Understanding The Structure Function Relationship Of Semiconducting Polymers Through Chemical And Electrochemical Doping

Conjugated polymers are a versatile class of materials useable in a variety of organic electronic applications, but their utilization is limited by their intrinsically low conductivity. However, doping of semiconducting polymers via oxidation of their backbone can add mobile charge carriers and increase their electrical conductivity. This can be accomplished via electrochemical doping, where an applied potential oxidizes the polymer, or via chemical doping, where a molecular oxidizer is introduced to the polymer.Electrochemical doping of semiconducting polymers is of interest because of this class of material's ability to be utilized in electrochemical cells, such as lithium-ion batteries (LIBs). This is explored in the first part of this dissertation (Chapters 2 through 7), where we investigate the application of semiconducting polymers as LIB binders. Binders are typically designed to be chemically and mechanically durable during cycling. Utilizing conjugated polymers as binders increases the electrical conductivity of the electrode, leading to reduced resistive losses and faster charging. We show that dihexyl-substituted poly(3-4-propylenedioxy-thiophene) (PPrODOT-Hx2) can serve as a binder at relevant electrochemical potentials. Additionally, we show that by either creating co-polymers with oligoether side-chains or by adding conjugation break-spacer units, we can tune ionic conductivity, heat generation, swelling, and the mechanical properties of the semiconducting polymers. While electrochemical doping has the advantage of allowing the selection of an exact potential (i.e., doping level), chemical doping is advantageous because it is fairly simple to accomplish. In the second half of this dissertation (Chapters 8 through 12), we study a variety of semiconducting polymers and dopants to understand what results in the highest conductivity in chemically doped semiconducting films. We explore the energetics and the role of crystallinity, dielectric constant, and Coulomb binding in chemical doping. Throughout this dissertation, we utilize grazing incidence wide-angle X-ray scattering (GIWAXS) to see how the structure of these polymers change upon doping, and how these structural changes map onto changes in both electronic and ionic conductivity, and optical properties.

Semiconducting polymers are a promising class of materials for many organic electronic applications because of their structural tunability, low cost, and solution processability, which allows for easy scale-up. However, semiconducting polymers have intrinsically poor conductivity which limits their performance in all device applications. Polymer conductivity can be improved either by adding mobile carriers to the system or by manipulating the system to make the polymer chains more ordered on a local and global scale. This thesis studies both of these methods with a goal of improving polymer conductivity, while simultaneously seeking to understand how changes in morphology affect both local and global polymer properties. We used a variety of X-ray and neutron scattering techniques to characterize polymer structure, coupled with electronic and spectroscopic experiments to gain a full picture of polymer structure-function relationship. The first half of this thesis studies the structural changes that result from introducing a molecular dopant and additional charge carriers into the polymer network, and how those change control the resulting electronic and optical properties. We start by studying a novel class of large, redox-tunable dodecaborane-based dopants. From these studies we are able to determine how redox potential controls both dopant infiltration into polymer films and the resulting film structure, providing insight into the relationship between structure and conductivity for doped conjugated polymer systems. Using traditional small-molecule dopants, we also studied various doping methods to assess scalability and application to thick polymer films. The second half of this thesis presents studies on various methods to manipulate the local morphology of polymer chains to increase their overall order. We first used an aqueous amphiphilic self-assembly system where we developed structural design rules for order assembly and demonstrate that they can be used to create polymer system that show straightened chains when self-assembled. Next, we explored a set of block-copolymers whose co-crystallization properties could be changed using the polymer molecular weight; here we show that crystallization behavior directly affects conductivity. Lastly, we studied a host-guest system of polymers aligned in straight silica mesoporous, with a goal of using confinement to understand the interplay between polymer microstructure and aggregation.

The field of semiconducting polymers has attracted many researchers from a diversity of disciplines. Printed circuitry, flexible electronics and displays are already migrating from laboratory successes to commercial applications, but even now fundamental knowledge is deficient concerning some of the basic phenomena that so markedly influence a device's usefulness and competitiveness. This two-volume handbook describes the various approaches to doped and undoped semiconducting polymers taken with the aim to provide vital understanding of how to control the properties of these fascinating organic materials. Prominent researchers from the fields of synthetic chemistry, physical chemistry, engineering, computational chemistry, theoretical physics, and applied physics cover all aspects from compounds to devices. Since the first edition was published in 2000, significant findings and successes have been achieved in the field, and especially handheld electronic gadgets have become billion-dollar markets that promise a fertile application ground for flexible, lighter and disposable alternatives to classic silicon circuitry. The second edition brings readers up-to-date on cutting edge research in this field.

