Conjugated Polymers: Properties, Processing, and Applications

Description

This book covers properties, processing, and applications of conducting polymers. It discusses properties and characterization, including photophysics and transport. It then moves to processing and morphology of conducting polymers, covering such topics as printing, thermal processing, morphology evolution, conducting polymer composites, thin films. Cover Half Title Conjugated Polymers: Properties, Processing, and Applications Copyright Contents Preface to Fourth Edition Acknowledgments Editors Contributors 1. Conjugated Polymer-Based OFET Devices 1.1 Introduction 1.2 State of OFET Technology/Applications/Commercialization Efforts 1.3 Recent Developments in Polymer OFET Materials – From Crystalline Polythiophenes to Donor–Acceptor Polymers 1.4 Charge Transport in Polymer OFETs 1.5 Role of Disorder 1.6 Charge Carrier Mobility and Artefacts 1.7 Stability of OFETs 1.8 Outlook References 2. Electrical Doping of Organic Semiconductors with Molecular Oxidants and Reductants 2.1 Introduction 2.2 Basics of Doping in Organic Materials Comparison to Doping of Inorganic Materials Effects of Doping 2.3 Criteria for Dopant Choice 2.4 Survey of Dopants p-Dopants n-Dopants 2.5 Device Examples OLEDs OFETs OPVs 2.6 Summary Acknowledgments References 3. Electric Transport Properties in PEDOT Thin Films 3.1 Introduction 3.2 Chemistry of PEDOT Chemical vs. Electrochemical Polymerization of PEDOT:X Chemical Water Dispersion: PEDOT:PSS PEDOT:Biopolymer Dispersion Polymerization Tuning the Oxidation/Doping Level Chemically vs. Electrochemically 3.3 Electronic Structure of PEDOT: From a Single Chain to a Thin Film Nature of Charge Carriers and Electronic Structure of PEDOT Chains Density of States of PEDOT: From a Single Chain to a Thin Film Band Gap and Optical Transitions in PEDOT 3.4 Morphology of PEDOT Brief Review of Experimental Data for PEDOT:X and PEDOT:PSS (GIWAXS, TEM, AFM) Morphology of PEDOT: A Theoretical Perspective 3.5 Electrical Conductivity Basic Thermodynamics of Thermoelectrical Processes Temperature Dependence Secondary Doping Acid-Base Effect 3.6 Optical Conductivity Basic Definitions and Relations Methodologies for Measuring the Dielectric Function Optical Conductivity and Permittivity of PEDOT Concluding Remarks on PEDOT Optical Conductivity 3.7 Transport Properties of PEDOT: A Theoretical Perspective Basics of the Hopping Transport: Semi-Analytical Approach and Kinetic Monte Carlo Boltzmann Approach to Conductivity Based on the Model of an Ideal Crystal Multi-Scale Modelling Based on the Realistic Morphology 3.8 Mixed Electron-Ion Transport in PEDOT Devices Utilizing Mixed Electron and Ion Conductivity Experimental Results Modelling of Mixed Electron-Ion Transport in PEDOT Calculation of Ion Diffusion in PEDOT 3.9 Conclusions and Outlook Acknowledgments References 4. Thermoelectric Properties of Conjugated Polymers 4.1 Introduction 4.2 Models of Thermoelectric Properties 4.3 Microstructure of Semiconducting Polymers 4.4 Thermoelectric Power Factor of Semiconducting Polymers Introduction Polyacetylene Polyaniline Poly(ethylenedioxythiophene) Poly(3-hexylthiophene) Poly( 2,5-bis(3- alkylthiophen-2 -yl) thieno [3,2- b]thiophene) Co-Polymers n-Type Polymers 4.5 Thermal Conductivity of Polymers Introduction Thermal Conductivity of Undoped Semiconducting Polymers Electronic Contribution to Thermal Conductivity 4.6 ZT for Polymers 4.7 Outlook References 5. Electrochemistry of Conducting Polymers Introduction 5.1 Fundamentals Electropolymerization: Mechanism, Techniques, Synthesis Control Electrochemical Doping: Charge Carriers, Redox vs. Capacitive Behavior and Related Properties Relaxation Effects Electrochemical Characterization of an ECP in a Given Electrolytic Medium Determination of HOMO–LUMO Levels by Cyclic Voltammetry 5.2 New Trends in Electrosynthesis of Conducting Polymers New Monomers New Electrolytic Media 5.3 Nano-Objects and Nanocomposites Nano-Objects Nanocomposites 5.4 Applications Energy Storage Actuators and Drug Delivery Molecular Imprinting ECP Biosensors and Related Materials Anticorrosion Electrochromism and