Ab Initio MD Study of the Mechanism of Carbonization of Si(001) Surfaces with Methane at High Temperatures

This study employs ab initio metadynamics to simulate the carbonization of Si(001) surfaces with chemical vapor deposition at a temperature of 1423 K. We reveal the complete reaction mechanism, including the beginning of silicon carbide crystal formation. The existence of surficial native oxide is incorporated into the theoretical model. The mechanism determination includes clarification of all intermediate products and transition states. The free-energy surface of the reaction chain has been found. Carbonization initiates with alkylated surface products and continues with consecutive dehydrogenation steps. Carbon is integrated in the volume, near the crystal surface, only if no covalent interactions with hydrogen atoms remain. The native oxide was not found to prohibit the process of carbonization. The oxygen atoms have certain surface mobility at high temperatures. It was revealed that hypervalency of carbon atoms is possible in transition state structures. The theoretical activation free energy of the rate-determining step was found to be only 166 kJ/mol. This work sheds light on the advantage of the practical use of Si(001) substrates for the synthesis of silicon carbide and Si-O-C glasses using direct carbonization via chemical vapor deposition. We also aim to enable more methodical designs of future synthetic routes and better-informed decisions for experimental investigations.