A CHARACTERIZATION OF THE OXIDATION-REDUCTION CYCLE AND SURFACE MORPHOLOGY OF ELECTROCHEMICAL SURFACE ENHANCED RAMAN SCATTERING
AuthorTuschel, David Daniel, 1957-
Raman effect, Surface enhanced.
MetadataShow full item record
PublisherThe University of Arizona.
RightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Degree ProgramGraduate College
Degree GrantorUniversity of Arizona
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Surface Pretreatment for Thin Film Surface ReactivityThorsness, Adam G.; Muscat, Anthony; Muscat, Anthony; Sáez, A. Eduardo; Blowers, Paul (The University of Arizona., 2006)The formation of a self-limiting interface layer for the integration of high-k dielectric materials into silicon based transistor devices was investigated. Chlorine atoms were used to activate a liquid cleaned Si(100) surface for the reaction with H₂O(g). A saturation coverage of 0.8 monolayers of chlorine atoms was deposited on a hydrogen terminated Si(100) surface by exposure to Cl₂ gas at 10 Torr under ultraviolet illumination at 300 K. The self-limiting interface layer was formed by exposing the chlorine terminated surface to water vapor at P(HOH)=100 Torr and temperatures ranging from 325 to 373 K. The coverage of oxygen resulting from H₂O exposures was directly correlated with a decrease in the Cl coverage and ranged from 0.2-1.2 monolayers. Complete removal of surface chlorine was achieved by 100°C water exposures in 45 minutes. The final chapter summarizes three papers published which describe the moisture absorption into borophosphosilicate glass (BPSG) films and an investigation of a gas phase etching process applied to borosilicate glass (BSG), phosphosilicate glass (PSG), and BPSG films. The absorption and reaction of water with doped and undoped oxides as well as the effect of annealing was investigated using a variety of annealed BPSG films. Asdeposited (AD) and annealed (500, 750, and 900°C) borophosphosilicate glass (BPSG) films were characterized during aging, baking, and etching using transmission Fourier transform infrared spectroscopy and ellipsometry. The water content in the BPSG films increased steadily during storage at ambient conditions. The B-O bond was shown to be the primary site for water adsorption on the surface of the film. Water absorption into the film was consistent with a reaction-limited model. It is likely that the water present reacted readily with P=O groups forming P-O and PO-H. This slower reaction with P=O species is proposed as the rate-limiting step for water absorption. The etching of BPSG with gas phase HF produced a low volatility residue consisting of a mixture of boric acid B(OH)₃, phosphoric acid H₃PO₄, and water. Partial removal of the residue was accomplished using both direct and indirect UV–Cl₂ processes.
The development of a mass spectrometry-based technique that uses low energy ion-surface collisions to characterize surfacesWysocki, Vicki H.; Angelico, Vincent James (The University of Arizona., 2002)Low energy (tens of eV) ion-surface collisions carried out in a tandem mass spectrometer are investigated as a tool to characterize self-assembled monolayer (SAM) films. The target films are prepared by spontaneous chemisorption of thiol-based (HS-R) compounds onto Au (111) substrates. Most of the films used as targets contain alkane or fluoro-alkane backbones, some with unique groups in the terminal position (e.g., -CD₃, -OH, -OC(O)CF₃). Pyrazine is the most frequently used probe ion, however in certain cases other small organic molecules are also used. Common interactions between the impinging ion and the target film that vary as a function of film characteristics include, but are not limited to, reactive scattering, neutralization and T → V conversion. Pyrazine ion readily reacts when colliding with hydrocarbon films at 20-eV, forming product ions that incorporate a hydrogen atom or a methyl group. Several examples of the utility of these processes to characterize film properties are presented. For hydrocarbon films, ion-surface reactions of pyrazine ion resulting in addition of a hydrogen atom or a methyl group are shown to vary with the quality, chemical composition and orientation of the target film. Experiments with isotopically labeled films show that the ion beam interacts predominantly with the end groups of the film, however interactions with underlying groups increase as the film or substrate quality decreases. The orientation difference of odd and even chain length n-alkanethiols produces a measurably different degree of hydrogen addition with the higher free energy odd chain length orientation being more reactive. The composition of mixed component films (H, D or H, F) is tracked by measuring the abundance of unique reaction products, energy transfer (translational to vibrational conversion) and charge exchange properties. When mixed films containing deuterium labeled and unlabeled n-alkanethiols are subjected to collisions of 20-eV pyrazine ion, the D-addition ion abundance increases linearly with the surface concentration of D-containing alkane chains. When mixed films containing different ratios of H and F components are the target, several processes track with the changing population of surface species. As the target films become more fluorocarbon in nature H-addition decreases, total ion current reaching the detector increases, and dissociation increases. Several properties of electron transfer from the film to the ion are examined. When the probe ion and collision energy remain consant, charge exchange is shown to be primarily governed by the work function of the film and the thickness of the adsorbed layer. Fluorocarbon films, which have a higher work function than hydrocarbon films, consistently show less charge exchange. When comparing hydrocarbon films of varying chain lengths (ranging from 15 to 18 carbons), a increase of ∼1% in total ion current measured at the detector is observed for each additional methylene in the chain.