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京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第18315号 / 農博第2040号 / 新制||農||1020(附属図書館) / 学位論文||H26||N4822(農学部図書室) / 31173 / 京都大学大学院農学研究科食品生物科学専攻 / (主査)教授 保川 清, 教授 安達 修二, 教授 入江 一浩 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

The state-of-the-art organic solar cells (OSC) use bulk heterojunction (BHJ) blend architecture in the photo-active layer. The BHJ is formed by finely mixing polymer donor and small molecule acceptor, which was predominantly fullerene derivatives until the last five years. However, the emergence of non-fullerene acceptor (NFA) materials has been the viable alternative to overcome high synthetic costs, limited optical absorption, and poor bandgap tunability of fullerene-based acceptors. These unique properties of NFA has resulted in a rapid improvement of OSC efficiency and opened doors for wide variety of applications including building integrated photovoltaics, green houses and agrivoltaics. Despite these advantages, the shorter device lifetime under light and heat is a major concern for their commercialization. This dissertation is focused on improving poor photo- and thermal stability of high efficiency OSC based on the widely used NFA, ITIC and Y-series derivatives. The light-induced changes in the acceptor molecular structure and the active layer nanostructure results in the photo-induced traps in photo-aged devices. The selective addition of third component to the active layer impedes the changes in the active layer nanostructure and suppress trap formation. Under constant thermal stress, the growth of acceptor crystals results increases the trap-assisted recombination in thermally aged devices. Similar to photo-stability the selective addition of third or more component/s arrests the crystal growth by minimizing the Gibbs free energy. The results suggest that the fabricated hexanary and ternary OSC display a superior thermal stability than the respective binary devices. In addition, the hexanary devices displayed thickness independent thermal stability, which is essential for the active layer thermal stability printed via high throughput techniques.

Organic solar cells (OSCs) have gained considerable attention from the scientific community in recent decades due to their remarkable power conversion efficiency (PCE), flexibility, and cost-effectiveness in producing large-area batteries. Despite the ongoing research efforts that have led to a PCE exceeding 19% for single-junction OSCs and surpassing 20% for multi-junction OSCs, the commercialization of these devices is hampered by their poor stability, reliance on specific additives, and the use of toxic solvents. To address these shortcomings, this study focuses on investigating the 3 * 3 thermosets matrix to facilitate the selection of precursors for in-situ crosslinking thermosets. Furthermore, in this study, we fabricated the devices using green solvents to narrow the gap between PCE and stability under environmentally friendly conditions. We utilized PTQ10: BTP-BO4Cl as the model system and employed tetrahydrofuran (THF) as an eco-friendly solvent. The research focused on examining the thermoset's glass transition temperature (Tg), modulus and morphology properties. The resulting cross-linked thermoset network has high-density hydrogen bonding and network grids, which helps to stabilize the morphology of the active layer. The findings indicated that selecting a thermoset with high Tg, high modulus (4-8 MPa), and good uniformity as an in-situ crosslinking additive would be beneficial. These results can guide the selection of universal in-situ crosslinking thermosets and aid in improving the stability of various organic electronic devices.

Silver-gold nanocages have attracted considerable research interest recently due to their excellent performance in the fields of biomedicine and photocatalysis. These applications oftentimes manipulate at elevated temperatures and therefore impose demands on the thermal stability of the cage structures. To better understand this subject, in this work, we systematically evaluated the thermal stability of two nanocages with different wall thicknesses of 3.8 nm and 13 nm, both in the solution-phase (diethylene glycol) and solid-phase (in-situ STEM). The results revealed that the nanocages with thicker walls exhibited better thermal stabilities in both phases. By monitoring and analyzing the morphology changes of the nanocages, we determined that the nanocages with thin and thick walls undergo deformation processes differently. Nevertheless, they both deformed into more thermodynamically stable structures eventually. The plasmonic properties of the nanocages were also examined.

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Multilayers provide an ideal tool to study thermodynamics of heterogeneous systems far from equilibrium. In this study, synthesis, characterization, thermal stability and phase equilibrium of multilayers are investigated based on Au-Pt system. Au-50%Pt multilayers were first formed by repeated rolling and folding. The microstructure was investigated by x-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). These methods revealed that the process reduced layer thicknesses to below 30nm. However, delaminating and non-uniform spacings were also observed in some regions. To get well- welded and regular multilayers, the experiment was redesigned. The improved approach, involving repeated cutting, stacking, annealing and cold rolling, has yielded uniform multilayers with interlamellar spacings as low as 6nm. XRD demonstrated the formation of a homogeneous solid solution during cold rolling at room temperature. TEM suggested that the multilayers were discontinuously homogenized via steady state motion of boundaries. The reason for the solid solution formation is that the stored interface energy is higher than the energy barrier for solid solution formation. The solid solution is unstable. It decomposes into Au and Pt after heating to 500°C at 50°C/min by differential scanning calorimetry (DSC). The phase diagram is strongly modified in the nanometer range when we take into account of interface energy. The grain size dependent phase diagram model of Au-Pt system shows that the melting points of Au and Pt can be lowered more than 300K if the average grain size is reduced to 10nm. The melting temperature of Au/Pt multilayers has been studied with theoretical and experimental approaches. High speed laser heating was used to minimize any modification of the multilayer structure prior to melting. The qualitative experimental results are shown to be in agreement with expectations. / Thesis / Master of Applied Science (MASc)

