Structure Function Relationships In Semiconducting Polymers For Organic Photovoltaics

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 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.

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.

The chemical structure of conjugated semiconducting materials strongly influences the performance of organic photovoltaic (OPV) devices. Thus a good understanding of the structure-function relationships that govern the optoelectronic and physical properties of OPV materials is necessary. In this dissertation, organic polymers and small molecules are evaluated in terms of OPV device output parameters, and molecular design rules are elucidated. The development of molecules with alternating electron-rich and electron-deficient backbone units provides materials with suitable optoelectronic properties for OPVs and favorable modularity for organic semiconductor design. The choice of specific aromatic units and side chains for conjugated materials are shown to modulate the energy levels and architecture of OPV devices, affecting each of the four mechanistic steps of OPV operation. In Chapter 2, the relationship between molecular packing parameters and the bulkiness of aliphatic solubilizing group extending away from a polymer backbone is elucidated, and high-performance OPV devices are achieved. In Chapter 3, the inclusion of a post-processing functionality on a polymer side chain is found to have a positive effect on the bulk morphology and overall performance of OPV devices. In Chapter 4, the influence of electron-withdrawing and quinoidal monomers on the optoelectronic properties of conjugated polymers is established, and energy level modulation is shown to affect the electron accepting and donating capabilities of OPV materials in a blended device. In Chapter 5, small molecules are designed with complementary light absorption properties in order to investigate a rarely observed charge generation mechanism.

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.

An international perspective on the latest research in polymer solar cell technology.

Endlich ein Fachbuch mit detaillierten Informationen zu einer der fortschrittlichsten Methoden zur Materialcharakterisierung. Ein herausragendes Team aus Herausgebern und Autoren von renommierten Einrichtungen und Institutionen beschäftigt sich mit Synchrotron-Verfahren, die sich in der Materialforschung bewährt haben. Nach einer Einführung in die Synchrotronstrahlung und ihrer Quellen werden die verschiedenen Techniken beschrieben, die von diesem besonders hellen Licht profitieren, u. a. Röntgenabsorption, Diffraktion, Streuung, Bildgebung und Lithographie. Zum Schluss folgt ein Überblick über die Anwendungen der Synchrotronstrahlung in den Materialwissenschaften. Dieses einzigartige, unabdingbare Referenzwerk für akademische Forscher und Forscher aus der Industrie verbindet Spezialisten aus der Synchrotronforschung und Materialwissenschaftler.

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.