Identification of the products from the reaction of chlorine with the silicon(111)-(7×7) surface

The various products from the reaction of chlorine (Cl) with the adatom layer of the Si(111)-(7×7) surface have been identified with scanning tunneling microscopy (STM). Initially, a single Cl atom reacts with the adatom dangling bond. At higher surface coverage, additional Cl atoms insert themselves into the Si-Si backbonds between the adatom and rest-atom layers, producing adatoms that have reacted with two or three Cl atoms. These products are characterized by different registries with respect to the underlying rest layer and appear in STM images as adatoms of different sizes, consistent with the breaking of Si-Si backbonds and the formation of new Si-Cl bonds.