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Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 117-122). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 117-122). Also available on the Internet.

Thesis (Ph. D.)--Ohio State University, 2004. / Title from first page of PDF file. Document formatted into pages; contains xvii, 208 p.; also includes graphics (some col.). Includes bibliographical references (p. 189-208).

Thesis (Ph. D.)--Montana State University--Bozeman, 2007. / Typescript. Chairperson, Graduate Committee: Max Deibert. Includes bibliographical references (leaves 74-77).

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (p. 63-66).

Ruthenium dioxide, zirconium dioxide and bismuth titanate thin films were deposited on Si, sapphire disks, and Pt/Ti/SiO₂/Si substrates by hot wall metalorganic chemical vapor deposition (MOCVD). Bis(cyclopentadienyl)ruthenium [Ru(C₅H₅)₂], zirconium tetramethylheptanedione [Zr(thd)₄], triphenylbismuth [Bi(C₆H₅)₃], and titanium ethoxide [Ti(C₂H₅O)₄] were used as precursors. MOCVD RuO₂ film structure was dependent on MOCVD process parameters such as bubbler temperature, dilute gas flow rates, deposition temperature, and total pressure. Either pure RuO₂, pure Ru, or a RuO₂ + Ru mixture was obtained under different deposition conditions. As-deposited pure RuO₂ films were specular, crack-free, and adhered well on the substrates. The Auger electron spectroscopy depth profile showed a good composition uniformity across the bulk of the films. The MOCVD RuO₂ thin films exhibited resistivities as low as 60 <i>μ</i>Ω-cm. In addition, the reflectance of RuO₂ in the NIR region showed a metallic character. Zr(thd)₄ was synthesized and the process was optimized. Purity of Zr(thd)₄ was confirmed by melting point determination, carbon and hydrogen elemental analysis and proton nuclear magnetic resonance spectrometer (NMR). The MOCVD ZrO₂ film deposition rates were very small (≤ 1 nm/min) for substrate temperatures below 530°C. The film deposition rates were significantly affected by: (1) source temperature, (2) substrate temperature, and (3) total pressure. As-deposited films are carbon free. Furthermore, only the tetragonal ZrO₂ phase was identified in as-deposited films. The tetragonal phase transformed progressively into the monoclinic phase as the films were subjected to high temperature post-deposition annealing. The optical properties of the ZrO₂ thin films as a function of wavelength, in the range of 200 nm to 2000 nm, were also reported. In addition, a simplified theoretical model which considers only a surface reaction was used to analyze the deposition of ZrO₂ film. The deposition rates can be predicted well for various deposition conditions in the hot wall reactor. The deposition rates of MOCVD Bi₄Ti₃O₁₂ were in the range of 3.9-12.5 nm/min. The Bi/Ti ratio was controlled by precursor temperature, carrier gas flow rate, and deposition temperature. As-deposited films were pure Bi₄Ti₃O₁₂ phase. The films were specular and showed uniform and fine-grain morphology. Optical constants as a function of wavelength were calculated from the film transmission characteristics in the UV-VIS-NIR region. The 550°C annealed film had a spontaneous polarization of 26.5 <i>μ</i>C/cm² and a coercive field of 244.3 kV/cm. / Master of Science

The purpose of this study was two-fold: firstly, the MOCVD deposition behavior of Pb(thd)2 was studied in detail and a one-dimensional kinetic model was proposed to successfully predict the effect of processing conditions on the deposition rate profile for PbO. Assuming the surface reaction is the rate-limiting step in the process, the effective activation energy for the process, Ea, was found to be 82 kJ/mol while the preexponential rate constant was found to be 33 g/cm2/min (0.15 moVcm2/min). The process was found to consistently produce a combination of the high temperature, orthorhombic modification of lead monoxide with randomly oriented plates of tetragonal lead monoxide. TEM electron diffraction was used to investigate the crystal orientation of the individual plates which was found to be in the plane normal to the <201> zone. Secondly, the deposition behavior of PbTi03 and the resulting film structure and properties were investigated. Pb(thd)2 was used in conjunction with titanium ethoxide (Ti(OEt)4) as a titanium source. Stoichiometric lead titanate films which were found to be smooth, specular and transparent, and well-adhered were deposited on a variety of substrates by careful control of the experimental conditions. Film structure, composition, and thickness were studied and correlated to changes in various experimental parameters. Additionally, a high temperature regime at which the film stoichiometry is relatively insensitive to experimental conditions was found to occur. The effects of post-annealing on the as-deposited films including compositional changes, morphological changes and crystal structure was also studied. Some problems were obtained with film peeling on the ruthenium oxide (Ru0₂)-coated substrates which could be alleviated somewhat by the use of (100) oriented silicon wafer rather than (111) oriented silicon; a possible mechanism to explain this behavior is also suggested. Optical properties were obtained using UV -VISNIR transmission and reflectance spectroscopy; the ferroelectric hysteresis behavior of the films was observed using standard R T -66 A test equipment. / Master of Science

The chemistry of chemical vapor deposition from copper (II) dimethylaminoethoxide onto single crystal strontium titanate has been studied by in situ infrared analysis of the vapor phase in the reactor, and by simultaneous mass spectrometer analysis of the reactor outlet gas. Species condensed from the reactor outlet gas in a liquid nitrogen trap were analyzed by proton nuclear magnetic resonance. Chemical information was also obtained by Auger electron and X-ray photoelectron spectrometer analysis of the deposited films. Deposition chemistry was studied with respect to deposition temperature, presence of ultraviolet light, and presence of a reactive gas cofeed. The goal was to determine the reaction pathway and relate it to deposited film composition. In a reduced pressure helium atmosphere, copper dimethylaminoethoxide deposits clean, conductive films of copper metal at 200°C. The ligands are eliminated by two interdependent reactions: β-hydride elimination produces dimethylaminoethanol, while reductive elimination produces dimethylaminoethanol. The minimum deposition temperature is 150°C. At substrate temperatures near 250°C some ligand fragmentation occurs, in addition to the clean elimination pathway, leading to carbon contamination of the deposited films. The deposition chemistry of copper dimethylaminoethoxide is not affected by irradiation with ultraviolet light of wavelengths between 360 nm and 600 nm. The ultraviolet light source was a Spectronics B-100 UV lamp. A light source with higher power might affect deposition chemistry. At a substrate temperature of 200°C in the presence of oxygen, dimethylaminoethanol and dimethylaminoethanol are not detected as products. Decomposition involves extensive ligand fragmentation, producing small amines and carbonyl species, carbon monoxide, and carbon dioxide. Films are free of carbon and nitrogen, because the ligand fragments are volatile and stable. Films are a mixture of copper metal and copper (I) oxide. Optimization of oxygen concentration in the reactor could lead to deposition of a pure copper oxide. / Ph. D.