Thesis (Ph. D.)--University of Washington, 1999. / Vita. Includes bibliographical references (leaves 160-172).

Thesis (M.A.)-- Brigham Young University. Dept. of Art.

Thesis (M. D. S.)--University of Hong Kong, 2002. / Also available in print.

Thesis (M.D.S.)--University of Hong Kong, 2002.

The etching of silicon by atomic and molecular chlorine and bromine was studied as a function of etchant pressure and reaction temperature. Various types of silicon were employed in the etching experiments including intrinsic and n-type polycrystalline silicon as well as the (100) face of intrinsic single crystal silicon. The pressures of Cl₂ and Br₂ varied from 0.1 to 30 Torr and the partial pressure of Cl and Br atoms was between 0.08 and 0.2 Torr. Temperatures of between 365 and 600°C were required for CI₂ and Br₂ etching, while lower temperatures of 25 to 470°C were sufficient for the more reactive Cl and Br atoms. The reaction between silicon and Br atoms was shown to be first order with respect to the partial pressure of atoms and a first order dependence was assumed for Cl atom etching. The rate constants were determined for the Cl and Br atom etching of intrinsic and n-type polycrystalline silicon, with a dopant concentration of 5x10¹⁸ atoms cm⁻³. The reactivity of Cl atoms with n-type silicon was approximately 90 times greater than with intrinsic silicon. This enhancement in reaction rate is primarily due to an increase in the preexponential factor in k₁, with the activation enthalpy for the process remaining unchanged at approximately 28 kJ mol⁻¹. For Br atom etching, the reaction rate for the n-type silicon was over 300 times greater than for intrinsic silicon and was characterized by activation enthalpies of 55 and 63 kJ mol⁻¹ respectively. The enhancement in reactivity can also be attributed principally to an increase in the preexponential factor. The preexponential factors for the rate constants are larger than those expected, based on the collision frequencies of Cl and Br atoms. This is interpreted as evidence for a preadsorption step in these reactions. The reactions of silicon with CI₂ and Br₂ were found to display a complex pressure dependence. The etch rates varied linearly with (etchant pressure)¹′² and the intercepts from a linear regression of the data were slightly negative. To account for the half order pressure dependencies observed in these etching reactions, a reversible dissociative adsorption mechanism is proposed whereby Br₂ (or CI₂) is dissociatively adsorbed, in a reversible reaction, onto the silicon surface yielding two atoms bound to the surface. This step is then followed by a first order reaction leading to the formation of a species which is either gaseous product or some precursor which forms that product in a subsequent non rate-determining step. From the slopes of etch rate versus (pressure)¹′² plots, composite half order rate constants were calculated and from the intercepts it was possible to evaluate the rate constant for dissociative adsorption of the halogen molecules. At high etchant pressures, where the reaction was half order with respect to Br₂ (or CI₂), a half order "composite" rate constant characterized the etching reaction. Values for the half order rate constant were determined for a number of wafers at various temperatures. From the temperature dependencies of these rate constants, activation enthalpies of 131±8 and 116±7 kJ mol⁻¹ were calculated for Br₂ and CI₂ etching of intrinsic polycrystalline silicon respectively. A value of 121±7 kJ mol⁻¹ was deterrnined for the Br₂ etching of silicon (100). Higher reaction rates were observed for the etching of n-type polycrystalline silicon, with greater enhancements observed for Br₂ relative to Cl₂ etching. The enhancements in etch rates were found to be principally due to a lower activation enthalpy for the half order rate constant. An activation enthalpy for the composite rate constant of 82±3 kJ mol⁻¹ was determined for Cl₂ etching of n-type silicon with a dopant atom concentration of 5x10¹⁸ atoms cm⁻³. Br₂ etching of the same wafer yielded an activation enthalpy of 86±3 kJ mol⁻¹. At low pressures, the reaction becomes first order and the temperature dependence of the corresponding first order rate constant yielded activation enthalpies of 109 and 83 kJ mol⁻¹ for intrinsic and n-type polycrystalline silicon. / Science, Faculty of / Chemistry, Department of / Graduate

In this dissertation, I present the mechanism of graphene hydrogenation via three different electron sources: scanning electron microscopy, e-beam irradiation and H2 and He plasma irradiation. in each case, hydrogenation occurs due to electron impact fragmentation of adsorbed water vapor from the sample preparation process. in the proposed model, secondary and backscattered electrons generated from incident electron interactions with the underlying silicon substrate are responsible for the dissociation of water vapor. Chemisorbed H species from the dissociation are responsible for converting graphene into hydrogenated graphene, graphane. These results may lead to higher quality graphane films having a larger band gap than currently reported. in addition, the dissertation presents a novel and scalable method of controllably removing single atomic planes from multi-layer graphene using electron irradiation from an intense He plasma under a positive sample bias. As the electronic properties or multi-layer graphene are highly dependent on the number of layers, n, reducing n in certain regions has many benefits. for example, a mask in conjunction with this thinning method could be used for device applications.

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ABSTRACT DEVELOPMENT OF A MICRO-FABRICATION PROCESS SIMULATOR FOR MICRO-ELECTRO-MECHANICAL SYSTEMS (MEMS) Yildirim, Alper M.S, Department of Mechanical Engineering Supervisor: Asst. Prof. Dr. Melik D&ouml / len December 2005, 140 pages The aim of this study is to devise a computer simulation tool, which will speed-up the design of Micro-Electro-Mechanical Systems by providing the results of the micro-fabrication processes in advance. Anisotropic etching along with isotropic etching of silicon wafers are to be simulated in this environment. Similarly, additive processes like doping and material deposition could be simulated by means of a Cellular Automata based algorithm along with the use of OpenGL library functions. Equipped with an integrated mask design editor, complex mask patterns can be created by the software and the results are displayed by the Cellular Automata cells based on their spatial location and plane. The resultant etched shapes are in agreement with the experimental results both qualitatively and quantitatively. Keywords: Wet Etching, Anisotropic Etching, Doping, Cellular Automata, Micro-fabrication simulation, Material Deposition, Isotropic Etching, Dry Etching, Deep Reactive Ion Etching

The formation of microstructural alterations in bearing steels under rolling contact fatigue (RCF) is systematically studied. A literature review summarizes current understanding in this field, leading to the key to the formation of these microstructural features being carbon redistribution as a consequence of cyclic rolling contact. In this context, a novel theory is postulated to describe the migration of carbon caused by gliding dislocations. The theory combines the Cottrell atmosphere theory with the Orowan equation and is capable of quantifying the dislocation-assisted carbon flux. Based on the proposed theory, models are suggested for different types of microstructural alterations formed in rolling contact fatigued bearings – dark etching regions (DERs), white etching bands (WEBs) and white etching areas (WEAs). Very good agreement is obtained between the predications made by the models and the experimental data from both this research and the literature. Moreover, the models consider the effects of contact pressure, temperature, rotational speed and number of cycles, and thus can be applied for universal RCF testing conditions. The reproduced microstructural features are also characterized using advanced characterization techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atom probe tomography (APT), with the observation validating the postulated formation mechanisms. It is demonstrated that DERs, WEBs and WEAs follow the same principle during formation – strain induced carbon redistribution. This is the first time that these microstructural alterations are quantitatively described using a unified theory. The achievements obtained from this research can be far reaching. It not only leads to great progress in understanding the phenomenology of RCF in bearing steels, but also can be further extended to other scenarios with similar phenomena such as severe plastic deformation and hydrogen embrittlement.

published_or_final_version / Dentistry / Master / Master of Dental Surgery