Sm2+ fluorescence and absorption in cubic BaCl2: Strong thermal crossover of fluorescence between 4f6 and 4f55d1 configurations

Abstract

The optical absorption and fluorescence spectra of polycrystalline cubic-phase barium chloride doped with divalent samarium is reported. X-ray diffraction shows that the cubic phase is stabilised at room temperature by the addition of 12.5% lanthanum trichloride; no evidence for the more common orthorhombic or hexagonal phases of barium chloride is found. Optical absorption measurements are in good agreement with a calculated spectrum for Sm2+ ions at a single site of cubic symmetry, even though the material must contain a substantial fraction of chlorine interstitials and lanthanum substitutional ions. The photoluminescence spectrum shows sharp red line emission from the 5D1 and 5D0 levels of the 4f6 configuration, again consistent with a single site of cubic symmetry, together with a broad emission, also in the red, which arises from the lowest levels of the 4f55d1 configuration. The relative strengths of these emissions are strongly temperature dependent; at room temperature the broad band from the lowest 4f55d1 levels peaking at 15,130cm−1 is dominant, while at low temperature (∼12K) sharp lines from the 5D0 level dominate. The most intense line corresponds to the 5D0→7F1 transition at 14,300cm−1, but the nominally forbidden 5D0→7F0 transition also has significant intensity. The marked temperature dependence of the intensity of the lines and bands is successfully modelled by rate equations and is explained on the basis of thermally activated crossovers between the 4f6 (5D0,1) levels and the lowest levels of the 4f55d1 configuration; it is necessary to include the three lowest levels of the 4f55d1 configuration sandwiched between the 5D0 and 5D1 levels.