CONDUCTING POLYMERS, FUNDAMENTALS AND APPLICATIONS A Practical Approach
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1 CONDUCTING POLYMERS, FUNDAMENTALS AND APPLICATIONS A Practical Approach by Prasanna Chandrasekhar Ashwin-Ushas Corp., Inc. * KLUWER ACADEMIC PUBLISHERS Boston / Dordrecht / London
2 TABLE OF CONTENTS LIST OF COMMON ABBREVIATIONS FOREWORD, Lawrence Dalton PREFACE xxv xxxiii xxxv PART I: FUNDAMENTALS 1 CHAPTER 1: BASICS OF CONDUCTING POLYMERS (CPs) WHAT ARE CONDUCTING POLYMERS (CPs)? Definitions and Examples Excluded Materials Classes (Those Not Treated as CPs in this Book) HISTORICAL BASIC CHARACTERISTICS OF CPs, DOPING AND STRUCTURE Conductivity Classification of Materials Doping and Dopants Doping Types Real and Idealized Structures BASICS OF CP SYNTHESIS Categories and Classes of Syntheses Representative Synmeses- Chemical Representative Synmeses- Electrochemical Simple Representation of Mechanisms 20 PROBLEMS AND EXERCISES 22
3 viii Table of Contents CHAPTER 2: SEMICONDUCTOR MODELS FOR CPs CONVENTIONAL SEMICONDUCTORS AND CPs Conventional Semiconductors CPs as Semiconductors STRUCTURAL DISTORTIONS: POLARONS, BIPOLARONS AND SOLITONS BAND STRUCTURE EVOLUTION DENSITIES OF STATES AND WAVEVECTOR REPRESENTA TIONS CORRELATION OF OPTICAL SPECTRA TO BAND STRUCTURE THEORETICAL AND PRACTICAL ASPECTS 41 PROBLEMS AND EXERCISES 41 CHAPTER 3: BASIC ELECTROCHROMICS OF CPs BASICS OF ELECTROCHROMISM AND SPECTROELECTRO- CHEMISTRY OF CPs Basics Spectral Regions Elementary Electrochemistry of CPs as Basis for Electrochromism Basic Methodology for Transmission- and Reflectance- Mode Electrochromism UV-VIS-NIR AND IR SPECTROELECTROCHEMICAL MEASUREMENTS Transmission-Mode SPELs Reflection-Mode Data IR-Region Data OTHER ELECTROCHROMIC PARAMETERS OF INTEREST OTHER MEASUREMENTS 72 PROBLEMS AND EXERCISES 75
4 CONDUCTING POLYMERS: Fundamentals and Applications ix CHAPTER 4: ELECTROCHEMISTRY OF CPs BASICS Introduction Basic Methodology Electrolytes and Electrodes BASIC VOLTAMMETRIC PARAMETERS AND INFORMATION OF INTEREST Cyclic Voltammograms (CVs) Electrochemical Windows Scan Rate Dependencies Other Parameters From CVs, Peak Broadening Surface-Active Behavior Charge Capacities Dopant and Structural Relationships Reversibility SOLVENT AND ph EFFECTS, MIXED SOLVENTS, DOPANTS RELATION WITH SEMICONDUCTOR PROPERTIES OTHER VOLTAMMETRIC METHODS CA, CC AND DIFFUSION COEFFICIENTS COMPLEX FILM THICKNESS AND DOPANT EFFECTS MODIFIED ELECTRODES 98 PROBLEMS AND EXERCISES 98 CHAPTER 5: ADVANCED POLYMERIZATION CONCEPTS ELECTROCHEMICAL POLYMERIZATION Mechanisms Generic Electropolymerization Mechanism Factors Favoring Polymerization and No Polymerization Mechanistic Notation and Rate Expressions 107
