title: Dominance of silylene chemistry in the decomposition of monomethylsilane in the presence of a heated metal filament.
abstract: The gas-phase reaction chemistry of the decomposition of monomethylsilane (MMS) has been studied in the presence of a heated metal filament in a hot-wire chemical vapor deposition (HWCVD) reactor. A 10.5 eV vacuum ultraviolet laser single-photon ionization time-of-flight mass spectrometry was employed in combination with isotope labeling and chemical trapping to examine the mechanistic details in the reaction chemistry. We have demonstrated the dominant involvement of the methylsilylene (HSiCH3) intermediate in the gas-phase reaction chemistry. Free radical and silene intermediates do not play a role. Major products are found to be H2, 1,2-dimethyldisilane (DMDS), and 1,3-disilacyclobutane (DSCB). The formation of DMDS proceeds by the insertion reaction of methylsilylene, whereas DSCB originates from the dimerization reaction of methylsilylene. Similar reaction chemistry has been observed when using the different filament materials of tungsten and tantalum in the HWCVD reactor. This indicates that changing the filament material from Ta to W does not affect the gas-phase reaction chemistry when using MMS in the HWCVD process. Finally, comparison of the reaction chemistry of MMS with those of dimethylsilane, trimethylsilane, and tetramethylsilane sheds light on the influence of increasing Si-H bonds. A switch in the dominated chemistry from free-radical short-chain reactions to silylene insertion/dimerization reactions occurs as the number of Si-H bonds increases in the four methyl-substituted silane molecules.
authors.affiliation: Department of Chemistry, University of Calgary , 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada.
authors.forename: R
authors.initials: R
authors.lastname: Toukabri
authors.forename: Y J
authors.initials: YJ
authors.lastname: Shi