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Semiconducting Polymers: Chemistry, Physics and Engineering, 2nd Edition, Two-Volume Set

ISBN: 978-3-527-31271-9
768 pages
December 2006
Semiconducting Polymers: Chemistry, Physics and Engineering, 2nd Edition, Two-Volume Set (3527312714) cover image

Description

The field of semiconducting polymers has attracted many researchers from a diversity of disciplines. Printed circuitry, flexible electronics and displays are already migrating from laboratory successes to commercial applications, but even now fundamental knowledge is deficient concerning some of the basic phenomena that so markedly influence a device's usefulness and competitiveness. This two-volume handbook describes the various approaches to doped and undoped semiconducting polymers taken with the aim to provide vital understanding of how to control the properties of these fascinating organic materials. Prominent researchers from the fields of synthetic chemistry, physical chemistry, engineering, computational chemistry, theoretical physics, and applied physics cover all aspects from compounds to devices.
Since the first edition was published in 2000, significant findings and successes have been achieved in the field, and especially handheld electronic gadgets have become billion-dollar markets that promise a fertile application ground for flexible, lighter and disposable alternatives to classic silicon circuitry. The second edition brings readers up-to-date on cutting edge research in this field.
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Table of Contents

Foreword V

Preface VII

List of Contributors XXI

VOLUME 1 Synthetic Methods

1 Synthetic Methods for Semiconducting Polymers 1
Alberto Bolognesi and Maria Cecilia Pasini

1.1 Introduction and Overview 1

1.2 Synthetic Pathways for PA 3

1.2.1 Classical Synthesis for PA 3

1.2.2 The Precursor Route 4

1.2.3 The Grafting Approach 5

1.3 Conjugated Polymers by Step-Growth Polymerizations 6

1.3.1 Poly(3-Alkylthiophenes) 7

1.3.2 Polyparaphenylenes 13

1.3.3 Polyfluorenes 18

1.3.4 Copolymers with Phenylenes and Other Aromatics 21

1.3.5 The PPV Family 25

1.3.6 Poly(phenyleneethynylenes) 31

1.3.7 Copolymers for Triplet Emitters 32

1.3.8 Polyazines and Polyazomethines 33

1.4 Block Copolymers 35

1.4.1 Anionic Polymerization Processes 36

1.4.2 BCs from Tetramethylpiperidinoxy-mediated Polymerization 37

1.4.3 BCs from Atom Transfer Radical Polymerization 41

1.4.4 BCs from Polyfluorenes 42

1.4.5 p–n Diblock Polymers 46

1.4.6 Conjugated–Conjugated BCs 46

1.4.7 The Oligomeric Approach 50

1.5 Towards Autoorganized Devices 51

References 62

2 Processable Semiconducting Polymers Containing Oligoconjugated Blocks 69
Joannis K. Kallitsis, Panagiotis K. Tsolakis, and Aikaterini K. Andreopoulou