5 x Table of Contents Solvents and Electrodes Potentiostatic, Galvanostadc Polymerizations, Threshold Concentrations Ill Dopants Electrochemical Monitoring of Polymerization CHEMICAL POLYMERIZATION Mechanisms and General Optimization in Solution Polymerizations Synopsis of Chemical Syntheses Unique Chemical Polymerization Methods DOPANTS, AND ALTERNATIVE DOPING TECHNIQUES Common Dopants Uncommon or Unusual Dopants Alternative Doping Techniques TEMPLATE-BASED POLYMERIZATIONS NANOSCALE POLYMERIZATIONS TRUE COPOLYMERIZATIONS BULK AND COMMERCIAL PRODUCTION 140 PROBLEMS AND EXERCISES 142 CHAPTER 6: CONDUCTION MODELS FOR CPs INTRODUCTION AND GENERAL ASPECTS Experimental Measurements Substantiating Conduction Models Nature of Conduction and Relation with CP Morphology Temperature, Frequency, Doping Dependencies Temperature Dependencies Frequency Dependencies Doping Dependencies Practical Aspects CONDUCTION MODELS Mott Variable Range Hopping (VRH) Model Sheng Model 152
6 CONDUCTING POLYMERS: Fundamentals and Applications xi Kivelson and Other Models Relationship of All Models EXPERIMENTAL CORRELATIONS General Temperature Dependencies Frequency Dependencies, Microwave Measurements Thermopower and Hall Effect Measurements Pressure Dependencies Stretching, Anisotropy, Crystallinity, Molecular Weight Effects Activation Energies and Mobilities Minor Structural Effects 171 PROBLEMS AND EXERCISES 172 CHAPTER 7: THEORETICAL TREATMENTS OF CPs AIMS OF THIS CHAPTER ONE-DIMENSIONAL SYSTEMS AND PEIERLS INSTABILITY OVERVIEW OF THEORETICAL METHODS USED EXTENDED HÜCKEL AND RELATED METHODS THE VEH METHOD AB INITIO, COMBINATION AB INITIO/SEMIEMPIRICAL STUD IES METHODS USING SSH HAMILTONIANS METHODS CONSIDERING e-e, e-p CORRELATIONS APPENDIX 7-1: SELECTED CALCULATED BAND STRUCTURES APPENDIX 7-2: SELECTED METHODOLOGY, CALCULATION DETAILS, AND RELEVANT EQUATIONS Extended Hiickel (EH) LCAO/ETB (Extended Tight Binding) 197
7 xii Table of Contents VEH Strictly Ab Initio Methods Representative Combination Ab Initio/Semi-Empirical Methods The SSH Hamiltonian Methods Considering e-e, e-p Correlations 200 PROBLEMS AND EXERCISES 206 CHAPTER 8: SOLUBILITY AND PROCESSING OF CPs INTRODUCTORY REMARKS AND TRULY SOLUBLE CPs Note on Commonality with Material in Other Chapters Truly Soluble and Processible CPs Most Common Processing Methods SOLUTIONS IN UNUSUAL OR DIFFICULT SOLVENTS TEMPLATE BASED AND SULFONATED CPs Template Based "Soluble" CPs "Self-Doped" and Other Sulfonated CP Systems LONG CHAIN ALKYL SUBSTITUTED POLY(THIOPHENES) POLY(DIACETYLENES) AS PROCESSIBLE CPs USE OF OTHER SOLUBILIZING GROUPS PROCESSING AND COATING OF CPs VIA in situ POLYMERIZA TION General Textile and Fiber Coating MELT AND OTHER HEAT PROCESSIBILITY TECHNIQUES USING COLLOIDAL SOLUTIONS PRECURSOR ROUTES LANGMUIR-BLODGETT FILMS OF CPs DIRECT VAPOR DEPOSITION 226
