Foreword ....................................................... xi
Preface ....................................................... xiii
Acknowledgments ............................................... xvii
Authors ........................................................ xix
Abbreviations .................................................. xxi
1 The Discovery and Development of Conducting Polymers .......... 1
1.1 The Scope of This Historical Overview .................... 1
1.2 Introduction ............................................. 2
1.3 An Early Example: Polyaniline ............................ 4
1.4 The First Electrically Conductive Poly(Heterocycle):
Polypyrrole .............................................. 9
1.5 The Fundamental Breakthrough: Doped Polyacetylene ....... 10
References ................................................... 15
2 Conductive Polymers versus Metals and Insulators ............. 21
2.1 Metals, Semiconductors, and Insulators .................. 21
2.2 Conjugated Polymers ..................................... 22
2.3 Temperature-Dependent Conductivity ...................... 24
2.4 Order and Disorder ...................................... 26
References ................................................... 29
3 Polythiophenes: A Chance for Maximum Conductivity? ........... 31
3.1 Introduction ............................................ 31
3.2 Oxygen-Substituted Polythiophenes ....................... 33
References ................................................... 38
4 A Short History of the PEDOT Invention ....................... 41
References ................................................... 46
5 The Synthesis of EDOT Monomer, and Its Physical and
Chemical Properties .......................................... 47
5.1 Monomer Synthesis ....................................... 47
5.2 Physical Properties ..................................... 50
5.3 Chemical Properties ..................................... 53
References ................................................... 63
6 From EDOT to PEDOT: Oxidative Polymerization and Other
Routes ....................................................... 67
6.1 Oxidative Polymerization and Doping ..................... 67
6.2 "Self-Oxidation" of EDOT Halogen Derivatives ............ 72
6.3 The Organometallic Route to PEDOT ....................... 74
6.4 Neutral, Undoped PEDOT by Oxidative Polymerization ...... 76
References ................................................... 79
7 Counterions for PEDOT ........................................ 83
7.1 Counterions in Electrochemically Polymerized PEDOT ...... 83
7.2 Counterions in Chemically Polymerized PEDOT ............. 86
References ................................................... 87
8 The In Situ Polymerization of EDOT to PEDOT .................. 91
8.1 Synthesis of In Situ PEDOT .............................. 91
8.2 Properties of In Situ PEDOT ............................. 97
8.3 In Situ Polymerization of EDOT Derivatives and
Relatives .............................................. 102
References .................................................. 109
9 PEDOT:PSS ................................................... 113
9.1 PEDOTPSS Dispersions ................................... 113
9.1.1 Introduction .................................... 113
9.1.2 Polyelectrolyte Complexes ....................... 113
9.1.3 Synthesis of a PEDOTPSS Complex ................. 117
9.1.4 Commercial PEDOTPSS Types and Their
Properties ...................................... 122
9.2 Properties of PEDOTPSS ................................. 123
9.2.1 Deposition of PEDOTPSS .......................... 123
9.2.2 Thin-Film Properties ............................ 123
9.2.2.1 Thermal and Lifetime Stability ......... 123
9.2.2.2 UV Stability ........................... 126
9.2.2.3 Water Uptake ........................... 128
9.2.2.4 Mechanical Properties .................. 130
9.2.2.5 Morphology: Surface and Bulk ........... 131
9.2.3 Electronic States ............................... 136
9.2.3.1 UV-Vis (Ultraviolet-Visible) Spectra ... 136
9.2.3.2 Energy Levels in PEDOT ................. 137
9.2.3.3 Optical Constants ...................... 142
9.2.3.4 Vibrational Spectra .................... 143
9.2.4 Electrical Properties ........................... 144
9.2.4.1 Conductivity ........................... 144
9.2.4.2 Microscopic Model for Conductivity
in PEDOTPSS ............................ 144
9.2.4.3 Free Charge Carrier Mobility ........... 147
9.2.4.4 Threshold Currents ..................... 148
9.3 Secondary Doping ....................................... 149
9.3.1 Introduction .................................... 149
9.3.2 The Chemical Nature of Secondary Dopants
in PEDOTPSS ..................................... 150
9.3.3 Properties of PEDOTPSS Films Including
Secondary Dopants ............................... 152
9.3.3.1 Conductivity as a Function of
Temperature ............................ 152
9.3.3.2 X-Ray Diffraction ...................... 152
9.3.3.3 Optical Characterization of PEDOTPSS
Films .................................. 153
9.3.3.4 Surface Analysis of PEDOTPSS Films ..... 153