2.1 Introduction 69

2.2 Rod–Coil Block Copolymers 70

2.2.1 Poly(p-Phenylene)-Type Rod–Coil Copolymers 70

2.2.2 Poly(p-Phenylene-vinylene)-Type Rod–Coil Copolymers 73

2.2.3 Polyfluorene-Type Rod–Coil Copolymers 79

2.2.4 Poly(p-Phenyleneethynylene)-Type Rod–Coil Copolymers 83

2.2.5 Polythiophene-Type Rod–Coil Copolymers 87

2.2.6 Other Luminescent Rod–Coil Copolymers 89

2.3 Alternating Conjugated–Nonconjugated Polymers 92

2.3.1 Oligo(Phenylene-vinylenes) 92

2.3.2 Oligophenylenes 99

2.3.3 Oligothiophenes 102

2.3.4 Anthracenes 106

2.3.5 Other Aromatic Structures 109

2.3.6 Heteroatom-containing Structures 111

References 113

Structure/Morphology

3 Interfacial Aspects of Semiconducting Polymer Devices 121
Richard A. L. Jones

3.1 Introduction 121

3.2 Some Basics of Polymer Blend Thermodynamics and Dynamics 122

3.3 Surface Segregation, Surface-driven Phase Separation, Wetting and Self-Stratification 126

3.4 Morphology in Thin Films of Semiconducting Polymer Blends 129

3.5 Surface Segregation in Polymer-doped Conducting Polymers 131

3.6 Interface Structure 134

3.7 Conclusions 136

References 137

Electronic Structure of Interfaces

4 Electronic Structure of Surfaces and Interfaces in Conjugated Polymers 141
Michael Lögdlund, Mats Fahlman, Stina K.M. Jönsson, and William R. Salaneck

4.1 Introduction 141

4.2 Photoelectron Spectroscopy 142

4.2.1 X-Ray Photoelectron Spectroscopy 145

4.2.2 Ultraviolet Photoelectron Spectroscopy 146

4.3 Theoretical Approaches 148

4.4 Materials 149

4.4.1 Trans-Polyacetylene 149

4.4.2 Poly(p-phenylenevinylene) 152

4.4.3 Poly(3,4-ethylenedioxythiophene) 154

4.4.4 Solvent Effect on Conductivity in PEDOT–PSS Films 156

4.5 Charge Storage States in Conjugated Polymers 158

4.6 Interface Formations in Conjugated Systems 161

4.7 Summary 172

References 172

Photophysics

5 Photophysics of Conjugated Polymers 179
Lewis Rothberg

5.1 Introduction and Overview 179

5.2 Definitions and Terminology 180

5.3 Spectroscopy 182

5.3.1 Spectroscopy of the Conjugated Polymers in Solution 182

5.3.2 Spectroscopy of Conjugated Polymer Films 183

5.4 Photophysics 188

5.4.1 Photophysics and Excited-State Decay Dynamics in Solution 188

5.4.2 Photophysics in Neat Conjugated Polymer Films 189

5.5 Summary 196

5.5.1 Spectroscopy 196

5.5.2 Exciton Binding Energy 197

5.5.3 Luminescence Quantum Yield 198

5.5.4 PL Decay Dynamics 199

5.6 Conclusion 200

References 201

6 Photophysics in Semiconducting Polymers: The Case of Polyfluorenes 205
Christoph Gadermaier, Larry Lüer, Alessio Gambetta, Tersilla Virgili, Margherita Zavelani-Rossi, and Guglielmo Lanzani

