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.

The physical properties of single crystals of samarium monosulfide exhibit a first order semiconductor-to-metal transition near 6.5 kbar. However, thin films of SmS show only a gradual change in their properties on applying pressure and this renders the technical utilization of the material difficult. Several mechanisms have been proposed as the cause of the smoothing of the transition. They include intrinsic stress, impurities, grain size, improper stoichiometry, and porosity, all of which can be traced to the physical vapor deposition techniques employed in preparing the films. In contrast, chemical vapor deposition was employed in this study because previous work had shown that it could minimize these detrimental modifications in thin films. A new CVD system was tested using a volatile organometallic as the samarium source and reacting it with H₂S. The deposited films contained considerable amounts of oxygen as evidenced by structure analysis, and the origin was traced to the samarium organometallic. The reaction of oxygen-free samarium tricyclopentadienyl with H₂S as well as chemical transport are suggested for deposition of stress-free SmS thin films in future work.

As the miniaturization keeps decreasing in semiconductor device fabrication, metal contamination on silicon surfaces becomes critical. An investigation of the fundamental mechanism of metal contamination process on silicon surface is therefore important. Kinetics and thermodynamics of the copper out-plating process on silicon surfaces in diluted HF solutions are both evaluated by several analytical methods.

Approved for public release, distribution is unlimited / 100 m/s). Low voltage electrical contact was not maintained for some experimental shots and non-parallel rails were the suspected cause. In this thesis, we used a non-contact capacitive sensor to determine rail spacing to within 2/kAcm10mael, so that the rails will be parallel within small tolerances. Several rails were used in these experiments: 75-25 copper-tungsten, chromium-plated 75-25 Cu-W, and chromium-plated pure copper rails. Improving the control of rail spacing and parallelity did not ensure low-voltage electrical contact for our configurations. The largest damage was observed for chromium-plated copper rails and the least damage occurred for chromium-plated 75-25 Cu-W rails. / Lieutenant, United States Navy

Solid oxide fuel cells (SOFCs) have attracted much interest as the most efficient electrochemical device to directly convert chemical energy to usable electrical energy. The porous Ni-YSZ anode known as the state-of-the-art cermet anode material is found to show serious degradation when using hydrocarbon as fuel due to carbon deposition, sulphur poisoning, and nickel sintering. In order to overcome these problems, doped strontium titanate has been investigated as a potential anode material due to its high electronic conductivity and stability in reducing atmosphere. In this work, A-site deficient strontium titanate co-doped with lanthanum and calcium, La₀.₂Sr₀.₂₅Ca₀.₄₅TiO₃ (LSCT[sub](A-)), was examined. Flat multilayer ceramics have been produced using the aqueous tape casting technique by controlling the sintering behaviour of LSCT[sub](A-), resulting in a 450µm thick porous LSCT[sub](A-) scaffold with a well adhered 40µm dense YSZ electrolyte. Impregnation of CeO₂ and Ni results in a maximum power density of 0.96Wcm⁻² at 800°C, higher than those of without impregnation (0.124Wcm⁻²) and with impregnation of Ni alone (0.37Wcm⁻²). The addition of catalysts into LSCT[sub](A-) anode significantly reduces the polarization resistance of the cells, suggesting an insufficient electrocatalytic activity of the LSCT[sub](A-) backbone for hydrogen oxidation, but LSCT[sub](A-) can provide the electronic conductivity required for anode. Later, the cells with the configuration of LSCT[sub](A-)/YSZ/LSCF-YSZ were prepared by the organic tape casting and impregnation techniques with only 300-m thick anode as support. The effects of metallic catalysts in the anode supports on the initial performance and stability in humidified hydrogen were discussed. The nickel and iron impregnated LSCT[sub](A-) cell exhibits a maximum powder density of 272mW/cm² at 700°C, much larger than 43mW/cm² for the cell without impregnation and 112mW/cm² for the cell with nickel impregnation. Simultaneously, the bimetal Ni-Fe impregnates have significantly reduced the degradation rates in humidified hydrogen (3% H₂O) at 700°C. The enhancement from impregnation of the bi-metal can possibly be the result of the presence of ionic conducting Wustite Fe₁₋ₓO that resides underneath the Ni-Fe metallic particles and better microstructure. Third, in order to improve the ionic conductivity of the anode support and increase the effective TPBs, ionic conducting ceria was impregnated into the LSCT[sub](A-) anode, along with the metallic catalysts. The CeO₂-LSCT[sub](A-) cell shows a poor performance upon operation in hydrogen atmosphere containing 3% H₂O; and with addition of metallic catalysts, the cell performance increases drastically by almost three-fold. However, the infiltrated Ni particles on the top of ceria layer cause the deposition of carbon filament leading to cell cracking when exposure to humidified methane (3% H₂O). No such behaviour was observed on the CeO₂-NiFe impregnated anode. The microstructure images of the impregnated anodes at different times during stability testing demonstrate that the grain growth of catalysts, the interaction between the anode backbone and infiltrates, and the spalling of the agglomerated catalysts are the main reasons for the performance degradation. Fourth, the YSZ-LSCT[sub](A-) composites including the YSZ contents of 5-80wt.% were investigated to determine the percolation threshold concentration of YSZ to achieve electronic and ionic conducting pathways when using the composite as SOFC anode backbone. The microstructure and dilatometric curves show that when the YSZ content is below 30%, the milled sample has a lower shrinkage than the unmilled one due to the blocking effect from the well distributed YSZ grains within LSCT[sub](A-) bulk. However, at the YSZ above 30% where two phases start to form the individual and interconnected bulk, the composites without ball milling process show a lower densification. The impact of YSZ concentration and ball milling process on the electrical properties of the composites reveals that the percolation threshold concentration is not only dependant on the actual concentration, but also related to the local arrangement of two phases. In Napier University, the electroless nickel-ceramic co-depositon process was investigated as a manufacturing technique for the anodes of planar SOFCs, which entails reduced costs and reduced high-temperature induced defects, compared with conventional fabrication techniques. The Ni-YSZ anodes prepared by the electroless co-deposition technique without the addition of surfactant adhere well to the YSZ electrolyte before and after testing at 800°C in humidified hydrogen. Ni-YSZ anodes co-deposited with pore-forming starch showed twice the maximum power density compared with those without the starch. It has therefore been demonstrated that a porous Ni-YSZ cermet structure was successfully manufactured by means of an electroless plating technique incorporating pore formers followed by firing at 450°C in air. Although the use of surfactant (CTAB) increases the plating thickness, it induces the formation of a Ni-rich layer on the electrolyte/anode interface, leading to the delamination of anode most likely due to the mismatched TECs with the adjacent YSZ electrolyte.