8 CONDUCTING POLYMERS: Fundamentals and Applications ХШ 8.13 OTHER NEW DEPOSITION METHODS 226 PROBLEMS AND EXERCISES 227 CHAPTER 9: STRUCTURAL ASPECTS, MORPHOLOGY AND FIBER/ FILM PROCESSING GENERAL CONSIDERATIONS IN MORPHOLOGY Idealized and Real Structures, Chain Defects and Order Polymerization Conditions Rotational Barriers Molecular Weight (MWt) Fibrillar and Globular Morphology Doping Effects Effects of Fundamental Structure and Substituents FIBERS AND ORIENTED FILMS Preparation: Fibers General Considerations in Fiber Preparation Representative Procedures in Detail Preparation: Oriented Films Enhancement of Conductivity, Conductivity Anisotropy Mechanical Properties Crystallinity True Single-Crystal Character THERMOCHROMISM AND SOLVATOCHROMISM 248 PROBLEMS AND EXERCISES 251 CHAPTER 10: "COMPOSITES" (BLENDS) AND COPOLYMERS INTRODUCTION AND DEFINITIONS Definitions Synopsis of Types of Syntheses IN SITU CHEMICAL POLYMERIZATIONS Chemical Polymerization via Sorption of Monomer Chemical Polymerization via Sorption of Oxidant Solution Evaporative Polymerization Catalytic and Omer In Situ Chemical Polymerization 259
9 XIV Table of Contents 10.3 IN SITU ELECTROCHEMICAL POLYMERIZATIONS DIRECT POLYMER BLENDS Blending in Solution Melt-Blending COMPOSITE FIBERS TRUE COPOLYMERS INTERPENETRATING POLYMER NETWORKS 272 PROBLEMS AND EXERCISES 272 CHAPTER 11: CHARACTERIZATION METHODS AND SALIENT RESULTS: PART INTRODUCTION, OUTLINE OF SKELETAL CHARACTERIZA TION CONDUCTIVITY AND RELATED MEASUREMENTS Ex-Situ DC Conductivity of Powders, Films and Fibers In-Situ DC Conductivity Electrochemical Impedance Spectroscopy (EIS) and AC Conductivity Thermopower Measurements INFRARED MEASUREMENTS MOLECULAR WEIGHT Indirect Methods Gel Permeation Chromatography (GPC) Viscosity Light Scattering RAMAN SPECTROSCOPY THERMAL AND ENVIRONMENTAL STABILITY MEASURE MENTS Thermogravimetric Analysis (TGA) Differential Scanning Calorimetry (DSC) Other Thermal and Environmental Stability Test Methods.. 303
10 CONDUCTING POLYMERS: Fundamentals and Applications xv 11.7 X-RAY PHOTOELECTRON SPECTROSCOPY NUCLEAR MAGNETIC RESONANCE METHODS ESR Basics of ESR of CPs P(Py) and Poly(thiophenes) Poly(acetylene) P(ANi)s Photo-Induced ESR Other CPs ENDOR ELECTRON ENERGY LOSS SPECTROSCOPY (EELS) 324 PROBLEMS AND EXERCISES 326 CHAPTER 12: CHARACTERIZATION METHODS AND SALIENT RESULTS: PART MICROWAVE PROPERTIES Interest in CPs, Properties Covered, Frequencies Parameters of Interest, and Cavity Perturbation Measurements Network Analyzer Based Methods Transmission and Reflection Measurements EMI Shielding Effectiveness (EMI-SE) Measurements Radar Cross Section (RCS) Salient Results PHOTO/ELECTRO-LUMINESCENCE, PHOTO-INDUCED PROP ERTIES Methods Salient Results THIRD ORDER NONLINEAR OPTICAL (NLO) PROPERTIES The NLO Effect and Practical Requirements Methodology Salient Results: Third Order NLO Effects Salient Results: Second Order NLO Effects Salient Results: Decay Times of Excited States 361
