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We report detailed optical studies of BaWO4:Ce and BaWO4:Ce,Na single crystals. The material does not emit any luminescence at ambient pressure under near-UV (325 nm) excitation. Efficient green light is emitted only at high pressure (HP) and low temperature (LT). The luminescence is of excitonic character, since the lowest Ce3+ 5d level is degenerate with the conduction band also under hydrostatic pressures. To explain these phenomena, absorption measurements were made together with powder X-ray diffraction (XRD) and confocal micro-Raman and Fourier transform infrared (FTIR) spectroscopy. Raman experiments confirm the existence of a metastable phase, induced by certain nonhydrostatic conditions, before the reversible transition at a high-pressure range above 9 GPa, where efficient photoluminescence (PL) occurs. Although the phase transition is reversible, it proceeds with a prominent hysteresis observed in luminescence and Raman experiments. FTIR focuses on the existence of Ce3+ multisites observed during LT measurements.

The structure of calcium europium orthoborate, Ca3Eu2(BO3)4, was determined using high-resolution powder X-ray diffraction data collected at the ID22 beamline (ESRF) under ambient conditions, as well as at high temperature. Rietveld refinement allowed determination of the lattice constants and structural details, including the Ca/Eu ratios at the three cationic sites and their evolution with temperature. Clear thermal expansion anisotropy was found, and slope changes of lattice-constant dependencies on temperature were observed at 923 K. Above this temperature the changes in occupation of the Ca/Eu sites occur, exhibiting a tendency towards a more uniform Eu distribution over the three Ca/Eu sites. Possible structural origins of the observed thermal expansion anisotropy are discussed.