X-ray absorption and emission spectroscopy of ZnO nanoparticle and highly oriented ZnO microrod arrays

Abstract

The electronic structures of ZnO nanoparticles and microrod arrays are studied by O 1s X-ray absorption spectroscopy (XAS) and O Kα X-ray emission spectroscopy (XES). We show that the present LDA+U SIC calculation approach is suitable to correct the LDA self-interaction error of the cation d-states. The atomic eigenstates of 3d in zinc and 2p in oxygen are energetically close, which induces strong Zn-3d-O-2p hybridization. This anomalous valence band cation-d-anion-p hybridization is affected when the localization of the Zn 3d-states is taken into account. Experimentally, the XES spectra show energy dependence in the spectral shape revealing selected excitations to the Zn 3d, 4s and 4p states, hybridized with O 2p states. Strong anisotropic effects are observed for the highly oriented ZnO rods, but not for the isotropic spherical nanoparticles. The nanostructured ZnO has primarily bulk XAS and XES properties.