Conjugated Polymers: Properties, Processing, and Applications

✍ Scribed by Reynolds J.R., Thompson B.C., Skotheim T.A. (ed.)

• Publisher: CRC Press
• Year: 2019
• Tongue: English
• Leaves: 844
• Series: Handbook of Conducting Polymers
• Edition: 4
• Category: Library

✦ Synopsis

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.

✦ Table of Contents

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