Degradation behavior of commercial lithium-ion pouch cells containing LiCoO2 cathode and graphite anode was investigated for a cycling under continuous overcharge condition. This condition is frequently experienced in electric vehicles in an event of Battery Management System (BMS) failure. Failure of BMS results in an unbalanced module further resulting in overcharging or overdischarging the cells. Commercial cells with 5Ah capacity were continuously cycled at different upper cutoff voltages and 1C-rate to develop a better understanding of the overcharge process. The results show that as the upper cutoff voltage is extended, the cell gains a higher initial capacity. However, the cycle life of the cell diminishes significantly. The extent of overcharge was found to be an important parameter not only for the electrochemical performance but also for cell integrity. Cells overcharged beyond 4.5 V had a significant volume increase and a rapid increase in the capacity fade. The cell starts to swell at this stage and a considerable increase in the temperature and internal resistance of the cells is observed. Thermal imaging of the cell revealed non-uniform temperature distribution and localized degradation sites were identified. Evidence of lithium plating and electrolyte deposits on anode was observed in cells charged beyond 4.4 V, with SEM-EDS verifying their presence. A comparative study of various State of Health (SoH) estimation parameters is presented and the proposed parameter Φ_R based on internal resistance measurement is found to be a good indicator of aggravated degradation in cells.<br>

Este trabalho procura desenvolver um novo modelo para análise estrutural de chapeamentos reforçados, que propõe ligar dois elementos estruturais de diferentes formulações, a saber: - Elementos de viga, analisados utilizando-se o método da rigidez, baseado na teoria linear de vigas, sendo, portanto, dentro das hipóteses inerentes à teoria , um método exato. Para tanto, desenvolve-se um novo elemento chamado viga excêntrica; - elementos de placa, analisados utilizando-se o método dos elementos finitos, podendo trabalhar com cargas em flexão e cargas no próprio plano acarretando um comportamento de membrana. O novo elemento de viga excêntrica é introduzido no programa SAP-VI (1) (podendo no entanto utilizar-se de outros programas), sendo realizados testes de interação com os elementos finitos de placa existentes no programa (2). O novo modelo revelou-se economicamente viável quando da sua utilização em chapeamentos reforçados, evitando-se a divisão em elementos finitos dos enrijecedores, que têm seu próprio comportamento dentro da teoria simples de vigas. / This work develops a new model for structural analysis of stiffened plating, involving two elements of different formulation, that is: - beam elements, analysed by the matrix method, based in the linear theory of beams, being then, with the hypothesis inherent to that theory, an exact method. For this purpose, it is developed a new element called \"eccentric beam\"; - plate elements, analysed by the finit element technique, working in bending and with loads in it\'s own plane, occasioning a membrane effect. The \"eccentric beam\" element is introduced in the SAP-IV (1) program (we might, however, use other programs). Tests were then carried out to assess the proper interaction of plate elements (2) and \"eccentric beam\". It was demonstrated that the new model is advantangeous when used in stiffened plating, avoinding the division in finite elements of the stiffeners.

