molecular) segments.
mam_ pomt m the IS that the nature of the electronic slate is molecular,
I.e. _locahzcd_ and discrete energy levels. In spi re of
of model, _m wh1ch plays a fundamental role, Lhe descrip-
tion ot the ba'iiC 1ntracham properttcs remains unsutisfactory. The nature of th
I ed e
owesr exc1L sl4.!te 111 m-LPPP is still elusive. Exlrinsit: dissociation mechanisms
charge transfer al accepting impurities) are not clearly distinguished from
mtnns1c ones, and Lhe question of intrachain vcP.>us intcrchain charge sepamtion is
nOl yet answered.
. Our show qui te unambiguously that the fate of the exci ted state is deter-
Wllhm t1_1e first 10 ps. This calls for new expcrimcms in the ultmfast time
to raised hen.:. 1l1e uvailabi lity of high quality materials,
m of punty, and processabili ty, is un essential re4uirement for suc-
In_ a complete optical and electrical characterization with cw
IS Ill h1gh demanJ in order to provi<.k a st:tble background onto which
_can be built. _For this_ reason we feel that an inter-disciplinary
approach. whtch mvolvcs chcnusts, cngmcers, anJ physicists, wi ll be the success-
ful stmtegy.
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9 Solid-state Aspects
of Conjugated Semiconductors
Wilhelm Graupner, Stefan Tasch, and Gunther Leising
9.1 Introduction
Conjugated semiconductor.; can exhibit energy bandgaps of 1 eV up to several
eVs depending on the choice of Lhe ( I) building blocks, (2) the number of such
building blocks, and (3) Lheir precise atTangemenl wiU1 respect to each olher.
Therefore, they cover the region of natTOW bandgap materials which absorb and
emit light in the infrared region (a) and show reasonable charge transpo11 proper-
ties. However, via the visible region (h). they evl!n extend to the ullraviolet spec-
Inti mnge (c), performing like inorganic wide bandgap materials. This versatility
and seveml other advantages such as mechanical llexibility, very high photolumi-
nescence quantum yields (PL QY), easy production of large an:as outweigh the
intrinsic instability of conjugated molecules to photl)-Oxidation. ExL-cpt for appli-
cations where long-term stability is not required 111. a proper encapsulation h;L-; to
be used to introduce conjugated semiconductors for technical applications; such
an encapsulaJion is for example intrinsic to applications such as capacitors and
batteries [2 ] .
This chapter is organized as follows: after a brief introduction into the class of
conjugated semiconductors we will discuss the solid state properties needed in or-
der to achieve the fuuctionalities required for efficient device operation, based on
this class of materials. Very different degrees of short aiUI long rctnge order can
be obtained in conjugated semiconducton;; we will describe U1em and discuss
their consequences on macroscopic properties of films of Lhese materials. Since
the properties of the excitt!d swtes in conjugated semiconductors are bolh a highly
relevant question of fundamental research and essential for applicat ions we will
treat the field of excited states spectroscopy in a scpamte section. This section
will be followed by a treatise of device cJlJJec:ts of light emiuing devices made
from conjugated molecules. Before concluding we will brielly discuss the photo.
physics of e.xciwtiou eucrgy trwufer and the propct1ies of hi ghly emissive conju-
gated systems under higlz excitation densities.
260 9 Solid-state Aspects of Colljugated Semiconductors
9.2 Materials
. th lOSt imponant conjugated semiconductors and
In Figure 9-1 we . e n 2 h s the chemical structures of the family
. their solid state propentes.
- s_ o:sed to describe the different synthetic
of para-phenylenes (PP). Thts IS b . na desirable properties from
str.ttegies are apphed in Refs. [3, 4]. Figure 9-
conjugated semaconductors, ted matetials are not processible in this
2 a shows the pure . be both evapomted or solution pro-
side-groups (R1 and R2d inAFig.
cesse . . . h I mers out of a solution to be processe . re-
9-2b), whtch enable t e po Y . nies of conjugated materials is pos-
markable improvement m the electromc prope
.. o -e
E - ? oev
cis (CH).
o=10 10 n em r
.. s .. I " t
trans (CH).' o=10. -10 U em '-11= ""'
t481SO 3 l I
!-doped Shirakawa (CH). . o=10 U em
ISO 3 1 I
doped polyaniline o=10 n em
148150 2 I I
doped polypyrrole o=10 n em
PLOY= 35

CN-PPP: PLOY = 46 %1s'{hlm)
para-hexaptlenyl: PLOY = 30 .4
mLPPP: PLOY = 30% lr-2 {likn)
. . - lheir properties have been
. w a few selected .:OnJugalcd po ymcrs arru 0-
l'igurc 9-1. Matcnab overvtc .. - 00-PPI' J>uly(2..<.JecyiOJty- 1.4 phcnytcnc). EH
r-J ,.Lbrcvtauons arc """" t '-I 4-
compilcd and the '"' owmg "" . ppp p
(2-(6' -cyano-6'-mcthyl-hcply oxy,
PPt> ... CN p
2rt enylcne). and J>LQY= photolumincs
phcnylene), m-LPPP ... mcthyl-substnutcd ladder-type o Y
.:cm:c l.jllantunt yield.
9.2 Matentlts 261

