Formation and characterization of the Cu2O overlayer on Zn-terminated ZnO(0 0 0 1)

Low-energy electron diffraction, X-ray photoelectron spectroscopy and synchrotron-radiation-excited angle-resolved photoelectron spectroscopy have been used to characterize Cu-oxide overlayers on the Zn-terminated ZnO(0 0 0 1) surface. Deposition of Cu on the ZnO(0 0 0 1)–Zn surface results in the formation of Cu clusters with (1 1 1) top terraces. Oxidation of these clusters by annealing at 650 K in O2 atmosphere (1.3 × 10−4 Pa) leads to an ordered Cu2O overlayer with (1 1 1) orientation. Good crystallinity of the Cu2O(1 1 1) overlayer is proved by energy dispersion of one of Cu2O valence bands. The Cu2O(1 1 1) film exhibits a strong p-type semiconducting nature with the valence band maximum (VBM) of 0.1 eV below the Fermi level. The VBM of ZnO at the Cu2O(1 1 1)/ZnO(0 0 0 1)–Zn interface is estimated to be 2.4 eV, yielding the valence-band offset of 2.3 eV.