First principles analysis of the initial oxidation of Si(001) and Si(111) surfaces terminated with H and CH3

Transition state analyses have been carried out within a density functional theory setting to explain and quantify the distinctly different ways in which hydrogen and methyl terminations serve to protect silicon surfaces from the earliest onset of oxidation. We find that oxidation occurs via direct dissociative adsorption, without any energy barrier, on Si(111) and reconstructed Si(001) that have been hydrogen terminated; oxidation initiates with a barrier of only 0.05 eV on unreconstructed Si(001). The commonly measured protection afforded by hydrogen is shown to derive from a coverage-dependent dissociation rate combined with barriers to the hopping of adsorbed oxygen atoms. Methyl termination, in contrast, offers an additional level of protection because oxygen must first undergo interactions with these ligands in a three-step process with significant energy barriers: adsorption of O(2) into a C-H bond to form a C-O-O-H intermediate; decomposition of C-O-O-H into C-O-H and C=O intermediates; and, finally, hopping of oxygen atoms from ligands to the substrate.