Thorium-229 doped calcium fluoride (Th:CaF) is a leading candidate for a solid-state nuclear clock, owing to the unusually low energy of the Th isomer transition at 8.3557,eV and the very high banggap of CaF around 12,eV. Here we report a temperature-dependent study of Th:CaF luminescence, covering radioluminescence, photoluminescence, thermoluminescence, and afterglow. Using synchrotron x-ray excitation together with a cryo-vacuum system, we resolve the thermal quenching of the self-trapped exciton (STE) scintillation into its triplet and singlet components, identify eleven thermoluminescence glow peaks together with their associated emission bands, and separate the temperature-dependent components that make up the long-lived afterglow. The trap depths obtained in this way are closely correlated with the temperature dependence of x-ray-induced isomer quenching, including the enhanced isomer yield near \SI{-60}{\celsius} and the minimum near \SI{-80}{\celsius}, supporting the carrier-trapping picture in which trapped carriers are unavailable to quench the nucleus. Taken together, these results connect the optical and nuclear observables of Th:CaF through a unified picture of electron defects and Th-related traps, while providing a comprehensive characterization of the material relevant to solid-state nuclear clock operation.

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