Kinetic Stability and Safety Management Protocols for High-Reactivity Precursors (Zr, Hf, and Si) in Semiconductor Manufacturing: Focusing on Thermal Runaway and Hydrolysis Risks

Abstract

The transition to sub-10 nm semiconductor nodes necessitates the use of highly reactive zirconium (Zr), hafnium (Hf), and silicon (Si) precursors, which introduce severe safety risks due to their low activation energies and high kinetic lability. This study investigates the critical degradation mechanisms of these precursors, specifically focusing on the self-accelerating thermal decomposition of organometallics and the rapid hydrolysis of chlorosilanes that generates explosive hydrogen gas. By analyzing representative accident scenarios─including canister rupture due to thermal runaway and hydrogen explosions in storage cabinets─we identify significant gaps in current safety guidelines that lack material-specific kinetic data. Consequently, we propose a comprehensive, kinetically based safety management protocol. Key measures include the implementation of a strict active cold chain to prevent thermal runaway, advanced multigas detection systems (H₂/HCl) for atmosphere control, and a dynamic shelf-life assessment based on thermal history. These strategies provide a scientific framework for mitigating catastrophic risks and ensuring process integrity in next-generation semiconductor fabrication.