Handbook of Oligo- and Polythiophenes

Handbook of Oligo- and Polythiophenes......Page 2
Contents......Page 10
1.1 Introduction......Page 28
1.2 Chemical Synthesis of Unsubstituted Polythiophene (PT)......Page 29
1.3.1.1.1 Metal Catalyed Cross-coupling Polymerizations......Page 32
1.3.1.1.2 FeCl3 Method for the Polymerization of PATs......Page 33
1.3.1.2 Comparison of the Above Methods......Page 35
1.3.1.3 Regioregular PATs......Page 36
1.3.1.3.1 Regioregular HH-TT and TT-HH PATs......Page 37
1.3.1.4.1 The McCullough Method......Page 39
1.3.1.4.2 The Rieke Method......Page 40
1.3.1.4.4 NMR Characterization of HT-PAT......Page 42
1.3.1.4.5 IR and UV-Vis......Page 43
1.3.1.4.6 Self-Assembly, X-ray, and Electrical Conductivity in HT-PATs......Page 45
1.3.1.4.7 Other Methods......Page 46
1.3.1.4.9 Head-to-Tail Coupled, Random Copolymers of Alkyl Thiophenes......Page 47
1.3.1.5 Branched Alkyl PATs......Page 48
1.4 Chemical Synthesis of Heteroatomic Functionalized Substituents on PTs: Recognition Sites for Self-Assembly and Chemical Sensing......Page 51
1.4.1 Chemical Synthesis of Alkoxy Polythiophenes......Page 52
1.4.2 Chemical Prepared Alkoxy PTs as Conducting Polymer Sensors......Page 54
1.4.3 Chiral Substituents on PT......Page 59
1.4.4 Carboxylic Acid Derivatives: Self-Assembly and Sensors......Page 60
1.4.5 Other Derivatives of PT......Page 61
1.5 Fused Rings Systems......Page 65
References......Page 66
2.1 General Aspects of Conducting Polymers......Page 72
2.2.1 Morphology and Crystal Structure......Page 75
2.2.2 Conformational Features......Page 79
2.3.1 Charge Excitations in Polythiophenes......Page 84
2.3.2 Charge Transport in Polythiophenes......Page 87
2.3.3 Carrier Recombination: Photoluminescence and Electroluminescence......Page 90
2.3.4.1 Charge Storage Configurations in Solids and their Anisotropic Properties......Page 92
2.3.4.2 Properties in Solutions......Page 100
2.4 Concluding Remarks and Future Outlook......Page 107
References......Page 109
3.1 Introduction......Page 116
3.2.1.1 Arene/arene-Coupling Methods by Oxidative Couplings......Page 120
3.2.1.2 Transition Metal Catalyzed Coupling Methods......Page 124
3.2.1.3 Ring Closure Reactions from Acyclic Precursors......Page 131
3.2.1.4 Physical Properties of α-Oligothiophenes and Isomers\n......Page 138
3.2.2 Substituted Oligothiophenes......Page 145
3.2.2.1 ββ\'-Substituted Oligothiophenes......Page 146
3.2.2.2 α,α\'-Substituted Oligothiophenes\n......Page 166
3.2.2.3 αβ-Substituted Oligothiophenes\n......Page 172
3.2.2.4 Functionalized Oligothiophenes......Page 182
3.2.2.5 Amphiphilic Oligothiophenes......Page 197
3.2.2.6 Transition Metal Complexes of Oligothiophenes......Page 198
3.3 Conclusion......Page 199
References......Page 200
4.1 Introduction......Page 210
4.2.1 General Description......Page 211
4.2.2.1 Bithiophene (α-2T) and Derivatives......Page 214
4.2.2.2 α-Terthiophene (α-3T) and Derivatives......Page 218
4.2.2.3  α-Quaterthiophene (α-4T) and Derivatives......Page 220
4.2.2.4 α-Quinquethiophene (α-5T) and Derivatives......Page 229
4.2.2.5 α-Sexithiophene (α-6T) and Derivatives......Page 230
4.2.2.6 α-Octithiophene (α-8T)......Page 234
4.2.2.7 Polythiophene and 3-Alkylated Derivatives......Page 240
4.2.3.2 Dimethylquarterthiophene......Page 241
4.2.3.3 α-Sexithiophene (α-6t)......Page 242
4.2.3.4 α-Octithiophene (α-8T)......Page 243
4.3.1.2 Preparation from Solution......Page 247
