Design of need-based phosphors and scintillators by compositional modulation in the ZnGa2−xAlxO4:Cr3+ spinel: pure compound versus solid solutions

Abstract

Materials that can depict persistent deep red light under both ultraviolet (UV) and X-ray illumination can be a boon to sustainable economy, particularly for optical imaging, solid state lighting, and anticounterfeiting applications. Herein, we have made a series of compounds starting from ZnGa₂O₄:Cr³⁺ to ZnAl₂O₄:Cr³⁺ (individual spinel) by substituting the varied concentration of Al³⁺ in place of Ga³⁺ in ZnGa_2−xAl_xO₄:Cr³⁺ (solid solution). By virtue of the structural and defect engineering doping strategy, the photo and radioluminescence are expected to be improved. Both Cr and Al doping was found to be energetically favorable in ZnGa₂O₄, where the same does not hold true for Ga doping in ZnAl₂O₄, as indicated by the DFT-calculated defect formation energies. There seems to be ordering around the dopant ion in the solid solutions compared to either ZnGa₂O₄ or ZnAl₂O₄ and is also reflected to as lower persistent luminescence (PerL) lifetimes. PerL under UV, in general. was found to be lower with the enhancement in the Al³⁺ content endowed by the formation of Cr–Cr ion pair, lower probability of antisite formation, and widening band gap. On the other hand, X-ray excited emission enhances in the solid solution due to the decrease in cation inversion and associated defects. Confocal Microscopy showed that larger particles depicted much brighter deep red emission but failed to percolate to the human cells to a detectable limit; hence, future work is needed for the functionalization of the ZnGa_2−xAl_xO₄:Cr³⁺ spinel. This work could be of great implication in designing need-based materials, where UV and X-ray excitation is required, for deep red emission with persistent characteristics from chromium-doped spinels.