Figure 9-2. Based on the conjugated backbone of a pam-phcnylenc the most common principle
tures of .:unjugatcd mukcuks arc (al the pure b.1cl..bone: (bJ a backbone with attached side-
groups R
and (c) a latklcr type-conjugated backbone: (d) and (c) represent diiTcrcnt types t l f
polymcrs. where (dl a side .:h.ain-1!-raft .:upulymo:r .JULI a single chain-block copulymcr.
sible by using a ladder-type approach to stabilize the conjugated backbone; gener-
ally speaking this strategy has advantages inherent to its chemistry but from the
solid slate physics point of view it also allows the suppression of torsional de-
grees of freedom. In Figure 9-2d and Figure 9-2e we have shown diflcrent types
of copolymers, whereby Figure 9-2d represents a side-chain graft-copolymer and
Figure 9-2 e a single-chain For completeness we would li ke to
mention that the methods of Jin:ct polymerization onto a substmte, e.g. electro-
chemically, and the subsequent conversion of a processible precursor-polymer are
also valuable approaches to obtaining films, consisting of the pure conjugated
In general, Figure 9-2 b to e show stmtegies to make conjugated polymers
more processiblc but it must be noted that the ditrerent synthetic approaches do
not only result in different degrees of (a) c:lzemica/ purity but also alter (b) the
physical propcnies due to intrinsic differences. Compared to a pure conju!!atcd
262 9 Solid-state Aspects of Conjugated Semiconductors
backbone the planarization of the backbone in the ladder-type or the in:
creased torsion of neighboring conjugated units due to solubtlwng
are such intrinsic differences which have direct consequences on the eleclromc
properties (see Section 9-5).
9.3 Functionalities in Devices
Solid state light emitt ing devices require several their
Figure 9-3 describes a conventional multilayer hght emtsston devtce (LED),
which consists of an hole injecting indium tin oxide (ITO) electrode, usually on a
substrate, and organic layers sandwiched between the ITO electrode . and a m_etal
electrode, which inj ecL-; electrons into the active luye_r. The three_ acttve, possibly
organi c layers (A, B, C) have to pcrfonn the tasks ol (I) enhancmg or (2) block-
ing charge transport, and (3) emission of light: these also (4)
enhance charge injecti on from the electrodes ellher v_w a better band alignment
good adaptation to the electrode surface. Another leature of A can be .ts
ability to (5) prevent diffusion of oxygen from the IT?. electrode the a.cu,ve
layers. Tasks ( 1) and (2) result from the fact pos1t1ve and negat1ve charges
can have very diflerent mobi lities in some the charge trans-
port properties in the respective layers should be op11m1zed. . , .
Figure 9-4 shows two more advanced on an
improvement or change in the light emiSSIOn ol layer B
In both cases the goal is to achieve a color conversiOn. In the process_ of
color conversion (ECC) (51 a highly photoluminescent color convers1on layer ts
brought close to the electroluminescem layer. This has the of
possessing just one electroluminescent blue or !Jitrav_Jolet (UV) and as
emission colors as color conversion layers are applied on top_ of 11. !herefore, a
red- reen-blue (RGB) pixel can consist of three blue or UV p1xels the color
r..-.m:fom1a1ion carried out by three different photoluminescent layers.
This technique can increase the of a convertmg r_he blue oc
UV light to other colors since our eye JS most sens111ve 111 the green at 555 nm.

ligure 9-3. CutJvemicmaf muhilayer light de
vice (LED): indium tin oxide (ITO) clectnl<le 01_1 a sub-
active layers A (hole WtllSJXll1). B (enuller): C
(clcclron and a melal ciCl:lrodc. A possable
layer has bt.-cn omiued. which would pre-
vcnl the cunjugat<-t.l nKIcculcs from phutn<>llidOJtion.
Y.J Fmu:timwlilies i11 Devices
9-4. Cutor (a) shows the llCl'tkd for cxtcntal color conversion. (b) for
tntemat l-otor converston - lop nght: cnlargco.J view of the layer whkh cunsisls of a matrix
Oll1d culur-cunvcnm:; dup;mo.J., (hlack duls).
However, the will nor_ enhance the external quantum yield of the LED,
moreover, proper opt1cal coupling between the layers has to be achieved in order
to the QY too much [61. One of the obvious problems is the princi-
pal requirement of havmg the ITO-covered glass substrate between the color con-
verter the layer. This can also lead to color bleeding, an etTect where
the enuuer _layer .excttes not only the conversion layer, it is supposed to
but also netghbonng ones.
:n1e process of inlemal color conversion (ICC) l'ill an eflicicm tmnsler of exci-
energy l7J can, however, not only change the emission color but it can also
mcrease the external quantum yield of the LED (see Section 9-7). The most sim-
ple approach to understand this is the fact that most emiuers show the effect of
concentration quenchi ng, i.e. cmiuers of the same kind brought close to each
other a very PLQY. Incorporating the same emiuer in a liquid or solid
state soluuon 111 a strong increase in the PLQY, often up to 100%. There-
fore, the sepamt1on of the tasks of charge tmnsport. CaJTied out by the major com-
ponent of an LED, the matrix, and li ght emission, perfom1Cd by an emiuer, which
up than I% of the active layer, can signilicamly increase the external
y1eld_ of an LED. One application of this lechniliUC is the producti on of
hgh_t _ LEDs based on only one active layer 181. Figure 9-5 summarizes the
functonaltlies to be expected from materials used in eiTicicnt light emitting de-
264 9 Solid-state Aspects of Conjugated Semi'01/ductors
Possibility to
preferential ordering
Ada plablc
High rnobtfity for charge
carriers of both polanties
Htgh PL
Figure 9-5. Funccionalities to be from materi:tls to be uset.l in cl'ficicnt light-cmining devices.
9.4 Order in Conjugated Semiconductors
While there is much to discuss about order in fi lms of different conjugated mole-
cules, a comprehensive survey of the structural properties of various conjugated
polymers can be found in Ref. (9}. This section focuses on the relati on between
microscopic order and macroscopic properties, and on structure-property relations.
An example of a highly ordered conjugated material is the conjugated para-hex-
aphenyl its crystal structure is shown in Figure 9-6. PHP adopts a monoclinic
crystal structure (a;;: 8.091 A, b=5.568 A, c=26241 A. P=98. 17") [1 0]. PHP fonns
hi ghly emi ssive polycrystalline films upon evaporation of the molecules onto a sub-
strate. Its morphology can be influenced by controlling the evapomtion conditions
[II]. It is possible to rub a NaCl subslr.tte with a teflon stick at cicvalcd tempera-
lures ( 138] in order 10 obtain a preferential orientation of the PHP molecules depos-
ited onto the substr,Jie during evapor..1tion. In the elastic electron diiTmcLion pauerns
of the textured hexaphenyl films in Figure 9-7 it is clearly visible that the material
represents a typicul polycrystullinc behavior wi th well developed diffml:lion peuks.
Moreover, the intensi ties of the (00 I) peuks in relation to, l<>r cxumpk, the (20-1 ),
(21- 1 ), (020), und ( 120) arc much too low for an isotropic polycrystalline material
with a random distribution of crystallite orientations. Therefore, the electron-diffrac-
tion pattern in Figure 9-7 provides evidence for the expected texturing due 10 the
teflon rubbing of the substr.Jte; a macroscopic slate of order was induced. Further-
more, in the inset of Figure 9-7 we show the intensily of the (020) electron diffrac-
tion peak as a function of the angle between the rubbing direction, which corre-
9.4 Order ;,, Coujugated Semiconductors
8 & &
(11-2) & & &