9.3.3.5 Atomic Force Microscopy and Scanning
Tunnel Microscopy ...................... 154
9.3.3.6 Work Function and Electron
Paramagnetic Resonance ................. 155
9.3.4 Discussion ........................................... 156
References .................................................. 158
10 Applications ................................................ 167
10.1 Solid Electrolyte Capacitors .......................... 167
10.1.1 Introduction .................................... 167
10.1.2 Capacitor Basics ................................ 169
10.1.3 Design of Solid Electrolyte Capacitors .......... 170
10.1.4 Deposition Methods for PEDOT Cathode ............ 172
10.1.4.1 Electrochemical Oxidative
Polymerization ......................... 174
10.1.4.2 Chemical Oxidative Polymerization ...... 175
10.1.4.3 Conducting Polymer Dispersions ......... 177
10.1.5 Reformation and High Voltage Application ........ 179
10.1.6 Self-Healing and Thermal Runaway ................ 182
10.1.7 Conclusions ..................................... 183
10.2 Through Hole Plating for Printed Wiring Boards ......... 184
10.3 ITO Substitution ....................................... 188
10.4 Antistatic Coatings .................................... 194
10.4.1 Solvents ........................................ 198
10.4.2 Surfactants ..................................... 199
10.4.3 Binders ......................................... 199
10.4.4 Hardness and Abrasion ........................... 200
10.4.5 Conductivity-Enhancing Additives ................ 201
10.4.6 Use of PEDOT in Antistatic Coatings ............. 202
10.5 Electroluminescent Lamps ............................... 204
10.6 Organic Light Emitting Diodes (OLEDs) .................. 205
10.6.1 Introduction .................................... 205
10.6.2 PEDOTPSS as a Hole-Injection Layer .............. 207
10.6.3 The PEDOTPSS-Semiconductor Interface ............ 209
10.6.4 Lifetime Restraints by PEDOT:PSS Hole
Injection Layers ................................ 213
10.6.5 Modified PEDOT-Based Materials for HILs ......... 214
10.7 PEDOTPSS in Organic Solar Cells ........................ 216
10.7.1 Introduction .................................... 216
10.7.2 PEDOTPSS as a Transparent Anode in OSCs ......... 217
10.7.3 PEDOTPSS as a Buffer Layer in OSCs .............. 218
10.7.4 PEDOTPSS in Dye-Sensitized Solar Cells .......... 221
10.8 Electrochromic Behavior ................................ 222
10.8.1 Introduction .................................... 222
10.8.2 Control of Optical Properties ................... 226
10.8.3 EDOT Derivatives ................................ 229
10.8.4 Copolymers ...................................... 231
10.8.5 Organic-Inorganic Hybrid Polymers ............... 233
10.8.6 PEDOT with Pendant Electrochromic Dyes .......... 233
10.8.7 Blends and Layer-by-Layer Deposition ............ 234
10.8.8 Electrolytes .................................... 235
10.8.9 Ion Storage Materials ........................... 236
10.8.10 Dual Polymer Cells ............................. 237
10.8.11 Substrates and Patterning ...................... 237
10.9 Organic Field-Effect Transistors ....................... 238
10.9.1 Introduction .................................... 238
10.9.2 PEDOTPSS as Electrodes .......................... 239
10.9.3 PEDOTPSS as an Interlayer ....................... 241
10.9.4 PEDOTPSS as an Active Layer ..................... 242
References .................................................. 244
11 Technical Use and Commercial Aspects ........................ 265
References .................................................. 269
12 EDOT and PEDOT Derivatives with Covalently Attached Side
Groups ...................................................... 271
12.1 EDOT-CH2OH and Its Derivatives ......................... 271
12.2 EDOT-CH2Cl and Its Follow-Up Products .................. 280
12.3 Alkyl EDOTs ............................................ 282
12.4 Water Soluble, "Self-Doping" EDOT Derivatives .......... 286
References .................................................. 289
13 XDOTs, EDXTs, EDOXs, and 2(5)-X(2)-EDOTs: Ring Size
Variations, Heteroanalogs, and Derivatives of EDOT with
Substituents at the Thiophene Ring .......................... 293
13.1 3,4-Methylenedioxythiophene (MDOT) ..................... 293
13.2 ProDOT (Propylenedioxythiophene) Derivatives ........... 295
13.3 Vinylenedioxythiophene (VDOT) and Benzo-EDOT ........... 299
13.4 3,4-Ethyleneoxythiathiophene (EOTT) .................... 301
13.5 3,4-Ethylenedithiathiophene (EDTT) ..................... 304
13.6 3,4-Ethylenedioxypyrrole (EDOP) and Its Derivatives .... 306
13.7 3,4-Ethylenedioxyselenophene (EDOS) .................... 309
13.8 2,5-Disubstituted EDOT Derivatives [2(,5)-X(2)-
EDOTs] ................................................. 311
References .................................................. 322
14 The Electrochemical Behavior of EDOT and PEDOT .............. 329
References .................................................. 340
Index .......................................................... 345
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