6.1 Introduction 205

6.2 Experimental 206

6.2.1 The Pump–Probe Technique 206

6.2.2 The Pump–Push–Probe Experiment 210

6.2.3 The Field-Assisted Pump–Probe Experiment 210

6.2.4 Excitation Cross-Correlation Photoconductivity 211

6.2.5 Quasi-Steady-State Photoinduced Absorption 211

6.3 Low-Dimensional Physics in Conjugated Chains 212

6.4 Ground-State Absorption and cw Photoluminescence 213

6.5 Long-Lived Photoexcitation in Polyfluorenes (PFs) 214

6.6 Singlet Exciton Dynamics 215

6.7 On-Chain Emissive Defects 218

6.8 Charged Excitations and Their Photogeneration Mechanism 221

6.9 Intrachain Dynamics 224

6.10 Three-Pulse Time-Resolved Experiments 226

6.11 Light-Emitting-Diode-Related Dynamics in the Ultrafast

Timescale 229

References 232

7 Spectroscopy of Photoexcitations in Conjugated Polymers 235
Z. Valy Vardeny and Markus Wohlgenannt

7.1 Introduction 235

7.1.1 Basic Properties of _-Conjugated Polymers 235

7.1.2 Optical Transitions of Photoexcitations in Conducting Polymers 238

7.1.3 Optical Transitions of Charged Excitations in NDGS Polymers 238

7.1.4 Optical Transitions of Neutral Excitations in NDGS Polymers 240

7.2 Experimental Methods 241

7.2.1 Photomodulation Spectroscopy of Long-Lived Photoexcitations 242

7.2.2 Picosecond Pump and Probe Spectroscopy 243

7.2.3 Optically Detected Magnetic Resonance Techniques 243

7.3 Experimental Results: cw PA Spectroscopy 245

7.3.1 Photophysics of Red-Emitting Polythiophenes: Regioregular, Regiorandom 245

7.3.2 Photophysics of a Blue-Emitting Polyfluorene 251

7.4 Transient Pump-and-Probe Spectroscopy 254

7.4.1 Ground and Excited State Absorption in PPV 254

7.5 Multiple-Pulse Transient Spectroscopy 257

7.5.1 mAg Relaxation Dynamics 258

7.5.2 kAg Relaxation Dynamics 260

7.6 ODMR Spectroscopy: Measurement of Spin-Dependent Polaron Recombination Rates 262

7.6.1 Spin-Dependent Exciton Formation Probed by PADMR Spectroscopy 262

7.6.2 Material Dependence of Spin-Dependent Exciton Formation Rates 264

7.7 Summary 265

References 267

Transport/Injection

8 Charge Transport in Neat and Doped Random Organic Semiconductors 275
Vladimir I. Arkhipov, Igor I. Fishchuk, Andriy Kadashchuk, and Heinz Bässler

