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Mn on the surface of ZnO(0001) - a resonant photoemisson study

The electronic structure of Mn/ZnO system has been invesigated by synchrotron radiation photoemission. Manganese vacuum deposition was done at room temperature onto a ZnO(0001) single crystal for coverage ΘMn ⩽ 4 ML. Photoemission spectra taken near the Mn3p–Mn3d absorption edge after each deposition step show resonant enhancement of Mn3d states within 10 eV of the Fermi edge. The experimentally deduced partial Mn3d density of states for Θ ⩾ 1.2 ML shows at least three features: a major Mn3d structure at 3.8–4.5 eV below the Fermi edge, a valence structure at lower binding energy (1–3 eV) and a broad satelite in the 5.5–9 eV range. The branching ratio of satellite/main structure increases with depostion from 0.33 for 0.4 ML to 0.65 for 4 ML. After annealing up to 500 °C the satellite/main ratio decreases to 0.43 indicating a high degree of hybridization between the Mn3d states and valence band of ZnO. After annealing no manganese cap layer was found at the crystal surfaces as was confirmed by the lack of metallic Fermi edge in photoemission spectra and by scanning Auger spectroscopy experiment. The photoemission Mn3p core level spectra taken after annealing consist of two components separated by about 4 eV, which shows that at least two manganese states are observed in the Mn–ZnO interface region.