4.3.2.1 General Remarks......Page 248
4.3.2.2 Monothiophene (IT) and Derivatives......Page 249
4.3.2.3 Small Oligomers (α-2T-α-4T) and Derivatives......Page 250
4.3.2.4 Quinquethiophene (α-5T) and Derivatives......Page 253
4.3.2.5 Sexithiophene (α-6T) and Derivatives......Page 261
4.3.2.6 Longer Obligothiophenes (α-7T, α-8T) and Derivatives......Page 271
4.3.2.7 Polythiophene and Derivatives......Page 272
4.3.3.1 Undoped Oligothiophenes......Page 274
4.3.3.2 Charges in Oligothiophenes......Page 284
4.3.4.1 General Remarks......Page 293
4.3.4.2 Contacts, I/V-Curves, Carrier Injection......Page 294
4.3.4.3 Influence of the Structure on Conductivity Data......Page 296
4.3.4.4 Influence of the Structure on Mobility Data......Page 297
4.3.4.5 Temperature Dependence......Page 298
4.3.4.7 Influence of Dopants......Page 299
References......Page 301
5 Charge Transport in Semiconducting Oligothiophenes Gilles Horowitz and Phillippe Delannoy......Page 310
5.1.1 The Band Model......Page 311
5.1.2.1 Localization......Page 315
5.1.2.2 Temperature Dependence......Page 316
5.1.3.1 Small Polaron......Page 318
5.1.3.2 Molecular ‘Nearly Small’ Polaron......Page 320
5.1.3.3 Polarons in n-Conjugated Polymers and Oligomers......Page 322
5.1.5 Summary......Page 324
5.2.1 Conductivity......Page 325
5.2.2 Time of Flight......Page 326
5.2.3 Space-Charge-Limited Current......Page 327
5.2.3.1 Profile of Injected Charges......Page 328
5.2.3.2 Estimation of the Space-Charge Limited Current......Page 329
5.2.3.3 Effect of Traps......Page 330
5.2.4 Field-Effect......Page 332
5.3 Transport properties of Oligothiophenes......Page 333
5.3.1.1 Variation with Chain Length......Page 334
5.3.1.2 Carrier Density......Page 335
5.3.1.3 Variation with Temperature......Page 336
5.3.2 Traps......Page 338
5.4 Concluding Remarks......Page 339
References......Page 340
6.1 Introduction......Page 344
6.2 Theoretical Methodology......Page 347
6.3.1 Nature of the Lowest Excited States......Page 349
6.3.2 Intersystem Crossing Processes......Page 351
6.3.3 Lattice Relaxation Phenomena......Page 353
6.3.4 Effects of Substitution......Page 355
6.4 Electronic and Linear Optical Properties of Charged Oligothiphenes......Page 360
6.5 Characterization of Metal/polymer Interfaces......Page 366
6.5.1 Geometric Structures......Page 367
6.5.2 Electronic Structures......Page 370
6.5.3 Vibrational Signature......Page 371
6.6 Nonlinear Optical Properties of Neutral Oligothiophenes......Page 374
6.6.1 Chain Length Dependence of the third-order Polarizabilities in Thiophene Oligomers......Page 376
6.6.2 Dynamic Third-order Response of Th7: Two-photon Absorption and Third-harmonic Generation......Page 379
Acknowledgements......Page 382
References......Page 383
7.1 Introduction......Page 388
7.2.1 General Concept......Page 389
7.2.2 Polythiophene......Page 390
7.3.1 Molecular Structure......Page 391
7.3.2.1 Assignments......Page 394
7.3.2.2 Chain Length Dependence......Page 395
7.3.2.3 Nature of the Lowest Singlet Transition......Page 396
7.3.2.4 Franck–Condon Coupling......Page 397
7.3.3 Triplet States......Page 399
7.4.1 Molecular Packing......Page 400
7.4.2.1 The Exciton Concept and the Lowest Excited State in 6T......Page 401
7.4.2.2 Higher Transitions – Extended States......Page 406
7.4.3.1 Structural and Morphological Aspects of Polycrystalline Thin Films......Page 407
7.4.3.2 Optical Properties of Thin Polycrystalline Films......Page 411
