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Ab initio chemical kinetics for reactions of H atoms with SiH x ( x = 1–3) radicals and related unimolecular decomposition processes
Author(s) -
Raghunath Putikam,
Lee YunMin,
Wu ShangYing,
Wu JongShinn,
Lin MingChang
Publication year - 2013
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24396
Subject(s) - chemistry , radical , isodesmic reaction , hydrogen atom abstraction , ab initio , basis set , thermochemistry , computational chemistry , standard enthalpy of formation , reaction rate constant , beta scission , ab initio quantum chemistry methods , molecule , kinetics , density functional theory , radical substitution , organic chemistry , physics , quantum mechanics
Hydrogen atoms and SiH x ( 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 SiH x 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, 1 SiH 2 , 3 SiH 2 , SiH 3 , and SiH 4 , 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 1 Si, 3 Si, SiH, and 1 SiH 2 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, SiH x + CH 4 = SiH 4 + CH x , 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. © 2013 Wiley Periodicals, Inc.