New Structural Model forSi/SiO2Interfaces Derived from Spherosiloxane Clusters: Implications for Si2pPhotoemission Spectroscopy

In this Letter, we investigate the $\mathrm{Si}/{\mathrm{SiO}}_2$ interface structure formed by the chemisorption of ${\mathrm{H}}_8{\mathrm{Si}}_8{\mathrm{O}}_{12}$ and other spherosiloxane clusters on Si(100). Using transition state calculations, we clearly demonstrate that the clusters do not bond to the Si(100) surface via single vertex attachment as proposed previously, but rather attach via Si-O bond cleavage. This alternative cracked cluster geometry allows us to predict the photoemission features of spherosiloxane clusters on Si(100) without invoking second nearest neighbor effects.