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Title page for ETD etd-02012010-124544

Type of Document Dissertation
Author Schmidt, Benjamin W
Author's Email Address ben.schmidt11@gmail.com
URN etd-02012010-124544
Title Fabrication and Characterization of Metal Oxycarbide Thin Films
Degree PhD
Department Chemical Engineering
Advisory Committee
Advisor Name Title
Professor Bridget R. Rogers Committee Chair
Professor G. Kane Jennings Committee Member
Professor Kenneth A. Debelak Committee Member
Professor M. Douglas LeVan Committee Member
Professor Timothy P. Hanusa Committee Member
  • x-ray photoelectron spectroscopy
  • precursor
  • hafnium oxide
  • aluminum oxide
  • chemical vapor deposition
Date of Defense 2009-12-17
Availability unrestricted
Ceramic materials in the Al-O-C and Hf-O-C systems were fabricated for electrical or thermal protection applications. AlOxCy films were produced via high-vacuum chemical vapor deposition (CVD) using dimethylaluminum isopropoxide as the precursor. The deposition process was investigated from nucleation to bulk film growth stages. In the reaction-limited regime, the activation energy of the deposition process was 113 or 74 kJ/mol depending on the deposition temperature range. Electron spectroscopy techniques were used to characterize chemical compositions and elemental bonding environments within deposited films. Carbon content within films increased with increased deposition temperature. Aluminum-carbon bonding was observed in films deposited at temperatures of 538 °C and higher. Studies showed that films containing Al-C bonds exhibited dielectric constants approximately one order of magnitude smaller than a film without Al-C bonds.

Cyclopentadienyl (Cp) hafnium compounds were investigated as precursors to HfOxCy films. Bis(Cp)n-butyl hafnium and bis(methyl-Cp)dimethyl hafnium were dismissed as CVD precursors due to thermal instability and cost of synthesis, respectively. Films were produced from bis(Cp)dimethyl hafnium and bis(methyl-Cp)dimethyl hafnium through liquid phase casting methods and annealed under high vacuum. Analysis of chemical bonding in the films revealed oxidation of hafnium atoms even though precursor compounds did not contain oxygen atoms. Oxygen in the films was attributed to atmospheric exposure.

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