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Ab Initio Chemical Kinetics for the Thermal Decomposition of SiH4 + Ion and Related Reverse Ion–Molecule Reactions of Interest to PECVD of a-Si:H Films

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Abstract

The thermal unimolecular decomposition of SiH4 + ion and its related reverse reactions, SiH3 + + H and SiH2 + + H2, have been investigated by ab initio molecular orbital and quantum statistical variational RRKM theory calculations. The potential energy surface has been calculated at different levels of theory; the results at the highest level, CCSD(T)/CBS//CCSD(T)/6-311++G(3df,2p), show that the decomposition of SiH4 + can mainly occur via a barrierless channel giving SiH2 + + H2 lying 11.8 kcal/mol above the reactant, or via a transition state forming SiH3 +···H complex to be followed by a barrierless decomposition yielding SiH3 + + H lying 23.5 kcal/mol above the reactant. Barrierless processes were calculated using the CASPT2 and CASSCF methods with the 6-311++G(3df,2p) basis set and fitted with Morse potentials. The rate constants were predicted by solving master equations based on the RRKM theory at the E,J-resolved level; the results show that the channel SiH4 + → SiH2 + + H2 is predominate under PEVCD conditions. For H- and H2-capturing by SiH3 + and SiH2 + ions, respectively, the rate constants were found to be weakly dependent on temperature at the high-pressure limit and decrease rapidly with pressure. The calculated heats of formation of the SiH +x (x = 2–4) ions are in close agreement with available thermochemical data.

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Authors and Affiliations

  1. Department of Applied Chemistry, Center for Interdisciplinary Molecular Science, National Chiao Tung University, Hsinchu, 300, Taiwan

    T. N. Nguyen & M. C. Lin

  2. Department of Mechanical Engineering, National Chiao Tung University, Hsinchu, 300, Taiwan

    Y. M. Lee & J. S. Wu

  3. Department of Physical Chemistry, Hanoi University of Science and Technology, Hanoi, Vietnam

    T. N. Nguyen

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Correspondence to M. C. Lin.

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Nguyen, T.N., Lee, Y.M., Wu, J.S. et al. Ab Initio Chemical Kinetics for the Thermal Decomposition of SiH4 + Ion and Related Reverse Ion–Molecule Reactions of Interest to PECVD of a-Si:H Films. Plasma Chem Plasma Process 37, 1249–1264 (2017). https://doi.org/10.1007/s11090-017-9825-7

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