Local Structure and Speciation-Driven UO22+ → Sm3+ Energy Transfer for Enhanced Luminescence in Li2B4O7.

Abstract

Herein, we report the uranyl sensitization of Sm3+ emissions in uranium-codoped Li2B4O7:Sm3+ phosphor. The uranyl speciation in codoped [Sm, U] LTB samples was determined by synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy that revealed two coordination shells for U(VI) ions with bond distances of U-Oax (∼1.81 Å) and U-Oeq (∼2.30 Å). EXAFS fitting suggested that the uranyl moiety is present as pentagonal bipyramids (UO7) and hexagonal bipyramids (UO8) with five and six equatorial oxygen ligands, respectively. The alteration of the local structure of Sm3+ from [SmO4] to [SmO7] polyhedra and the changes in the coordination number of equatorial oxygen for uranyl were observed with different codoping concentrations of Sm3+ and uranium. Density functional theory (DFT) calculations suggested the lowering of defect formation energy for Li vacancies on codoping of Sm and U. Hence, we proposed the increase of the equatorial coordination number of UO22+ on the increase in the lithium vacancies in LTB. In addition, DFT supported the feasibility of efficient energy transfer (ET) due to the overlap of uranium and Sm3+ excited state levels. The influence of the same on the spectral features and UO22+ → Sm3+ energy transfer was investigated by time-resolved photoluminescence (PL) studies. The ET efficiency from the UO22+ to Sm3+ was 70.5% in 0.5 mol % codoped [Sm, U] LTB samples. The correlation of EXAFS and luminescence properties indicated a red shift in vibronic features of uranyl emission with increase in the equatorial coordination of the uranyl moiety from five to six. Additionally, a higher probability of ET was observed for uranyl speciation as UO8 hexagonal bipyramids. Temperature-dependent emissions and decay profiles were collected under uranyl excitation to investigate the thermal dependence of ET. A high energy barrier (Ea ∼ 4027 cm-1) was evaluated for the thermal quenching of Sm3+ emissions. This work provides insights into the modulation of luminescence and ET efficiency via structural changes in uranyl and Sm local environment in LTB phosphor.