Characterization of the charge transfer luminescence of the [WO6]6- octahedron in Ca3WO6 and the [WO5]4- square pyramid in Ca3WO5Cl2.

Charge transfer (CT) luminescence of different types of polyhedra, [WO5]4- in Ca3WO5Cl2 and [WO6]6- in Ca3WO6, is characterized by spectroscopic experiments and ab initio calculations. According to the geometry optimization, W6+ ions form five-fold [WO5]4- square pyramids in Ca3WO5Cl2 because of a large interatomic distance between W6+ and Cl- of 3.266 Å. The analysis of the density of electronic states reveals the ionic character of Cl- ions to the W6+ ions in the Ca3WO5Cl2 lattice, resulting in the observed broad luminescence band peak at 488 nm of the single-crystal Ca3WO5Cl2 sample being assigned to the CT transition in the [WO5]4- square pyramid. Compared with the [WO6]6- octahedron in Ca3WO6, the [WO5]4- square pyramid shows an inconsistent CT energy shift: higher CT absorption and lower luminescence energies. The larger bandgap brings about higher absorption energy due to the structural and compositional features of the orthorhombic Ca3WO5Cl2. The redshifted CT luminescence band and small activation energy for the thermal quenching of the Ca3WO5Cl2 sample are explained, assuming that the CT states of the anisotropic [WO5]4- square pyramid take a larger offset in the configurational coordinate diagram than the [WO6]6- octahedron.

Deep-red to near-infrared luminescence from Eu2+-trapped exciton states in YSiO2N.

The valence state of Eu ions doped in inorganic compounds is easily influenced by the synthesizing conditions. In this study, X-ray absorption spectroscopy revealed that almost half of Eu ions incorporated in the YSiO2N host were reduced into the divalent state through the sintering process at 1600 °C under a N2 gas atmosphere without any annealing processes. The prepared Eu2+/3+-doped YSiO2N sample showed anomalous deep-red to near-infrared luminescence below 300 K under violet light illumination, whose luminescent properties are discussed through detailed spectroscopic analyses. In the photoluminescence spectra at 4 K, the broad luminescence band ranging from 550 to 1100 nm with a large Stokes shift of 5677 cm-1 was observed, assigned to the recombination emission related to the Eu2+-trapped exciton state. The temperature dependence of luminescence lifetime suggests that the thermal quenching of Eu2+-trapped exciton luminescence takes place through complicated processes in addition to thermal ionization. The energy diagrams based on the spectroscopic results indicate that Eu2+-trapped exciton luminescence in the YSiO2N:Eu2+/3+ sample was observed because all the Eu2+: 5d excited levels are degenerated with the host conduction band, and the relatively stable Eu2+-trapped exciton state in the Y3+ sites is formed just below the conduction band bottom. A comprehensive discussion on the deep-red to near-infrared luminescence in the YSiO2N host could give new insights into the mechanism of Eu2+-trapped exciton luminescence in Y3+ sites, which has potential in near-infrared emitting devices.

A brief review of characteristic luminescence properties of Eu3+ in mixed-anion compounds.

Trivalent europium (Eu3+) ions show red luminescence with sharp spectral lines owing to the intraconfigurational 4f-4f transitions. Because of their characteristic luminescence properties, various Eu3+-doped inorganic compounds have been developed to meet the demands of optoelectronic devices. Regardless of shielding by the outer 5s and 5p orbitals, the properties of the Eu3+:4f-4f transition depend on the local environment, such as the shapes of the coordination polyhedra, site symmetry, nephelauxetic effects, crystal field effects, and bonding character. Mixed-anion coordination, where multiple types of anions surround a single Eu3+ ion, can directly affect the optical properties of Eu3+. We review the luminescence properties of Eu3+ ions in mixed-anion compounds of the oxynitride YSiO2N and oxyhalides YOX (X = Cl or Br). Oxynitride and oxyhalide coordination results in characteristic transition probabilities and branching ratios of the 5D0 → 7F0-6 transitions due to distorted structural environments and red-shifted charge transfer excitation bands due to an upward shift of the valence band. The expected and experimentally observed features of Eu3+ luminescence in mixed-anion compounds are outlined based on band and Judd-Ofelt theories. Future applications of the intense red luminescence at ∼620 nm under near-ultraviolet light illumination in Eu3+-doped mixed-anion compounds are introduced, and material design guidelines for new functional Eu3+-doped phosphors are presented.

Addressing Current Challenges in OSL Dosimetry Using MgB4O7:Ce,Li: State of the Art, Limitations and Avenues of Research.

The objective of this work is to review and assess the potential of MgB4O7:Ce,Li to fill in the gaps where the need for a new material for optically stimulated luminescence (OSL) dosimetry has been identified. We offer a critical assessment of the operational properties of MgB4O7:Ce,Li for OSL dosimetry, as reviewed in the literature and complemented by measurements of thermoluminescence spectroscopy, sensitivity, thermal stability, lifetime of the luminescence emission, dose response at high doses (>1000 Gy), fading and bleachability. Overall, compared with Al2O3:C, for example, MgB4O7:Ce,Li shows a comparable OSL signal intensity following exposure to ionizing radiation, a higher saturation limit (ca 7000 Gy) and a shorter luminescence lifetime (31.5 ns). MgB4O7:Ce,Li is, however, not yet an optimum material for OSL dosimetry, as it exhibits anomalous fading and shallow traps. Further optimization is therefore needed, and possible avenues of investigation encompass gaining a better understanding of the roles of the synthesis route and dopants and of the nature of defects.

Formation of PbCl2-type AHF (A = Ca, Sr, Ba) with partial anion order at high pressure.

The high-pressure structures of alkaline earth metal hydride-fluorides (AHFs) (A = Ca, Sr, Ba) were investigated up to 8 GPa. While AHF adopts the fluorite-type structure (Fm3[combining macron]m) at ambient pressure without anion ordering, the PbCl2-type (cotunnite-type) structure (Pnma) is formed by pressurization, with a declining trend of critical pressure as the ionic radius of the A2+ cation increases. In contrast to PbCl2-type LaHO and LaOF whose anions are fully ordered, the H-/F- anions in the high-pressure polymorph of SrHF and BaHF are partially ordered, with a preferential occupation of H- at the square-pyramidal site (vs. tetrahedral site). First-principles calculations partially support the preferential anion occupation and suggest occupation switching at higher pressure. These results provide a strategy for controlling the anion ordering and local structure in mixed-anion compounds.