- Reaction of Hydrogen Peroxide with Organosilanes under Chemical Vapour Deposition Conditions
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When a stream of vapour at low pressure which contained a mixture of H2O2 with an organosilane, RSiH3 (R = alkyl or alkenyl), impinged on a silicon wafer, deposition of oxide films of nominal composition RxSiO(2-0.5x), where x 3 or higher alkenyl groups. or higher alkenylgroups. Possible mechanism for the Si-C bond cleavage reaction are discussed, with energetic rearrangement of radical intermediates of type Si(H)(R)(OOH)' being favoured.
- Moore, Darren L.,Taylor, Mark P.,Timms, Peter L.
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p. 2673 - 2678
(2007/10/03)
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- Kinetics and Mechanism of the Reactions of O(3P) with SiH4, CH3SiH3, (CH3)2SiH2, and (CH3)3SiH
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The reactions of O(3P) atoms with the silanes Me4-nSiHn (n = 1-4) have been investigated at room temperature in a discharge flow system with mass spectrometric detection and also in stationary photolysis experiments.Analysis of the end products provided conclusive evidence that the only primary process occuring in each case was the abstraction of hydrogen from the Si-H bond by the O atom leading to the formation of the OH and silyl radicals.The values of the rate constants obtained are k/10-13 cm3 s-1): k(O + SiH4) = 3.5, k(O + SiD4) = 1.4, k(O + MeSiH3) = 8.9; k(O + Me2SiH2) = 18.0, k(O + Me3SiH) = 30.6, and k(O + Me3SiD) = 16.0.The marked increase in rate constant with methylation is unexpected in view of the known similarity of the Si-H bond dissociation energy in SiH4 and the methylsilanes.A possible explanation is offered in terms of a reaction model involving partial charge transfer from Si to the attacking O, followed by proton transfer.
- Horie, O.,Taege, R.,Reimann, B.,Arthur, N. L.,Potzinger, P.
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p. 4393 - 4400
(2007/10/02)
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- Determination of the Molecular Structures of Bis(methylsilyl) Ether and Bis(dimethylsilyl) Ether in the Gas Phase by Electron Diffraction
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The molecular structures of the title compounds, O(SiH2Me)2 and O(SiHMe2)2, in the gas phase, have been determined by electron diffraction.The monomethylsilyl ether has at least two conformers, the major one (64percent) having the methyl groups twisted by 124(4) and 58(8) deg away from the positions in which the Si-C bonds are trans to O-Si bonds.Other important parameters (ra) are: r(Si-C) 186.4(3), r(Si-O) 164.2(3) pm; SiOSi 143.0(6) and OSiC 109.7(5) deg.In the dimethylsilyl ether the silyl groups are twisted by 101(8) and 41(4) deg away from the symmetrical position in which both Si-H bonds are cis to O-Si bonds, so that the dimethylsilyl groups are staggered with respect to each other.Principal parameters (ra) are: r(Si-C) 186.4(3), r(Si-O) 163.5(2) pm; SiOSi 148.4(9), OSiC 110.1(6), and CSiC 107.4(17) deg.
- Rankin, David W. H.,Robertson, Heather E.
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p. 265 - 270
(2007/10/02)
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- Studies of silyl and germyl Group VI species. Part IV. Dimethyl- and tetramethyl-disilyl chalcogenides and related species
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The symmetrically substituted disilyl chalcogenides (MenH3-nSi)2E where E = O, S, Se, Te; n = 0 -> 3, have been prepared and characterized spectroscopically and by cleavage reactions.The synthetic routes include reactions of halogenosilanes with water, mercury(II) sulfide, lithium telluride, and complex thio- and seleno-aluminates.The spectroscopic properties of the (MeH2Si)2E and (Me2HSi)2E species, which have not been reported previously, are discussed in some detail.
- Drake, John E.,Glavincevski, Boris M.,Hemmings, Raymond T.
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p. 2161 - 2166
(2007/10/02)
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