Additional Information
Book Details
Abstract
Semiconducting polymers are of great interest for applications in electroluminescent devices, solar cells, batteries and diodes. In recent years vast advances have been made in the area of controlled synthesis of semiconducting polymers, specifically polythiophenes. The book is separated into two main sections, the first will introduce the advances made in polymer synthesis, and the second will focus on the microstructure and property analysis that has been enabled because of the recent advances in synthetic strategies.
Edited by one of the leaders in the area of polythiophene synthesis, this new book will bring the field up to date with more recent models for understanding semiconducting polymers. The book will be applicable to materials and polymers chemists in industry and academia from postgraduate level upwards.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Contents | ix | ||
| Preface | vii | ||
| Section I: Controlled Synthesis of Semiconducting Polymers | 1 | ||
| Chapter 1 Controlled Synthesis of Conjugated Polymers in Catalyst-transfer Condensation Polymerization: Monomers and Catalysts | 3 | ||
| 1.1 Introduction | 3 | ||
| 1.2 Kumada–Tamao Coupling Polymerization of Grignard Monomers | 4 | ||
| 1.2.1 Background and Discovery | 4 | ||
| 1.2.2 Mechanistic Studies | 6 | ||
| 1.2.3 Monomers | 9 | ||
| 1.2.4 Catalysts | 11 | ||
| 1.2.5 Initiators | 13 | ||
| 1.2.6 Functionalization of Polymer Ends | 16 | ||
| 1.3 Suzuki–Miyaura Coupling Polymerization of Boronic Acid (Ester) Monomer | 16 | ||
| 1.3.1 Background and Discovery | 16 | ||
| 1.3.2 Monomers | 17 | ||
| 1.3.3 Initiators and Catalysts | 20 | ||
| 1.3.4 Functionalization of Polymer Ends | 22 | ||
| 1.4 Other Coupling Polymerization Reactions | 24 | ||
| 1.4.1 Negishi Coupling Polymerization of Zn-containing Monomers | 24 | ||
| 1.4.2 Stille Coupling Polymerization of Tin-containing Monomers | 28 | ||
| 1.4.3 Murahashi Coupling Polymerization of Aryllithium Monomers | 29 | ||
| 1.4.4 Mizoroki–Heck Coupling Polymerization of Non-metallated Monomers | 30 | ||
| 1.4.5 Nucleophilic Substitution Polymerization of Silylated Monomers | 30 | ||
| 1.5 Conclusions | 31 | ||
| Acknowledgments | 32 | ||
| References | 32 | ||
| Chapter 2 Controlled Chain-growth Synthesis of Conjugated Polymers: Moving Beyond Thiophene | 38 | ||
| 2.1 Introduction | 38 | ||
| 2.2 Mechanism of Controlled Chain Growth in Conjugated Polymers | 41 | ||
| 2.3 Chain-growth Synthesis of Conjugated Homopolymers | 44 | ||
| 2.4 Chain-growth Synthesis of Alternating Copolymers | 56 | ||
| 2.5 Mixed-mechanism Chain-growth Synthesis of Block Copolymers | 63 | ||
| 2.6 Chain-growth Synthesis of Fully Conjugated Block Copolymers | 66 | ||
| 2.7 Chain-growth Synthesis of Other Copolymers | 71 | ||
| 2.8 Future Outlook | 78 | ||
| References | 80 | ||
| Chapter 3 Application of Catalyst Transfer Polymerizations: From Conjugated Copolymers to Polymer Brushes | 85 | ||
| 3.1 Introduction | 85 | ||
| 3.2 Fully Conjugated Block Copolymers | 86 | ||
| 3.2.1 Donor-Donor Type Conjugated Block Copolymers | 86 | ||
| 3.2.2 Donor-Acceptor Type Fully Conjugated Block Copolymers | 91 | ||
| 3.3 Conjugated Gradient Copolymers | 97 | ||
| 3.4 Block Copolymers Consisting of Conjugated and Non-conjugated Blocks | 99 | ||
| 3.4.1 Synthesis via Macromolecular Coupling Reactions | 99 | ||
| 3.4.2 Synthesis with Macromolecular Initiators | 102 | ||
| 3.4.3 Synthesis via One-pot Polymerization | 107 | ||
| 3.5 Conjugated Polymer Brushes | 109 | ||
| 3.6 Other Applications | 111 | ||
| 3.7 Summary and Outlook | 113 | ||
| References | 114 | ||
| Chapter 4 Controlled Synthesis of Chain End Functional, Block and Branched Polymers Containing Polythiophene Segments | 121 | ||
| 4.1 Introduction | 121 | ||
| 4.2 Controlled Synthesis of Polythiophenes | 122 | ||
| 4.3 Regio-regularity | 123 | ||
