Cation influence on exciton localization in homologue scheelites

Homologue scheelite crystals CaWO4, SrWO4, and BaWO4 possess similar crystal and electronic structure, but their luminescence exhibits drastically different thermal stabilities. By measuring the temperature dependence of the decay time of the intrinsic luminescence and fitting it to a three level model, we have qualitatively shown the effective exciton radius to increase in the order CaWO4 → SrWO4 → BaWO4, which explains the differences in the thermal stability. The origin of the variation in the exciton radii is suggested to be related to differences in the excited state dynamics in these crystals. From the decay kinetics measured under conditions of high excitation density, the efficiency of dipole-dipole interaction between excitons is shown to grow with exciton delocalization.