Organic semiconductors are envisioned to have widespread applications in flexible displays, radio-frequency identification (RFID) tags, bio- and chem-sensors, as well as organic solar cells. Polymer semiconductors are particularly suitable for the low-cost manufacture of organic electronics using printing techniques due to their excellent solution processability and mechanical properties. This work focuses on the development of two novel building blocks, IBDF and DTA, which can be used for the construction of high performance organic thin film transistors (OTFTs) and organic photovoltaics (OPVs). Two copolymers, P6-IBDF-T and P5-IBDF-T, and a homopolymer P6-IBDF were prepared using the IBDF building block. Copolymer P6-IBDF-T has been prepared via the Stille-coupling polymerization. This polymer exhibits a small band gap of 1.36 eV with HOMO/LUMO energy level of -5.69 eV/-4.43 eV. P6-IBDF-T showed stable electron transport performance in encapsulated thin film transistors and ambipolar transport performance in non-encapsulated TFTs. Balanced hole/electron mobilities of up to 8.2 ??10-3/1.0 ??10-2 cm2V-1s-1 was achieved in bottom-contact, bottom-gate organic thin film transistors. In addition, the broad absorption of the polymer over the UV-Vis range suggested that this polymer is suitable for applications in solar cells. The effect of conjugation on mobility and UV-vis spectra of the polymer was studied by comparing P5-IBDF-T with P6-IBDF-T. The ideal of indirect electron transition was proposed to explain the difference between UV-Vis light absorption spectra for these two polymers. DTA building block was used to construct four D-A copolymers, namely PDTA-T, PDTA-BT, PDAT-BTV, and PDTA-TT. These polymers were characterized by UV-Vis, CV, DSC, TGA, AFM and XRD. Device performance was also investigated on OTFTs. The device performance of DTA based polymer increased as the area of electron donor increase from T in PDTA-T to BTV in PDTA-BTV. PDTA-BTV exhibits hole mobility of 1.3??10-3 cm2 V-1 s-1 with Ion/Ioff value of ~103-4 in bottom-contact, bottom-gate organic thin film transistors. All DTA based copolymers exhibited small optical bandgaps (1.18 ??? 1.27 eV) and required none or moderate thermal treatment during fabrication process. These make them promising candidates for cost-effective OPV applications.

A novel polymer semiconductor with side chains thermally cleavable at a low temperature of 200 °C was synthesized. The complete cleavage and removal of the insulating 2-octyldodecanoyl side chains were verified with TGA, FT-IR, and NMR data. The N-H groups on the native polymer backbone are expected to form intermolecular hydrogen bonds with the C=O groups on the neighboring polymer chains to establish 3-D charge transport networks. The resulting side chain-free conjugated polymer is proven to be an active p-type semiconductor material for organic thin film transistors (OTFTs), exhibiting hole mobility of up to 0.078 cm2V-1s-1. This thermo-cleavable polymer was blended with PDQT to form films that showed a higher performance than the pure individual polymers in OTFTs. MoO3 or NPB was used as a hole injection buffer layer between the metal electrodes and the polymer semiconductor film layer in OTFT devices. This buffer layer improved hole injection, while its use in the OTFT, improved the field-effect mobility significantly due to better matched energy levels between the electrodes and the polymer semiconductor.

The thesis is divided into two parts. One is about the preparation of discotic liquid crystals Acid-6. The other is about the growth of Acid-6 thin film by thermal evaporation on silicon oxide surfaces and modified silicon oxide surfaces such as self-assembled monolayer(SAM) in different temperature. The surface morphology and molecular orientation of the thin film were studied by Atomic Force Microscopy(AFM) , X-ray Diffraction (XRD) , and then they were applicated to organic thin film transistor and measured properties by Semiconductor Parameter Analyzer. In the second part of our research, our expectative characteristics was not observed in different temperature and substructure. In the other side, we guessed that because discotic liquid crystals Acid-6 is negative semiconductor materials, so it is susceptible to hydrosphere, thus we can¡¦t observe the electric characteristic of OTFT in the atmosphere. In addition, due to discotic liquid crystals Acid-6 have biggish moleculer weight, thus its viscosity was so big that cause the diameter of Acid-6 crystals to be too small. Therefore, it influenced the carrier mobility. Finally, from the aspect of procedure about fabrication of the devices we can discuss whether this parameter of this device can apply to OTFT.

