Understanding Microstructure and Charge Transport in Semicrystalline Polythiophenes
Understanding Microstructure and Charge Transport in Semicrystalline Polythiophenes

Author: Leslie Hendrix Jimison

Publisher: Stanford University

Published: 2011

Total Pages: 142

ISBN-13:

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Semiconducting polymers are a promising class of organic electronic materials, with the potential to have a large impact in the field of macroelectronics. In this thesis, we focus on understanding the relationship between microstructure and charge transport in semicrystalline polythiophenes. A method is presented for the measurement of complete pole figures of polymer thin films using an area detector, allowing for the first time quantitative characterization of crystalline texture and degree of crystallinity. Thin film transistors are used to measure electrical characteristics, and charge transport behavior is modeled according to the Mobility Edge (ME) model. These characterization methods are first used to investigate the effect of substrate surface treatment and thermal annealing on the microstructure of polythiophene thin films, and the effect of microstructural details on charge transport. Next, we investigate the semicrystalline microstructure in confined polythiophene films. Pole figures are used to quantify a decrease in the degree of crystallinity of films with decreasing thickness, accompanied by an improvement in crystalline texture. Next, we investigate the influence of the degree of regioregularity, molecular weight and the processing solvent on microstructure (degree of crystallinity and texture) and charge transport in high mobility P3HT thin films. Surprisingly, when processing conditions are optimized, even a polymer with moderate regioregularity can form a highly textured film with high charge carrier mobility. Finally, we use films of P3HT with engineered, anisotropic in-plane microstructure to understand the importance and mechanism of transport across grain boundaries in these semicrystalline films. Results from this study provide the first experimental evidence for the application of a percolation model for charge transport in high molecular weight semicrystalline polymer semiconductors. Understanding how characteristics of the polymer as well as details of the processing conditions can affect the film microstructure and device performance is important for future materials design and device fabrication.

Understanding Microstructure and Charge Transport in Semicrystalline Polythiophenes
Understanding Microstructure and Charge Transport in Semicrystalline Polythiophenes

Author: Leslie Hendrix Jimison

Publisher:

Published: 2011

Total Pages:

ISBN-13:

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Semiconducting polymers are a promising class of organic electronic materials, with the potential to have a large impact in the field of macroelectronics. In this thesis, we focus on understanding the relationship between microstructure and charge transport in semicrystalline polythiophenes. A method is presented for the measurement of complete pole figures of polymer thin films using an area detector, allowing for the first time quantitative characterization of crystalline texture and degree of crystallinity. Thin film transistors are used to measure electrical characteristics, and charge transport behavior is modeled according to the Mobility Edge (ME) model. These characterization methods are first used to investigate the effect of substrate surface treatment and thermal annealing on the microstructure of polythiophene thin films, and the effect of microstructural details on charge transport. Next, we investigate the semicrystalline microstructure in confined polythiophene films. Pole figures are used to quantify a decrease in the degree of crystallinity of films with decreasing thickness, accompanied by an improvement in crystalline texture. Next, we investigate the influence of the degree of regioregularity, molecular weight and the processing solvent on microstructure (degree of crystallinity and texture) and charge transport in high mobility P3HT thin films. Surprisingly, when processing conditions are optimized, even a polymer with moderate regioregularity can form a highly textured film with high charge carrier mobility. Finally, we use films of P3HT with engineered, anisotropic in-plane microstructure to understand the importance and mechanism of transport across grain boundaries in these semicrystalline films. Results from this study provide the first experimental evidence for the application of a percolation model for charge transport in high molecular weight semicrystalline polymer semiconductors. Understanding how characteristics of the polymer as well as details of the processing conditions can affect the film microstructure and device performance is important for future materials design and device fabrication.

