Photochemistry of silicon compounds.  6.  The 147-nm photolysis of tetramethylsilane

Gammie, L.; Sándorfy, C.; Strausz, O. P.

doi:10.1021/j100487a004

Cited by 17 publications

(6 citation statements)

References 21 publications

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“…These experiments are performed without discharge and using the VUV light source. Because of the low dissociation yield, due to the low VUV photon flux of the lamp, these experiments are usually performed at high pressure, typically 2 × 10 4 Pa. − However, because of their high reactivity, some of the radicals produced in the photolysis quickly recombine and only stable radicals and recombined molecules can be detected at high pressure. Reactive radicals produced by the photolysis can only be detected by mass spectrometry at low pressure, when HMDSO is largely diluted in argon.…”

Section: Photolysis Of Hmdsomentioning

confidence: 99%

Comparison of Hexamethyldisiloxane Dissociation Processes in Plasma

Jauberteau

2012

J. Phys. Chem. A

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Different hexamethyldisiloxane (HMDSO) dissociation processes are investigated by means of absorption spectroscopy and mass spectrometry. All of these processes are expected to occur in plasma containing Ar-HMDSO gas mixture. We successively study interactions of the HMDSO molecule with electrons (energy ranges from 15 to 70 eV), with Ar((3)P(2)) metastable species (internal energy 11.55 eV) and with VUV photon (7.3 to 10.79 eV). The studies of HMDSO interactions with Ar((3)P(2)) and VUV photon provide new results concerning the dissociation pathways and the collision cross-sections. In the case of Ar((3)P(2)), the dissociation mechanisms result mainly in Si-C or Si-O bond breaking, producing SiMe(2,1) radicals. Less efficient mechanisms involve also Si-C and Si-O bond breaking producing Me, Si(2)Me(5)O, or SiMe(3), on one hand, and, on the other hand, Si-C and C-H bond breaking producing Si(2)Me(4)OH. In the case of photon interaction, the dissociation process is more selective and mainly produces Si(2)OMe(5) pentadisiloxane and methyl radicals due to Si-C bond breaking. Si-O bond breaking produces also SiMe(3) in a lower concentration. Dissociation cross-section values of HMDSO ranging from σ = 45 × 10(-20) m(2) to 180 × 10(-20) m(2) and from σ = 0.7 × 10(-22) m(2) to 18.3 × 10(-22) m(2), correspond to a global dissociation mechanism by Ar((3)P(2)) collision and to a selective dissociation mechanism (producing Si(2)OMe(5) and Me) by VUV photon interaction, respectively. All results are compared and discussed.

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Section: Photolysis Of Hmdsomentioning

confidence: 99%

Comparison of Hexamethyldisiloxane Dissociation Processes in Plasma

Jauberteau

2012

J. Phys. Chem. A

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“…The system studied by Tokach and Koob, viz., the vacuum-UV photolysis of Me4Si, is considerably more mechanistically complex than their interpretation suggests. 52,53 Chemically activated methylsilanes formed by } 2 insertion reactions have been studied by Simons, Hase, and co-workers. 54 The decomposition processes of these hot silanes are in need of reinterpretation in the light of increased Si-C bond strengths.…”

Section: Some Applicationsmentioning

confidence: 99%

Bond dissociation energy values in silicon-containing compounds and some of their implications

Walsh¹

1981

Acc. Chem. Res.

829

420

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“…This process was found as a very minor in the 147-nm photolysis of TMS in the gas phase, whereas the abstraction of the methyl groups appeared to be a major photochemical reaction. 27 Moreover, mechanistic consideration of the activation of TMS in the PCVD reported by Rynders et al,28 accounts for cleavage of the Si-C bonds as a predominant process. Although atomic hydrogen has been detected in the TMS plasma by the optical emission spectroscopy,29 we assume it originates mainly from a number of secondary plasma reactions rather than from the primary reaction involved in the electron impact.…”

Section: Resultsmentioning

confidence: 99%