t' igure 9-6. Crystal structure of hexa-
phcnyl, whereby the solid gray bar rc-
che substr.ttc pl:mc. n
c muno-
unit c.:cll is sketched in thin solid
- 'iij
"' 180
1.5 2.0 2.5
momentum transfer (A-1)
F'.gurc 'J-7. clcch'Oit-diiTr.JCtion . altern of . .
dtCCS arc using the intn,Janar . akh:ghlt.ly hcxaphcnyl lilm. The Miller in-
....,,. . ( - - .,. u..,tc 10 Ret I I 37( 1 1
.....-.. as a Ulk:tiOn u( th.: lllc lllcnSJty of the \020)
teAt) - t.skcn fi\1111 Ref. II lltt.: ntum tmnsfcr aut! the Tcnun rubbing t.lirt!t.' tion (,.,c
266 9 Solid-state Aspects of Conjugated Semiconductors
. . th N Cl cr stals and the measured momentum
sponds to the [001] dre:cton of e a fi Y
' o l80 225 and 315. This
y, harp maxtma are observed or ' ' ' ' 001
trans er. ery s . d' . th t the PHP b axis is aligned par.tllcl to the [I
d ery good 1n tcatt on a - . . 'd b
provt cs a . f tJ N Cl substmtes This assumption Is also confirmt: y
und lll 0) dnecttons o 1e a .
polarized. diffraction, one can also study the momen-
In addtlt on to e e asltc e e . . . in contrast to those photons that only
tum-transfer-dependent energy loss results of this electron energy loss
transfer energy to the sample ;_8 In the two figures (top and bot-
spectroscopy (EELS) are shown PHP films are shown, which are
tom) the electron energy loss spectra d r )endicular to the molecu-
dependent on momentum trdnsfer both pe_ b til o' the sample
k' d 1 ge of the mtrmstc amsotropy o 'J
ltJr axis, therefore, ta mg a van a transfer amllel to the PHP axis (see
and of the experiment. For the . . pf 0 07 or 0.1 A - the tmnsi -
Figure 9-8. top) ut low transfer to the si tuation ob-
tions are nearly vertica_l m the th . . k cuused by the plasmons
served for optical expenments. For thts sttuallon_ e pea I rb' t I (HOMO) 10
. . h h' h t occupted molccu .tr o a
related to an lrom ' . e .:. is the dominant peuk (peak I, in
the lowest unoccupted molt.:cular o ua
2 4 5 6 1 8 9
energy (eV)
.2 4
:1: q=0.1 A
2 3 4 5 6 1 8 9
energy (cV)
. . . . ' ccxturoo hcxaphcnyl lilms for diiTen:nt value:, of
f<iuurc 9..g . TCJfJ: loss funcllon Ol lughJy . . pl . . n'"loo lo the same CXCIIallon. f3o<
<> 1 . 1. . . . The wnn<X:t . . .
tmnsfcr ro the mo ccu m axis. I rr . r, r <.liiTcrcnl value..' of momentum lr.JIL\Icr pcrpcodic
tom: Los:. function of texrurcd ms u I :-d lo equal ai'Cil.\ under the
Icc l . . . In both PnpltS the speclm were llllnna JLC ular to the mo u ar axis. .,..- .
between 6 and I! cV - taken from Rt:l . II JIS).
9.4 Order in Co11jugared Semico11ductors
Figure 9-8, top). For higher values of momentum transfer (0.2 A-1) a new peak
(II, in Figure 9-8, top) appeetrs which is related to lhe excitations from HOMO to
LUMO+ I. In u quasi band structure dt:scription this peak is equivalent to the tran-
sition from HOMO-I to LUMO [1 38). COJTespondingly, increasing the momen-
tum lranstcr leads to the transi tions HOMO- I to LUMO+ I as well as IIOMO to
LUM0+2, which are depicted as peaks III and IV in Figure 9-8, lop. The strong
momentum-transfer-independent peak at 7 eV corresponds to excitations where
the ini tial and the final state belong to bands derived from the benzene orl>ital,
with a high electron densi ty at the C-atoms which arc not invol ved in the C-C
bridging between tl1e rings. In Figure 9-8 (bottom) the corresponding transitions
for momentum transfer perpendicular to the PHP chains are shown. The peaks be-
tween 3 and 4.5 eV result from the fact that there is a slight contribution from
chains which arc oriented in such a way to give a momentum transfer parallel to
the chains. The excitation at 4.2 eV is also observed in optical experiments l i39J
(see Fig. 9-9) and was predicted by band structure calculations I12J;- it is u con-
sequence of the three-dimensional nature of the PHP electron system in the solid
crystalline slate. The higher lying transitions are due to tmnsitions from the
HOMO 10 a non-bonding state and are polarized in the direction perpendicular to
the molecular axis I 13j.
From the optical absorption of two different hexaphenyl films, one with its
chains predominantly stanJing upright on the subsu-ate, lhe other with the chains
randomly di stributed in all orientations, similar structure property relations can be
concluded [139j. By compari ng the calculated absorption coefficient [1391 per-
perulicular to the chains with the observed optical absorption spectm of bolh
films we see thut the optical absorption, plotted in Figure 9-9, in the visible and

