Transmission Fourier transform infrared spectroscopy has been used to identify gas-phase and surface-bound products and intermediates formed during the gas-phase photooxidation of trichloroethylene (TCE) on TiO2 and ZnO. Several factors are found to influence the gas-phase product distribution for this reaction. On clean TiO2 and ZnO surfaces and at high TCE and O2 pressures, gas-phase CO, CO2, COCl2, CCl2HCOCl, CHCl3, C2HCl5, and HCl are produced, whereas at low TCE and O2 pressures, TCE is converted to gas-phase CO and CO2 only. In addition to TCE and O2 pressure, the product distribution of the photooxidation of TCE is strongly dependent upon the coverage of adsorbed species on the surface of the photocatalyst. It is shown here that the complete oxidation of adsorbed TCE can occur on clean photocatalytic surfaces whereas only partial oxidation of adsorbed TCE occurs on adsorbate-covered surfaces. The role of adsorbed surface products in TCE photooxidation is discussed.

Radicals produced by the hot wire-induced decomposition of silane have been identified using vacuum ultraviolet single photon ionization (SPI). This laser-based technique uses 118 nm photons (10.5 eV) to ionize gas phase species; the resulting photoions are detected using time-of-flight mass spectrometry. The major silicon-containing gas-phase species identified by SPI during hot-wire activation of silane gas are Si, SiH3, and Si2H6. These results demonstrate that single photon ionization can be a powerful probe for in situ, real-time detection of multiple species in hot wire chemical vapor deposition.

A vacuum ultraviolet single photon ionization technique has been used to probe gas-phase species important in the hot wire chemical vapor deposition (HW-CVD) of amorphous silicon carbide(a-SiC:H) films using different single-source precursors. This study focuses on monomethylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, and 1,1-dimethyl-1-silacyclobutane, and the reactions of these precursors on tungsten and rhenium filaments between 1000 and 1950°C. Silane is also considered for comparison. Si radicals are found to be major products of hot wire decomposition for all the organosilicon precursors; CH3 is also observed. C and H radicals are expected to be produced as well but are not detected at the ionization energy used in these experiments. Within the series of methylsilanes, the reaction rate on the filament is found to decrease with increasing number of methyl groups on the precursor. We propose a model in which Si–H bonds are cleaved with lower activation barriers than Si–CH3 bonds as the molecule adsorbs onto the hot metal surface. 1,1-dimethyl-1-silacyclobutane produces Si with a lower apparent activation energy than the other molecules. Coverage-dependent reaction pathways are proposed to play a role in the temperature profile of CH3 generation. Infrared spectra of films deposited by HW-CVD show that the film composition and growth rate for the different precursors correlate with the hot wire chemistry studied by single photon ionization.

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