The valence band offset of ZnO/AlN heterojunctions is determined by high resolution x-ray photoemission spectroscopy. The valence band of ZnO is found to be 0.43±0.17 eV below that of AlN. Together with the resulting conduction band offset of 3.29±0.20 eV, this indicates that a type-II (staggered) band line up exists at the ZnO/AlN heterojunction. Using the III-nitride band offsets and the transitivity rule, the valence band offsets for ZnO/GaN and ZnO/InN heterojunctions are derived as 1.37 and 1.95 eV, respectively, significantly higher than the previously determined values
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