Radiative decay of self-trapped excitons in CaMoO₄and MgMoO₄crystals

Abstract

Spectroscopic properties of CaMoO4 and MgMoO4 crystals were studied in view of their application to cryogenic scintillation detectors. Luminescence spectra and the luminescence decay kinetics were measured over a wide range of temperatures (8–300 K). For the first time we measured time-resolved luminescence spectra of CaMoO4. In addition to the green emission arising from the triplet state of self-trapped excitons (STEs), a new band at around 430 nm with a decay time constant 10 ± 3 ns was observed at T = 8 K. This emission is assigned to the radiative decay of a singlet STE. The relaxation of electronic excitations in the crystals under study is discussed on the basis of our current understanding of their electronic structures and a configuration coordinate model for the radiative decay of STEs. The model includes adiabatic potential energy surfaces (APESs) associated with singlet and triplet states and explains the variation of the luminescence kinetics with temperature as a result of a re-distribution in the population of these states. Thus, judging from the change of the singlet STE emission due to temperature variation, we infer the existence of an energy barrier between the singlet and triplet APESs. The multi-exponential character of the decay of the triplet emission can be understood assuming that the relevant radiative transitions originate from different minima of the triplet APES. Non-radiative energy transfer processes control the population of these states, resulting in thermal variation of the intensities of the different emission components.