It was the objective of this research to develop high temperature and high performance polyimides that also display (a) thermal stability; (b) crystallinity in the initial material and ability to crystallize from the melt; (c) fast crystallization kinetics and (d) melt processability. This unique combination of properties is presently unavailable in any other polyimide. In this regard, the present work investigates the crystallization, morphology and thermal stability of two novel semicrystalline polyimides based on the same diamine, 1,3-bis (4-aminophenoxy) benzene (TPER), but two different dianhydrides, 3,3',4',4'-biphenyltetracarboxylic dianhydride (BPDA) and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA). Phthalic anhydride was used as an endcapper to improve the thermal stability of the polyimides. The BPDA based polyimide was also tested extensively as a structural adhesive using Ti-6Al-4V coupons. Additionally, these polyimides are based on monomers, that are presently commercially available. The bulk thermal stability of the polyimides was first evaluated using dynamic and isothermal thermogravimetric experiments. DSC was utilized to test the ability of the polyimides to crystallize from the melt after exposures to varying melt times and temperatures. Exceptional thermal stability was demonstrated by BPDA based polyimide with no change in the melting behavior after 40 min at 430°C or 30 min at 440°C. The semicrystalline morphology of the material was studied using hot stage polarized optical microscopy (OM) and atomic force microscopy. The spherulitic growth rates were determined as a function of crystallization temperature after quenching from various melt times and temperatures. The effect of crystallization temperature, previous melt time and melt temperature on the morphology was considered. The spherulitic growth rates increased with increasing undercooling in the temperature range studied (nucleation controlled), while the growth rate at a specific crystallization temperature decreased on increasing the previous melt time and temperature. The melting behavior was studied after different crystallization times and temperatures and also as a function of different heating rates. Crystallization kinetics was followed both isothermally and non-isothermally using DSC and OM. Avrami analysis was performed for TPER-BPDA and the obtained results were correlated with microscopic observations. Melt viscosity measurements were carried out as a function of melt temperature, melt time and frequency. The adhesive investigations for TPER-BTDA utilized lap-shear test, wedge test and double cantilever beam tests. The durability of the adhesive and the fracture surface was studied after exposure to various solvents and after high aging and testing temperatures. The polyimide demonstrated very high average room temperature lap-shear strengths (8400 psi or 59 MPa), excellent solvent resistance and durability of strengths at high aging and testing temperatures. / Ph. D.

This work included two separate studies; the common theme in each was the use of mode-I fracture testing to evaluate wood adhesion. In the first study, mode-I fracture testing was used to compare the thermal stability of polyurethane (PUR) and resorcinol-formaldehyde (RF) wood adhesives. Bonded specimens for both adhesives were subjected to prolonged thermal exposure, and fracture testing was subsequently conducted after re-equilibration to standard test conditions. It was found that both PUR and RF suffered a significant fracture energy loss after heat treatment, and that RF was more thermally stable than PUR, as expected. However, both adhesives suffered significant thermal degradation, and fracture testing did not distinguish the RF system as being clearly superior to PUR. Dynamic mechanical analysis (DMA) was also used to analyze and compare the thermal softening of PUR and RF in terms of the decline in storage modulus. DMA results indicated that PUR specimens suffered greater stiffness loss due to simple thermal softening. Because fracture testing indicated that both adhesives suffered significant degradation, the DMA results suggested that the generally superior fire resistance of RF adhesives is born from greater high temperature stiffness; whereas the more compliant PUR suffers greater immediate softening during thermal exposure. In other words, both systems suffer from thermal degradation, but the more highly cross-linked RF system suffers less thermal softening and therefore maintains a greater load carrying capacity during fire exposure. In the second study, mode-I fracture testing was used to test the effects of wood surface thermal deactivation (surface energy reduction) on the adhesion between southern pine wood (Pinus spp.) and polyethylene (PE). Pine specimens were progressively surface deactivated by 185°C heat treatments for periods of 5, 15, and 60 minutes. Control and deactivated pine laminae were subsequently hotpressed/bonded using PE film as the adhesive. Mode-I fracture testing was conducted under the assumption of linear elasticity, however load/displacement test curves suffered from a severe degree of nonlinearity believed to be caused by PE bridging behind the advancing crack tip. Instead of applying a nonlinear data analysis, a standard linear elastic analysis was conducted and deemed acceptable for comparative purposes within this study. Under dry conditions (unweathered specimens), 5 and 15 minute thermal treatments resulted in progressively worse adhesion (lower fracture energies) when compared to control surfaces; but the 60 minute heat treatment improved adhesion relative to 5 and 15 minute treatments, and showed a trend of improving adhesion as surface deactivation became more extreme. Simulated-weather resistance was also studied and it was determined that the highest degree of surface deactivation slightly improved weather durability in comparison to control surfaces. Overall, the findings here were similar to those in a previously published work- thermal deactivation of wood surfaces shows promise as a method to improve adhesion between wood and nonpolar polyolefins. / Master of Science