Growth of Ultrathin Iron Oxide Films on Ag(100)

Ultrathin iron oxide films are useful model materials for fundamental studies of surface processes and exhibit intriguing properties as catalysts, as demonstrated recently in a number of studies utilizing platinum as a substrate. We report a study of the initial stages of iron oxide film growth on an Ag(100) surface using scanning tunneling microscopy, low energy electron diffraction, X-ray photoelectron spectroscopy, and near-edge X-ray absorption fine structure spectroscopy, with the goal of elucidating the effects of the substrate material on FeOx film growth and physical properties. We demonstrate that a well-ordered, monolayer-thick FeO(111) film can be prepared which is similar to the well-studied structure formed on Pt(111), though with a significantly expanded lattice constant indicative of smaller FeO buckling and weaker interactions with the substrate. Increased oxygen pressure during deposition leads to formation of a multilayer phase taking the form of well-ordered islands. Although superficially similar to FeO(111), spectroscopic measurements show a substantial proportion of Fe3+ in the phase. FeO(100) grains are observed upon deposition at elevated substrate temperatures, which is proposed to result from formation and oxidation of iron clusters embedded in the surfac