Unraveling the complex chemistry using dimethylsilane as a precursor gas in hot wire chemical vapor deposition.

The gas-phase reaction chemistry when using dimethylsilane (DMS) as a source gas in a hot-wire chemical vapor deposition (CVD) process has been studied in this work. The complex chemistry is unraveled by using a soft 10.5 eV single photon ionization technique coupled with time-of-flight mass spectrometry in combination with the isotope labelling and chemical trapping methods. It has been demonstrated that both free-radical reactions and those involving silylene/silene intermediates are important. The reaction chemistry is characterized by the formation of 1,1,2,2-tetramethyldisilane (TMDS) from dimethylsilylene insertion into the Si-H bond of DMS, trimethylsilane (TriMS) from free-radical recombination, and 1,3-dimethyl-1,3-disilacyclobutane (DMDSCB) from the self dimerization of either dimethylsilylene or 1-methylsilene. At low filament temperatures and short reaction time, silylene chemistry dominates. The free-radical reactions become more important with increasing temperature and time. The same three products have been detected when using tantalum and tungsten filaments, indicating that changing the filament material from Ta to W does not affect much the gas-phase reaction chemistry when using DMS as a source gas in a hot-wire CVD reactor.

Decomposition of hexamethyldisilane on a hot tungsten filament and gas-phase reactions in a hot-wire chemical vapor deposition reactor.

To study the effect of an Si-Si bond on gas-phase reaction chemistry in the hot-wire chemical vapor deposition (HWCVD) process with a single source alkylsilane molecule, soft ionization with a vacuum ultraviolet wavelength of 118 nm was used with time-of-flight mass spectrometry to examine the products from the primary decomposition of hexamethyldisilane (HMDS) on a heated tungsten (W) filament and from secondary gas-phase reactions in a HWCVD reactor. It is found that both Si-Si and Si-C bonds break when HMDS decomposes on the W filament. The dominance of the breakage of Si-Si over Si-C bond has been demonstrated. In the reactor, the abstraction of methyl and H atom, respectively, from the abundant HMDS molecules by the dominant primary trimethylsilyl radicals produces tetramethylsilane (TMS) and trimethylsilane (TriMS). Along with TMS and TriMS, various other alkyl-substituted silanes (m/z = 160, 204, 262) and silyl-substituted alkanes (m/z = 218, 276, 290) are also formed from radical combination reactions. With HMDS, an increasing number of Si-Si bonds are found in the gas-phase reaction products aside from the Si-C bond which has been shown to be the major bond connection in the products when TMS is used in the same reactor. Three methyl-substituted 1,3-disilacyclobutane species (m/z = 116, 130, 144) are present in the reactor with HMDS, suggesting a more active involvement from the reactive silene intermediates.