Optical density (abSOfbance)


1 a \
\ I \
!: I \
1: \
? \
\ , _____ _
c ----- -
300 400 500
Wavelength (nm)
Figure 9-9. G!kula!-.-d ab,orption L'(lCilidcn! pc.-p.:ndicular 10 fl<lllt hcxaphcnyl (c) comp.ncd 111
!he experimentally dctcnnin-.-d absvrptiun J>e.-p.:tk.lkular (b) and parullcl (il) lo rhc - tal.cn I rom
Rcr. 1 13<JJ.
268 9 Solid-state of Conjugated Semicmrductm:s
ultrnviolet range is mainly determined by the dielectric function parallel to the
polymer chain. Again the peak around 4.2 eV is predicted and found for absorp-
tion with the electric field perpendicular to the chains.
l n on:Ier to summari ze thi s section it must be nmed that the possibility to eva-
porate conjugated oligomers in such a way that their chain axes point predomi-
nantly in one direction allows us to determine the anisotropic electronic properties
of conjugated molecules. From these studies i t becomes evident that in order to
obtain polarized absorption or emission of light as required in polarization filters
or LCD-backlights, the application of conjugated molecules is one of the most at-
tractive areas of application for these materials.
9.5 Excited-state Spectroscopy
The term excited slate spectroscopy can have two ditfcrent meanings, both of
which will be treated in thi s chapter: (I) probi11g the dijfertnt excited states of a
material, the pathways to reach them, and the properties of these states and (2) a
significant population of one or more of the (xc:ited states and the subsequent
probing of the contribution of these stales to the material's properties. Before
going into details, a selected set of principal experiments in the area of excited
states spectroscopy wi ll be oullined. In order to detect the excitation process with-
in a bulk material one can use:
I . The most ubiquitous method of tra11smission spectroscopy, in which the
amount of light passi ng through a sample is determined. Very often the influ-
ence of reflection and scattering is neglected and the rntio of incident and trans-
milled intensity (/Eo) is linked to the absorption coefficient (a) and the sample
thickness (d) by Lambert-Beer's law (see Eq. (9. 11 )).
E = Eo exp( - ad) (9.1)
2. One way of measuring true absorption is to employ photothermal deflection
spectroscopy (sec Fig. 9-1 ). ln this case the absorbed light, leading to a slight
heating up of the sample, is detected by the tempcr.Iture-depcndent deflection
of a laser beam passing dose by the sample. The obvious advantage of this
method is that it really measures the absorption coefficient (a).
3. Photoluminescence (PL) and photocurrent (PC) excitation spectroscopy provide
insight into the contribution of the excitation to the population of emissive and
conduct ive states. However, in both cases the shape of the spectra is highly de-
pendent on sample geometry; in PL excitation spectm the samples have to be
opticall y thin and in PC excitati on spectra the location of the charge-genernting
region influences the magni tude and shape of the spectra.
4. The technique of trJnsiem or quasi steady state photoinduced absorption (PIA)
allows the papulation of excited states and also probing the optical
!i.5 Excited-state Spectroscopy
of these states or of the states into which the excited states dec .
g. 9- I_Q). The advantage or this technique is that it probes both .. (seed
absorpuve states. emss1ve an
9.5.1 Excited States
_9- 1 0 the principal scheme of excited states involved i .
cesses n a conJugated molecule. After the abso lion of li n optical
ferenl CJUantum eneruies (A A A ) . .
'"!' ght (hv) of several df-
involvement f o . '!' " 2 '. smg el excnons (SE) are formed due to the
o phonons. Smglet excJtons can create t j 1 . ,..
tersystem crossin<> (ISC) Tt . b . . . . . r pet excJtons (TE) vw m-
o 1c a sorption Wlthm the triplet ch
posed of lrunsitions of sever. 1 -rr . s eme s agam com-
. a uJ ' enng quantum energies (T. T T ) d
mvolvement or phonons. Tile emission pruc .. b d" 0 lh . . 2 . ue 10 the
singlet excitons to the ground tia of the
solved photoluminescence s x:. H . ., _I A./}. nse to a well re-
into charged states .called swgl,et can also dissociate
optical tmnsitions p p p Th,
. e ploucd pos111ve polaron with its
served i . h . . ,d, . ! l c_ po aromc and the lnplet tr .lllsitions can be ob-
n an p otom uced absoq)lJon (PIA) experiment.
- - - - - -r-..--
L l t l.

I urn inescence
--_..;L.....- ---L-.l......J._ 0 - - - - -
absorption PIA
Frgure 9-10. &heme or excited of a conu tcc.l mukcul .
sever.JI tliiTen:m ,
uamum (II
11 1
. c. Ancr Lhe absorpuou of (Ill) uf
(pi "" . I
1l. "lllglcl exciluus (Sc) an: li>OI cd d h
meru o Singlet cxc.:itons can cre:uc in

