Shock-induced kinetics of the disilane decomposition and silylene reactions with trimethylsilane and butadiene

Dzarnoski, J.; Rickborn, S. F.; O’Neal, H. E.; Ring, M. A.

doi:10.1021/om00069a020

Cited by 56 publications

(34 citation statements)

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“…34 Hydrogenation of these clusters was not included. Therefore, this pure silicon nucleation pathway did not interact directly 15 ∆Hrxn,1000 Si2H6 T Si2H4B + H2 silylene elimination from a silane Si2H6 T SiH2 + SiH4 SinH2m T SilH2kB + Sin-lH2(m-k) 2×10 15 ∆Hrxn,1000 Si3H8 T Si2H4B + SiH4 silylene elimination from a silene Si3H6A T SiH2 + Si2H4A Si4H8A T Si2H4B + Si2H4A…”

Section: Clustering Reaction Mechanism and Kineticsmentioning

confidence: 99%

“…[1][2][3][4][5][6][7] There is also a substantial body of work on the kinetics of gas-phase reactions of small silicon hydrides. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] On the basis of this body of research, models of thermal CVD of silicon from silane can now predict film growth rates and precursor utilization with reasonable accuracy and reliability, at least under conditions where particle formation is negligible. However, understanding of the processes that lead to gas-phase particle nucleation is still quite limited, and models for nucleation and growth of particles in this system do not have the level of predictive capability that has been achieved in modeling film growth rates and gas-phase chemical composition.…”

Section: Introductionmentioning

confidence: 99%

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Thermochemistry and Kinetics of Silicon Hydride Cluster Formation during Thermal Decomposition of Silane

1998

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Product contamination by particles nucleated within the processing environment often limits the deposition rate during chemical vapor deposition processes. A fundamental understanding of how these particles nucleate could allow higher growth rates while minimizing particle contamination. Here we present an extensive chemical kinetic mechanism for silicon hydride cluster formation during silane pyrolysis. This mechanism includes detailed chemical information about the relative stability and reactivity of different possible silicon hydride clusters. It provides a means of calculating a particle nucleation rate that can be used as the nucleation source term in aerosol dynamics models that predict particle formation, growth, and transport. A group additivity method was developed to estimate thermochemical properties of the silicon hydride clusters. Reactivity rules for the silicon hydride clusters were proposed based on the group additivity estimates for the reaction thermochemistry and the analogous reactions of smaller silicon hydrides. These rules were used to generate a reaction mechanism consisting of reversible reactions among silicon hydrides containing up to 10 silicon atoms and irreversible formation of silicon hydrides containing 11-20 silicon atoms. The resulting mechanism was used in kinetic simulations of clustering during silane pyrolysis in the absence of any surface reactions. Results of those simulations are presented, along with reaction path analyses in which key reaction paths and rate-limiting steps are identified and discussed.

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Section: Clustering Reaction Mechanism and Kineticsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Thermochemistry and Kinetics of Silicon Hydride Cluster Formation during Thermal Decomposition of Silane

1998

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“…Deducing primary process yields from the hydrogen yield data is complicated by the fact that secondary reaction hydrogen production must and does occur (that is, total HDIDZ yields exceed unity). In the disilane decomposition system [9] we found that a t temperatures above 950 K, secondary hydrogen is produced by decomposition of the silylene dimer [reaction (XIV)], with Arrhenius parameters which fit the data as shown, log k13 = 11.88 log k-13 = 15.8 -58,000 ca112.303RT log k14 = 14.5 -53,000 ca112.303RT…”

Section: Primary Processesmentioning

confidence: 99%

The gas‐phase decomposition of methylsilane. Part I. Mechanism of decomposition under shock‐tube conditions

Sawrey

O’Neal

Ring

et al. 1984

Int J of Chemical Kinetics

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“…The decomposition of disilane was also part of numerous experimental and theoretical investigations, see [3 -5, 19 -231. As a conclusion of all these articles, kl can be represented quite well by the value of Moffat et al [22] and k : by the value of Dzarnoski et al [ 5 ] . The extrapolation of these data to the experimental conditions of the present study results in a branching ratio k f / k l 50.07, which is not in disagreement with the present findings.…”

Section: Si2h6/ar Reaction Systemmentioning

confidence: 76%

“…Martin et al 131 and Bowrey and Walsh [4] studied the dissociation reaction in low temperature static systems by product analysis using the gaschromatographic technique. Dzarnoski et al [5] performed experiments in a single-pulse shock tube coupled to a mass spectrometer and gaschromatograph. All these studies were made at temperatures below 1000 K .…”

