Deciphering competing radiative relaxation pathways observed in Pr3+-Activated yttrium-based compounds: UV emission versus visible emission

Abstract

Pr3+-activated yttrium-based compounds have garnered significant research interest as the electronic transition of Pr3+ dopant incorporated in host lattices are quite versatile, giving rise to the production of either UV or visible electromagnetic radiation. The tunable 5d orbital energy level of Pr3+ with an electronic configuration [Xe]4f15d1 depending on the external crystal fields, coordinating anion ligands (mainly determined by covalency of anion ligands), and symmetry of crystal structures can indeed control the radiative decay processes whether to generate UV or self-trapped exciton-mediated visible emission. We have investigated three different Pr3+-activated crystals of YPO4, YBO3, and Y2SiO5 using two different excitation processes including direct host lattice excitation (cathodoluminescence: CL) and f-d excitation of Pr3+ dopants (photoluminescence: PL). Such radiative decay mechanism observed in Pr3+-doped yttrium-based compounds has been deciphered that photoexcitation of Pr3+ ions results in 4f15d1→4f2 electronic transition with UV emission (PL) whereas above-bandgap excitation of host lattices brings about the efficient production of visible emission mediated through self-trapped excitons (CL). When changing the anion sublattices, the emission peak corresponding to 4f15d1→4f2 transition shifted to longer wavelength as a result of modulated covalency and crystal field strength. As the host lattices changes as a function of anion sublattices, the bandgap reduced from 8.6 eV (for YPO4) to 7.6 eV (for YBO3) and to 6.1 eV (for Y2SiO5), directly influencing rate of trapping of exciton and their formation of self-trapped exciton, which further give rise to production of the self-trapped exciton mediated visible emission. The fundamental understanding of the multiple, radiative relaxation pathways provides a designing principle for achieving more efficient UV emitting phosphors (at the same time by suppressing visible emission or vice versa) for germicidal and medical applications.