Charge Transport in Semiconducting Polymers
Charge Transport in Semiconducting Polymers

Author: Scott Himmelberger

Publisher:

Published: 2015

Total Pages:

ISBN-13:

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Organic semiconductors have emerged as an alternative to conventional silicon-based electronics in a number of large-area applications including lighting, displays, and sensors. Their ease of processing and compatibility with solution-based deposition techniques makes them attractive for low-cost, roll-to-roll production processes. However, despite significant progress in recent years, the electronic performance of these materials remains modest relative to silicon, limiting their potential applications. In order for organic semiconductors to truly flourish in industry, electronic figures of merit such as charge carrier mobility must be improved further. The material microstructure is one of the key determinants of charge carrier mobility in organic semiconductors. While many new microstructure characterization tools have been developed and our understanding of the relationship between microstructure and electronic properties has greatly improved, significant questions remain, limiting our ability to rationally design and process new materials with improved performance. The focus of this dissertation has been in attempting to improve this understanding. In this dissertation, I discuss several ways in which the microstructure of semiconducting polymers affects their electronic properties. First, I present a procedure for determining the precise thin-film structure of a semiconducting polymer using two-dimensional grazing incidence X-ray diffraction. These packing structures can then be used in a variety of electronic structure calculations. Next, I discuss the role of molecular weight distribution as well as the impact of film confinement on the microstructure and electronic properties of two semicrystalline polythiophenes. I show how disorder, crystallinity, and chain orientation are strongly influenced by these factors and quantify their impact on charge carrier mobility. Finally, I describe our latest understanding of the factors governing charge transport in state-of-the-art materials. I suggest that disorder is an inextricable feature of semiconducting polymers that need not be highly detrimental to charge transport if it is embraced and planned for by designing materials which are resilient to this disorder.

Microstructure and Charge Transport in Conjugated Polymers
Microstructure and Charge Transport in Conjugated Polymers

Author: Chenchen Wang

Publisher:

Published: 2013

Total Pages:

ISBN-13:

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Conjugated polymers have attracted broad interest in the past few decades due to their potential applications in organic light emitting diodes, low-cost flexible circuits, biosensors and photovoltaics. Because of their semicrystalline nature, the spatial arrangement of the crystallites and the disordered regions would have strong impact on the charge transport properties of conjugated polymer thin films. Therefore, in this presentation, I will focus on understanding the relationship between the film's morphology, microstructure and electronic properties, and how to fabricate desired structure to achieve devices with novel electronic performance. In the first part of the presentation, I will show that the device's electronic performance can be greatly improved by engineering its structure in solution based fabrication process. The binary blends of regioregular (rr) and regiorandom (RRa) P3HT are used to form desired FET structures. X-ray diffraction of the blended films is consistent with a vertically-separated structure, with rr-P3HT preferentially crystallizing at the semiconductor/dielectric interface. Because of the ultra-thin rr-P3HT active layer at the interface, these devices not only preserve high mobility in rr-P3HT, but also eliminate the short channel effects due to bulk currents, suggesting a new route to fabricate high performance, short-channel and reliable organic electronic devices. After that, I will discuss the microstructural origin of high mobility in poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophenes) (PBTTT) thin-film transistors (TFTs). Charge transport in PBTTT TFTs is analyzed with a mobility edge (ME) model and compared to these in poly(3-hexylthiophene) (P3HT) TFTs. With TEM characterization of delaminated films, we conclude that the improved performance of PBTTT compared to P3HT is not due to a low trap density but rather to a high mobility in the crystallites. Finally, the third part of the presentation will focus on optical characterization of doping in conjugated polymers. UV-vis and IR absorption spectra of 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) doped P3HT at different doping concentration are measured and analyzed. Absorption peaks from P3HT, F4TCNQ, F4TCNQ anion and P3HT polaron/bipolarons are identified and decomposed. The P3HT polaron/bipolarons cross sections in UV-vis region are estimated, which can be used to evaluate doping efficiency in this material.

