Scanning tunneling microscopy and spectroscopy of wet-chemically prepared chlorinated Si(111) surfaces

Chlorine-terminated Si(111) surfaces prepared through the wet-chemical treatment of H-terminated Si(111) surfaces with PCl₅ (in chlorobenzene) were investigated using ultrahigh vacuum scanning tunneling microscopy (UHV cryo-STM) and tunneling spectroscopy. STM images, collected at 77 K, revealed an unreconstructed 1 × 1 structure for the chlorination layer, consistent with what has been observed for the gas phase chlorination of H-terminated Si(111). However, the wet-chemical chlorination is shown to generate etch pits in the Si-(111) surface, with an increase in etch pit density correlating with increasing PCl₅ exposure temperatures. These etch pits were assumed to stabilize the edge structure through the partial removal of the 〈112̄〉 step edges. Tunneling spectroscopy revealed a nonzero density of states at zero bias. This is in contrast to the cases of H-, methyl-, or ethyl-terminated Si(111), in which similar measurements have revealed the presence of a large conductance gap.