To understand how the substrate temperature influences the deposition rate and spatial profile of deposits formed using laser chemical vapor deposition (LCVD), spatially resolved multi-wavelength pyrometry measurements of the substrate temperature have been made during LCVD of titanium nitride (TiN) on Ti-6Al-4V substrates. The precursors that have been used are TiCl$sb4,$ N$sb2,$ and H$sb2.$ Also, deposition has been studied as a function of the N$sb2$:H$sb2$ gas ratio, the TiCl$sb4$ partial pressure, the total chamber pressure, and the laser power. Also, film thickness has been measured by stylus profilometry, and film composition and microstructure have been determined by Scanning Electron Microscopy (SEM), Auger Electron Spectroscopy (AES), and X-ray Photoelectron Spectroscopy (XPS). While the substrate temperature and the gas composition have the greatest influence on TiN film growth, H$sb2$ exerts the greatest influence on TiN film growth. Also, enhanced mass transport associated with localized laser beam heating has led to film growth rates on the order of 1 $mu$m/sec; however, there is still evidence of reactant depletion at the center of the laser heated spot. In addition to calculating film growth rates based on film height, two new methods of characterizing the film growth rate have been developed. Using these growth rates, three insights have been obtained. First, the film growth rates are 1-1/2 orders of magnitude greater than typical CVD deposition rates. Second, radial growth of the films continues after reactant depletion occurs at the center of the deposit. Third, comparison of the growth rates with LIF measurements supports the concept of a temperature-dependent sticking coefficient. Based on the experiments, reaction rate equations have been postulated as a function of N$sb2$/H$sb2$ gas ratio and TiCl$sb4$ partial pressure. Also, the apparent activation energy for deposition is 108.9 kJ/mol when one calculates the deposition rate based on film height. Using alternate definitions of film growth rates, the apparent activation energies are 65.2 and 81.4 kl/mol. The discrepancy in these activation energies has occurred because part of the measured film volume is actually TiCl$sb4$ rather than TiN.

Thin titanium dioxide films were produced by metalorganic chemical vapor deposition on sapphire(0001) in an ultrahigh vacuum (UHV) chamber. A method was developed for producing controlled submonolayer depositions from titanium isopropoxide precursor. Film thickness ranged from 0.1 to 2.7 nm. In situ X-ray photoelectron spectroscopy (XPS) was used to determine film stoichiometry with increasing thickness. The effect of isothermal annealing on desorption was evaluated. Photoelectron peak shapes and positions from the initial monolayers were analyzed for evidence of interface reaction. Deposition from titanium isopropoxide is divided into two regimes: depositions below and above the pyrolysis temperature. This temperature was determined to be 300 deg C. Controlled submonolayers of titanium oxide were produced by cycles of dosing with titanium isopropoxide vapor below and annealing above 300 deg C. Precursor adsorption below the pyrolysis temperature was observed to saturate after 15 minutes of dosing. The quantity absorbed was shown to have an upper limit of one monolayer. The stoichiometry of thin films grown by the cycling method were determined to be TiO2. Titanium dioxide film stoichiometry was unaffected by isothermal annealing at 700 deg C. Annealing produced a decrease in film thickness. This was explained as due to desorption. Desorption ceased at approximately 2.5 to 3 monolayers, suggesting bonding of the initial monolayers of film to sapphire is stronger than to itself. Evidence of sapphire reduction at the interface by the depositions was not observed. The XPS O is peak shifted with increased film thickness. The shifts were consistent with oxygen in sapphire and titanium dioxide having different O is photoelectron peak positions. Simulations showed the total shifts for thin films ranging in thickness of 0.1 to 2.7 nm to be -0.99 to -1.23 eV. Thick films were produced for comparison.