Thermal decomposition of di-tertiarybutyl selenide and dimethylzinc in a metalorganic vapour phase epitaxy reactor

• Published in: Journal of crystal growth 1997-01, Vol.170 (1-4), p.485-490
• Main Authors: Fan, G.H., Maung, N., Ng, T.L., Heelis, P.F., Williams, J.O., Wright, A.C., Foster, D.F., Cole-Hamilton, D.J.
• Format: Article
• Language: English
• Subjects: Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Materials science; Methods of deposition of films and coatings; film growth and epitaxy; Physics; Vapor phase epitaxy; growth from vapor phase
• ISSN: 0022-0248; 1873-5002
• DOI: 10.1016/S0022-0248(96)00539-8

The thermal decomposition of di-tertiarybutyl selenide (DtBSe), both alone and in the presence of dimethylzinc (DMZn), was investigated using “ex-situ” Fourier transform infrared (FTIR) absorption spectroscopy in a low-pressure metalorganic vapour phase epitaxy (LP-MOVPE) reactor. The decomposition of DtBSe alone, yields isobutene as the major product, with a much smaller proportion of isobutane detected. Pyrolysis of DMZn in dihydrogen in the presence of DtBSe is very similar to pyrolysis of DMZn alone in dihydrogen with methane the exclusive product. This indicates that co-pyrolysis of the DMZnDtBSe mixture occurs via radical attack by H on DMZn and largely independent pyrolysis of DtBSe via a β-hydrogen elimination reaction. Traces of the intermediate tertiarybutyl selenol (tBuSeH) were also detected. The small difference observed in the decomposition behaviour of the DtBSe-DMZn mixture in a dihydrogen compared to a helium ambient further indicate that the pyrolysis processes are independent. These conclusions are supported by PM3 semi-empirical molecular orbital calculations, which indicate that the most likely pathway for unimolecular dissociation of DtBSe is via β-hydrogen elimination with CSe bond homolysis only likely to be an effective competing mechanism at higher growth temperatures and reactor pressures.