The major body of this work investigates how the chemical structure of conjugated polymers relates to the fundamental operating mechanism of organic photovoltaic devices. New conjugated polymers were characterized and their optical and electronic properties tested and correlated with their power conversion efficiencies as the active layer in polymer solar cells. From these experiments general structure/function relationships are drawn with an eye toward developing universal guidelines for conjugated polymer design and synthesis. Starting with light absorption, three major steps in the photovoltaic mechanism are examined. First, photogeneration of excited states and the migration of these states through the active layer are correlated to the polymeric backbone chemistry and the resulting device performance. Next, separation of these excited states at an interface between electron donors and electron acceptors is examined as a function of donor-acceptor distance and active layer dielectric constant. These two variables were tuned by chemical modification of polythiophene side groups. Third, charge carrier conduction is related to both polymer electronic states and to solid-state packing morphology. Design principles for effective conduction of both holes and electrons are outlined and the ambipolar nature of conjugated organic materials is discussed. In the final chapters, the solid-state polymer morphology in a solution processed thin film is examined. The impact that this morphology has on all steps in the photovoltaic mechanism is highlighted. How chemical modification of the polymer can influence this packing structure is examined as well as how new fabrication procedures can be used to pre-form nanostructured materials in solution before thin film deposition.

Semiconducting polymers are of great interest for applications in electroluminescent devices, solar cells, batteries, and diodes. This volume provides a thorough introduction to the basic concepts of the photophysics of semiconducting polymers as well as a description of the principal polymerization methods for luminescent polymers. Divided into two main sections, the book first introduces the advances made in polymer synthesis and then goes on to focus on the photophysics aspects, also exploring how new advances in the area of controlled syntheses of semiconducting polymers are applied. An understanding of the photophysics process in this kind of material requires some knowledge of many different terms in this field, so a chapter on the basic concepts is included. The process that occurs in semiconducting polymers spans time scales that are unimaginably fast, sometimes less than a picosecond. To appreciate this extraordinary scale, it is necessary to learn a range of vocabularies and concepts that stretch from the basic concepts of photophysics to modern applications, such as electroluminescent devices, solar cells, batteries, and diodes. This book provides a starting point for a broadly based understanding of photophysics concepts applied in understanding semiconducting polymers, incorporating critical ideas from across the scientific spectrum.

This work is focused on understanding how molecular-level structural control can improve charge carrier properties in -conjugated polymers. Conjugated polymers are characterized by extended conjugation along their backbone, making them intrinsically semiconducting materials that are of interest for a wide variety of flexible, thin-film electronic applications. Polymeric semiconductors possess advantages over inorganic materials such as being lightweight, low-cost and solution processable. However, due the disordered nature of conjugated polymers and their anisotropic transport, charge carrier dynamics can be highly sensitive to structural effects. The first chapter of this dissertation gives an introduction to conjugated polymers and their relevant applications as well as how tuning morphology and doping level can influence their charge carrier properties. The second introduces a technique, known as sequential processing (SqP), that affords control over polymer domain orientation when preparing polymer films as the active layer in optoelectronic devices. We show that conventional processing methods lead to disordered, isotropic polymer networks. By contrast, SqP can be used to preserve the preferred face-on chain orientation seen with some polymer materials, yielding advantages for photovoltaics and other devices via increased vertical hole mobility. Chapter 3 turns to molecular doping of conjugated polymers and studies the effects of a bulky boron cluster dopant used to modify the charge transport properties of conjugated polymers. The design of the dopant is such that it sterically protects core-localized electron density, resulting in shielding of the electron from holes produced on the polymer. This allows the charge carriers to be highly delocalized, as confirmed both spectroscopically and by AC-Hall effect measurements. The dopants allow for high carrier mobilities to be achieved even for non-crystalline polymers. The implication is that the counterion distance is the most important factor needed to produce high carrier mobility in conjugated polymers. In the last chapter, we study a series of boron cluster dopants in which the redox potential is tuned over a large range but the anion distance is fixed. In the last chapter, we study a series of boron cluster dopants in which the redox potential is tuned over a large range but the anion distance is fixed. This allows us to disentangle the effects of energetic offset in doping on the production of free carriers. We find that the redox potential not only affects the generation of free carriers, but also the infiltration of dopants into the polymer films.

The unique properties of conducting and semiconducting (conjugated) polymers make them one of the most attractive areas of interdisciplinary materials science and technology. Written by a pioneer in the field, this book is the first aimed at teaching graduate students, postdoctoral scientists, and specialists in industry about this exciting field.

