Manifestation of strong d-p hybridization in photoluminescence spectra of ZnO:Ni and ZnO:Co

For the first time photoluminescence and photoluminescence excitation spectra for ZnO:Co and ZnO:Ni crystals were obtained at the excitation by the synchrotron radiation in the interval of energy of (3.7-21) eV, T = 8 K. It is shown that these spectra are formed by intense radiative transitions through 3d charge transfer states in the band gap. This fact evidences about much stronger hybridization between d-states of impurity and p-states of anions in comparison with other II-VI:3d compounds. It is very important for applications in optoelectronics, for visualization of ultraviolet radiation and understanding of photocatalytic activity of ZnO:3d nanocrystals in the visible region of the spectrum. From the comparison of PLE spectra for ZnO:Co and ZnO:Ni with the spectrum of calculated DOS for ZnO it is revealed a visible transformation of part of valence band states due to a strong d-p hybridization. Obtained results allow us to consider ZnO:3d as a compounds with a strong correlations