Electrofluorochromism Conclusion and Future References 6. Electrochromism in Conjugated Polymers – Strategies for Complete and Straightforward Color Control 6.1 Introduction to Electrochromic Polymers 6.2 Electrochromism in Conjugated Polymers 6.3 The Electrochromic Toolbox Electrochromic/Optical Contrast Colorimetric Analysis Switching Speed/Response Time Coloration Efficiency/Charge-to-Switch Optical Memory/Bistability Switching Stability 6.4 Synthesis of Soluble Electrochromic Polymers 6.5 Developing Structure– Property Relationships for Color Control in Cathodically Coloring ECPs Effect of the Choice of Heterocycle, the Building Block of ECPs Steric Effects of Introducing Functional Groups Expanding the Color Palette through Copolymerization Developing Broadly Absorbing Systems for Black and Brown Hues 6.6 Anodically Coloring Systems 6.7 Controlling Solubility, Contrast, and Redox Properties Tuning Solubility Tuning Contrast Tuning Redox and Switching Properties 6.8 Conclusions Acknowledgments and Notes References 7. Mechanical Properties of Semiconducting Polymers 7.1 Introduction and Background Semiconducting Polymers as a Subset of All Solid Polymers 7.2 Deformation in Solid Polymers Mediation of Mechanical Energy Elasticity and Plasticity Fracture 7.3 Mechanical Properties and Measurement Techniques Overview of Mechanical Properties Common Measurement Techniques 7.4 Effects of Physical Parameters Effects of Elastic Mismatch and Adhesion Effects of Film Thickness Effects of Strain Rate 7.5 Effects of Molecular Structure and Microstructure Role of Molecular Weight Role of Alkyl Side Chains Role of Molecular Structure and Backbone Rigidity Role of Intermolecular Packing 7.6 Glass Transition Temperature and Measurement Techniques The Glass Transition in Semiconducting Polymers Techniques to Measure the T[sub(g)] of Semiconducting Polymers 7.7 Theoretical Modeling Molecular Structure and Atomistic Simulations Polymer-Chain Size and Phase Behavior Coarse-Grained Simulations and Continuum-Based Methods 7.8 Composite Systems Effects of Molecular Mixing Polymer–Fullerene Composites 7.9 Conclusion and Outlook References 8. Magnetic Field Effects in Organic Semiconductors; Low and High Fields, Steady State and Time Resolved 8.1 Introduction 8.2 Review of Various Mechanisms The Hyperfine Mechanism Mechanisms Related to Triplet Excitons The Δg Mechanism Thermal Spin Polarization Magnetic Field Effect in Excited-State Spectroscopies of Films; Steady State Time Resolved Magnetic Field Effects 8.3 Experimental Studies Magnetic Field Effects in Organic Devices at Low Fields Magneto-Photo-Induced Absorption in Films High Field Magneto-Photocurrent in Organic Bulk Hetero-Junction Photo-Voltaic Cells Transient Magneto-Photoinduced Absorption in Donor–Acceptor Copolymers 8.4 Summary References 9. Organic Electro-Optic Materials 9.1 Historical Overview 9.2 Introduction to Electro-Optic (EO) Activity 9.3 Pre-2005 Polymeric OEO Materials and Devices 9.4 Post-2005 Macromolecular OEO Materials and Devices 9.5 Applications 9.6 Other Organic Materials for Optical Modulation 9.7 Future Prognosis Acknowledgments References 10. Establishing the Thermal Phase Behavior and its Influence on Optoelectronic Properties of Semiconducting Polymers 10.1 Introduction 10.2 Single-Component Systems Crystallization and Melting Glass Transition Polymorphism Liquid Crystallinity 10.3 Multi-Component Systems Polymer Semiconductor:Solvent Systems Polymer Semiconductor:Small Molecule Systems Polymer Semiconductor:Polymer Systems 10.4 Time/Temperature/Transformation Phase Diagrams 10.5 Conclusions References 11. Poly(3-alkylthiophenes): Controlled Manipulation of Microstructure and its Impact on Charge Transport 11.1 Introduction 11.2 P3AT Structural Characterization Small Angle Neutron Scattering UV–Vis Absorbance Differential Scanning Calorimetry X-Ray Scattering Atomic Force Microscopy Charge Carrier Mobility Concluding Remarks 11.3 Advances in Solution Processing Methods 11.4 Deposition Methods Spin-Coating Drop-Casting Inkjet Printing Dip-Coating Solution Shearing 11.5 Semiconductor Crystalline Structure in Flexible and Stretchable Devices 