Charge transport in semiconductor channels of organic field-effect transistors (FETs) depends largely on the molecular ordering of organic semiconductor molecules. This is particularly demanding for polymer-based FETs, where channel semiconductors are non-molecular in nature, and generally form semiconductor films of low crystallinity. As a result, great theoretical and practical interests have been directed towards facile solution processes that can transform a low molecular weight (MW) and low mobility conjugated polymer into a high crystalline order and high-mobility semiconductor. This research focuses on developing effective strategies for achieving high mobility as well as other desirable FET properties through properly controlling the morphology and molecular ordering of conjugated polymer channel layers. The relationships between morphologic/microstructural properties of the polymer semiconductor films and charge transport characteristics in the films are systematically investigated and elucidated. The purpose of this work is to achieve high performance solution-processed polymer FETs with high mobility, excellent ambient stability, and performance uniformity that display practical significance for application in next-generation electronics. In the first part of this thesis, functionalization of the gate dielectric surface by grafting highly ordered and dense coverage of hybrid silane self-assembled monolayers (SAMs) is discussed. A two-step solution-processed method using a combination of trichlorooctadecylsilane (OTS-18) and trichlorooctylsilane (OTS-8) has been developed to create high-performance hybrid dual-silane SAM on the surface of silicon dioxide (SiO2), thus enabling the achievement of both high field-effect mobility and current on/off ratio, together with other desirable FET properties. The hybrid SAM approach is also adopted for attaining high performing polymer FETs using a different SAM agent combination of phenyltrichlorosilane (PTS) and OTS-18. With the progress in functionalizing the surface of gate dielectric insulator by two-step grafting SAMs, the advancement in enhancing the crystalline structural order of the polymer channel layer is highlighted. This was realized by the incorporation of polar insulator of polyacrylonitrile (PAN) into the polymer semiconductor solution at appropriate loadings, enabling the formation of excellent semiconductor films with high crystalline order. PAN serves as an efficient mediating medium for the crystallization of polymer semiconductor, leading to the creation of large crystalline domains within the PAN matrix. A 1̃0-nm thick semiconductor layer with richer semiconductor crystalline domains is constructed near the vicinity of the gate dielectric surface, facilitating efficient charge conduction in the channel semiconductor. Enhancements in field-effect mobility by as much as about one order in magnitude and current on/off ratio of two to three orders in magnitude have been realized in polymer FETs. PAN incorporation also dramatically enhances the stability and processability of semiconductor solutions, enabling rapid fabrication of channel semiconductors in polymer FETs via common graphic art printing techniques such as inkjet printing for practical adoption. Another unique facile solution process which transforms a lower-MW and low-mobility conjugated polymer, e.g., diketopyrrolopyrrole-dithienylthieno[3,2-b] thiophene (DPP-DTT), into a high crystalline order and high-mobility nanowire network for high performance polymer FETs has been also developed in this work. This approach involves solution fabrication of a channel semiconductor film using a lower MW DPP-DTT/polystyrene blend system. With the help of cooperative shifting motions of polystyrene chain segments, an interpenetrating nanowire semiconductor network is readily self-assembled and crystallized out in the polystyrene matrix, and thereby providing significantly enhanced mobility (over 8 cm2 V-1 s-1) and current on/off ratio (107). Finally, the concept of generating polymer nanowire network in the effective photoactive channel is extended for the development of highly sensitive near-infrared (NIR) organic phototransistors (OPTs). The NIR-OPTs based on DPP-DTT nanowire network exhibit high responsivity of 2̃46 A W-1 under an NIR illumination source with the wavelength of 850 nm at a low intensity of ̃0.1 mW cm-2. This value is over one order in magnitude higher than that of the structurally identical planar DPP-DTT thin film based OPTs. The high performance of the nanowire network-based phototransistors is attributed to the excellent hole transport ability, reduced density of the structural defects in the polymer nanowire network, and improved contact at the channel layer/electrode interfaces. The high sensitivity and low cost solution-fabrication process render this OPT technology appealing and practically viable for application in large area NIR sensors.

