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

TL;DR

This study investigates NiO luminescence under XUV excitation, revealing evidence of self-trapped d-d charge transfer excitons through narrow emission lines, supported by time-resolved measurements and cluster modeling, marking the first such observation.

Contribution

It presents the first experimental evidence of self-trapping of d-d charge transfer excitons in NiO, using XUV excitation and time-resolved luminescence spectroscopy.

Findings

Detection of narrow emission lines near 3.3 eV indicating self-trapped excitons

Identification of two charge transfer mechanisms with distinct decay times

Validation of the bulk origin of luminescence through XUV excitation

Abstract

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.