11.6 Conclusions References 12. Microstructural Characterization of Conjugated Organic Semiconductors by X-Ray Scattering 12.1 Introduction 12.2 Fundamentals of X-Ray Scattering Wide-Angle X-Ray Scattering (WAXS) Small Angle X-Ray Scattering (SAXS) 12.3 Applications in Conjugated Semiconductors (Selected Examples) Crystal Structure and Molecular Packing of Small-Molecules for Organic Thin-Film Transistor (OTFT) Estimation of Volume Fraction of Phases in Bulk Heterojunction (BHJ) Photovoltaics Probing the Surface and the Bulk of Small-Molecule Thin Films Microstructural Evolution for P3HT:PCBM During Spin-Coating from One Solvent In Situ GISAXS for Probing Phase-Separation Evolution using Multiphase Modeling Based onTSI Co-Solvent Processing for Reducing Domains Over-Coarsening by Influencing the Liquid-Liquid Phase Separation 12.4 Summary and Outlook Acknowledgment References 13. Soft X-Ray Scattering Characterization of Polymer Semiconductors 13.1 Introduction 13.2 Basic Principles and Parameters of Soft X-Ray Scattering 13.3 Soft X-Ray Scattering of Various Semiconducting Polymer Systems Soft X-Ray Scattering of Neat Semiconducting Polymers Soft X-Ray Scattering of Binary Semiconducting Polymer Blends Soft X-Ray Scattering of Multi-Component Semiconducting Polymer Blends 13.4 Conclusions and Outlook Acknowledgments References 14. Morphology Evolution and Interfacial Design of Conjugated Polymer- Based Photovoltaics Introduction 14.1 Polymer:fullerene-Based BHJs P3HT:fullerene System PCPDTBT:fullerene System DPP Polymer:fullerene System BDT Polymer:fullerene System 14.2 Polymer:non-fullerene Acceptor-Based BHJs Polymer:PDI Acceptor Polymer:NDI Acceptor Polymer:calamitic Shaped Acceptor 14.3 Interfacial Design with Polymers 14.4 Summary and Outlook References 15. The Relevance of Solubility and Miscibility for the Performance of Organic Solar Cells 15.1 Introduction 15.2 Principles of Mixing The Solubility Parameter Concept Flory–Huggins Interaction Parameter Spinodal Demixing 15.3 Computational Methods Implicit Solvation Model: Conductor Like Screening Model Prediction of HSP and Physical-Chemical Values 15.4 Solubility and Miscibility: Experimental Methods Solubility Polymer–Solvent Miscibility Solute–Solute Miscibility via Melting Point Depression 15.5 Miscibility and Phase-Stability in Organic Photovoltaics Introduction to OPV Stability Microstructure Instabilities in Polymer-Fullerene Composites 15.6 Conclusion 15.7 Acknowledgments References 16. Processing-Structure-Function Relationships of Polymer-Acid-Templated Conducting Polymers for Solid-State Devices 16.1 Introduction 16.2 Structural Heterogeneity across Multiple Length Scales 16.3 Processing of Dispersions of Conducting Polymer/Polymer Acid Complexes 16.4 Processing of Thin Films of Conducting Polymer/Polymer Acid Complexes 16.5 Conclusions Acknowledgments References 17. Conjugated Polymer Thin Films for Stretchable Electronics 17.1 Introduction 17.2 Engineering Approach for Stretchable/Flexible Electronics Criteria for Flexible Electronics Designing Stretchable Electronics 17.3 Molecularly Stretchable Polymers for Organic Electronics Introduction of Section Design Strategies and Structure-Property Relationship of Polymers Backbone Engineering Crosslinks and Dynamic Bonds Sidechain Engineering Additives 17.4 Closing Remarks References 18. Conducting Polymers for Electrochemical Capacitors 18.1 Introduction 18.2 Storing Electrochemical Energy in Conducting Polymers Theoretical Limits of Conducting Polymers Electrolytes, Ions and Stability 18.3 Synthesis and Processing of Conducting Polymers for Energy Storage Solution-Based Chemical Polymerization Electrochemical Polymerization Vapor Phase Polymerization Summary 18.4 Materials and Device Engineering Types of Electrochemical Capacitors Novel Types of Polymer Electrochemical Capacitors 18.5 Conclusions Acknowledgments References 19. Redox-Active Polymers as an Organic Energy Storage Material 19.1 Introduction 19.2 Design of Redox-Active Polymers for Charge Transport and Storage Redox-Active Groups Main Chains 19.3 Charge Transport Properties 19.4 Charge Storage Performances Charge Storage