Title: Ab Initio Chemical Kinetics for Reactions of H Atoms with SiHx (x=1-3) Radicals and Related Unimolecular Decomposition Processes
Authors: Raghunath, Putikam
Lee, Yun-Min
Wu, Shang-Ying
Wu, Jong-Shinn
Lin, Ming-Chang
Department of Mechanical Engineering
Department of Applied Chemistry
Keywords: ab initio calculation;silane chemistry;reaction mechanism;rate constant
Issue Date: 15-Jun-2013
Abstract: Hydrogen atoms and SiHx (x = 1-3) radicals coexist during the chemical vapor deposition (CVD) of hydrogenated amorphous silicon (a-Si: H) thin films for Si-solar cell fabrication, a technology necessitated recently by the need for energy and material conservation. The kinetics and mechanisms for H-atom reactions with SiHx radicals and the thermal decomposition of their intermediates have been investigated by using a high high-level ab initio molecular-orbital CCSD (Coupled Cluster with Single and Double)(T)/CBS (complete basis set extrapolation) method. These reactions occurring primarily by association producing excited intermediates, (SiH2)-Si-1, (SiH2)-Si-3, SiH3, and SiH4, with no intrinsic barriers were computed to have 75.6, 55.0, 68.5, and 90.2 kcal/mol association energies for x = 1-3, respectively, based on the computed heats of formation of these radicals. The excited intermediates can further fragment by H-2 elimination with 62.5, 44.3, 47.5, and 56.7 kcal/mol barriers giving Si-1, Si-3, SiH, and (SiH2)-Si-1 from the above respective intermediates. The predicted heats of reaction and enthalpies of formation of the radicals at 0 K, including the latter evaluated by the isodesmic reactions, SiHx + CH4 SiH4 + CHx, are in good agreement with available experimental data within reported errors. Furthermore, the rate constants for the forward and unimolecular reactions have been predicted with tunneling corrections using transition state theory (for direct abstraction) and variational Rice-Ramsperger-Kassel-Marcus theory (for association/decomposition) by solving the master equation covering the P, T-conditions commonly employed used in industrial CVD processes. The predicted results compare well experimental and/or computational data available in the literature. (C) 2013 Wiley Periodicals, Inc.
URI: http://dx.doi.org/10.1002/qua.24396
ISSN: 0020-7608
DOI: 10.1002/qua.24396
Volume: 113
Issue: 12
Begin Page: 1735
End Page: 1746
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