Solution processable organic semiconducting materials for thin film transistors and photovoltaic applications

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Organic transistors and solar cells offer the potential advantages of low-cost, large-scale fabrication by solution processing techniques, and compatibility with both flexible and lightweight plastic substrates. Continuous development of new organic materials has improved their performance, thus enabling the commercialization of these conducting polymers in recent years. However, understanding the relationship between polymer packing structures and mobilities is still lacking. Furthermore, to enable a polymer to serve as an effective donor material in bulk heterojunction (BHJ) solar cells, several important properties have to be considered, such as band gap, absorption coefficient, effective charge transport, and a relatively deep HOMO. Needless to say, careful balancing of these properties remains challenging. Thus, this thesis aims to gain a better understanding of materials design rules to address the above issues using two types of conjugated polymers. First, new donor-acceptor copolymers were designed and synthesized to gain insights into designing efficient donor materials in BHJ solar cells. Second, poly(3,4-disubstituted thiophene) derivatives were designed and synthesized to study relationships between structural design, packing, charge transport property, and solar cell performance. In the first part of my thesis, I have prepared vinylene linked co-polymers in order to achieve low bandgap polymers by extending [Pi]-conjugation lengths. I found that the hole mobilities of the polymers scaled with the molecular weights in these amorphous polymers. Optical absorption at longer wavelengths was improved by eliminating torsions along the polymer backbones. Current density (Jsc) in BHJ solar cells depended on the overall intensity of absorption and hole mobility of donor materials. Comparing to the amorphous vinylene linked co-polymers, charge carrier mobility could be enhanced by employing thienopyrazine based co-polymers, which contain rigid fused aromatic rings promoting well ordered inter-chain packing. Removing of the adjacent thiophene groups around the thienopyrazine acceptor core markedly increased the optical absorption of the polymer and raised its ionization potential, resulting in power conversion efficiency (PCE) of 1.57%. This investigation on the new co-polymers could provide a useful guideline for designing efficient donors for BHJ solar cells. In the second part of my thesis, I designed and synthesized polythiophene derivatives to understand structure-property relationships in detail. Despite their slightly larger band gaps, polythiophene derivatives are nonetheless important active materials due to their high absorption coefficients and high charge transport mobilities. Furthermore, their facile synthesis and ease of structural modifications with various substituents are the advantages of using polythiophene derivatives as model conjugated polymer systems. To examine the influence of backbone twisting on performance of transistors and BHJ solar cells, I systematically imposed twists within the conjugated backbones of poly(3,4-disubtituted thiophene (P34AT) using a unsubstituted thiophene spacer of varying sizes. When a moderate twist was introduced to the P34AT backbone, a 19% enhancement in the open-circuit voltage vs. poly(3-hexylthiopene) based devices and high PCE (4.2%) were achieved without sacrificing the short-circuit current density and the fill factor. Despite the high charge transport mobility (0.17 cm2/Vs), P34AT hardly showed [Pi]-[Pi] stacking in X-ray diffraction, suggesting that a strong [Pi]-[Pi] stacking is not always necessary for high charge carrier mobility; in which other potential polymer packing motifs (in addition to the edge-on structure) can lead to a high device performance. To gain further knowledge in structure-property relationships of the less explored 3,4-disubstituted polythiophene system, various P34AT derivatives were prepared and their opto-electronic property, packing structure, and device performance were studied. Among P34AT derivatives containing fused thiophene rings, a higher PCE was achieved with a benzodithiophene based polymer (PDHBDT) having a larger absorption coefficient, higher hole mobility, and deeper HOMO. The PDHBDT also exhibited a thermotropic phase transition behavior, leading to mobility up to 0.46 cm2/Vs where the polymer backbones adapt an edge-on lamellar packing structure. In the last part of this thesis, low band gap P34AT derivatives, which incorporate electron withdrawing groups, were prepared to improve photocurrent. However, I observed that a low absorption coefficient and a low hole mobility limited current density in solar cells. Thus, this indicates that low band gap polymers with strong absorption properties and good charge transports are critical towards molecular design for achieving high PCE. Collectively, through rational design and characterization of these novel polymers, this thesis has illustrated that better understanding of molecular design rules for engineering opto-electronic properties and packing behavior, will lead to higher device performance.


Type of resource text
Form electronic; electronic resource; remote
Extent 1 online resource.
Copyright date 2012
Publication date 2011, c2012; 2011
Issuance monographic
Language English


Associated with Ko, Sang-wŏn
Associated with Stanford University, Department of Chemistry
Primary advisor Bao, Zhenan
Thesis advisor Bao, Zhenan
Thesis advisor Huestis, Wray
Thesis advisor Sellinger, Alan
Advisor Huestis, Wray
Advisor Sellinger, Alan


Genre Theses

Bibliographic information

Statement of responsibility Sang Won Ko.
Note Submitted to the Department of Chemistry.
Thesis Thesis (Ph. D.)--Stanford University, 2012.
Location electronic resource

Access conditions

© 2012 by Sang Won Ko
This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).

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