with Redox Polymers Organic Batteries with Redox Polymer Electrode-Active Materials 19.5 Conclusion References 20. Electrochromics: Processing of Conjugated Polymers and Device Fabrication on Semi-Rigid, Flexible, and Stretchable Substrates 20.1 Introduction Components of an Electrochromic Device Electrochromic Device Parameter Background 20.2 Conducting Substrate Rigid Conducting Substrate Flexible Conducting Substrate Conducting Stretchable Substrate Fabric Conducting Substrate 20.3 Electrochromic Layer Processing of Insoluble Electrochromic Polymers Processing of Soluble Polymers onto Substrates Novel Methods of Processing Electrochromic Polymers Electrochromic Conjugated Polymer Theory 20.4 Electrolyte Layer Polymers in Electrolyte Layer Solvents in Electrolyte Layer Salts in Electrolyte Layer 20.5 Charge Storage Layer 20.6 Optimization of an Electrochromic Device Electrochromic Layer Electrolyte Layer 20.7 Novel Fabricated Devices 20.8 Conclusions and Outlook References 21. Separation Techniques Using Conjugated Polymers 21.1 Gas Separation Membranes Using Conjugated Polymers Outline of the Review Overview Polyaniline Films for Gas Separation Other Conjugated Polymers and Composite Membranes Conclusions 21.2 Conjugated Polymer–Based Membranes for Water Purification Introduction Fouling and Antifouling Membranes Polyaniline-Based Membranes Other Conjugated Polymer–Based Membranes Conclusions 21.3 Capacitive Deionization Using Conjugated Polymers Introduction The History of Capacitive Deionization Capacitive Deionization Mechanism Conjugated Polymers Composite with Carbon-Based Materials Other Conducting Polymer–Based Composites Conclusions Acknowledgments References 22. Organic Bioelectronics Based on Mixed Ion–Electron Conductors 22.1 Introduction 22.2 Electronic Surface Switches and Scaffolds to Regulate Development of Cell Cultures: From Seeding to Harvesting Tissue Organic Bioelectronic Surface Switches: Mechanism Targeting the Extracellular Matrix: Epithelial Cells Growth Factors Modulation: Embryonic Neural Stem Cells Electrochemical Gradients, Cell Gradient 3-Dimensional and Topographical Surface Switches Electronic Control of Cell Release, Matrix-Addressed Surface Switches 22.3 Iontronics for Controlled Delivery of Ions and Biomolecules Iontronics for Bioelectronic Applications Organic Electronic Ion Pumps Bipolar Membrane–Based Diodes, Transistors, and Logic Circuits Ionic Diode Rectifiers to Circumvent Electrode Capacity Limitations Fast Delivery Circuits for Neurotransmitter Release In Vitro Applications of Iontronics Delivery of Therapeutic Substances In Vivo 22.4 Conclusion References 23. Conducting and Conjugated Polymers for Biosensing Applications 23.1 Introduction 23.2 Optical Properties of Conjugated Polymers and Associated Transduction Mechanisms 23.3 Electronic Properties of Conjugated Polymers and Associated Transduction Mechanisms Polymer-Based Transistors 23.4 Biorecognition Element Immobilization/Integration on/with Conjugated Polymers 23.5 Conjugated and Conducting Polymer Biosensor Applications Based on the Biorecognition Element Nucleic Acid Sensors Proteins Lipids Bacteria Cells Toward More Biomimetic Systems for Biosensing 23.6 Perspectives References 24. Conjugated Poly/Oligo-Electrolytes for Cancer Diagnosis and Therapy 24.1 Introduction 24.2 Diagnosis Tumor Marker Tests Genetic Tests 24.3 Therapy Drug Delivery System Gene Delivery Systems PhotodynamicTherapy Photothermal Therapy 24.4 Summary and Outlook References 25. Biomedical Applications of Organic Conducting Polymers 25.1 Introduction 25.2 Optimising Polymer Composition Polymer Backbone Synthetic and Biological Dopants Dopant Loading Chemical Functionalisation of the OCP Surface 25.3 Implantable Electrodes for Monitoring. Neurotransmitters, Metabolites, Firing Patterns from Excitable Cells 25.4 Implantable Electrodes for Electrical Stimulation 25.5 Controlled Delivery Systems Controlled Drug Delivery Systems Controlled Delivery of Growth Factors 25.6 Implantable Energy Systems Biofuel cells Biobatteries 25.7 Materials Processing and Fabrication Options 25.8 Conclusions and Future Developments References Index