Chain Conformation and Disorder in High Mobility Semiconducting Polymers
Chain Conformation and Disorder in High Mobility Semiconducting Polymers

Author: Rodrigo Javier Noriega-Manez

Publisher:

Published: 2012

Total Pages:

ISBN-13:

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A critical step to understanding charge transport in complex systems is being able to characterize them accurately and extensively. In particular, the microstucture of conjugated polymers exhibits a coexistence of ordered and amorphous regions, with the size of the ordered regions being smaller than the length of individual polymer chains. In order to study the ordered regions we use advanced X-ray diffraction analysis in combination with computational modeling and measurements of optical and electrical properties. It was possible to uncover fundamental relationships between short-range order in pi-aggregates, aggregate connectivity and macroscopic charge transport in semiconducting polymers. An unusually high and materials-independent amount of paracrystalline disorder was found in all high-performing polymers. Computer simulations and analytical models made the connection between fluctuations in molecular arrangement and electronic traps. Charge transport studies elucidated the predominant role of paracrystallites in semicrystalline and strongly disordered polymer films. The other component of the microstructure -- the amorphous regions -- deserves our attention as well since aggregate connectivity depends on it. A model for charge transport in strongly disordered polymers was developed for this reason. The morphology of individual polymer chains can be determined by well-known statistical models. Likewise, the electronic coupling between units along a polymer chain and on different molecules can be determined by Marcus theory. Combining knowledge from both areas into an analytical and computational model that incorporates the structural and electronic properties of polymers, it is possible to explain observations that previously relied on phenomenological models. The multi-scale behavior of charges in these materials (high mobility at short scales, low mobility at long scales) is naturally described with this framework. Additionally, the dependence of mobility with electric field and temperature is explained in terms of conformational fluctuations and correlations. Bringing all these concepts together it is possible to provide a more complete description of the way in which charges move in conjugated polymers, a set of materials that occupies an intermediate region between ordered and disordered systems, with a great amount of complexity at various length scales. Doing so will facilitate the feedback cycle between molecular design, microstructure optimization, and device performance.

Organic Flexible Electronics
Organic Flexible Electronics

Author: Piero Cosseddu

Publisher: Woodhead Publishing

Published: 2020-09-29

Total Pages: 666

ISBN-13: 012818891X

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Organic Electronics is a novel field of electronics that has gained an incredible attention over the past few decades. New materials, device architectures and applications have been continuously introduced by the academic and also industrial communities, and novel topics have raised strong interest in such communities, as molecular doping, thermoelectrics, bioelectronics and many others.Organic Flexible Electronics is mainly divided into three sections. The first part is focused on the fundamentals of organic electronics, such as charge transport models in these systems and new approaches for the design and synthesis of novel molecules. The first section addresses the main challenges that are still open in this field, including the important role of interfaces for achieving high-performing devices or the novel approaches employed for improving reliability issues.The second part discusses the most innovative devices which have been developed in recent years, such as devices for energy harvesting, flexible batteries, high frequency circuits, and flexible devices for tattoo electronics and bioelectronics.Finally the book reviews the most important applications moving from more standard flexible back panels to wearable and textile electronics and more futuristic applications like ingestible systems. Reviews the fundamental properties and methods for optimizing organic electronic materials including chemical doping and techniques to address stability issues Discusses the most promising organic electronic devices for energy, electronics, and biomedical applications Addresses key applications of organic electronic devices in imagers, wearable electronics, bioelectronics

Handbook of Conducting Polymers, Fourth Edition - 2 Volume Set
Handbook of Conducting Polymers, Fourth Edition - 2 Volume Set

Author: John R. Reynolds

Publisher: CRC Press

Published: 2019-11-14

Total Pages: 1488

ISBN-13: 1351660233

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In the last 10 years there have been major advances in fundamental understanding and applications and a vast portfolio of new polymer structures with unique and tailored properties was developed. Work moved from a chemical repeat unit structure to one more based on structural control, new polymerization methodologies, properties, processing, and applications. The 4th Edition takes this into account and will be completely rewritten and reorganized, focusing on spin coating, spray coating, blade/slot die coating, layer-by-layer assembly, and fiber spinning methods; property characterizations of redox, interfacial, electrical, and optical phenomena; and commercial applications.

Conjugated Polymers
Conjugated Polymers

Author: John R. Reynolds

Publisher: CRC Press

Published: 2019-03-25

Total Pages: 832

ISBN-13: 1315159295

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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