We have investigated the influence of ZnO orientation on the valence band offset (ΔEV) of Mg0.2Ni0.8O(111)/ZnO (112¯0) and Mg0.2Ni0.8O(111)/ZnO(0002) heterostructures by x-ray photoelectron spectroscopy. Combining with the experimental optical energy band gap extracted from UV-vis transmittance spectra, the energy band alignment at the interfaces has been determined. The ΔEV has been found to be 1.8 ± 0.1 eV and 1.4 ± 0.1 eV for Mg0.2Ni0.8O(111)/ZnO (112¯0) and Mg0.2Ni0.8O(111)/ZnO(0002), respectively. Both the heterostructures show type-II band configurations with conduction band offsets (ΔEC) of 2.4 ± 0.1 eV and 2.0 ± 0.1 eV, respectively. The ZnO orientation correlated electronic structure in p-Mg0.2Ni0.8O/n-ZnO interfaces can be explained well by the effect of spontaneous polarization in ZnO. Furthermore, the results offer opportunity that desired band offsets in MgxNi1−xO/ZnO heterostructures can be obtained by appropriately adjusting Mg composition.
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