by Li Chi Pui. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (leaves [105]-[109]). / Abstracts in English and Chinese. / Abstract / Acknowledgement --- p.Page no / Chapter Chapter 1. --- Introduction / Chapter 1.1 --- Metal silicides --- p.1 / Chapter 1.2 --- Cobalt silicides --- p.3 / Chapter 1.3 --- Ion beam synthesis of metal silicides by metal implantation into silicon --- p.4 / Chapter 1.4 --- Feature of MEVVA implantation --- p.5 / Chapter 1.5 --- Motivation and organisation of this thesis --- p.6 / Chapter Chapter 2. --- Sample Preparation and Characterisation Methods / Chapter 2.1 --- MEVVA implantation --- p.7 / Chapter 2.2 --- Simulation by TRIM --- p.9 / Chapter 2.3 --- Sample preparation --- p.12 / Chapter 2.4 --- Sheet resistivity measurements --- p.14 / Chapter 2.5 --- Rutherford backscattering spectroscopy (RBS) --- p.17 / Chapter 2.6 --- Transmission electron microscopy (TEM) --- p.19 / Chapter 2.6.1 --- Transmission electron microscopy (TEM) sample preparation --- p.21 / Chapter 2.7 --- Atom force microscopy (AFM) and conducting AFM --- p.31 / Chapter Chapter 3. --- Characterisation of As-implanted Samples / Chapter 3.1 --- Experimental details / Chapter 3.1.1 --- Sheet resistance measurements --- p.33 / Chapter 3.1.2 --- Rutherford backscattering spectroscopy (RES) --- p.36 / Chapter 3.1.3 --- Sputtering depth measurements --- p.43 / Chapter 3.1.4 --- Transmission electron microscopy (TEM) --- p.44 / Chapter 3.1.5 --- Spreading resistance profiling (SRP) --- p.61 / Chapter 3.1.6 --- Atom force microscopy (AFM) and conducting AFM --- p.64 / Chapter 3.2 --- Results and discussion --- p.71 / Chapter 3.3 --- Summary --- p.81 / Chapter Chapter 4. --- Characterisation of Annealed Samples / Chapter 4.1 --- Experimental details / Chapter 4.1.1 --- Rutherford backscattering spectroscopy (RBS) --- p.82 / Chapter 4.1.2 --- Transmission electron microscopy (TEM) --- p.87 / Chapter 4.1.3 --- Sheet resistance measurements --- p.98 / Chapter 4.2 --- Summary --- p.101 / Chapter Chapter 5. --- Conclusion --- p.102 / Appendix / Reference

by Lee, Chun-Sing. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (leaves 98-105). / Abstracts in English and Chinese. / Acknowledgements --- p.2 / Abstract --- p.3 / Table of Contents --- p.7 / List of Figures --- p.10 / List of Tables --- p.13 / Chapter Chapter 1 --- Introduction --- p.14 / Chapter 1.1. --- Ion implantation --- p.14 / Chapter 1.2. --- Scope of the thesis --- p.15 / Chapter Chapter 2 --- Background Theory --- p.17 / Chapter 2.1. --- Ion stopping --- p.17 / Chapter 2.2. --- The energy-loss process --- p.17 / Chapter 2.3. --- Kinematics of binary elastic collision --- p.20 / Chapter 2.4. --- Nuclear and electronic stopping --- p.21 / Chapter 2.5. --- Radiation Damage --- p.22 / Chapter 2.6. --- Spikes --- p.24 / Chapter 2.7. --- Topography of ion bombarded surface --- p.26 / Chapter Chapter 3 --- Equipment Reviews --- p.31 / Chapter 3.1. --- Metal Vapour Vacuum Arc Ion Source Implanter --- p.31 / Chapter 3.2. --- Atomic Force Microscopy --- p.34 / Chapter 3.3. --- Rutherford Backscattering Spectrometry --- p.37 / Chapter 3.4. --- X-ray Diffraction --- p.40 / Chapter Chapter 4 --- Study of Ion Beam Implanted Germanium by Atomic Force Microscopy and Rutherford Backscattering Spectrometry --- p.43 / Chapter 4.1. --- Introduction --- p.43 / Chapter 4.2. --- Experiments --- p.45 / Chapter 4.3. --- Results and discussion --- p.47 / Chapter 4.3.1. --- AFM --- p.47 / Chapter 4.3.2. --- RBS and ion channeling --- p.64 / Chapter 4.4. --- Conclusions --- p.71 / Chapter Chapter 5 --- Ion Beam Synthesised Cobalt Germanide Alloy by Metal Vapour Vacuum Arc Implantation --- p.73 / Chapter 5.1. --- Introduction --- p.73 / Chapter 5.2. --- Experiments --- p.74 / Chapter 5.3. --- Results and discussion --- p.74 / Chapter 5.3.1. --- XRD --- p.74 / Chapter 5.3.2. --- AFM --- p.78 / Chapter 5.3.3. --- RBS and ion channeling --- p.82 / Chapter 5.4. --- Conclusions --- p.87 / Chapter Chapter 6 --- Tip Artifacts in Atomic Force Microscope Imaging of Ion Bombarded Nanostructures on Germanium Surfaces --- p.89 / Chapter 6.1. --- Introduction --- p.89 / Chapter 6.2. --- Experiments --- p.90 / Chapter 6.3. --- Results and discussion --- p.90 / Chapter 6.4. --- Conclusions --- p.95 / Chapter Chapter 7 --- Conclusions --- p.96 / Bibliography --- p.98 / Publications --- p.105