Dissociation of SiCl4 based on Cl- and Si-concentration measurements

Kunz, Andreas; Roth, P.

doi:10.1016/s0082-0784(98)80413-x

Cited by 14 publications

(8 citation statements)

References 15 publications

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“…The photoinitiated Cl-atom formation studied over a certain temperature range showed a clear temperature dependence. At those conditions the thermal decomposition of SiCl 4 is unimportant, , which agrees with our observation in cases where the laser was not fired. An ineffective, temperature-dependent, photolytical Cl-atom abstraction from SiCl 4 must be proposed.…”

Section: Discussionsupporting

confidence: 91%

“…Therefore, series of shock wave calibration experiments have been performed to relate the measured absorptions to the correspond-ing concentrations. Cl-atom calibration was based on the thermal decomposition of CH 3 Cl, , and SiCl 4 . Shock tube experiments were performed with mixtures of 0.1−5 ppm CH 3 Cl and 0.05−5 ppm SiCl 4 in Ar at temperatures above 3000 K and pressures around 1.5 bar.…”

Section: Methodsmentioning

confidence: 99%

“…The decomposition of SiCl 4 into SiCl 3 and Cl was recently investigated in our laboratory by indirect kinetic measurements in a SiCl 4 /H 2 /Ar system by Catoire et al A simplified mechanism of the thermal dissociation of SiCl 4 is given by Kunz and Roth, which is based on direct Si- and Cl-concentration measurements in highly diluted SiCl 4 /Ar mixtures. In the literature only theoretical considerations of SiCl 4 dissociation were found …”

Section: Introductionmentioning

confidence: 99%

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Laser Flash Photolysis of SiCl₄ at High Temperatures Based on Si- and Cl-Concentration Measurements

Kunz¹,

Roth²

1999

J. Phys. Chem. A

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Laser flash photolysis of SiCl4 at 193 nm was studied behind reflected shock waves at temperatures 1000 K ≤ T ≤ 2050 K and pressures between 1.4 and 1.8 bar. The atomic resonance absorption spectroscopy (ARAS) was applied for time-resolved measurements of Si- and Cl-atom concentrations in gas mixtures containing 10−100 ppm SiCl4 highly diluted in argon. The atoms formed during photolysis of SiCl4 were analyzed in terms of yields, defined as the fractions of the maximum atom concentration to the initial SiCl4 concentration behind the shock wave. At temperatures 1000 ≤ T ≤ 1510 K, Cl atoms were detected immediately after the laser flash. The Cl yield was found to be temperature dependent in the range between 0.1 and 2% of the initial SiCl4 concentration. Si atoms first occurred at temperatures T > 1750 K, when SiCl4 already has started to decompose. In contrast to Cl, the Si yield obtained correlates with both the temperature and the delay time between the shock-induced gas heating and the laser pulse. This effect was attributed to the photolysis of SiCl2, which is formed during the thermal decomposition of SiCl4. A reaction model including the thermal dissociation of SiCl4 and the photodissociation of SiCl2 is suggested and discussed, in which also reactions of Cl and Si atoms with SiCl4 are considered to describe the measured concentration profiles.

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Section: Discussionsupporting

confidence: 91%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Laser Flash Photolysis of SiCl₄ at High Temperatures Based on Si- and Cl-Concentration Measurements

Kunz¹,

Roth²

1999

J. Phys. Chem. A

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“…It is also important for silane oxidation by nitrous oxide [2,3] because the thermal decomposition of silane is faster than that of nitrous oxide and results in the release of molecular hydrogen [4]. Silane-nitrous oxide mixtures are widely used in the semi-conductor industry [5] in order to form insulator or protective layers [6,7,8,9] in a wide variety of applications [10,11,12]. These mixtures have been involved in some accidental combustion events [13].…”

Section: Introductionmentioning

confidence: 99%

Detonation in hydrogen–nitrous oxide–diluent mixtures: An experimental and numerical study

Mével

Davidenko

Lafosse

et al. 2015

Combustion and Flame

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“…The high temperatures used indicate that a large number of silicon-containing species may be involved, including silicon oxyhalides and compounds containing multiple silicon atoms. − In contrast with silane oxidation/combustion, which has been extensively studied, very little is known about the thermochemistry and kinetics of species involved in SiCl 4 oxidation. Thermodynamic data (heats of formation, entropies, and heat capacities) for silicon oxyhalides are almost totally unavailable; in the Si−O−Cl system of monomeric silicon compounds, only two oxychloride species have been characterized: ClSiO , and Cl 2 SiO. − Reaction rates relevant to SiCl 4 oxidation in the literature largely concern either qualitative observations or global reaction rates. ,− Several investigations of the pyrolysis of chlorinated silanes have recently appeared, − however, and reaction rates of SiCl 2 and SiCl 3 with molecular oxygen have been reported. The overall lack of information represents a major barrier to the construction of mechanisms composed of elementary chemical reactions.…”

Section: Introductionmentioning

confidence: 99%

BAC-MP4 Predictions of Thermochemistry for Gas-Phase Compounds in the Si−H−O−Cl System

Allendorf

Melius

2002

J. Phys. Chem. A

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A self-consistent set of thermochemical parameters for 39 molecules in the Si−H−O−Cl system have been calculated using the BAC-MP4 method. The BAC-MP4 method combines ab initio electronic structure calculations with empirical corrections to obtain accurate heats of formation. Both stable and radical species are included in the study, as well as several complexes formed by reaction with gas-phase water. Although there are almost no experimental data available for comparison, trends within homologous series and calculated bond dissociation energies are consistent with previous BAC-MP4 predictions for silicon compounds. Polynomial fits of the predicted thermodynamic data over the 300−3000 K temperature range are included in the Supporting Information. The thermodynamic data are used to evaluate the energetics of reactions that may be involved in the oxidation and hydrolysis of silicon tetrachloride, in particular the reactions of SiCl3 and SiCl2 with O2 and H2O.

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Dissociation of SiCl4 based on Cl- and Si-concentration measurements

Cited by 14 publications

References 15 publications

Laser Flash Photolysis of SiCl₄ at High Temperatures Based on Si- and Cl-Concentration Measurements

Laser Flash Photolysis of SiCl₄ at High Temperatures Based on Si- and Cl-Concentration Measurements

Detonation in hydrogen–nitrous oxide–diluent mixtures: An experimental and numerical study

BAC-MP4 Predictions of Thermochemistry for Gas-Phase Compounds in the Si−H−O−Cl System

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Dissociation of SiCl4 based on Cl- and Si-concentration measurements

Cited by 14 publications

References 15 publications

Laser Flash Photolysis of SiCl4 at High Temperatures Based on Si- and Cl-Concentration Measurements

Laser Flash Photolysis of SiCl4 at High Temperatures Based on Si- and Cl-Concentration Measurements

Detonation in hydrogen–nitrous oxide–diluent mixtures: An experimental and numerical study

BAC-MP4 Predictions of Thermochemistry for Gas-Phase Compounds in the Si−H−O−Cl System

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Laser Flash Photolysis of SiCl₄ at High Temperatures Based on Si- and Cl-Concentration Measurements

Laser Flash Photolysis of SiCl₄ at High Temperatures Based on Si- and Cl-Concentration Measurements