7.4.3.3 Highly Ordered Systems......Page 414
7.4.3.5 Extended States......Page 419
7.4.3.6 Triplet States......Page 420
7.4.3.7 Excited States Ordering......Page 421
7.5 Polarized Electroluminescence......Page 422
7.6 Nonlinear Optical Properties of Polythiophene and Thiophene Oligomers......Page 424
References......Page 427
8.1.1 Relationship Between polymers and Oligomers......Page 432
8.2.2 Polymers......Page 435
8.2.3 Oligomers......Page 436
8.2.4.1 Substitution with Side-chains......Page 437
8.2.4.2 Using a Soluble Partially-conjugated Precursor Polymer......Page 439
8.3.2 Intra-molecular Non-radiative Decay Channels......Page 440
8.3.2.1 Internal Conversion......Page 442
8.3.2.2 Intersystem Crossing......Page 443
8.3.3.1 Aggregation and Davydov Splitting......Page 444
8.3.3.2 Charge-transfer Excitons......Page 445
8.3.4 Effects of Inter-ring Torsion and Coplanarity of Oligomers......Page 446
8.3.4.2 Solid State......Page 447
8.4.1 Introduction......Page 448
8.4.2.1 LEDs Based on Molecular Semiconductors......Page 451
8.4.2.2 Polymeric LEDs......Page 452
8.4.3 LEDs Based on Oligothiphenes......Page 454
8.4.4 LEDs Based on Polythiophenes......Page 456
8.4.4.1 Polythiophene LEDs Covering the Whole Visible Spectrum and a Bit More......Page 457
8.4.4.2 Intrinsically-polarised Polymer LEDs......Page 459
8.4.4.3 Polythiophenes in Microcavity Structures......Page 461
8.4.4.4 Sub-wavelength Size Polymer LEDs......Page 463
8.4.4.5 Voltage-controlled Colours......Page 464
8.5.1 Introduction......Page 466
8.5.2 Mechanism of Photoconductivity in Sexithiophene......Page 467
8.5.3 Photovoltaic Applications (Solar Cells)......Page 468
8.5.4 Photovoltaic Devices Based on Polythiophenes......Page 470
8.6 Electro-Optical Modulator Devices......Page 471
8.6.1 Optical Probing of Field-induced Charge in α-Sexithiphene......Page 473
8.7 All-optical Modulator and Memory Devices......Page 476
References......Page 479
9.1 Introduction......Page 486
9.2 Operation of a Field-effect Transistor......Page 487
9.3.1 Analytical Modeling......Page 488
9.3.2 Numerical Modeling......Page 490
9.3.3 Interface Effects......Page 491
9.3.4 Short-channel Effects......Page 492
9.3.5 Sub-threshold Characteristics......Page 493
9.3.6 Energy Levels......Page 494
9.4.1 Synthesis and Purification......Page 495
9.4.2 Morphology......Page 498
9.4.3 Substituted Oligothiophnenes......Page 500
9.4.4 Fused Ring Materials......Page 502
9.5 FETs Based on Polythiophenes......Page 503
9.5.2 Regioregular Polythiophene FETS......Page 505
9.5.3 All-printed Plastic FETs......Page 508
9.6 Heterojunction FETs......Page 510
9.7 Summary......Page 512
Acknowledgments......Page 513
References......Page 514
10.1 Introduction......Page 518
10.2 Conducting Materials......Page 519
10.3 Antistatic Coatings......Page 522
10.4 Electromagnetic Shielding Materials......Page 523
10.5 Materials for Rechargeable Batteries, Capacitors......Page 524
10.7 Resists, Recording Materials and Fabrication of Patterns......Page 528
10.8 Electrochromic Devices......Page 530
10.9.1 Sensors for Gases......Page 533
10.9.2 Sensors for Ions in Aqueous Solution......Page 534
10.9.4 Sensors for Bio-organic Materials......Page 535
10.10 Other Applications......Page 539
10.10.1 General Consideration......Page 540
10.1 1 Summary, Conclusions and Future Trends......Page 543
References......Page 545
Index......Page 552