A novel polymer semiconductor with side chains thermally cleavable at a low temperature of 200 °C was synthesized. The complete cleavage and removal of the insulating 2-octyldodecanoyl side chains were verified with TGA, FT-IR, and NMR data. The N-H groups on the native polymer backbone are expected to form intermolecular hydrogen bonds with the C=O groups on the neighboring polymer chains to establish 3-D charge transport networks. The resulting side chain-free conjugated polymer is proven to be an active p-type semiconductor material for organic thin film transistors (OTFTs), exhibiting hole mobility of up to 0.078 cm2V-1s-1. This thermo-cleavable polymer was blended with PDQT to form films that showed a higher performance than the pure individual polymers in OTFTs. MoO3 or NPB was used as a hole injection buffer layer between the metal electrodes and the polymer semiconductor film layer in OTFT devices. This buffer layer improved hole injection, while its use in the OTFT, improved the field-effect mobility significantly due to better matched energy levels between the electrodes and the polymer semiconductor.

京都大学 / 新制・課程博士 / 博士(情報学) / 甲第24746号 / 情博第834号 / 新制||情||140(附属図書館) / 京都大学大学院情報学研究科通信情報システム専攻 / (主査)教授 佐藤 高史, 教授 橋本 昌宜, 教授 新津 葵一 / 学位規則第4条第1項該当 / Doctor of Informatics / Kyoto University / DFAM

A range of small molecules of interest for use in organic semiconductor devices were studied computationally. Trends in geometry, absorption spectra, molecular orbitals, electrostatic potentials, reorganisation energies were studied. Results suggest that, as with acenes, the performance of non-linear cata-condensed polyaromatic hydrocarbons improves as number of fused benzene rings increases. The torsion in these molecules did not appear to have a large impact on the conjugation across the core and little effect on the absorption spectra, although it did affect the reorganisation energies on which charge mobilities depend. Computational studies of mobilities of anthradithiophene molecules were broadly able to reproduce trends seen experimentally and emphasised the importance of crystal morphology. Experimental work was also carried out to search for cocrystals between anthradithiophene derivatives. Many examples were found with some mixtures forming different cocrystals at different mixture ratios. These results were rationalised by a computational study that showed molecules which had a similar binding energy were more likely to be able to form cocrystals. Cocrystal devices were fabricated and 3 out of 7 showed a larger mobility than devices made out of its constituent materials alone. The best of these had a mobility 65% higher than a device made out of the constituent material with the largest mobility. An energy decomposition analysis was carried out on a novel thallophilic system, a complex of thallium with a neutral β-triketimine ligand which was found to form dimers with close Tl-Tl interactions. Calculations show the electrostatic interaction to be repulsive for the dimer with no counter ions, but attractive when 3,5-bistrifluoromethylphenyl borate counter ions are included. This suggests the metallophilic interaction is counter ion-mediated, requiring the anions to provide favourable electrostatics, even in the case of spatially diffuse and distant counter ions such used here. To enable the studies described here software was written for simulating absorption spectra. An implementation into the Gaussian Suite of programs of an energy decomposition scheme and its extension to include an empirical dispersion correction was also carried out.

Le travail entre dans le cadre de la nouvelle tendance à la recherche d’une électronique mécaniquement flexible basée sur des transistors en couche mince constitués uniquement de matériaux organiques (OTFT). OTFT de type n et de type p ont été fabriqués par la technique de dépôt par impression (inkjet) et étudiés. Les paramètres d’impression (jetabilité, mouillabilité, imprimabilité et possibilité d’obtention de différentes formes), de chaque encre permettant le dépôt de couches conductrices, isolantes et semiconductrices, ont été systématiquement étudiés. Les OTFT de type n basés sur du C60 se sont montrés non fiables, principalement du fait de la faible solubilité du C60 dans les solvants organiques. Les OTFT de type basés sur du Tips-pentacene ont montré par contre une grande fiabilité. Le travail global constitue une large revue des problèmes et difficultés rencontrés dans la fabrication de transistors fabriqués entièrement par impression jet d’encre. Des solutions ont été trouvées et de nouvelles idées sont proposées. / Present work deals with the new trend to get highly flexible electronics by using fully Organic Thin-Film Transistor (OTFT) as the basic element of this electronics. Fully organic n-type as well as p-type OTFT processed by inkjet printing are studied. Printing parameters of each ink, jettability, wetting, printability, and patterns optimization, leading to the deposition of conductive contacts, gate insulator and semiconducting active layer are studied. Process of n-type OTFT based on C60 is shown as unreliable, mainly due to the poor solubility of C60 in organic solvent. In the contrary, p-type OTFTs based on Tips-pentacene are much more reliable. The work is a large overview of the issues and the difficulties that have been to jump and to solve in the way to fabricate fully printed organic transistors. Some solutions have been given and new ideas have been proposed.