Controlling disorder in the ZnGa₂O₄:Cr³⁺ persistent phosphor by Mg²⁺ substitution

We have studied in this work the effect of increasing structural disorder on the persistent luminescence of Cr$^{3+}$ doped zinc gallate spinel. This disorder was introduced by progressive substitution of Zn$^{2+}$ by Mg$^{2+}$ ions, and was studied by photoluminescence, X-ray diffraction, extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES) and electron paramagnetic resonance (EPR) spectroscopy. It was found that increasing Mg/Zn substitution decreases the number of Cr$^{3+}$ in undistorted sites, and increases the number of Cr$^{3+}$ with neighbouring antisite defects and with neighbouring Cr$^{3+}$ ions (referred as Cr clusters), which in turn decreases the intensity of persistent luminescence. Both XANES and EPR spectra could be simulated by a linear combination of Cr$^{3+}$ spectra with three types of Cr$^{3+}$ environments. The increasing disorder was found to be correlated with a decrease of the average Cr-O bond length and a decrease of crystal field strength experienced by Cr$^{3+}$ ions.