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

•Blue components of defect PL originate from transitions in molybdate groups.•Red-orange luminescence components of PL are related to crystal defects.•The 360–380 nm absorption band is related to oxygen vacancies.•WMo, NaLi and KLi defects form shallow charge carrier traps.•High hygroscopicity of Li2MoO4 is related to macro-defects of crystal. 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 luminescence, 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