| 4.4 Control of Molecular Weight and Dispersity | 124 | ||
| 4.5 Dehydrogenative Synthesis of Polythiophene | 126 | ||
| 4.6 Chain End Functional Polythiophenes | 128 | ||
| 4.7 Block Copolymers with Polythiophene Segments | 134 | ||
| 4.7.1 All-conjugated Block Copolythiophenes | 134 | ||
| 4.7.2 All-conjugated Block Copolymers Containing Polythiophene and Other Polymer Segments | 137 | ||
| 4.7.3 All-conjugated Donor-Acceptor Block Copolymers | 139 | ||
| 4.7.4 Semi-conjugated Block Copolymers Containing Polythiophene Segments | 142 | ||
| 4.8 Graft Copolymers with Polythiophene Segments | 146 | ||
| 4.9 Star-branched Polymers with Polythiophene Segments | 149 | ||
| 4.10 Hyperbranched Polythiophene with a Controlled Degree of Branching | 154 | ||
| 4.11 Conclusions | 155 | ||
| Acknowledgments | 155 | ||
| References | 155 | ||
| Section II: Microstructure of Semiconducting Polymers | 163 | ||
| Chapter 5 Characterization of Polymer Semiconductors by Neutron Scattering Techniques | 165 | ||
| 5.1 Introduction | 165 | ||
| 5.2 Small-angle Neutron Scattering | 166 | ||
| 5.2.1 SANS of Dissolved Conjugated Polymers | 167 | ||
| 5.2.2 SANS of Colloidal Polymer Nanostructures | 168 | ||
| 5.3 Neutron Scattering in Thin Films | 171 | ||
| 5.3.1 Transmission SANS | 172 | ||
| 5.3.2 Neutron Reflectometry | 174 | ||
| 5.3.3 Grazing Incidence Small-angle Neutron Scattering | 175 | ||
| 5.4 Quasi-elastic Neutron Scattering | 177 | ||
| 5.4.1 Theory | 178 | ||
| 5.4.2 Instrumentation and Methods for Analysis | 179 | ||
| 5.4.3 QENS of Polymer Semiconductors | 180 | ||
| References | 184 | ||
| Chapter 6 Structural Control in Polymeric Semiconductors: Application to the Manipulation of Light-emitting Properties | 187 | ||
| 6.1 Introduction | 187 | ||
| 6.2 Approach 1: Chemical Design | 189 | ||
| 6.3 Approach 2: Physical and Physicochemical Methods | 195 | ||
| 6.3.1 Solvent Vapour and Solvent Quality | 195 | ||
| 6.3.2 Pressure | 196 | ||
| 6.3.3 Dewetting | 196 | ||
| 6.3.4 Chemical Cross-linking | 198 | ||
| 6.3.5 Controlled Aggregation | 199 | ||
| 6.3.6 Processing in Confined Spaces | 199 | ||
| 6.3.7 Stretchable Structures | 200 | ||
| 6.4 Approach 3: Blending | 200 | ||
| 6.5 Approach 4: Metal-enhanced Fluorescence | 207 | ||
| 6.6 Conclusions | 212 | ||
| References | 212 | ||
| Chapter 7 Structure and Order in Organic Semiconductors | 219 | ||
| 7.1 Introduction | 219 | ||
| 7.2 Differential Scanning Calorimetry | 220 | ||
| 7.2.1 Introduction to Differential Scanning Calorimetry | 220 | ||
| 7.2.2 Qualifying and Quantifying Crystallinity in Semiconducting Polymers | 221 | ||
| 7.2.3 Determination of the Equilibrium Melting Temperature | 225 | ||
| 7.2.4 Determination of the Enthalpy of Fusion Per Repeat Unit | 228 | ||
| 7.2.5 Self-nucleation and Successive Annealing | 231 | ||
| 7.2.6 Methods for Characterizing Thin Film Samples | 232 | ||
| 7.3 Solid-state NMR Spectrometry | 235 | ||
| 7.3.1 Introduction | 235 | ||
| 7.3.2 Crystallinity and Order | 236 | ||
| 7.3.3 Relaxation and Dynamics | 238 | ||
| 7.3.4 Domain Sizes and Interfacial Structures in Donor/Acceptor Blends | 248 | ||
| 7.3.5 Future Prospects | 252 | ||
| 7.4 Transmission Electron Microscopy of Organic Semiconductors | 252 | ||
| 7.4.1 Introduction to Transmission Electron Microscopy | 252 | ||
| 7.4.2 Challenges for Characterizing Polymeric Materials in TEM | 253 | ||
| 7.4.3 Methods for Characterizing Order and Morphology in Polymer Materials | 254 | ||
| 7.5 Grazing Incidence Scattering | 261 | ||
| 7.5.1 Introduction to X-ray Scattering | 261 | ||
| 7.5.2 Grazing Incidence X-ray Diffraction | 261 | ||
| 7.5.3 Grazing Incidence Small-angle X-ray Scattering | 263 | ||
| 7.5.4 Polarized Resonant Soft X-ray Scattering | 264 | ||
| 7.5.5 In situ X-ray Scattering Studies of Structure Evolution | 265 | ||
| References | 266 | ||
| Subject Index | 275 |