8.1 Introduction 275

8.2 Charge Generation 276

8.3 Charge-Carrier Hopping in Noncrystalline Organic Materials 279

8.3.1 Outline of Conceptual Approaches 279

8.3.2 Stochastic Hopping Theory 287

8.3.3 Effective-Medium Approximation Theory of Hopping Charge-Carrier Transport 310

8.4 Experimental Techniques 333

8.4.1 Charge-Carrier Generation 333

8.4.2 Experimental Techniques to Measure Charge Transport 336

8.5 Experimental Results 342

8.5.1 Analysis of Charge Transport in a Random Organic Solid with Energetic Disorder 342

8.5.2 The Effect of Positional Disorder 353

8.5.3 Trapping Effects 356

8.5.4 Polaron Effects 361

8.5.5 Chemical and Morphological Aspects of Charge Transport 365

8.5.6 On-Chain Transport Probed by Microwave Conductivity 371

8.6 Conclusions 373

References 375

9 Charge Transport and Injection in Conjugated Polymers 385
Paul W.M. Blom, Cristina Tanase, and Teunis van Woudenbergh

9.1 Introduction 385

9.2 Charge Transport 388

9.2.1 Disorder-Induced Localized States 388

9.2.2 Charge Transport in Polymer LEDs and FETs 391

9.2.3 Unification of the Charge Transport in Disordered PolymerLEDs and FETs 396

9.2.4 Origin of the Enhanced SCLC in PPV-Based Diodes 401

9.2.5 Thickness-Dependence of SCLC in PPV-Based LEDs 405

9.2.6 Summary 407

9.3 Charge Injection 407

9.3.1 Introduction 407

9.3.2 Classical Injection Models 408

9.3.3 Hopping-Based Injection 409

9.3.4 Temperature-Dependence of the Charge Injection 411

9.3.5 Application of the Hopping Injection Model 414

9.3.6 Conclusion 416

References 417

VOLUME 2 Applications

10 Physics of Organic Light-Emitting Diodes 421
Ian H. Campbell, Brian K. Crone, and Darryl L. Smith

10.1 Introduction 421

10.2 Thin Films of Organic Semiconductors 423

10.2.1 Electronic Energy Structure 424

10.2.2 Optical Properties 425

10.2.3 Electrical Transport Properties 426

10.3 Device Electronic Structure 427

10.3.1 Internal Photoemission Measurements of Schottky Energy Barriers 427

10.3.2 Built-in Potentials in Device Structures 430

10.4 Single-Layer Devices 434

10.4.1 Single-Carrier Structures 435

10.4.2 Two-Carrier Structures 440

10.5 Multilayer Devices 444

10.5.1 Blocking Layers 445

10.5.2 Transport Layers 447

10.5.3 Two-Carrier Multilayer Devices 449

10.6 Conclusions 451

References 452

11 Conjugated Polymer-Based Organic Solar Cells 455
Gilles Dennler, Niyazi Serdar Sariciftci, and Christoph J. Brabec

11.1 Introduction 455

11.1.1 Photovoltaics 455

11.1.2 Technology Overview and Forecasts 456

11.1.3 Motivation for OPV 459

11.2 Conjugated Polymers as Photoexcited Donors 460

11.2.1 Optical Properties 461

11.2.2 Sensitivation of Conductivity 467

11.2.3 Magnetic Properties 468

11.3 Bulk-Heterojunction Solar Cells 469

11.3.1 Basics of Organic Solar Cells 469

11.3.2 Pure Conjugated-Polymer Photovoltaic Devices 472

11.3.3 Conjugated Polymer-Based Bilayer Devices 474

11.3.4 Conjugated Polymer-Based Bulk-Heterojunction Devices 478

11.4 Determining Parameters of Bulk-Heterojunction Solar Cells 481

11.4.1 Voltage at Open Circuit 481

11.4.2 Light Harvesting 485

11.4.3 Morphology of the Photoactive Donor: Acceptor Blends 489

11.4.4 Charge-Carrier Transport in Bulk-Heterojunction Blends 493

11.4.5 Modeling Bulk-Heterojunction-Device Operation 502

11.5 From Basics to Applications 507

11.5.1 Production Scheme 507

11.5.2 Encapsulation of Flexible Solar Cells 511

11.5.3 Routes for Improvements 516

11.6 Conclusions 519

References 520

12 Organic Thin-Film Transistors 531
Gilles Horowitz

12.1 Introduction 531

12.2 The MISFET – A Reminder 532

12.2.1 The Metal–Insulator–Semiconductor (MIS) Junction 532

12.2.2 The Metal–Insulator–Semiconductor Field-Effect Transistor (MISFET) 539

12.3 The Organic Transistor – What’s Different? 544

12.3.1 Threshold Voltage 545

12.3.2 Depletion Regime 546

12.3.3 Contact Resistance 546

12.3.4 Charge Distribution Across the Conducting Channel 551

12.4 Charge-Transport Mechanisms 555

12.4.1 Band-Like Transport 556

12.4.2 Polaron Transport 556

12.4.3 Hopping Models 558

12.4.4 Trap-Limited Transport 559

12.4.5 Gate-Voltage-Dependent Mobility 560

12.4.6 Role of the Insulator 562

12.5 Concluding Remarks 563

References 564

13 n-Channel Organic Transistor Semiconductors for Plastic Electronics Technologies 567
Howard E. Katz

13.1 Plastic Electronics Technology and Organic Semiconductors 567

13.2 n-Channel OFET Semiconductors 571

13.3 Conclusion 575

References 575

14 Photochromic Diodes 579
Xavier Crispin, Peter Andersson, Nathaniel D. Robinson, Yoann Olivier, Jérôme Cornil, and Magnus Berggren

14.1 Introduction 579

14.2 Photochromic Molecules 580

14.3 Organic Diodes 585

14.4 Electronic Switches – Device Concepts 586

14.4.1 Electronic Write Mode 587

14.4.2 Optical Write Mode 593

14.5 Conclusions 609

References 610

15 Organic/Polymeric Thin-Film Memory Devices 613
Yang Yang, Jianyong Ouyang, Liping Ma, Jia-Hung Tseng, and Chih-Wei Chu

