Ab initio study of luminescence in Ce-doped Lu2SiO5: The role of oxygen vacancies on emission color and thermal quenching behavior

We study from first principles the luminescence of Lu$_2$SiO$_5$:Ce$^{3+}$ (LSO:Ce), a scintillator widely used in medical imaging applications, and establish the crucial role of oxygen vacancies (V$_O$) in the generated spectrum. The excitation energy, emission energy and Stokes shift of its luminescent centers are simulated through a constrained density-functional theory method coupled with a ${\Delta}$SCF analysis of total energies, and compared with experimental spectra. We show that the high-energy emission band comes from a single Ce-based luminescent center, while the large experimental spread of the low-energy emission band originates from a whole set of different Ce-V$_O$ complexes together with the other Ce-based luminescent center. Further, the luminescence thermal quenching behavior is analyzed. The $4f-5d$ crossover mechanism is found to be very unlikely, with a large crossing energy barrier (E$_{fd}$) in the one-dimensional model. The alternative mechanism usually considered, namely the electron auto-ionization, is also shown to be unlikely. In this respect, we introduce a new methodology in which the time-consuming accurate computation of the band gap for such models is bypassed. We emphasize the usually overlooked role of the differing geometry relaxation in the excited neutral electronic state Ce$^{3+,*}$ and in the ionized electronic state Ce$^{4+}$. The results indicate that such electron auto-ionization cannot explain the thermal stability difference between the high- and low-energy emission bands. Finally, a hole auto-ionization process is proposed as a plausible alternative. With the already well-established excited state characterization methodology, the approach to color center identification and thermal quenching analysis proposed here can be applied to other luminescent materials in the presence of intrinsic defects.