Structural Chemistry and Raman Spectra of Niobium Oxides

The pyrolysis of TVSb has been investigated in a flow tube reactor using Dz and He carrier gases. For TVSb alone, the most likely pyrolysis reaction involves an Sbcentered reductive elimination pathway. A less likely possibility is pyrolysis via homolysis of the Sb-C bonds, yielding vinyl radicals. Unfortunately, examination of the organic byproducts in both He and D, yields insufficient information to form a definitive hypothesis. However, in He the pyrolysis rate for TVSb is more rapid than for TMSb. Since vinyl radicals form stronger bonds than methyl radicals, this datum contradicts the Sb-C bond homolysis mechanism. Again, the activation energy for pyrolysis is less than the expected Sb-vinyl bond strength. Finally, the addition of C7D, produces no CH,=CHD, indicative of the absence of vinyl radicals. To elucidate our understanding of GaSb growth by using TMGa and TVSb, the pyrolysis rates for this combination of reactants were also studied. CH, radicals from (CH3N), pyrolysis were found to enhance TVSb pyrolysis in He. TMGa also increases the TVSb pyrolysis rate, mainly due to the methyl radicals produced. A heterogeneous pyrolysis reaction appears a t high surface area. At V/III ratios normally used for OMVPE growth, carbonaceous deposits were formed. Thus, TVSb may be a useful precursor for OMVPE only a t V/III ratios less than unity.