We report the results of the investigation of Ga-doping effects on the electronic structure of the yttrium–aluminum garnet. The bandgap structure was studied both experimentally using thermally stimulated luminescence technique and theoretically by first-principles density functional theory calculations. We observe a nonlinear decrease in the conduction band minimum with respect to the vacuum referred binding energy with an increase in Ga doping and argue that the effect can be explained by taking into account different influences of the distorted crystal field on the molecular orbitals of the crystal unit cell. The reported nonlinear behavior is important for the band engineering of scintillators based on multicomponent garnets.

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Afterglow is an important phenomenon in luminescent materials and can be desired (e.g. persistent phosphors) or undesired (e.g. scintillators). Understanding and predicting afterglow is often based on analysis of thermally stimulated luminescence (TSL) glow curves assuming the presence of one or more discrete trap states. Here we present a new approach for the description of the time-dependent afterglow from TSL glow curves using a model with a distribution of trap depths. The method is based on the deconvolution of the energy dependent density of occupied traps derived from TSL glow curves using Tikhonov regularization. To test the validity of this new approach, the procedure is applied to experimental TSL and afterglow data for Lu 1 Gd 2 Ga 3 Al 2 O 12 :Ce ceramics co-doped with 40 ppm of Yb 3+ or Eu 3+ traps. The experimentally measured afterglow curves are compared with simulations based on models with and without the continuous trap depth distribution. The analysis clearly demonstrates the presence of a distribution of trap depths and shows that the new approach gives a more accurate description of the experimentally observed afterglow. The new method will be especially useful in understanding and reducing undesired afterglow in scintillators.

Light yield, time response, afterglow, and thermoluminescence of Ce-doped garnet scintillators and persistent luminescent materials are controlled by a complex interplay between recombination and trapping/detrapping processes. Extensive research has contributed to a good qualitative understanding of how traps, impurities, and the presence of Ce4+ affect the materials properties. In this work we present a quantitative model that can explain the thermoluminescence and afterglow behavior of complex garnets. In particular, the model allows the determination of capture rates and effective capture radii for electrons by traps and recombination centers in Lu1Gd2Ga3Al2O12:Ce garnet ceramics. The model relies on solving a set of coupled rate equations describing charge carrier trapping and recombination in garnet ceramics doped with Ce and also codoped with a known concentration of an intentionally added electron trap, Yb3+. The model is supported by analysis of a complete set of experimental data on afterglow, rise-time kinetics, and X-ray excited luminescence which show that thermoluminescence/afterglow are governed by trapping/detrapping processes following interactive kinetics with dominant recombination channel. The underlying reason for dominant recombination is the presence of a small fraction of Ce4+ (≈2 ppm in the 0.2% Ce-doped sample) which have a very high capture cross section (≈2.7 Å effective radius) because of the Coulomb attractive nature of this recombination center. The quantitative insights on capture cross sections and concentrations of Ce4+ help to better understand the optical properties of Ce-doped garnet scintillators and persistent luminescent materials and serve in optimizing synthesis procedures by tuning the Ce3+/Ce4+ ratio by codoping with divalent cations and annealing in an oxygen-containing atmosphere.

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