Oxidation of step edges on Si(001)-c(4×2)

The initial oxidation process of the ultraclean Si(001)-c(4×2) surface is studied using scanning tunneling microscopy at low temperature. At the early stage of oxygen adsorption, reactions with Si atoms at SB steps are dominant over those at terraces by more than 2 orders of magnitude, and they proceed in two distinct stages to high oxidation states. Guided by the ab initio calculations, the oxidation structures at each stage are proposed. The extreme reactivity of the step edge is due to the presence of rebonded adatoms with dangling bonds and weak rebonds, and their proximity allows the formation of -Si-O- chain structures along the step edge, unlike those on the Si(111) surface.