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Williams, W.S. Kaloyeros, Alain Elie 2011-06-20T15:39:36Z 2011-06-20T15:39:36Z 10000-01-01 1987 Amorphous hydrogenated titanium carbide films (a-TiC :H , X y 0.88<x<0.95 and O.OS<y<0.12) were successfully prepared by low-temperature (150-300°C) and low-pressure (<10-S torr) metallorganic chemical vapor deposition (MOCVD) of the organometallic compound tetraneopentyl-titanium. X-ray and electron diffraction studies confirmed the amorphicity of the coatings, while controlled-heating experiments emphasized their stability against crystallization to higher temperatures (-1100°C) than typical glassy metals. Analyses of the coatings by Auger electron spectroscopy (AES), electron energy-loss spectroscopy (EELS), and x-ray photoelectron spectroscopy (XPS) led to an understanding of the film morphology and microchemistry, and to a quantitation of H concentrations in the coatings. This work necessitated, in a preliminary stage, performing MOCVD of the Ti-coordination compound titanium-bipyridine and completing the characterization studies started by Morancho and Constant on the corresponding deposited films. Other amorphous titanium carbide films (a-TiC), with X 0.91<x<0.93, were produced by electron beam evaporation (EBV) and were analyzed with various spectroscopies. EBV thus provided single phase a-TiC films to compare to TiC :H The X X y purpose was to investigate the local structure in both types of films and to confirm the critical role of hydrogen in the formation and stability of the amorphous structure obtained by MOCVD. A major investigative tool in this structural determination was the analysis of the extended fine structure above the Ti x-ray K-edge, the Ti energy-loss L 2 , 3 -edges and C energy-loss K-edge, using extended x-ray absorption fine structure (EXAFS), and extended energy-loss fine structure (EXELFS). The thesis presents a detailed description of the physical mechanism associated with EXAFS and EXELFS, a simple theoretical derivation of the EXAFS expression, a comparison of EXAFS and EXELFS, and a discussion of their suitability to structural investigations. Details of the first application of the combination EXAFS-EXELFS to perform structural studies on amorphous a-TiC and a-TiC :H films are then presented. This study yielded information on the dynamic and static disorder, local arrangement of both C and Ti atoms, location of hydrogen and its effect on the short-range order (SRO) in the films. Finally, a theoretical model, based on the Nagel-Tauc rule and Harrison formulation, is proposed to explain the stability of the amorphous phase. XPS valence band measurements confirmed the predictions of these theoretical calculations, and showed a transfer of charge from Ti to H in a-TiCx:Hy. Submitted by Carolyn Mead (cmead2@illinois.edu) on 2011-06-20T15:39:36Z No. of bitstreams: 1 1987_kaloyeros.pdf: 8482035 bytes, checksum: 380d7ef6cad74856f4bd6e17e3b22e14 (MD5) Made available in DSpace on 2011-06-20T15:39:36Z (GMT). No. of bitstreams: 1 1987_kaloyeros.pdf: 8482035 bytes, checksum: 380d7ef6cad74856f4bd6e17e3b22e14 (MD5) Previous issue date: 1987 Restriction data tranferred 2014-07-01T11:15:46-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: Thesis Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Carolyn Mead (cmead2@illinois.edu) on 2011-06-20T15:39:36Z Item is restricted indefinitely. Thesis U of I Only 1322697 http://hdl.handle.net/2142/25456 en 1987 Alain Elie Kaloyeros amorphous hydrogenated titanium carbide films hydrogen doping metallorganic chemical vapor deposition tetraneopentyl-titanium A study of amorphous hydrogenated titanium carbide films: Structure, stability, and role of hydrogen doping Dissertation / Thesis text Physics Physics University of Illinois at Urbana-Champaign Dissertation Ph.D.