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GGAG:Ce crystals with various Ca concentrations were grown by the Czochralski technique. The introduction of Ca2+ ions into a trivalent site results in a change in the Ce valence state as well as an additional F+ luminescence center. The changes of Ce valence state could be affected by various annealing atmospheres and were investigated via measuring the Ce3+ absorbance and observing the color change of the sample. Photoluminescence spectra and photoluminescence decay were used to reveal the occurrence of F+ center related to the oxygen vacancies during the annealing. A redox mechanism and a charge compensation process are proposed to explain the change in Ce state charge and F+ center during the annealing. [ABSTRACT FROM AUTHOR]