A scanning tunneling microscopy study of water on Si(111)-(7 × 7): adsorption and oxide desorption

Scanning tunneling microscopy and temperature-programmed desorption have been used to investigate the chemistry of water on Si(111)-(7 × 7) substrates which were misoriented 2° toward the 10] direction. Upon room temperature exposure to water, the adatoms of the (7 × 7) unit cell are still evident even after high exposures, implying that major modifications of the substrate do not occur. At high coverages, the distribution of reacted adatoms shifts from one controlled by dissociative adsorption across the adatom-rest atom pair to a statistical distribution based on the availability of dangling bonds. Desorption of the oxide layer which remains after water adsorption and the desorption of hydrogen have also been characterized. The oxide desorption occurs along well-defined wavefronts which originate at step edges and advance in directions consistent with the underlying substrate symmetry, primarily the 2] direction (i.e. the wave vector points in the 2] direction). In regions of the surface where the oxide has desorbed, the (7 × 7) unit cell can be seen clearly. Vacancies resulting from the loss of surface silicon atoms (via the etching) coalesce into islands in the clean regions of the terraces, but unlike desorption of oxide layers from Si(100), the desorption does not occur from the boundaries of these vacancy islands.