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The research presented in this dissertation examines the oxidation of semiconductor and semimetal surfaces using a novel, one-of-a-kind instrument that combines a supersonic molecular beam with an in-line scanning tunneling microscope (STM) in ultra-high vacuum. This new approach to surface reaction dynamics provides spatio-temporal information on surface oxidation over nanoscopic and mesoscopic length scales. We have uncovered the kinetic and morphological effects of oxidation conditions on three technologically relevant surfaces: Si(111)-7×7, highly oriented pyrolytic graphite (HOPG), and GaAs(110). A complete understanding of the oxidation mechanism of these surfaces is critical due to their technological applications and roles as model systems. Samples were exposed to O2 with kinetic energies from 0.4-1.2 eV and impingement angles 0-45° from normal, with STM characterization between exposures. In some cases, we were able to monitor the evolution of specific features by revisiting the same nanoscopic locations. Our study of Si(111)-7×7 revealed two oxidation channels, leading to the formation of dark and bright reacted sites. The dark sites dominated the surface and exhibited almost no site selectivity while the bright sites preferred the corner sites of the 7×7 unit cell. Our observations suggest that two adsorption pathways, trapping-mediated and direct chemisorption, occur simultaneously. On HOPG, we found that different oxygen energies, incident angles, and surface temperatures produce morphologically distinct etching features: Anisotropic channels, circular pits, and hexagonal pits. Reaction probability increased with beam energy and demonstrated non-Arrhenius behavior with respect to surface temperature, peaking at around 1375 K. Finally, oxidation of GaAs(110) was found to proceed by two morphologically distinct, competing mechanisms: a homogeneous process leading to layer-by-layer oxide growth, and a heterogeneous process with oxide islands nucleating from surface defects. The rates of both mechanisms change with O2 kinetic energy, with homogeneous oxidation dominating at lower energies (<0.7 eV) and heterogeneous oxidation with higher energies (>1.0 eV). In all three cases multiple oxidation mechanisms existed simultaneously on the surface, which could only be distinguished with exacting control over reaction conditions and high spatial resolution. The results obtained in this work provide vital information about the morphological evolution and kinetics of semiconductor and semimetals, offering a comprehensive overview of the spatio-temporal correlations that govern oxidation dynamics on surfaces.


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