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Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15390号 / 工博第3269号 / 新制||工||1492(附属図書館) / 27868 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 大江 浩一, 教授 辻 康之, 教授 村田 靖次郎 / 学位規則第4条第1項該当

Quick and early detection of abnormalities in the body's metabolism is of paramount importance to monitor, control, and prevent the associated diseases and pathologies. Biosensors technology is rapidly advancing, from the first electronic biosensor reported by Clark and Lyons in 1962 for blood glucose monitoring to today’s devices that can detect multiple metabolites in bodily fluids continuously and simultaneously within seconds. This rapid growth in point-of-care devices promises for the development of novel devices with different form factors and the ability to detect a wide range of biomarkers. These advancements mainly stem from the development of electronic materials that have properties better aligning with the biotic interface compared to the traditional metal electrodes. A promising class of electronic materials for biosensors is conjugated polymers. Conjugated polymers are carbon-based, organic semiconducting materials made of long chains comprising conjugated repeat units. The fundamental property that makes these materials so attractive is, however, not their electronic conductivity, but their ionic conductivity. As living organisms use ionic fluxes to relay signals, materials that can conduct ionic currents are believed to facilitate the communication between the electronics and living systems. This communication happens at various levels: organs, complex tissues, cells, cell membrane, proteins, and small biomolecules. Besides, the inherently soft nature of these materials facilitates mechanical conformity with soft biological systems. The field of organic bioelectronics has experienced tremendous growth over the past two decades, thanks to the design of new conjugated polymers customized for the biotic interface. While hole conducting (p-type) polymers have been widely investigated, electron conducting (n-type) counterparts are relatively new. This dissertation aims to explore the capabilities of n-type conjugated polymers for bioelectronics applications. Chapter 1 overviews the key properties of conjugated polymers and the resulting electronic devices that leverage these properties for specific applications in bioelectronics. Chapter 2 presents microfabricated metabolite (lactate and glucose) sensors based on an n-type polymer in combination with enzymes, and how this communication can enable energy production from bodily fluids. Finally, Chapter 3 reports the development of engineering and design strategies to enhance the performances of n-type polymers in bioelectronics.

Mostly new acetylene based monomers were prepared. All monomers were prepared by the means of standard spectroscopic methods. All monomers were successfully polymerized using standard metathesis TaCl5 based catalyst. Prepared polymers were characterized by the means of GPC/GPC-MALLS chromatography and standard spectral methods. Fluorescence properties of all prepared compounds were also studied: quantum fluorescence yields were determined and excitation and emission fluorescence spectra were recorded. Polymerization on modern metathesis Grubbs-Hoveyda catalytic systems of all prepared monomers was also tested. These reactions were only partially successful and only low molecular weight oligomers in mediocre yields were obtained.

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ABSTRACT SYNTHESIS OF MONOMERS FOR NEW CONJUGATED POLYMERS This dissertation addresses the problem of synthesis of different monomers for donor and acceptor polymers in photovoltaic applications. In general, functionalization of conjugated polymers and understanding of molecular packing of electron donors and electron acceptors are very important to produce efficient solar cells. As a result, it is important to design and synthesize novel monomers which will require making new π-conjugated donors and acceptors polymers and understand the influence of these new polymers in bulk heterojunction to design polymer solar cells. In this study, two different monomers were synthesized. The first monomer was designed and synthesized to investigate the effect of π-conjugated linker directly attached to the polymer backbone where the polymer backbone was based on thiophene unit and conjugated linker was 1,2,3-triazole. In a different study, a conjugated monomer based on benzthiadiazole was designed and synthesized in order to synthesize new acceptor homopolymers and alternating copolymers. Two different monomers with different alkyl side chains based on benzthiadiazole were synthesized and subject to Suzuki and Stille polymerization to get respective polymers.

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Conjugated tetrazine-containing polymers that undergo Inverse Electron Demand Diels-Alder (IEDDA) reactions with trans-cyclooctenes are interesting not only for their intrinsic optoelectronic properties, but also their interactions with π-conjugated surfaces. Here, we prepared a series of poly(fluorene-co-tetrazine) polymers and carried out IEDDA reactions to decorate them with hydroxyl, hexadecyl, or triethylene glycol side chains. The polymers were investigated pre- and post-IEDDA coupling in terms of their ability to disperse single-walled carbon nanotubes (SWNTs) in organic solvent. It was found that polymer molecular weight, side chain structure, and degree of conjugation all impacted the quality of SWNT dispersions. While the starting poly(fluorene-co-tetrazine) polymer produced concentrated dispersions, the post-IEDDA polymer containing dihydropyridazine groups did not produce dispersions of equal concentration. However, upon oxidation to the fully aromatic pyridazines, the polymers regained their ability to form concentrated dispersions. Furthermore, the post-IEDDA polymers exhibited increased selectivity toward metallic SWNTs relative to the starting polymer. In addition, due to the efficiency of the IEDDA reaction, it was possible to perform modification of the polymer-SWNT dispersion formed with poly(fluorene-co-tetrazine) to modify the polymer structure while on the SWNT surface. Overall, this work demonstrates the first use of reactive polytetrazines to disperse SWNTs and to rapidly modify the solubility of polymer-nanotube complexes. / Thesis / Master of Science (MSc)

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