. . . TE . . ' uc lo I c lnvolvc-
within the triplet is ag:uu ( . ! IWI crossing (ISC). llu:
ergtcs (r, . T1. 7-,) due lu the involvement ,,. e u !>l:vcr..tl dtffcn:nt quantum en-
lion of the exciton' lo the g\und sllatcphunun,. CIIII,Siun pmce"s by mdiativc rccomhina
I . I'ICI lr.Jnstlluus L L L ivc . . II
.., .. >l.o ununcsccnuc 'JlCClrum However si
1 1 1
. I 1 ' .; s nsc lo a we 1\:solved
polarons. We have llolt' . . ... .. ,: ' g c can aiMl di:..,ociate into charged M<llcs
. "" a pusr "c pu .nun wuh ns opt1 1 . r p
lllplet can be ol>!.crvr..'ll in a phot . ttl ccd . b c.l
' P,. l llc polai\Kli.: and
u a '"!Jlltun (PIA) cxpcnmcur - l<1l.en from lkf.
270 9 Solid-state Aspects of Coujugated Semicouductors
It was shown that the wide gap semiconductor poly(para-phenylene) (PPP)
1 h d v es [14) The electrontc
be used as lhe active layer m blue- tg t-emtumg e tc . . .
ro erties of conjugated polymers depend strongly on lhetr structural
Th p p for the synthesis of poly(para-phenylenc-ladder
e mottvatton h' cd b a plananzauon
(LPPPs) was the increased overlap of lhe rr-e_lectrons, ac . . Y _. _
1 mer backbone [15). AL the same ttme lhe synthests vw a polymer
closure reaction of a substituted polymer _[16) results tn _a
s!:ucture with a very narrow conjugation length dtstnbutton. For all
::ons some results from this material are used to illustrate lhe field
state spectroscopy in conjugated materials. In 9-11 have:. . e
transmission difference speclr'J, which were obtamed by a transtent PI tee
for methyl-substituted ladder-type
K excited at 3.2 eV (for details see Ref. [17)). tgure s ows, . . . m-
sarnplc transmission aL differem times after the laser pulse_ .the S:.
1, Since the tempoml extent of the laser pulse ts below 200 fs, l e pro.
c. . f 4 40 and 400 ps represent the Li me-resolved PIA spcclrJ after the am-
tunes o ' r. , 9 10 an be seen
al of the excitation. Most of the shown 111 .- . c . :
2.3 and 2.5 cV stimulat..:d emission from singkL exctlon ..:mtsston (L,, L2) ts
,.' 400ps(X 10)
1.4 1.6 1.8 2.0 2.2
Energy (eV)
.. .. n cncc s ctr.t of m-LPPP at T=77 K excited at 3.2 _cV li>r var-
l'gurc 9-11. Twnsamsst011 cia crfi /rr 1141) l11C inset :rooms nut the low energy rcgton for 0 ps
ious pu_mp-probc c.lcluys absorption (DIA) arc also shown for
(solid hllC) and 400 p:; (uas ICu IIIC "'
c.:omparisnn (accnrdiug Ill )142)1.
9.5 Excited-state Spectroscopy
detected. Around 1.9 eV we can observe the polaronic transition P
with its vibro-
nic replica P
at 2. 1 eV. The polaronic nature of this tmnsition is establi shed by
comparison of the spectral signature at 400 ps with that of a sample after redox
reaction. producing singly charged slates. At 1.5 cV a transition from the exciLL-d
singlet exciton stale into higher lying levels was detected. The triplet transition 7j
at 1.35 cV is only ohscrvCll al longer tim..:s, because of its slow formation
due to intersystem crossing. In lhe following sections these states and transitions
will be discussed in greater detail.
9.5.2 Neutral Photocxcitations
Singlet excitons with binding energies of a few tenths of eV arc lhe primary
photocxcitations in conjugated molecules. The mosl basic spectroscopic experi-
ments concerning their propetties are optical Lmnsmission measurements. Figure
9- 12 compares the absorption calculated from a transmission experiment with the
PL excitation spectrum of a thin m-LPPP lilm. It is evident that the spectra are
identical and lhal lhcy show Lhe tmnsitions A
, A
, A
and higher, depicted in
Figure 9- 10. We have also included both the elcctrolumincscence (EL) and PL
emission spectra of m-LPPP, showing the transitions f...z, and higher, as de-
picted in Figure 9-10. As pointed out before, one of the best methods to measure
absorption is photothennal deflection spccuoscopy. This was also applied to m-
LPPP and the result is shown in Figure 9- 13. The result of this experiment is
highly encourJging in tem1s of the very low absorption below the onset of ab-
sorption due to the rr-rr* tmnsition, which is found at 465 nm in Figure 9- 12.
From the photothermal deflection experimem, it can be concluded that the absorp-
tion changes between 465 and 500 nm by about four orders of magnitude. In inor-
ganic semiconductors such a low subgap absorption is indicative of a very small
defect content. Regardless of lhe origin of the subgap absorption in conjugated
molecules, the result shows that m-LPPP is suitable as a laser medium in that re-
gion as far as loss due to absorption is com.:erncd. In addition, the photothermal
deflect ion method does not probe scauering, therefore this loss mechanism must
be treated separately. In conjugated polymers with a well delined effective conju-
gation length a steep onset of the density of staLes at the band edges is expected.
The fuctthat this is confirmed by the results in Figure 9-13 further establishes the
high chemical Jefinition of m-LPPP.
A further clear establishment of the absorption due to singlet excitons and the
phonons coupled to them is lhe elcctroabsorption experimem reported in Re[
[18] . The main results are shown in Figure 9- 14: the top panel shows Lhe absorp-
tion spccuum of m-LPPP at 20 K. It becomes clear that the peaks at 2.7, 2.9, and
3. 1 eV, representing A0, A., and A2 (see Fig. 9- 10) are not the only vibronic repli-
cas. There arc additional peaks between these dominant ones if the experiment is
conducted at low temperature. The bottom panel in Figure 9- 14 shows a so-called
clectroabsorplion spectrum which is obtained as the modulation (or change) of Lhe
absorption under the application of au electric field. Below 3.2 eV the electroah-
272 Y Solid-stule Aspects uf Ccmjuguted Semicouductors


(/) _____ /
<( 300 350



..8 0,1
"" E
[ O,Ol
I E-3
__ .. , ,
0 300

400 450 500
Wavelength (nm)
Figure 9-12. Absorption photolumi-
nt!SCencc excitation spectrum (PL.,.). photo
lummcsccnce (PL). aud electrulumincscmce
(EL) of mLPPP.
400 500 600 700 800
... _, '.
_........satUJ" tion of P ps
.... ..
J. r


