Band bending at the ZnO(0001)-Zn surface produced by electropositive, electronegative and atmospheric adsorbates

We have analysed the surface band bending (SBB) at the clean ZnO(0001)-Zn surface and after its modification by electropositive, electronegative and atmospheric adsorbates. The evolution of the band bending with increasing adsorption was monitored by measuring core-level and valence-band X-ray photoelectron spectra. We found that the SBB produced by the adsorption of electropositive elements was always downwards, reaching in all cases the limit imposed by the crossing of the conduction-band minimum with the Fermi level. The adsorption of electronegative elements produced always upward band bending, but in this case a pinning of the SBB was observed that kept the valence-band maximum far from the Fermi level. A self-consistent equation relating the adsorbate level occupation with the band bending is shown to qualitatively reproduce the observed SBB pinning effect. In contrary to the commonly assumed upwards SBB for the ZnO/air interface, a downward SBB was observed after exposing the clean surface to atmospheric air. A downward SBB was also observed when the surface was bombarded with 1 keV Ar+ in vacuum.