Gas-phase photofragmentation of tris(methyl vinyl ketone) tungsten(0) and the relationship to laser-assisted CVD of tungsten oxide thin films.

The gas-phase laser-induced photofragmentation of tris(methyl vinyl ketone) tungsten(0) is studied, and the photoproducts are identified by time-of-flight mass spectroscopy. The initially populated excited electronic state of the complex is attributed to metal-to-ligand charge transfer by analysis of the electronic and preresonance Raman spectra. The major metal-containing photofragmentation products are W(+) and WO(+); smaller amounts of WC(+) and W(C(2)H(2))(+) are also observed. Intramolecular ligand coupling occurs, and dimeric products and their fragments are identified. Reaction pathways that explain the observed products are proposed. Thin films on silicon substrates are produced by laser-assisted chemical vapor deposition. The films consist of polycrystalline tungsten oxide with less than 10% tungsten carbide and are characterized by X-ray diffraction, SEM, and Auger electron spectroscopy. Relationships between the composition of the gas-phase photofragments and that of the solid films are discussed.