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This dissertation study describes the development of novel heteroepitaxial growth of 3C-SiC layers by chemical vapor deposition (CVD). It was hypothesized that chloride addition to the "traditional" propane-silane-hydrogen precursors system will enhance the deposition growth rate and improve the material quality via reduced defect density. Thermodynamic equilibrium calculations were performed to obtain a criterion for which chloride specie to select for experimentation. This included the chlorocarbons, chlorosilanes, and hydrogen chloride (HCl) chloride containing groups. This study revealed no difference in the most dominant species present in the equilibrium composition mixture between the groups considered. Therefore, HCl was the chloride specie selected to test the hypothesis. CVD computerized fluid dynamic simulations were developed to predict the velocity, temperature and concentration profiles along the reactor. These simulations were performed using COMSOL Multiphysics and results are presented. The development of a high-temperature (1300 °C -1390°C) 3C-SiC growth process resulted in deposition rates up to ~38 µm/h. This is the highest value reported in the literature to date for 3C-SiC heteroepitaxy. XRD FWHM values obtained varied from 220 to 1160 arcsec depending of the process growth rate or film thickness. These values are superior or comparable to those reported in the literature. It was concluded from this study that at high deposition temperatures HCl addition to the precursor chemistry had the most significant impact on the epitaxial layer growth rate. Low-temperature (1000-1250°C) 3C-SiC growth experiments evidenced that the highest deposition rate that could be attained was ~2.5 µm/h. The best quality layer achieved in this study had a FWHM of 278 arcsec; which is comparable to values reported in the literature and to films grown at higher deposition temperatures in this study. It was concluded from this work that at lower deposition temperatures the HCl addition was more beneficial for the film quality by enhancing the surface. Surface roughness values for films grown with HCl additive were 10 times lower than for films grown without HCl. Characterization of the epitaxial layers was carried out via Nomarski optical microscopy, FTIR, SEM, AFM, XRD and XPS.

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This dissertation research focused on the growth of 4H-SiC epitaxial layers in low-pressure horizontal hot-wall chemical vapor deposition (CVD) reactors. The goal of the research was to develop a growth process that maximized the growth rate and produced films of smooth morphology. The epitaxial growth of SiC was carried out in two different reactor sizes, a 75 mm reactor and a 200 mm reactor. The maximum repeatable growth rate achieved was 30-32 um/h in the 200 mm reactor using the standard chemistry of hydrogen-propane-silane (H2-C3H8-SiH4) at growth temperatures <̲ 1600 °C, which is the highest growth rate reported to date in a horizontal hot-wall reactor at these temperatures. This growth rate was achieved with a silane flow rate of 30 sccm. The process development and characterization of 4H-SiC epitaxial films grown using the standard chemistry are presented. There are many ways to increase the growth rate, such as changing the pressure, increasing the reactant flow rates, or increasing the temperature. The method of choice for this dissertation work was to first increase the reactant flow rates, i.e. silane flow rate, and then to alter the growth chemistry by using a growth additive. When the silane flow is increased, while maintaining a specific growth temperature, supersaturation of silicon may occur. When this happens, particulates may form and deposit onto the sample surface during growth which degrades the film morphology of the epitaxial layers. In order to overcome this severe limitation in the growth of SiC, hydrogen chloride (HCl) was added to the standard chemistry of H2-C3H8-SiH4 during growth when the SiH4 flow was increased beyond 30 sccm. With the addition of HCl, the Si supersaturation was suppressed and the growth rate was increased from ~32 um/h to ~ 49 um/h by increasing the silane precursor up to 45 sccm, while maintaining the Si/C ratio of the standard chemistry process. The addition of HCl to the standard chemistry for growth of SiC films was pioneering work that has since been duplicated by several research groups.

In this work we present the results of the analysis of the surface structures and absorption properties with respect to the CO and O2 molecules of the Sn/Rh and Rh/SnO2 model systems. In the part dedicated to the Sn structures on Rh surfaces with two different orientations - Rh(110) and Rh(111) - we have investigated the development of the core electron levels and valence band during the development of surface reconstructions and absorption of CO molecules. The surface reconstructions of the Sn/Rh(110) systems were studied for the first time. Difference in behaviour w.r.t. Sn/Rh(111) was observed and explanation offered. Finally, on in-situ prepared epitaxial SnO2 layers, the surface reconstruction (4×1) was observed. The CO adsorp- tion properties of Rh on polycrystalline and epitaxial SnO2 layers were also studied and difference in behaviour explained.

abstract: Carrier lifetime is one of the few parameters which can give information about the low defect densities in today's semiconductors. In principle there is no lower limit to the defect density determined by lifetime measurements. No other technique can easily detect defect densities as low as 10-9 - 10-10 cm-3 in a simple, contactless room temperature measurement. However in practice, recombination lifetime &tau;r measurements such as photoconductance decay (PCD) and surface photovoltage (SPV) that are widely used for characterization of bulk wafers face serious limitations when applied to thin epitaxial layers, where the layer thickness is smaller than the minority carrier diffusion length Ln. Other methods such as microwave photoconductance decay (µ-PCD), photoluminescence (PL), and frequency-dependent SPV, where the generated excess carriers are confined to the epitaxial layer width by using short excitation wavelengths, require complicated configuration and extensive surface passivation processes that make them time-consuming and not suitable for process screening purposes. Generation lifetime &tau;g, typically measured with pulsed MOS capacitors (MOS-C) as test structures, has been shown to be an eminently suitable technique for characterization of thin epitaxial layers. It is for these reasons that the IC community, largely concerned with unipolar MOS devices, uses lifetime measurements as a "process cleanliness monitor." However when dealing with ultraclean epitaxial wafers, the classic MOS-C technique measures an effective generation lifetime &tau;g eff which is dominated by the surface generation and hence cannot be used for screening impurity densities. I have developed a modified pulsed MOS technique for measuring generation lifetime in ultraclean thin p/p+ epitaxial layers which can be used to detect metallic impurities with densities as low as 10-10 cm-3. The widely used classic version has been shown to be unable to effectively detect such low impurity densities due to the domination of surface generation; whereas, the modified version can be used suitably as a metallic impurity density monitoring tool for such cases. / Dissertation/Thesis / M.S. Materials Science and Engineering 2013