Theoretical investigation of the initial steps of the adsorption of N atoms on Si(1 0 0)-2×1

Structural, energetics, and mechanistics aspects of initial steps of the reaction of a N atom with Si(1 0 0)-2×1 modeled by the Si₉H₁₂+N system are reported. Hybrid density functional B3LYP calculations predict a barrierless first step leading to an adsorbate where N is bound to one of the dimer Si. Two possible activated routes for internal rearrangements were found, with that leading to the incorporation of Si below the first layer predicted to be kinetically dominant (98%) under the experimental conditions. This structure and frequency calculations are consistent with the experimental finding of a planar NSi₃ moeity and with the experimental SiN asymmetric stretching frequency of the NSi₃ groups.