Local Aspects of Hydrogen-Induced Metallization of the ZnO(10$\mathbf{\overline{1}}$0) Surface

Abstract

This study combines surface-sensitive photoemission experiments with density functional theory (DFT) to give a microscopic description of H adsorption-induced modifications of the ZnO(10${\overline{1}}$0) surface electronic structure. We find a complex adsorption behavior caused by a strong coverage dependence of the H adsorption energies: Initially, O--H bond formation is energetically favorable and H acting as an electron donor leads to the formation of a charge accumulation layer and to surface metallization. The increase of the number of O--H bonds leads to a reversal in adsorption energies such that Zn--H bonds become favored at sites close to existing O--H bonds, which results in a gradual extenuation of the metallization. The corresponding surface potential changes are localized within a few nanometers both laterally and normal to the surface. This localized character is experimentally corroborated by using sub-surface bound excitons at the ZnO(10${\overline{1}}$0) surface as a local probe. The pronounced and comparably localized effect of small amounts of hydrogen at this surface strongly suggests metallic character of ZnO surfaces under technologically relevant conditions and may, thus, be of high importance for energy level alignment at ZnO-based junctions in general.