Difference of Eu3+ luminescent properties in YOCl and YOBr oxyhalide hosts

The photoluminescence spectra and luminescence lifetimes of Eu3+-doped oxyhalides, YOX:Eu3+ (X = Cl or Br), and their temperature dependence on different halide species of mixed-anion coordinations were investigated and analyzed. In terms of the ionic and covalent nature of bonding, Eu3+ ions form different coordination polyhedra in the isostructural YOCl and YOBr hosts: a ninefold [Eu3+O4Cl5] and an eightfold [Eu3+O4Br4] polyhedra. The Judd–Ofelt Ω2 parameter for YOCl:Eu3+ takes a very large value (=8.81 × 10−20 cm2) due to the ninefold polyhedron with C4v symmetry. On the other hand, despite the same C4v symmetry, YOBr:Eu3+ shows a very small Ω2 parameter (=2.72 × 10−20 cm2) because of its structural similarity to the square antiprism polyhedron with D4 symmetry. The Ω4 parameters for YOX:Eu3+ are much larger than those for other Eu3+-doped oxides, possibly related to the covalency of halide anions, Cl− and Br−, showing an intense luminescence band (5D0 → 7F4) at around 700 nm. The Eu3+ ions in these YOX hosts were excitable by charge transfer bands in 270–280 nm regions. The relaxation pathways from the charge transfer states to the initial states for luminescence are discussed, using the configuration coordinate diagrams with the spectroscopic characterization.