--a sorption
ir cnsity o
- U lv-VIS at sorption
. .A. I t
ifiV" r
., v'
400 500 600 700 800
wavelength (nm]
0. 1
I E-3
Figure 9-13 .. Absorption spectrum
of mLPPP. <.lc:ll:m1ined using
pholothermal dc:tlcclion spectros-
copy (PDS)- from Rd. [143[.
sorprion (EA) specrrum of m-LPPP can be described by the rigid red-shift of an
excitonic state located at 2 ..711 eV, which is caused by coupling this state to even-
parity states staning at 3 .. 2 eV (so called nAK) (1 8] .. 1l1is is also expressed by the
good agreement of the first derivative of the absorbance spectrum and the EA
spectrum; all the significant features of the EA spectrum ure well by
the fi rst derivative of the ubsorbance. Therefore, the binding energy of the exciton
in m-LPPP cun be esti mated to be about 0.5 eV .. Moreover, there is no significant
contribution to the EA spectrum from the second derivutive of the ubsorbance,
which is very often present in the EA of disordered polymer films. This
fuel points to large conjugation lengths in m-LPPP. Above 3.2 cV a different
mechanism, namely the electric inlluence on the continuum stutes, is responsible
for the EA spectrum.
Fimtlly, we would like to point that one of the easiest to intluence
electronic protx:rties of conjugated oligomers and polymers IS to vary the cham
, .
9.5 Exdted-stale Spectmscopy
--opCJcal deflslty
2.9 3.0 3.1 32 3.3 J ...C 3 ..5 3.6
- - d(ad)/dE
--6ad. 53 kV/cm, 20 K

2.5 2.6
3.1 32 3.3 3.-e 3.5 3.6
9- 14 .. Absorption (lop) and clt.."o.:rruabsorptiun uf a mLVPP lilm at 2() K. Nuh: the resolution of
at least two phonon (sec text).
Jn 9-15 the chain length-depenllence of a sample of the tr.Jnsitions
an Fagure 9- J 0 !s the tmnsitions include the singlet exciton ab-
A2. the tnplet excuon absorption T
, T., T
, and finully the emis-
Sive lmnsllJOns ith Lit L2 of the singlet excitons. The position of these transi tions
on the chain length and also on the stale of the conjugated backbone. It
IS obvaou_s that the spectrum of the planar-backbone m-LPPP is com-
pletely that of the non-planar oligophenyls. Consequently, a very
Stokes shtft 1s observed between absorption spectra anll photoluminescence
emtssaon spectra of the m-LPPP .. This is the rcsul! of the suppression of geometri -
cal reluxatt on of the upon electronic excitation. In orllinary PPP, how-
the coplunar (qumOJd) suucturc exists only in the excited state due to rotu-
uonal degrees of frecllmn between neighboring rings.
274 9 Solid-state Aspects of Coujuguted Scmricouductors
2 3 4 5
Energy [eV]
l'igurc 9-15. Triplet absorpliun. singlcl cmb>iun. and ah>nrpliuu (from left lu righl) uf (frum lnp lo
bouom) m-LPPP [1441 and hcxaphcnyl tilm.\ [145) :tl 90 K. and pura-<1ua1cr- and lcrvhcnyl m 77 K
in lclrclhydro-2-mclhylfuran [ 146[.
In summary, all the transitions expected for the neutral states of a model sys-
tem for conjugated polymers, the m-LPPP. were observed and described and all of
these transitions aJso show clearly resolved vibronic replicas due to coupling to
vibronic modes of the backbone.
9.5.3 Charged Photoexcitations
One of the charged species encountered in conjugated systems is the singly
charged positive or negative polaronic state. Polarons are characterized by their
charge, by the lauice distortion around them, and their electron paramagnetic ac-
tivity due to the unpaired spins. Furthermore, they can be detected in PIA experi-
ments by the transitions P., P
, P
, sketched in Figure 9-10 and by the infrared
active vibmti onal (IRAV) modes due to a charge redistribution along the back-
In Figure 9- 16 we show the PIA spectra of m-LPPP, which exhibit the P
si tion and lhe IRAV-modes for different qualities of the LPPP. In conventional
routes to PPPs. defects such as bmnchcd chains and !urge torsion anglc.o; of neigh-
boring rings are known to appear. These defects act as electron and/or hole, shal-
low or deep Imps [19, 20], which limit the mobility of charge carriers [21). The
synthetic route towaros the LPPPs prcvems the described defects. One of the man-
ifestations of this behavior is the well resolved vibronic structure seen, e.g., even
in the EA spectm in Figure 9-14. However, even within the class of LPPPs there
are different qualities; we have selected three diOcrent materials:
'- 2000
.6 g