15.1 Introduction 613

15.2 Review of Polymer and Organic Memory 614

15.2.1 Electric-Field-Induced Charge-Transfer Effect 614

15.2.2 Ionic Diffusion Effect 615

15.2.3 Nanoparticle Layered Structures 615

15.2.4 Crossbar Molecular Switch 616

15.3 OMO Nanoparticle Layered Memory Devices 616

15.3.1 Device Fabrication 617

15.3.2 Electrical Characteristics 619

15.3.3 Conduction and Switching Mechanisms 621

15.4 Polymer-Blend Composite System 621

15.4.1 Device Fabrication 622

15.4.2 Electrical Characteristics 623

15.4.3 Conduction and Switching Mechanisms 625

15.5 Advanced Memory Device Architecture 629

15.5.1 WORM Memory Devices 630

15.5.2 All-Organic Donor–Acceptor System 632

15.5.3 Polymer with Built-In Nanoparticle System 634

15.6 Conclusion 637

References 639

16 Biosensors Based on Conjugated Polymers 643
Hoang-Anh Ho and Mario Leclerc

16.1 Introduction 643

16.2 Different Types of CPs 644

16.3 Colorimetric Methods 644

16.4 Fluorometric Methods 651

16.5 Electrochemical Methods 658

16.6 Conclusions and Perspectives 661

References 662

Processing

17 Manufacturing of Organic Transistor Circuits by Solution-Based Printing 667
Henning Sirringhaus, Christoph W. Sele, Timothy von Werne, and Catherine Ramsdale

17.1 Introduction to Printed Organic Thin-Film Transistors 667

17.2 Overview of Printing-Based Manufacturing Approaches for OTFTs 670

17.2.1 Screen Printing 671

17.2.2 Offset Printing 671

17.2.3 Gravure Printing 673

17.2.4 Flexography 673

17.2.5 Inkjet Printing 674

17.2.6 Laser-Based Dry Printing Techniques 675

17.2.7 Other Nonlithographic Manufacturing Approaches 676

17.3 High-Resolution, Self-Aligned Inkjet Printing 677

17.3.1 Self-Aligned Printing by Selective Surface Treatment 680

17.3.2 Self-Aligned Printing by Surface Segregation 680

17.3.3 Self-Aligned Printing by Autophobing 682

17.4 Performance and Reliability of Solution-Processed OTFTs for Applications in Flexible Displays 688

17.5 Conclusions 693

References 694

18 High-Resolution Composite Materials for Organic Electronics 699
Graciela Blanchet

18.1 Introduction 699

18.2 Building Blocks 699

18.3 Large-Area Printing Process and Devices 701

18.3.1 Process: Thermal Imaging 701

18.3.2 Printed Devices: From TFTs to Large-Area Backplanes 702

18.4 Printable Materials 710

18.4.1 Polyaniline-Nanotube Composites: A High-Resolution Printable Conductor 710

18.4.2 Conducting Composites in an Insulating Matrix 715

18.4.3 Semiconducting Composites 720

18.5 Conclusion 728

References 729

Subject Index 731

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Author Information

Georges Hadziioannou is Director of the Polymer Department and the European School of Chemistry Polymers and Materials (ECPM) since 2001 at Louis Pasteur University in Strasbourg, France. Prior to this appointment, he spent most of the 80s in the USA, first as postdoc at the University of Massachusetts, then as a research staff member for IBM in San José. From 1986 to 1989, he led the Surface and Interface Dynamics group at IBM's Almaden Research Center. Twelve years as professor of polymer chemistry at Groningen University in the Netherlands followed.
He was named Americal Physical Society Fellow in 1994 and received a Humboldt Research Award in 1998. He has authored over 190 scientific papers in peer-reviewed journals, contributed 10 chapters to books and edited the first edition of this book together with P. F. van Hutten in 2000.

George Malliaras studied physics as an undergraduate and did his doctoral research on photorefractivity in polymers. Before joining the faculty at Cornell in 1998, he was a post-doctoral fellow at the University of Groningen (1996) and the Center for Polymer Interfaces and Macromolecular Assemblies (CPIMA), at the IBM Almaden Research Center (1997-98). He is a recipient of the NSF Early Career Development Award, a member of the American Physical Society and of the Materials Research Society.
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