Experimental and Theoretical Studies of the Site Occupancy and Luminescence of Ce3+ in LiSr4(BO3)3 for Potential X-ray Detecting Applications

Abstract

Ce³⁺-doped LiSr₄(BO₃)₃ phosphors have been prepared by a high-temperature solid-state reaction method, and structural refinement of the host compound has been performed. The excitation and emission spectra in the vacuum ultraviolet-ultraviolet-visible range at cryogenic temperatures reveal that Ce³⁺ ions preferentially occupy eight-coordinated Sr²⁺ sites in LiSr₄(BO₃)₃. Such experimental attribution is well corroborated by the calculated 4f-5d transition energies and defect formation energies of Ce³⁺ ions at two distinct Sr²⁺ sites in the first-principles framework. In addition, the doping concentration-dependent luminescence and the temperature-dependent luminescence are systematically investigated by luminescence intensity and lifetime measurements, respectively. This shows that concentration quenching does not occur in the investigated doping range, but inhomogeneous broadening exists in the concentrated samples. With the estimated thermal quenching activation energy, the discussions on the thermal quenching mechanisms suggest that the thermal-ionization process of the 5d electron is a dominant channel for thermal quenching of Ce³⁺ luminescence, despite the fact that thermally activated concentration quenching cannot be excluded for the highly doped samples. Finally, the X-ray excited luminescence measurement demonstrates the promising applications of the phosphors in X-ray detection.