2000 3000 4000
Wa v e number (.l/cm]
2. 6 2.6 3 3.2 3.4 3.6
Eneray [eV]
9.5 Exerted-state Specl1vscopy
9-.16. absorption of (a) s-LPPP. (b) 1-LPPP, and (c) Ccnrcr: photornduced ab-
of (a) :\LPPP. (b) m-LPPP. Top: pholoinduccd abS<lrplion spectrn of
(a) s LPPI. (b) 1-LPPP .md m-LPPP allcr login/oxygen trcalmcm (sec lcxl).
- the . s-LPPP, which consists of a ladder-type PPP bockbone wi th an
cham lengLh of 20 phenyl rings, average
- the . 1-LPPP, which consists of a ladder-type PPP b kb h
ac one wu an averdge
chatn lenglh of 40 phenyl rings, and finally
- m-LPPP, which _consists of_ a melhyl-subslillllcd ladder-type ppp backbone
Wllh an average cham length of 50 phenyl rings.
absorption speclra of these ma1erials arc shown in the bouom panel of
9-.1 ? spectra II becomes clear lhat I he m-LPPP shows the lon-
gest length 1_231 lhe best resolution of vibronic progression.
and the ons:t of 1231. Thcn:forc, one would ussume the m-
LPPP to be a malcnal of the htghcst chemical definition. This is indeed con-
9 Solid-stute Aspects of Conjugated Semicvnducwrs
firmed by the PIA spectra. The top panel of Figure 9- 16 shows the PLA spectra of
these materials. As expected the high definition of the m-LPPP and consequentl.Y
its low defect content lead to a very low polaron signal in the pure san1ple. Th1s
can be understood by recalling that a quasi steady state PIA spectrum
the absorption of photogenemted stales such as polarons. Polarons are stabllzcd
or tr.1pped by defects within a conjugated polymer, consequently. a low ddect
content is connected to a low polaronic PIA signal. This statement 1S for example
in excellent agreement with the work of Pichler el al. on
poly(para-phenylenc vinylene) (PPV), where basically no polaromc PIA IS found
in comp<rison to a strong signal in standard PPV. . . .
Furthermore, the shape of the polaronic PIA in the three IS
also quite revealing, especially the relative strength of the electron1c
as compared to the IRAV-modes. As described in L23J and Refs. thercm, the larg-
er the r.ltio of the intensity of the P
-transi tion with respect to the IRAV modes,
the larger the effective mass of the associated charged defcc.t polaron).
The PIA spectm confinn our assumpt ions concerning the sample quahty deduced
from the absorption spectra and: (a) the polaronic signal weakest (or de-
tectable) in the high-quality m-LPPP. and (b) the e1Tect1ve 1s. al so
highest in the lowest quality s-LPPP. In order to clabomte on the
ent LPPPs can be photo-oxidized, in order to introduce chem1cal wh1ch
wi ll stabilize the polarons. The effect of this procedure on PIA spec-
tm is shown in the center panel of Figure 9- 16. The most stnkmg d1fferences are:
-; : -!-----
:.. !
...... .!
150 2 10 270
Temperature [K]
Figure 9-17. Pholoinduccd absorpt.ion in s-LPPP at 0.26eV _versus (filled Full
lines reprc.o;cnt the model results (lower curve for two acllvallon encrg.cs, haghcr. curve for one). 1bc:
dolled lines reprc.scnt the decay nates for the -0. 12 eV (a) ami - 0.37 cV (b) actavatcd processes; the
dash-dolled horizontal line ro:prc:.ents the tcmper.!turc-indcpendcnt part .
9.5 Excited-state Spec:Iroscopy 277
- even the photo-oxidized m-LPPP shows a clear polaronic PIA spectrum due to
the introduction of chemical defects which were barely present in the pure m-
LPPP but present in the s- and 1-LPPP;
- as expected from the defect-mass-to-PIA relationshi p: as the lowest quality ma-
terial s-LPPP shows the strongest P
-tr.1nsition relative to the IRAV-modes;
- furthermore, there is dear correlati on between the shape of the P
and the materials: s-LPPP always shows the peak at the highest photon quan-
tum energy, followed by 1-LPPP.
In order to study the charged photoexcitutions in conjugated materials in detail
their contribution to charge transport can be measured. One possible experiment is
to measure thennally stimulated currents (TSC). Next, we will compare the results
of the TSC-expcriments, whi ch are sensitive to mobile thermally released charges
tmppro after photoexcitation, to the temperature dependence of the PIA signal
(sec Fig. 9-17) which is also due lo char6ed states as discussed previously.
First, we would like to address the question how sample quality inll uem:es the
obsecved results. Synthesis and sample treutmcm inlluence Jhe electronic proper-
ties of conjugated materials in a deli ned way 123). We have already shown 131 J
that the shape and intensity of photoinduced absorption spectra in ditlcrent repre-
sentatives of the LPPPs may vary Fig. (}-16), indicating at least differclll tmp
densities but also different electronic properties of these traps. depending on the
synthesis and subsequent treatment of the polymers. However, the electronic prop-
erties for this class of polymers can be understood in terms of eflccti ve conjuga-
tion length 123- 251 charge tmnslcr by photocxcitation or redox reactions L31 J and
also upon intense visible inadiation under the influence of oxy-
gen [23]. Therefore, by optical spectroscopy (absorption, photoluminescence, or
photoinduced absorption) we can assess the quality of a sample.
f'Or the chamctcrization of the trap levels we appl ied the thennally stimulated
cunent technique following the initial rise method [26J which was successfully
applied to other conjugated polymers [27]. The device consisted of a sapphire
substrate with an interdigital gold electrode structure on top of which a 200 nm
thick polymer fil m was drop-cast. The gold electrodes had an overall length of
87.5 em and a gap of 20 11111. The substrate was mounted in a cryostat and cooled
to 90 K. After illumination of the active area of the device at 454 nm for 2 min a
voltage was turned on yielding an electrical field of 4x 10
V/cm across the elec-
trodes. Any increase in the dur.1tion of ill umination above 2 min does result in no
greater TSC, therefore 2 min of illumination under the chosen condit ions result in
satur.ttion (filling of all avai lable traps). As the temperature, T, of the device was
increased we observed the stimulated current depicted in Figure 9-18 a. Trapped
charge carriers arc thermally released and an electric current is gcner.ttcd. As the
linear heating rates were varied between 0.06 K/s and 0.25 K/s, the maximum
current al ways appeared at 167 K. This can be attributed to monomolecular ki-
netics with non-retrappi1tg traps L26]. Without prior ill umination, no significant
current change is detectable during the heating cycle (b).
It must be noted that the prerequisite to sec distinct in a TSC experi ment
is a steep onset of the dcn)oity of states at the band edges. This is fully fulfilled
278 9 Solid-state Aspects of Conjugated Semicouductors
3 4 5 6 7 8 9
1000/T (K
10 11
Figure 9-18. Themmlly stimulated current of s-
LPPP with (a) and without (b) p rior to illumina-
for LPPP as discussed in the previous paragraphs, especially by the results plotted
in Figure 9-13.
The electrical cum:nt of a coplanar imerdigital gold/LPPP/gold device is space
charge limited due to p-type charge canier traps localized in the bandgap [28].
This can be inferred from the field dependence of the dark current at room tem-
perature. The thermally stimulated cutTent exhibits two peaks, corre-
sponding to two distinct trap levels E: and ;, which can be calculated from the
rise in cunent, /, below the peak temperature:
In(/) =-+ consl.
By the integrating the current over the time for each peak we determine the num-
ber of charge carriers which equals the number of tmps N, (under the condition
that all traps were occupied at the starting tempemture):
J ldt = eN,
where e denotes the elementary charge. In Table 9-1 the results for the trJ.p depth and
the trap concentration n, are summarized. The schematic band diagram in Figure 9-
19 illustmtes the trap distribution in the bandgap. The assumption of a trJ.p-distribu-
tion mainly centered around two energetic levels is backed by the results obtained
upon varying the heating mte. We found only a corresponding change in the current
intensity but no changes in the peak shape and the position of the maximum of the
TSC (curve A) (see Fig. 9- 18); no additional teatures appear in the peak.
The PIA-investigations were carried out under dynamic vacuum (p< w-
and at 77 K with films cast from toluene solution onto KBr substrates. For the
dispersive method f29, 30] the globar, the KBr-prism premonochromator, and the
gmting monochromator of a Perkin Elmer were used in the
spectral range of 0.25 to 1.24 e V. The pump beam was chopped mechanically
9.5 Excited-state Spectroscopy
f. Table I. Trnp depth and dens it in LPPP T .
1: levels obtained from the TSC PIA temper-.uure at peak current, and EftA are the tmp
c.; .; lh expcnments N . d th
e trap coucentrmion, res!X-"Ctivcly " 'an 11, are c number of tmps and
1;,. (K)
t;sc (cV)
,, (<.:111-.1)
0. 12
Figure 9-19. Band diagram of LPPP with hnle tr.r sand ' . . ' . .
valence txuu.l 1:: ..: .r .
. gnlt.l o.:k"Ctmdcs With EvA< vacuum level. Ec
. . ro.: 1111 eve f. lnudw
, n r c r .o L
trap ISlrrbution, X affiruty and </> ; ,.. " "gy. anu trap tlcptll,, 11,tt.)
Au wor" oun.:trun of the gold clct:tnxk"'.
using the chopper frequency the reteren f . EG .
Research lock-in amplifier 124. ll1e probe ;: . . or \&? Pnncet?!1 Applied
quency, which W<Lo; used <Lo; the . , . ..