11 xvi Table of Contents 12.4 MAGNETIC SUSCEPTIBILITY MISCELLANEOUS METHODS 366 Problems and Exercises 369 CHAPTER 13: CLASSES OF CPs: PART Note on Chapter Focus POLY(ACETYLENES) (P(Ac)s) Simple Syntheses and Basic Properties Doping of P(Ac) Orientation of P(Ac) Special Syntheses Substituted P(Ac)s POLY(DIACETYLENES) (P(DiAc)s) POLY(PYRROLES) (P(Py)s) Chemical Polymerizations Electrochemical Syntheses Substituted P(Py)s POLY(ANILINES) (P(ANi)s) Structure and Nomenclature Representative Chemical Syntheses Electrochemical Synthesis P(ANi) DERIVATIVES OTHER POLY(AROMATIC AMINES) 388 PROBLEMS AND EXERCISES 391 CHAPTER 14: CLASSES OF CPs: PART Note on Chapter Focus POLY(THIOPHENES)(P(T)'s) Chemical Syntheses 394
![CONDUCTING POLYMERS: Fundamentals and Applications xvii 14.1.2 Electrochemical Syntheses 395 14.1.3 Properties 398 14.2 DERIVATIVES OF POLY(THIOPHENES) 400 14.2.1 P(ITN) and Poly(naphtho[c]thiophene) 401 14.](/docs-images/87/96071030/images/12-0.jpg "2.2 Poly(thienylene vinylenes) P(TV)s 403 14.2.3 Other Poly(thiophene) (P(T)) Derivatives 406 14.3 POLY(p-PHENYLENE)s (P(PP)s) AND DERIVATIVES 409 14.3.1 Poly(p-phenylene) P(PP) 409 14.3.2 Poly(phenylene vinylene) (P(PV)) 412 14.")
12 CONDUCTING POLYMERS: Fundamentals and Applications xvii Electrochemical Syntheses Properties DERIVATIVES OF POLY(THIOPHENES) P(ITN) and Poly(naphtho[c]thiophene) Poly(thienylene vinylenes) P(TV)s Other Poly(thiophene) (P(T)) Derivatives POLY(p-PHENYLENE)s (P(PP)s) AND DERIVATIVES Poly(p-phenylene) P(PP) Poly(phenylene vinylene) (P(PV)) Poly(phenylene sulfide) (P(PS)), Poly(phenylene oxide) (P(PO)) and Related Poly(phenylene chalcogenide)s POLY(AZULENES) LADDER POLYMERS: BBL, BBB, PBT, PBO POLY(QUINOLINES) AND DERIVATIVES OTHER POLYMERS 428 PROBLEMS AND EXERCISES 428 PART П: APPLICATIONS 431 CHAPTER 15: BATTERIES TYPES OF BATTERIES INCORPORATING CPs Summary of Applications Advantages of CPs Battery Parameters and Performance Li SECONDARY BATTERIES Principles Li/CP Batteries Problems Associated with Li/CP Batteries POLY(ACETYLENE) (P(Ac)) POLY(PYRROLE) (P(Py)) 442
13 xviii Table of Contents 15.5 POLY(ANILINE) (P(ANi)) POLY(THIOPHENES) (P(T)s) OTHER CPs NON-Li-BATTERIES COMMERCIALIZATION OF CP-BASED BATTERIES 449 PROBLEMS AND EXERCISES 452 CHAPTER 16: LIGHT EMITTING DIODES (LEDs) INTRODUCTION PRINCIPLES OF CP-BASED LEDs VARIETIES OF CPs USED EXEMPLARY DEVICE ASSEMBLY ADDRESSING PROBLEMS AND TAILORING PERFORMANCE TAILORING OF COLOR AC-DRIVEN LEDs LEDs EMITTING POLARIZED LIGHT SUBMICRON AND OTHER SPECIALTY APPLICATIONS ADDITIONAL DEVELOPMENTS RELATING TO DEVICE AND COMMERCIAL APPLICATIONS "LECs" AND OTHER DEVICE TYPES 480 PROBLEMS AND EXERCISES 482
