Tuning the surface metal work function by deposition of ultrathin oxide films: Density functional calculations

Changes in the work function Φ of metal surfaces upon deposition of ultrathin oxide films have been studied by means of band structure density functional theory calculations. Four systems have been considered: MgO∕Ag(100), MgO∕Mo(100), TiO₂∕Mo(100), and SiO₂∕Mo(112). MgO films induce a decrease of Φ of 1 to 20.3em0exeV compared to the clean metal substrate; SiO₂ and TiO₂ induce an increase of Φ of about 0.5--10.3em0exeV. The reasons for this behavior are different: for TiO₂ and SiO₂ the work function increase can be explained with the classical model of surface dipole due to metal-to-oxide charge transfer at the interface. On MgO∕metal interfaces, where the charge transfer is negligible, the shift is due to the compression of the metal electron density enforced by the oxide layer, with consequent change in surface dipole. The results suggest that by appropriately choosing the metal support and the oxide film one can design nanostructured materials with new properties.