The effects of methane (CH4), diborone (B2H6) and nitrogen (N2) concentrations on the structure and photoelectron emission properties of chemical vapor deposition (CVD) polycrystalline diamond films were studied. The diamond films were grown on single-crystal Si substrates using the hot-tungsten filament CVD technique. Raman spectroscopy and x-ray photoelectron spectroscopy (XPS) were used to characterize the different forms of carbon in the films, and the fraction of sp3 carbon to sp3 plus sp2 carbon at the surface of the films, respectively. Scanning electron microscopy (SEM) was used to characterize the surface morphology of the films. The photoelectron emission properties were determined by measuring the energy distributions of photoemitted electrons using ultraviolet photoelectron spectroscopy (UPS), and by measuring the photoelectric current as a function of incident photon energy.

Amorphous and nano- or micro- crystalline silicon thin films are intensively studied materials for photovoltaic applications. The films are used as intrinsic layer (absorber) in p-i-n solar cells. As opposed to crystalline silicon solar cells, the thin films contain about hundred times less silicon and can be deposited at much lower temperatures (typically around 200 0 C) which saves energy needed for production and makes it possible to use various low cost (even flexible) substrates. However, these films have a complex microstructure, which makes it difficult to measure and describe the electronic transport of the photogenerated carriers. Yet, the understanding of the structure and electronic properties of the material at nanoscale is essential on the way to improve the efficiency solar cells. One of the main aims of this work is the study of the structure and mechanical properties of the mixed phase silicon thin films of various thicknesses and structures. The key parameter of microcrystalline silicon is the crystallinity, i.e., the microcrys- talline volume fraction. It determines internal structure of the films which, in turn, decides about many other properties, including charge transport and mechanical sta- bility. Raman microspectroscopy is a fast and non-destructive method for probing the...

Since the first successful isolation and subsequent characterization of graphene, the interest in two dimensional (2-D) materials has expanded exponentially. Despite the dozens of graphene-like van der Waals materials that have been found and their interesting properties, a significant obstacle in realizing their promise is their instability especially for monolayer and thin layers at elevated temperature. To overcome the obstacle of passivating the 2-D materials and study their properties at elevated temperature, we take advantage of the potential improvements afforded by assembling heterostructures by stacking the atomic thick 2-D materials together hexagonal boron nitride (ℎ-BN) which possess high chemical stability and thermal stability. In this dissertation, several experiments are described in detail in which we utilized h-BN encapsulation to passivate atomically-thin transition metal dichalcogenide and studied their properties at elevated temperature. In the first project we demonstrated that chemical vapor deposition (CVD)-grown flakes of high-quality monolayers of WS₂ can be stabilized at elevated temperatures by encapsulation with only top ℎ-BN layers in the presence of ambient air, N₂ or forming gas. The best passivation occurs for ℎ-BN covered samples with flowing N₂. In the second project, we demonstrated that encapsulating monolayer MoSe₂ and WS₂ with top and bottom ℎ-BN can improve their thermal stability at high temperature and increase their photoluminescence (PL). The increased PL likely occurs because impurities are laterally expelled from the TMD stack during heating. In the third project, we demonstrated the passivation of different modes of ℎ-BN encapsulation on thin layer FeSe sample by using temperature dependent Raman scattering. The complete encapsulation showed the best protection of thin layer FeSe. Finally, we utilized the temperature dependence of the Raman mode of thin-layer FeSe with complete encapsulation and applied a noncontact method to measure the thermal conductivity of the thin-layer FeSe.