14 CONDUCTING POLYMERS: Fundamentals and Applications xix CHAPTER 17: SENSORS MODES OF SENSING WITH CPs CONDUCTOMETRIC-MODE SENSORS POTENTIOMETRIC SENSING AMPEROMETRIC SENSING CONDUCTOMETRIC/AMPEROMETRIC SENSING WITH MICRO SENSORS VOLTAMMETRIC SENSING GRAVIMETRIC-MODE SENSING OPTICAL-MODE SENSING OTHER SENSING MODES COMMERCIAL IMPLEMENTATION 508 PROBLEMS AND EXERCISES 508 CHAPTER 18: ELECTRO-OPTIC AND OPTICAL DEVICES DEVICE TYPES AND MOTIVATIONS FOR DEVELOPMENT WAVEGUIDES OTHER SECOND-ORDER NLO APPLICATIONS SEMICONDUCTOR/CP (SC/CP) INTERFACES CP-BASED LASERS OTHER OPTICAL DEVICES PRACTICAL IMPLEMENTATION 525 PROBLEMS AND EXERCISES 526
15 xx Table of Contents CHAPTER 19: MICROWAVE- AND CONDUCTIVITY-BASED TECHNOLOGIES INTRODUCTION, APPLICATIONS COVERED, FREQUENCIES ELECTROMAGNETIC IMPULSE (EMI) SHIELDING ELECTROSTATIC DISCHARGE AND ANTISTATIC MICROWAVE ABSORPTION AND RADAR CROSS SECTION (RCS) REDUCTION COMPREHENSIVE PROPERTIES' STUDIES CONDUCTIVE TEXTILES MICROWAVE SMOKE MICROWAVE WELDING 540 PROBLEMS AND EXERCISES 541 CHAPTER 20: ELECTROCHROMIC DEVICES INTRODUCTION AND DEVICE TYPES VISIBLE-REGION DEVICES Structure Function of Devices, Laboratory vs. Actual Devices Examples of Actual, Functional Devices IR-REGION DEVICES OTHER SPECTRAL REGIONS 560 PROBLEMS AND EXERCISES 561
16 CONDUCTING POLYMERS: Fundamentals and Applications xxi CHAPTER 21: ELECTROCHEMOMECHANICAL AND CHEMO- MECHANICAL DEVICES INTRODUCTION, HISTORY, AND PRINCIPLES ARTIFICIAL MUSCLES OTHER ELECTROCHEMOMECHANICAL ACTUATION CHEMOMECHANICAL ACTUATORS AND SENSORS 570 PROBLEMS AND EXERCISES 571 CHAPTER 22: CORROSION PROTECTION PRINCIPLES, DRIVING FORCES AND HISTORY Principles of Other Anti-Corrosion Methods Driving Forces Behind Development Principles of CP Anti-Corrosion Coatings Brief Historical Development Advantages of CP Coatings CANDIDATES AND METHODS Most-Studied Candidates and Coating Methodology Testing Methodology SALIENT RESULTS P(ANi)'s Other Poly(Aromatic Amines) Other CPs PROGNOSIS FOR THE FUTURE 588 PROBLEMS AND EXERCISES 589 CHAPTER 23: SEMICONDUCTOR-, LITHOGRAPHY-, AND ELECTRICALLY-RELATED APPLICATIONS LITHOGRAPHY AND PHOTOPATTERNING Lithography 592
17 xxii Table of Contents Other Photopatterning Other Related Applications PHOTOVOLTAICS, HETEROJUNCTIONS AND PECs Use of CPs in General PVs, Heterojunctions, Diodes Photoelectrochemical Cells (PECs) CAPACITORS ELECTROLYTIC AND ELECTROLESS METAL PLATING CP-BASED "MOLECULAR ELECTRONIC DEVICES" 617 PROBLEMS AND EXERCISES 624 CHAPTER 24: CATALYSIS AND DRUG/CHEMICAL DELIVERY INTRODUCTION AND COMMON FEATURES CATALYSIS DRUG/CHEMICAL DELIVERY 631 PROBLEMS AND EXERCISES 634 CHAPTER 25: MEMBRANES INTRODUCTION ION PERMEATION AND EXCHANGE CHEMICAL/DRUG PERMEATION GAS SEPARATION 640 PROBLEMS AND EXERCISES 644 LITERATURE CITED 645
18 CONDUCTING POLYMERS: Fundamentals and Applications xxiii INDEX 703 ABOUT THE AUTHOR 719
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