Reaction of the oxygen molecule at the Si(100)-SiO2 interface during silicon oxidation.

Using constrained ab initio molecular dynamics, we investigate the reaction of the O2 molecule at the Si(100)-SiO2 interface during Si oxidation. The reaction proceeds sequentially through the incorporation of the O2 molecule in a Si-Si bond and the dissociation of the resulting network O2 species. The oxidation reaction occurs nearly spontaneously and is exothermic, irrespective of the O2 spin state or of the amount of excess negative charge available at the interface. The reaction evolves through the generation of network coordination defects associated with charge transfers. Our investigation suggests that the Si oxidation process is fully governed by diffusion.