abstract: A highly uniform and repeatable method for synthesizing the single-layer transition metal dichalcogenides (TMDs) molybdenum disulfide, MoS2, and tungsten disulfide, WS2, was developed. This method employed chemical vapor deposition (CVD) of precursors in a custom built cold-wall reaction chamber designed to allow independent control over the growth parameters. Iterations of this reaction chamber were employed to overcome limitations to the growth method. First, molybdenum trioxide, MoO3, and S were co-evaporated from alumina coated W baskets to grow MoS2 on SiO2/Si substrates. Using this method, films were found to have repeatable coverage, but unrepeatable morphology. Second, the reaction chamber was modified to include a pair of custom bubbler delivery systems to transport diethyl sulfide (DES) and molybdenum hexacarbonyl (MHC) to the substrate as a S and Mo precursors. Third, tungsten hexacarbonyl (WHC) replaced MHC as a transition metal precursor for the synthesis of WS2 on Al2O3, substrates. This method proved repeatable in both coverage and morphology allowing the investigation of the effect of varying the flow of Ar, varying the substrate temperature and varying the flux of DES to the sample. Increasing each of these parameters was found to decrease the nucleation density on the sample and, with the exception of the Ar flow, induce multi-layer feature growth. This combination of precursors was also used to investigate the reported improvement in feature morphology when NaCl is placed upstream of the substrate. This was found to have no effect on experiments in the configurations used. A final effort was made to adequately increase the feature size by switching from DES to hydrogen sulfide, H2S, as a source of S. Using H2S and WHC to grow WS2 films on Al2O3, it was found that increasing the substrate temperature and increasing the H2S flow both decrease nucleation density. Increasing the H2S flow induced bi-layer growth. Ripening of synthesized WS2 crystals was demonstrated to occur when the sample was annealed, post-growth, in an Ar, H2, and H2S flow. Finally, it was verified that the final H2S and WHC growth method yielded repeatability and uniformity matching, or improving upon, the other methods and precursors investigated. / Dissertation/Thesis / Doctoral Dissertation Physics 2019

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19721号 / 工博第4176号 / 新制||工||1644(附属図書館) / 32757 / 京都大学大学院工学研究科電子工学専攻 / (主査)教授 藤田 静雄, 教授 髙岡 義寛, 准教授 須田 淳 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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While investigations of semiconductor nanowires (NWs) has a long history, a significant progress is yet to be made in silicon carbide (SiC) NW technologies before they are ready to be utilized in electronic applications. In this dissertation work, SiC NW polytype control, NW axis orientation with respect to the growth substrate and other issues of potential technological importance are investigated. A new method for growing SiC NWs by vapor-liquid-solid mechanism was developed. The method is based on an in-situ vapor phase delivery of a metal catalyst to the growth surface during chemical vapor deposition. This approach is an alternative to the existing seeded catalyst method based on ex-situ catalyst deposition on the target substrate. The new SiC NW growth method provided an improved control of the NW density. It was established that the NW density is influenced by the distance from the catalyst source to the substrate and is affected by both the gas flow rate and the catalyst diffusion in the gas phase. An important convenience of the new method is that it yields NW growth on the horizontal substrate surfaces as well as on titled and vertical sidewalls of 4H-SiC mesas. This feature facilitates investigation of the NW growth trends on SiC substrate surfaces having different crystallographic orientations simultaneously, which is very promising for future NW device applications. It was established that only certain orientations of the NW axes were allowed when growing on a SiC substrate. The allowed orientations of NWs of a particular polytype were determined by the crystallographic orientation of the substrate. This substrate-dependent (i.e., epitaxial) growth resulted in growth of 3C-SiC NWs in total six allowed crystallographic orientations with respect to the 4H-SiC substrate. This NW axis alignment offers an opportunity to achieve a limited number of NW axis directions depending on the surface orientation of the substrate. The ease of controlling the NW density enabled by the vapor-phase catalyst delivery approach developed in this work, combined with the newly obtained knowledge about how to grow unidirectional (wellaligned) NW arrays, offer new opportunities for developing novel SiC NW electronic and photonic devices.

High Power Impulse Magnetron Sputtering (HiPIMS) comes as a new and promising PVD method for the development of high-performance coatings for cutting applications. This technique utilizes high energy and ionization which can produce a denser and stronger ceramic in comparison to traditional deposition techniques. Important coating characteristics that arise from this method such as enhanced hardness, adhesion, and less defects, can be applied when machining hard-to-cut materials. In this study, investigation of tool life and wear mechanisms, mechanical and physical properties of AlTiN coatings deposited on carbide tools by HiPIMS and Cathodic Arc Evaporation (CAE) were analyzed when machining Inconel 718 and Stainless Steel 304. Experimental turning tests were performed to evaluate tool life, and the wear mechanisms were analyzed by optical and scanning electron microscopy. Nanohardness, scratch test, fracture toughness and other methods were carried out to evaluate the coating properties. Impedance experiments were performed to determine the coating porosity and resistance to corrosion. The results showed that HiPIMS coating presented higher hardness, toughness to fracture and adhesion to the substrate in comparison to CAE coatings. The HiPIMS coated tool substantially improved tool life when machining Inconel. The dominant wear mechanism found was abrasion, which is induced by the presence of hard carbides. The main wear patterns observed were flank, notch, and crater wear. The tool performance of HiPIMS was found to have enhanced mechanical properties, lower porosity, and form a larger amount of tribo-oxides when machining, in comparison to CAE. / Thesis / Master of Applied Science (MASc)

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