High temperature chlorosilane corrosion of iron and AISI 316L stainless steel

Abstract

Chlorosilane gas streams are used at high temperatures (>500°C) throughout the semiconductor, polycrystalline silicon, and fumed silica industries, primarily as a way to refine, deposit, and produce silicon and silicon containing materials. The presence of both chlorine and silicon in chlorosilane species creates unique corrosion environments due to the ability of many metals to form both metal-chlorides and metal-silicides, and it is further complicated by the fact that many metal-chlorides are volatile at high-temperatures while metal-silicides are generally stable. To withstand the uniquely corrosive environments, expensive alloys are often utilized, which increases the cost of final products. This work focuses on the corrosion behavior of iron, the primary component of low-cost alloys, and AISI 316L, a common low-cost stainless steel, in environments representative of industrial processes. The experiments were conducted using a customized high temperature chlorosilane corrosion system that exposed samples to an atmospheric pressure, high temperature, chlorosilane environment with variable input amounts of hydrogen, silicon tetrachloride, and hydrogen chloride plus the option of embedding samples in silicon during the exposure. Pre and post exposure sample analysis including scanning electron microscopy, x-ray diffraction, energy dispersive x-ray spectroscopy, and gravimetric analysis showed the surface corrosion products varied depending on the time, temperature, and environment that the samples were exposed to. Most commonly, a volatile chloride product formed first, followed by a stratified metal silicide layer. The chlorine and silicon activities in the corrosion environment were changed independently and were found to significantly alter the corrosion behavior; a phenomenon supported by computational thermodynamic equilibrium simulations. It was found that in comparable environments, the stainless steel corroded significantly less than the pure iron. This is likely due to the alloying elements present in stainless steel that promote formation of other stable silicides. Mechanistic models were developed to describe the formation and evolution of metal silicide and/or metal chloride surface corrosion products in chlorosilane environments. These models will help inform materials selection and/or support process development for next-generation chlorosilane-based production and deposition systems. The implementation of low cost materials of construction in these systems could lower the cost of final products in these industries.