Rate constants for the reactions of hydrogen atoms with some silanes and germanes

Austin, E. R.; Lampe, F. W.

doi:10.1021/j100527a003

Cited by 136 publications

(60 citation statements)

References 4 publications

(5 reference statements)

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“…From the figure it can be seen that our results are in good agreement with our previous work [3], and with the values obtained by Stief and co-workers [10]. Not shown are the rate constants reported by Choo et al [11] and Austin and Lampe [12], which differ markedly from the more recent data.…”

Section: Reaction Of H Atoms With Gehsupporting

confidence: 92%

Kinetic isotope effect for the reaction of H atoms with GeH4 and GeD4

Arthur

Cooper

Miles

1997

Int. J. Chem. Kinet.

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Rate constants for H atom attack on GeH 4 and GeD 4 have been measured in pulsed photolysis experiments in which H atoms were produced by the mercury-sensitized photolysis of H 2 and monitored by Lyman-␣ absorption. The values obtained for GeD 4 in the temperature range 293 -550 K may be represented by the expressionCombination of the rate constants for GeH 4 measured in this work with those previously determined in this laboratory gives, for the temperature range 293 -455 K,The kinetic isotope effect indicated by these expressions is given bywhich yields k H /k D ϭ 2.0 Ϯ 0.4 at 300 K. This is the first determination of the kinetic isotope effect for radical attack on a Ge 9 H bond.The present results for the reaction of H atoms with GeH 4 have been combined with previously reported data, and the best value for the rate constant over the temperature range 210 -473 K is recommended to be k H ϭ (1.18 Ϯ 0.08) ϫ 10 Ϫ10 exp[(Ϫ 981 Ϯ 22)/ T]

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Section: Reaction Of H Atoms With Gehsupporting

confidence: 92%

Kinetic isotope effect for the reaction of H atoms with GeH4 and GeD4

Arthur

Cooper

Miles

1997

Int. J. Chem. Kinet.

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“…The reported rate constants for hydrogen abstraction from methylsilane by H atoms cover almost a power of ten ranging from (1.5 ± 0.4) • 10~1 3 cm 3 s _1 [20] over (6.1 ± 1.0) • lO^cmV [21] to (11.5 ± 2) • 10~1 3 cm 3 s~' [3]. Here again the value obtained in a flow experiment is the highest one.…”

Section: Discussionmentioning

confidence: 92%

The Reaction of Hydrogen Atoms with Silyl Radicals; the Decomposition Pathways of Chemically Activated Silanes

Reimann

Potzinger

1983

Zeitschrift Für Naturforschung A

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The reactions of hydrogen atoms with silane and the methylated silanes -with the exception of tetramethylsilane -have been investigated in a fast flow reactor. Under our experimental conditions hydrogen abstraction from the Si-H bond is followed by combination of hydrogen atoms with the corresponding silyl radicals. The molecules formed in this way are activated by about 375 kJ/mol of vibrational energy. Two decomposition channels have been unequivocally identified, namely the elimination of molecular hydrogen and of methane, both with concomittant formation of the respective silylenes. In a subsequent step, silylene inserts into the substrate under formation of disilanes. With increasing degree of methylation. stabilization of the activated molecule competes with decomposition and dominates the kinetics in the case of trimethylsilane. With methyl-and dimethyl-silane, methyl radicals are observed as an additional reaction product. On the basis of RRKM calculations it is unlikely that they originate from a direct decomposition of the activated molecules.Absolute values for the room temperature rate constants of the abstraction reactions are given; for H + CH 3 SiH 3 , Arrhenius parameters have been determined.

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“…9 Diffusion coefficients of hydrogen atoms for the present experimental conditions were evaluated from this value while taking into account the difference in atomic hydrogen temperature, collision cross sections of the gases and gas pressure. The residence times then were evaluated from the diffusion coefficients thus determined using Eq.…”

Section: B Estimation Of Residence Time Of Hydrogen Atoms In the Plamentioning

confidence: 99%

Atomic hydrogen temperature in silane plasmas used for the deposition of a-Si:H films

Miyazaki

Kajiwara²,

Uchino³

et al. 1999

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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Atomic hydrogen temperature in a silane plasma used for the deposition of a-Si:H films was measured using a two-photon laser-induced fluorescence technique. The temperature was found to be 2200±600 K and higher than both the parent-gas temperature and the atomic hydrogen temperature in a hydrogen plasma. We considered the mechanism of atomic hydrogen temperature determination in the plasma as follows. Hydrogen atoms generated by the dissociation of gas molecules due to electron impact in the plasma have a kinetic energy of several eV, which they then lose through collisions with gas molecules. At the same time, they disappear from the plasma due to chemical reactions and diffusion before thermal equilibrium with gas molecules has been established. Thus, an atomic hydrogen temperature higher than that of gas molecules becomes the equilibrium value in the plasma. We show, in the new experiment, that this model provides a good estimation of atomic hydrogen temperature in the plasma under various conditions of silane-hydrogen mixtures.

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Rate constants for the reactions of hydrogen atoms with some silanes and germanes

Cited by 136 publications

References 4 publications

Kinetic isotope effect for the reaction of H atoms with GeH4 and GeD4

Kinetic isotope effect for the reaction of H atoms with GeH4 and GeD4

The Reaction of Hydrogen Atoms with Silyl Radicals; the Decomposition Pathways of Chemically Activated Silanes

Atomic hydrogen temperature in silane plasmas used for the deposition of a-Si:H films

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