Section: Introductionmentioning

confidence: 99%

A Shock Tube Study of the Thermal Decomposition of Si₂H₆ Based on Si and SiH₂ Measurements

Mick¹,

Markus²,

Roth³

et al. 1995

Ber Bunsenges Phys Chem

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In the present investigation the thermal dissociation of disilane (Si2H6) mixed with different additives was measured behind reflected shock waves. Atomic Resonance Absorption Spectroscopy (ARAS) was applied for detecting Si atoms and Ring Dye Laser Absorption Spectroscopy (RDLAS) for detecting SiH2 radicals. Three different series of experiments were performed. In the first group of experiments mixtures of 0.1 to 0.25 ppm Si2H6 diluted in Ar were shock heated to temperatures 2000 K≤T≤3135 K and pressures between 0.8 and 1.4 bar. From the Si‐measurements silane and silylene were found to be the main primary products during disilane decomposition. The SiH2 absorption measurements were carried out at temperatures 1070 K ≤T≤ 1381 K and pressures between 0.35 and 1.3 bar. In these experiments the SiH2 formation was found to be mainly caused by the dissociation reaction Si2H6⇌ SiH4+SiH2 (R1). The rate coefficient k1 was determined by fitting SiH2 profiles calculated based on a simplified reaction mechanism to measured profiles with k1 to be a variable parameter. The value obtained was interpreted based on RRKM calculations. For bath gas concentrations of 3.1 × 10−6≤[M]≤ 4.6 × 10−6 mol cm−3 the rate coefficient k1 can be summarized by the Arrhenius expression k1 = 5.2×1010 exp(‐16850 K/T) s−1. For longer reaction times the SiH2 radicals were consumed due to the reaction SiH2+SiH2 ⇌Si2H2 (R4). The rate coefficient k4 was determined to be k4 = 6.5×1014 cm3 mol−1 s−1 (70%). The second group of experiments was carried out in mixtures with molecular hydrogen as an additive. SiH2measurements were performed in the temperature range 1082 K≤T≤1417 K at pressures 0.24 bar ≤p≤ 1.23 bar by using initial mixtures of 15 to 30 ppm Si2H6 and 5 to 50% H2 diluted in Ar. The aim of this part was to increase the influence of the recombination reaction SiH2 + H2→ SiH4 (R‐2) and to measure the dissociation barrier for the silane decomposition via the equilibrium constant. The data evaluation results in a mean value of E0,2 = 244.1 kJ/mol which is in good agreement to previous investigations. In the last part of this study the influence of silane used as an additive during Si2H6 decomposition was investigated. Initial mixtures of 30 ppm Si2H6 and 300 to 1000 ppm SiH4 diluted in Ar were used under conditions 1060 K ≤ T ≤ 1198 K at pressures between 0.36 and 1.3 bar. From SiH2 concentration measurements an estimation for the rate coefficient of the disproportionation reaction SiH2+SiH4 →H3SiSiH+H2 (R5), k5 = 1.3 × 1013 cm3 mol−1 s−1, was found.

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Shock-induced kinetics of the disilane decomposition and silylene reactions with trimethylsilane and butadiene

Cited by 56 publications

References 0 publications

Thermochemistry and Kinetics of Silicon Hydride Cluster Formation during Thermal Decomposition of Silane

Thermochemistry and Kinetics of Silicon Hydride Cluster Formation during Thermal Decomposition of Silane

The gas‐phase decomposition of methylsilane. Part I. Mechanism of decomposition under shock‐tube conditions

A Shock Tube Study of the Thermal Decomposition of Si₂H₆ Based on Si and SiH₂ Measurements

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Shock-induced kinetics of the disilane decomposition and silylene reactions with trimethylsilane and butadiene

Cited by 56 publications

References 0 publications

Thermochemistry and Kinetics of Silicon Hydride Cluster Formation during Thermal Decomposition of Silane

Thermochemistry and Kinetics of Silicon Hydride Cluster Formation during Thermal Decomposition of Silane

The gas‐phase decomposition of methylsilane. Part I. Mechanism of decomposition under shock‐tube conditions

A Shock Tube Study of the Thermal Decomposition of Si2H6 Based on Si and SiH2 Measurements

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A Shock Tube Study of the Thermal Decomposition of Si₂H₆ Based on Si and SiH₂ Measurements