DETECTION OF THE $SiH_{2}$ BY $(A^{1}B_{1}-X^{1}A_{1})$ TRANSITION IN THE EMISSION SPECTRUM OF THE RARIFIED FLAME OF THE OXIDATION OF SILANE

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1999

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Ohio State University

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This work is aimed at the detection of the active intermediates in the emission spectra of rarified flames of SiH4 and dichlorosilane oxidation. A blackbody radiation from the solid aerosol particles markedly complicates the detection of the visible emission bands in the flames of silanes. We have shown that the application of constant electrical field reduces the amount of aerosol formed during the ignition of silanes- oxygen mixtures as well as the addition of SF6a. The both ways were used for decreasing the intensity of blackbody radiation. The experiments have been carried out under static and flow conditions at 293 K and total pressures in the range of 0,6 to 10 Torr. We have observed the intensive emission bands at 580, 589, 613 nm in the spectrum of the rarified flame of SiH4+SF6+O2. These bands are due to the transitions 1B1(O,v1,O)−1A1(O,v1,O) of SiH2:(020)−(000),(030)−(010),(020−010) according to reported spectra of SiH3b obtained under discharge conditions from SiH4. The bands are also observed in the spectrum obtained under conditions of discharge (SiH4+O2) and yet are missing from the spectra of the oxidation of SiH2Cl2 in discharge as well as in the presence of SF6SiH2 reacts nearly with gas kinetic collision frequency with SiH4; the reaction of SiH4 with O2 proceeds also rapidly leading to electronically excited SiO. These are the basic reactions of SiH2 in SiH4 oxidation. The emission spectra in the region 425 - 530 nm of the rarified flames under static conditions appear at [SF6]>40% to total pressure for SiH4 oxidation and [SF6]>10% for SiH2Cl2 oxidation. The equidistant (∼1200cm−1) bands are common for the both reactions. This emission is caused by electronically excited H2SiO particles in accordance with theoretical calculationsc.

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a N.M. Rubtsov, V.I. Chernyah, G.I. Tsvetkov, Kinet. Catal. 38, 498, (1997) b I.Safarik, V. Sandhu, E.M. Lown et. al. Res.on Chem Intermed, 14, 105, (1990) c R.J. Glinski, J.L. Gole, D.A. Dixon.J.Am.Chem.Soc., 107, 5891, (1985)


Author Institution: Institute for Structural Macrokinetics RAS, Russia, Moscow region

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