Increasing demand for computers and smart devices is driving the research area of next-generation electronic materials. Among semiconducting materials, silicon nitride is used as insulating and passivating materials in integrated circuits due to its wide band-gap. Also, employing SiN nanomaterials in anode applications improves rate performances and cycling stability of the lithium-ion batteries. However, a fundamental understanding of the SiN synthetic process remains elusive. SiN gas-phase synthesis can be tailored with a comprehensive understanding of the underlying thermodynamics and kinetics. Silicon nitride can be prepared in several synthetic routes such as PECVD, catalytic, and laser-enhanced techniques, as well as via co-pyrolysis in the gas phase. Although silicon nitride has been researched intensively, the fundamental understanding of the hydrogenated silicon nitride synthesis process is still unclear. In comparison to the characterization data available for solid-state SiN materials, high-level theoretical studies on gas-phase materials possessing Si-N bonds and comprehensive investigation of the SiN chemistry, particularly for nanoclusters, are very uncommon. Thus, we performed theoretical studies of Si and SiN alloy acyclic hydrides and polycyclic clusters to predict electronic structures, thermochemistry, and kinetics using quantum chemical calculation and statistical thermodynamics. Electronic properties by way of HOMO-LUMO energy gap and natural bonding orbitals analysis were calculated to explore the influence of elemental composition and geometry on stability. Our studies provide characteristic data of SiN species for a data-driven approach to map the design space for the discovery of novel silicon-nitride-based ceramic materials for advanced electronic and coating applications. The kinetic and thermodynamic information for key reaction classes investigated will support automated network generation techniques as a database for predicting complex reaction mechanisms.

Monosilane and ammonia co-pyrolysis to silicon-nitride-based ceramic nanomaterials: A thermochemistry and kinetics Investigation

ACS Fall 2021

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