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Ab Initio Chemical Kinetics for the Thermal Decomposition of SiH2+ and SiH3+ Ions and Related Reverse Ion–Molecule Reactions of Interest to PECVD of α-Si:H Films

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Abstract

The mechanisms and kinetics for the thermal decomposition of SiH2+ and SiH3+ ions, and related reverse reactions involving their ion fragments have been investigated for the first time by using ab initio molecular orbital and variational RRKM calculations. Geometries of all species involved the title reactions have been optimized by the CCSD(T), CCSD, and MP2 methods with the Aug-CC-pVTZ basis set while their single point energies have been refined by the CCSD(T)/CBS calculation for all the three levels for comparison. The barrierless processes involved have been calculated at the CASPT2//CASSCF/Aug-CC-pVTZ level of theory. The potential energy surfaces indicate that the SiH2+ and SiH3+ ions can eliminate an H atom via barrierless processes with dissociation energies of 48.4 and 91.5 kcal mol−1, respectively, or eliminate an H2 molecule via tight transition states at TS1 (38.5 kcal mol−1) and TS3 (59.9 kcal mol−1) giving H2 + Si+ (21.3 kcal mol−1) and H2 + SiH+ (36.7 kcal mol−1), respectively, at the CCSD(T)/CBS//CCSD(T)/Aug-CC-pVTZ level of theory. The rate constants for the reactions predicted for a wide range of T,P-conditions reveal that they increase with rising temperature and pressure and H2 elimination is the major channel in each of the decomposition reactions. The relative energies predicted by different methods agree closely; the predicted heats of formation for various species are in good agreement with available experimental values. The predicted rate constants for the forward and reverse reactions may be employed for kinetic modeling of PECVD processes.

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Acknowledgements

This paper (work) is supported by Ministry of Science and Technology, Taiwan (Grant No. MOST107-3017-F009-003) and Ministry of Education, Taiwan (SPROUT Project–Center for Emergent Functional Matter Science of National Chiao Tung University). We also acknowledge the National Center for High-Performing Computers for the use of its facility.

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Authors and Affiliations

  1. Center for Emergent Functional Matter Science, National Chiao Tung University, 1001 Ta-Hsueh Rd., Hsinchu, 30010, Taiwan

    T. N. Nguyen & M. C. Lin

  2. Department of Mechanical Engineering, National Chiao Tung University, Hsinchu, 30010, 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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Nguyen, T.N., Lee, Y.M., Wu, J.S. et al. Ab Initio Chemical Kinetics for the Thermal Decomposition of SiH2+ and SiH3+ Ions and Related Reverse Ion–Molecule Reactions of Interest to PECVD of α-Si:H Films. Plasma Chem Plasma Process 39, 1559–1573 (2019). https://doi.org/10.1007/s11090-019-10012-x

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