Substoichiometric cobalt oxide monolayer on Ir(100)-(1 × 1).

A substoichiometric monolayer of cobalt oxide has been prepared by deposition and oxidation of slightly less than one monolayer of cobalt on the unreconstructed surface of Ir(100). The ultrathin film was investigated by scanning tunnelling microscopy (STM) and quantitative low-energy electron diffraction (LEED). The cobalt species of the film reside in or near hollow positions of the substrate with, however, unoccupied sites (vacancies) in a 3 × 3 arrangement. In the so-formed 3 × 3 supercell the oxide's oxygen species are both threefold and fourfold coordinated to cobalt, forming pyramids with a triangular and square cobalt basis, respectively. These pyramids are the building blocks of the oxide. Due to the reduced coordination as compared to the sixfold one in the bulk of rock-salt-type CoO, the Co–O bond lengths are smaller than in the latter. For the threefold coordination they compare very well with the bond length in oxygen terminated CoO(111) films investigated recently. The substoichiometric 3 × 3 oxide monolayer phase transforms to a stoichiometric c(10 × 2)-periodic oxide monolayer under oxygen exposure, in which, however, cobalt and oxygen species are in (111) orientation and so form a CoO(111) layer.