An A-to-Z of doping including its definition, its importance, methods of measurement, advantages and disadvantages, properties and characteristics—and role in conjugated polymers The versatility of polymer materials is expanding because of the introduction of electro-active behavior into the characteristics of some of them. The most exciting development in this area is related to the discovery of intrinsically conductive polymers or conjugated polymers, which include such examples as polyacetylene, polyaniline, polypyrrole, and polythiophene as well as their derivatives. "Synmet" or "synthetic metal" conjugated polymers, with their metallic characteristics, including conductivity, are of special interest to researchers. An area of limitless potential and application, conjugated polymers have sparked enormous interest, beginning in 2000 when the Nobel Prize for the discovery and development of electrically conducting conjugated polymers was awarded to three scientists: Alan J. Heeger, Alan G. MacDiarmid, and Hideki Shirakawa. Conjugated polymers have a combination of properties—both metallic (conductivity) and polymeric; doping gives the conjugated polymer's semiconducting a wide range of conductivity, from insulating to low conducting. The doping process is a tested effective method for producing conducting polymers as semiconducting material, providing a substitute for inorganic semiconductors. Doping in Conjugated Polymers is the first book dedicated to the subject and offers a comprehensive A-to-Z overview. It details doping interaction, dopant types, doping techniques, and the influence of the dopant on applications. It explains how the performance of doped conjugated polymers is greatly influenced by the nature of the dopants and their level of distribution within the polymer, and shows how the electrochemical, mechanical, and optical properties of the doped conjugated polymers can be tailored by controlling the size and mobility of the dopants counter ions. The book also examines doping at the nanoscale, in particular, with carbon nanotubes. Readership The book will interest a broad range of researchers including chemists, electrochemists, biochemists, experimental and theoretical physicists, electronic and electrical engineers, polymer and materials scientists. It can also be used in both graduate and upper-level undergraduate courses on conjugated polymers and polymer technology.

Improving knowledge of structure-function relationships in semiconducting polymers will help design new materials that unlock new applications. This work harnesses recent advances in transmission electron microscopy of soft materials to study length scales of microstructure in these materials that have previously been difficult to probe. Further, it combines electron microscopy with structural and charge transport simulations to study the effects of mesoscale defects on charge transport in highly ordered semicrystalline polymers. Spatially resolved nanodiffraction (4D-STEM) is used to create maps of chain direction and local order in conjugated polymers. Simulations are then built upon this experimental map, first by generating molecular geometries consistent with diffraction data, then by tracking the paths of test charges across the region. A case study in this combined method is conducted using the polymer PBTTT. Short-range charge transport is shown to be more chaotic than is often pictured, with the drift velocity accounting for a small portion of overall charge motion. Local transport is sensitive to the alignment and geometry of polymer chains. At longer length scales, the curves of this PBTTT microstructure funnel charges to specific regions, creating inhomogeneous charge distributions. While alignment generally improves mobility, these funneling effects limit the overall efficiency of charge transport. The structure is modified \textit{in silico} to explore possible design rules, showing chain stiffness and alignment to be beneficial while local homogeneity has no positive effect. These observations provide direct guidance for improving mesoscale structure for future materials.

Semiconducting polymers show promise for use in a variety of applications such as photovoltaic cells, light emitting diodes, and thermoelectric generators. For many of these devices, the electronic properties are tuned through the introduction of chemical dopants. This dissertation is focused on understanding several key aspects of the chemical doping process. The first chapter gives an overview of semiconducting polymers, introduces doping by sequential processing methods and looks at how the chemical doping process works on a basic level. We also explore dopant transport methods, discuss the electrical and thermoelectrical characterization of these materials, and finally consider the structural morphology of conjugated polymer thin films. Chapter 2 takes an analytical approach to understanding how the underlying morphology and electrical/thermoelectrical properties of doped polymer films are affected when introducing the dopant either via the solutionphase or using vapor transport. Chapter 3 explores the fundamental charge transfer interactions that occur between polymer and dopant. We introduce a novel processing technique that enables the tunable production of dopant-polymer charge transfer complexes (CTCs), which represent a poorly understood but widely seen doping mechanism in these materials. We provide the first comprehensive picture of the forces that drive CTC formation and offer guidelines for limiting CTC occurrence in doped conjugated polymers as their electrical properties are usually undesirable. Finally, in Chapter 4 we solve a long-standing mystery in the literature of the highly variable vibrational spectra of certain dopant molecules, which should nominally show consistent and predictable frequencies. We show that the wide range of vibrational energies observed for these dopant molecules can be fully understood through the framework of the vibrational Stark effect. Our experimental evidence shows a clear and predictable shift for these modes as a function of their locally experienced electric field, which arises due to Coulomb interactions with the charge carriers on the polymer. Thus, the vibrational shifts of these dopant molecules are actually exquisite reporters on the local environment of the charge carriers in doped conjugated polymers. We use our experimentally-measured shifts to quantitatively estimate the change in polaron coherence length, the extent to which the charge carriers on the polymer spread over multiple polymer repeat units. These chapters cover a variety of themes which highlight the sometimes unexpected path from experiment to manuscript. I sincerely hope they can be of use to others who study similar systems and motivate additional works in the future.