## 摘要

Gas-phase reactions of SiH_{x} with Si_{2}H_{y} (x = 1,2,3,4; y = 6,5,4,3) species, respectively, which may coexist under chemical vapor deposition (CVD) conditions, have been investigated by means of ab initio molecular orbital and statistical theory calculations. Potential energy surface (PES) predicted at the CCSD(T)/CBS//B3LYP/6–311++G(3df,2p) level shows that these reactions take place primarily via trisilany radicals, n-Si_{3}H_{7} and i-Si_{3}H_{7}. For example, SiH_{2} can associate with Si_{2}H_{5} producing n-H_{2}SiSiH_{2}SiH_{3} exothermically by 55.8 kcal/mol; SiH_{3} can undergo addition to H_{2}SiSiH_{2} to produce n-Si_{3}H_{7} or associate with H_{3}SiSiH barrierlessly forming i-Si_{3}H_{7}; whereas SiH can insert into one of the Si─H bonds of Si_{2}H_{6} to give excited n-Si_{3}H_{7}. Similarly, H_{2}SiSiH and SiSiH_{3} can undergo insertion reactions with SiH_{4} producing n/i-Si_{3}H_{7} intermediates, respectively, to be followed by fragmentation to various smaller species. These processes are fully depicted in the complete PES. The predicted heats of formation of various species agree well with available thermochemical data. The rate constants and product branching ratios for the low-energy channel products have been calculated for the temperature range 300–1000 K by variational RRKM (Rice–Ramsperger–Kassel–Macus) theory with Eckart tunneling corrections. The results may be employed for realistic kinetic modeling of the plasma-enhanced chemical vapor deposition growth of a-Si:H thin films under practical conditions.

原文 | English |
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頁（從 - 到） | 197-208 |

頁數 | 12 |

期刊 | International Journal of Chemical Kinetics |

卷 | 49 |

發行號 | 3 |

DOIs | |

出版狀態 | Published - 1 3月 2017 |

## 指紋

深入研究「Ab Initio Chemical Kinetics for SiH_{x}Reactions with Si

_{2}H

_{y}(x = 1,2,3,4; y = 6,5,4,3; x + y = 7) under a-Si:H CVD Condition」主題。共同形成了獨特的指紋。