at a different frc-
Princcton Appl" .I R I tclcrence l o .t SC(ond lock-m ampli fier (EG\&G
teu esearc 1 model 521 0).
1be PIA spectm obtained show ,
1 . .
Fig 9-17) . . . . : . at e ectromc lransuton peaking at 0.26 eV (see

on perature is depicted in Figure 9- 7. ]. c dependence of the PIA mtcnstty
1o mterpret the magnitude of the PIA si , . . .
generation of states will be discussed It :, equatton for the photo-
. uescn s l e change of the n be f
s a es, n, wtlh respect
d d. . urn r o
p=excitation density) and the'

rate kp (k==const.,
nctics) and can be wriuen as follows: c " -mversc Cltme, (Jl=Order of ki-
- = kJJ - ,,,,
dt .
The number of photoexcitcd states in dynamic equilibriut . . . . .
cay rate =creation rate (dn!dt=O): n "q s obt,uned lor de-
9 Solid-state Aspects of Conjugated Semiconductors

ncq = l ex !Pl"
In a steady state experiment the PIA signal Y is proportiona! to 11eq. the
PIA with a lock-in amplifier means exciting the sample w1th a penochc
pendent pump photon flux. The latter can be by a ':ave
switches between a constant flux and zero photons w1th a l-1( As
shown in Refs. [321 and [33] the PIA signal, measured with a lock-m an1phfier Y.
shows the same functional dependence on pas ne._. in Eq. (9.5). For the monomo-
lecular (jt = I) and bimolecular (jt =2) case the influence of r depends on r., the
lifetime of the observed states, as follows:
consl. for r 1 r
y = ex r for > r
Upon varying the l:hopper period between 6 and 9-+ we a increase
in the signal with increasing chopper period

S_mce Y 1:. not hnear tn r '?D

ms r has to be in the order of 100 ms. I 1:-. the only tcmpcmture-dc.:pcn-
factor, which represents a decay rate varying with 1; changes Eq. (9.5) to:
kp ] ; [ I
nC<! = l(T) ex l(T)
A satisfactory description for our experimental results is obtained for a nOXJ <n of
the following form:
) ]
_ 1
[ (
-w.) (-w2 . ,.
nC<!(T) = A exp kuT + Bexp kuT + E
Here ku is the Boltzmann's constant, A represents a W1
w are the activation energies for a thermally enhanced decay of the photom-
slates, E is the temperature-independent part of the deC<.Jy factor . and B re-
presents the relative weight of the W:!-activated . .
The exponent 1/p in Eq. (9.2) was found to be 0.65_ for_our sampl es [31 ]. W1th thts
value we attempted to model the experimental curve 111 F1gure by Eq. (9.8). We
obtained 0. 12 and 0.37 eV for the energies W1 and W2. respectively. numbers
mean that the 0. 12 eY process reaches the magnitude of the
decay rate, , al 170 K, while the 0.37 eY process re<iche:> th1s level at 200 K .md
becomes the dominant decay channel above 220 K (see F1g. 9-17). .
The photoinduced absorption and the e_lcctrical c.:haracteristics of the
LPPP show that the optoelectrical propert1es are strongly on car
rier traps in the bandgap. From aromatic ll 1s known that
rities and structural imperfections fonn Jocahzed states L34). LPPP f'lnns
neous and dense films with a interehain distance of about 20 A and ncghgt-
9.5 Excited-swte Spectroscopy 281
ble long range order. We propose that the --.. 0. 1 eV tr:.tp level is a result of local
variations in the electronic band structure due to the influence of neinhborino
b 0
molecules (aggregates or small crystallites). The -0.4 eV level occurs in a much
lower concentration and results from chemical defects in the polymer backbone or
impurities which break the conj ugation of the polymer.
An alternative interpretation for the activated behavior of the photocurrem and
the PIA-decrease with temperature was proposed by Townsend et a/. [35]. They
assigned their experimental to a thern1ally activated interclwin-hopping
mechanism for bipolaron-like charged soliton pairs, the experiments of which
were carried out on Durham trans-polyacctylene.
In electroluminescencc