Role of Lithium Codoping in Enhancing the Scintillation Yield of Aluminate Garnets

Abstract

The aim of this work is to clarify the scintillation-yield enhancement in $\mathrm{Lu}\mathrm{YAG}:\mathrm{Pr}$ scintillators obtained by $\mathrm{Li}$ codoping via integrated study of the valence state of activators, the preferential site occupancy of $\mathrm{Li}$ codopants, and defect structures from experimental and theoretical insights. With $\mathrm{Li}$ codoping, the light yield and energy resolution of $10\ifmmode\times\else\texttimes\fi{}10\ifmmode\times\else\texttimes\fi{}10\phantom{\rule{0.1em}{0ex}}{\mathrm{mm}}^{3}$ $\mathrm{Lu}\mathrm{YAG}:\mathrm{Pr}$ samples are improved from 15 600 to 24 800 photons/MeV, and 5.3 to 4.3% at 662 keV, respectively. The optical absorption spectra indicate that $\mathrm{Li}$ codoping does not induce conversion of stable ${\mathrm{Pr}}^{3+}$ to ${\mathrm{Pr}}^{4+}$ in $\mathrm{Lu}\mathrm{YAG}:\mathrm{Pr}$ single crystals. Based on the formation energies of substitutional and interstitial $\mathrm{Li}$ sites using density-functional-theory (DFT) calculations and the ${}^{7}\mathrm{Li}$ nuclear magnetic resonance results, it is shown that the $\mathrm{Li}$ ions prefer to dominantly occupy the fourfold coordinated interstitial sites and fourfold coordinated $\mathrm{Al}$ sites. The systematic analysis of thermoluminescence glow curves, positron annihilation lifetime spectroscopies, and defect formation energies derived from DFT calculations reveals that the concentration of isolated $\mathrm{Lu}$ and $\mathrm{Al}$ vacancies as dominant acceptor defects is reduced by $\mathrm{Li}$ codoping, whilst the shallow ${\mathrm{Li}}_{i}$ interstitial defects and the deep ${V}_{O}$ oxygen vacancies are introduced simultaneously. We propose that the lowering of hole trapping at defects resulting from $\mathrm{Li}$ codoping contributes to the scintillation-yield enhancement.