No description available.

付記する学位プログラム名: デザイン学大学院連携プログラム / 京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21099号 / 工博第4463号 / 新制||工||1693(附属図書館) / 京都大学大学院工学研究科機械理工学専攻 / (主査)教授 西脇 眞二, 教授 椹木 哲夫, 教授 松原 厚 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.

No description available.

No description available.

No description available.

No description available.

Many studies and experiments have been conducted over the years to find solutions to the electricity problem. This issue is not just related to how fossil fuels are dispensed. Also, the environmental concerns associated with using fossil fuels have become a severe issue, which is a major cause of environmental pollution and ozone layer damage. As such, the need for energy becomes one of the essential goals. Therefore, research has begun to revolve around thermoelectrics, which is a straightforward approach for generating energy, by converting heat directly into electricity. Cobalt antimonide (CoSb3) belongs to a broad family of materials with the skutterudite structure, which have been recently identified as potential new thermoelectric materials with high performance. The CoSb3 is one of the numerous promising thermoelectric materials in the intermediate temperature range. The binary CoSb3 is a narrow bandgap semiconductor with a relatively flat band structure and excellent electrical performance. The thermoelectric performance efficiency of binary CoSb3 is measured by its figure of merit. The figure of merit is important for thermoelectric materials and is primarily governed by the Seebeck coefficient because it exhibits a square dependence. The Seebeck coefficient of the CoSb3 can be affected by many factors that can either increase or decrease it. Strain is an important aspect for the transport properties, including the Seebeck coefficient. The goal of this thesis project is to study the effect of point defects and strain on the Seebeck coefficient of skutterudite CoSb3. The binary CoSb3 skutterudite was explored through density functional theory (DFT) to calculate the ground-state properties, in particular the Seebeck coefficient. Two different CoSb3 structures were considered, an ideal one (without any defects) and the other was termed real (containing defects). In both cases, the Seebeck coefficient and its response were studied while strain was applied by changing the volume of the structure. The non-equilibrium Green's function was used within a DFT simulation to get a transmission distribution, where it was essential for calculating the Seebeck coefficient. Moreover, oxygen molecules were placed over the (001) surface of 2 × 2 × 1 CoSb3 supercell to establish if oxidation leads to point defect formation. These simulations were carried out by DFT-based molecular dynamics. It is found that the strain affects the Seebeck coefficient in the ideal structure. At compression, the absolute value of the Seebeck coefficient increases.  By contrast, the Seebeck coefficient changed its sign from negative to positive and increased to 894 μVK−1at tension, which was unexpected. The electron density distribution map was explored to explain the behavior of the Seebeck coefficient at equilibrium, compression, and tension. It can be seen that the electron distribution between Co and Sb is increased at compression, implying an increased orbital overlap (covalent interaction). By contrast, the tension reduces the electron distribution between Sb and Co. The real structure induced by oxidation exhibits Sb vacancies. The See-beck coefficient is affected differently than that of the ideal structure. At equilibrium, the Seebeck coefficient increases to 151 μVK−1. The electron density distribution between Sb and Co is enhanced in the real structure compared to the ideal one. The most drastic change is found at tension, where the Seebeck coefficient reaches−270 μVK−1. It may be speculated that this occurs due to O which increases the orbital overlap. The strategy introduced in this work, an interplay of defects and strain effects, may be beneficial for other thermoelectric materials.

Thermoelectric (TE) materials are used to directly interconvert heat and electricity. The semiconductor PbTe with narrow band gap is one of the leading thermoelectric materials in mid-temperature range due to intrinsically low lattice thermal conductivity and large Seebeck coefficient. Recently, various strategies have produced p-type and n-type PbTe-based materials with greatly enhanced TE properties. However, there are still many fascinating features which are needed to be studied. First, phase analysis and TE properties of binary polycrystalline Pb‒Te samples prepared by various heat treatments have been investigated. Since europium with its 4f electrons was expected to have strong influence on the thermoelectric behavior of PbTe, the constitution and thermoelectric behavior of two substitution schemes with possible Eu2+ and Eu3+ in the Pb–Eu–Te ternary system have been examined. As sodium is widely used as substituting element for p-type PbTe-based TE materials, the crystal structural features and TE properties of two series of polycrystalline samples Pb1-yNayTe1-y/2 and Pb1-xNaxTe have been studied. The local atomic arrangement of sodium by different substitution schemes has been revealed by NMR. Finally, we present the reproducibility of TE properties and microstructure evolutions of high-ZT Eu-substituted and Na-substituted PbTe during different heat treatments. From binary PbTe to ternary Pb–Eu–Te and Pb–Na–Te, and final with quaternary Pb–Eu–Na–Te, the comprehensive picture of the structure and TE properties for Pb–Eu–Na–Te system is constructed.

Results of this research are available online in two published papers. / The main focus of this research was to synthesize and then to characterize the potential high-performance thermoelectric materials. In this regard, we have prepared a series of pure RECuSe2 (with RE = Pr, Sm, Gd, Dy and Er) and RECuTe2 (with RE = Er, Dy and Gd) and analyzed their crystal structure, electronic and physical properties. We used powder and single crystal X-ray diffraction techniques to analyze their crystal structures and employed energy dispersive X-ray spectrometry (EDS) to verify their chemical compositions. The temperature stability of the synthesized samples was examined by differential thermal and gravimetrical analysis. The high-purity consolidated pellets were prepared for physical properties measurements. We analyzed the relationship between their crystal structures and pertinent electronic properties through the LMTO calculations. The RECuSe2 phases adopt two structures, monoclinic and trigonal. The monoclinic structure (P21/c, z = 4) is observed for lighter rare earths (RE = Pr, Sm and Gd) and Cu-disordered trigonal structure for heavier rare earths (P m1, z = 1, RE = Dy and Er). The resistivity and Seebeck coefficient measurements indicate that the studied selenides are p-type semiconductors with relatively small activation energies (0.045-0.12 eV). However, their electrical resistivities are too high (0.49-220 Ohmcm at room temperature) to make them competitive thermoelectric materials. Electronic structure calculations indicate presence of a band gap in the RECuSe2 phases. The synthesized RECuTe2 phases (RE = Er, Dy and Gd) adopt a monoclinic-distorted variant (C2/m, z = 2) of the trigonal structure (P m1, Z= 1) observed for the RECuSe2 (with RE = Dy, Er). While such disorder may be beneficial for lowering their thermal conductivity, large values of electrical resistivity (0.02-0.87 Ohmcm at room temperature) make these phases unsuitable for practical applications. Comparing to the corresponding semiconducting selenides, the tellurides have lower resistivities, and display a metallic type resistivity. Such behavior stems from the closure of band gaps, which is verified by the electronic structures calculations. Structurally the RECuTe2 phases (with RE = Er, Dy and Gd) are similar to RECuSe2 with the P m1 structure. The monoclinic distortion in RECuTe2 is driven by Cu displacement inside the larger tetrahedral voids in the hexagonal close packing of the Te atoms. Most likely, Cu shifts to one side of the Te tetrahedra to optimize the Cu-Te interactions. / Thesis / Candidate in Philosophy