Role of native and impurity defects in optical absorption and luminescence of Li2MoO4 scintillation crystals

The Li2MoO4 crystals have been considered as perspective cryogenic scintillation materials to be used in elementary particle physics experiments related to dark matter search and properties of neutrino. Since the crystals may be used as cryogenic scintillators, the native vacancies, uncontrolled impurities and other defects play the key role in worsening of their scintillation characteristics. The paper presents complex experimental and computational studies of the electronic structure and optical properties of Li2MoO4 crystals. The studies are aimed to explain peculiarities of the optical (luminescence) properties of Li2MoO4 using the electronic structure results obtained for a wide range of point defects and their combinations. For investigations, several samples of Li2MoO4 with different defectiveness were grown using Czohralski method and characterized by SEM and ICP-OES technique. Luminescence emission spectra of the samples under X-ray and laser excitations, optical and IR absorption spectra, TSL characteristics of the samples were recorded and analyzed. Ability to incorporate some gases was examined by measuring absorption spectra after one-year storage of the samples at ambient conditions. The electronic structures of several kinds of point defects (natural vacancies, iso- and aliovalent cationic and anionic substitutions, interstitial ions and molecular groups) in Li2MoO4 were calculated using the DFT-based plane-wave pseudopotential method. Geometries of lattice relaxations around defects, partial densities of states and energies of defect formation were calculated and analyzed together with experimental results. Performed analysis allowed making several conclusions regarding the origin of spectral components of intrinsic and defect-related lumines-cence, formation of defect-related bands in the optical and IR absorption spectra, dependence of TSL characteristics on sample defectiveness. It was found that isovalent cationic substitutions on lithium positions are presented in substantial concentrations in the Li2MoO4 samples and such defects form shallow traps which can affect scintillation characteristics in cryogenic experiments. Substantial effect of gases inclusions on the optical characteristics of crystals can be related to the peculiarity of the crystal lattice structure - the presence of empty channels, which can incorporate molecular objects like H2O, -CH3 or -OH. (C) 2021 Elsevier B.V. All rights reserved.

Automated summary

Li2MoO4 crystals are considered as promising cryogenic scintillation materials for use in elementary particle physics experiments. This study presents experimental and computational investigations into the electronic structure and optical properties of the crystals, analyzing the spectral characteristics and the impact of defects on their scintillation properties.