Unusual X-ray excited luminescence spectra of NiO suggestive of a self-trapping of the d-d charge transfer exciton

Luminescence spectra of NiO have been investigated under vacuum ultraviolet (VUV) and soft X-ray (XUV) excitation. Photoluminescence (PL) spectra show broad emission bands centered at about 2.3 and 3.2 eV. The PL excitation (PLE) spectral evolution and lifetime measurements reveal that two mechanisms with short and long decay times, attributed to the d($e_g$)-d($e_g$) and p($\pi$)-d charge transfer (CT) transitions in the range 4-6\,eV, respectively, are responsible for the observed emissions, while the most intensive p($\sigma$)-d CT transition at 7\,eV appears to be a weak if any PL excitation mechanism. The PLE spectra recorded in the 4-7\,eV range agree with the RIXS and reflectance data. Making use of the XUV excitation allows us to avoid the predominant role of the surface effects in luminescence and reveal bulk luminescence with puzzling well isolated doublet of very narrow lines with close energies near 3.3\,eV characteristic for recombination transitions in self-trapped \emph{d}-\emph{d} CT excitons formed by coupled Jahn-Teller Ni$^+$ and Ni$^{3+}$ centers. This conclusion is supported both by a comparative analysis of the luminescence spectra for NiO and solid solutions Ni$_{x}$Zn$_{1-x}$O, and by a comprehensive cluster model assignement of different \emph{p}-\emph{d} and \emph{d}-\emph{d} CT transitions, their relaxation channels. To the best of our knowledge it is the first observation of the self-trapping for \emph{d}-\emph{d} CT excitons. Our paper shows the time resolved luminescence measurements provide an instructive tool for elucidation of the \emph{p}-\emph{d} and \emph{d}-\emph{d} CT excitations and their relaxation in 3d oxides.Comment: 7 pages, 6 figure

Self trapping of the d-d transfer exciton in bulk NiO evidenced by X-ray excited luminescence

Soft X-ray (XUV) excitation did make it possible to avoid the predominant role of the surface effects in luminescence of NiO and revealed a bulk luminescence with a puzzling well isolated doublet of very narrow lines with close energies near 3. 3 eV which is assigned to recombination transitions in self-trapped d-d charge transfer (CT) excitons formed by coupled Jahn-Teller Ni + and Ni 3+ centers. The conclusion is supported both by a comparative analysis of the CT luminescence spectra for NiO and solid solutions Ni xZn 1 - xO, and by a comprehensive cluster model assignment of different p-d and d-d CT transitions, their relaxation channels. To the best of our knowledge, it is the first observation of the luminescence due to self-trapped d-d CT excitons. © 2012 Pleiades Publishing, Ltd