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Molecular beam epitaxy (MBE) grown CaF₂-CdF₂ superlattices (SLs) and CaF₂ thin films doped with Eu ions were investigated by laser spectroscopic techniques. Eu ions were selectively doped into CaF₂ layers and were used as an optical probe to the SLs and thin films. Physical properties of the SLs and thin films were inferred from optical transitions of divalent and trivalent Eu centres. The 4ƒ⁶5d → 4ƒ⁷ transition of Eu²⁺ has shown strain dependent peak shifts of the zero phonon line. These shifts were thought to be a result of deformation in the crystal structure primarily due to the lattice mismatch with the Si substrate. Based on the amount of shifts, the strains associated with the MBE samples were calculated. Photoluminescence (PL) bleaching and its recovery of the same transition of Eu²⁺ in SLs were also explored. At low temperature the bleaching is best described as bi-exponential decay. Localisation of the liberated electrons from the 4ƒ⁶5d absorption band was considered for the bleaching effect. It was observed that at elevated temperatures the PL intensity of the 4ƒ⁶5d → 4ƒ⁷ transition was recovered. Combined excitation-emission spectroscopy (CEES) was employed to investigate trivalent Eu centres in SLs. The strong ⁷F₀ → ⁵D₁ excitation and the ⁵D₀ → ⁷F₁ emission of Eu³⁺ were studied. A novel centre, which is assigned as I, of Eu³⁺ in SL was observed and investigated in comparison with the cubic centre (O centre) of Eu³⁺. Relative to the O centre the I centre has shown a strong thickness dependent PL which can be demonstrated with a mono layer (1 ML = 3.15 Å) resolution. Possible transformation of the I centre to the O centre was also observed by additional thermal and UV excitations. The I and the O centres are proposed as the same centre except for having an electron in the vicinity of the I centre.

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The Bear Lodge alkaline complex in northeastern Wyoming (USA) is host to potentially economic rare-earth mineralization in carbonatite and carbonatite-related veins and dikes that intrude heterolithic diatreme breccias in the Bull Hill area of the Bear Lodge Mountains. The deposit is zoned and consists of pervasively oxidized material at and near the surface, which passes through a thin transitional zone at a depth of ~120-183m, and grades into unaltered carbonatites at depths greater than ~183-190m. Carbonatites in the unoxidized zone consist of coarse and fine-grained calcite that is Sr-, Mn- and inclusion-rich and are characterized by the presence of primary burbankite, early-stage parisite and synchysite with minor bastnäsite that have high (La/Nd)cn and (La/Ce)cn values. The early minerals are replaced with polycrystalline pseudomorphs consisting of secondary rare-earth fluorocarbonates and ancylite with minor monazite. Different secondary parageneses can be distinguished on the basis of the relative abundances and composition of individual minerals. Variations in key element ratios, such as (La/Nd)cn, and chondrite-normalized profiles of the rare-earth minerals and calcite record multiple stages of hydrothermal deposition involving fluids of different chemistry. A single sample of primary calcite shows mantle-like δ18O V-SMOW and δ13C V-PDB values, whereas most other samples are somewhat depleted in 13C (δ13C V-PDB ≈ –8 to –10‰) and show a small positive shift in δ18O V-SMOW due to degassing and wall-rock interaction. Isotopic re-equilibration is more pronounced in the transitional and oxidized zones; large shifts in δ18O V-SMOW (to ~ 18‰) reflect input of meteoric water during pervasive hydrothermal and supergene oxidation. The textural relations, mineral chemistry, and C and O stable-isotopic variations record a polygenetic sequence of rare-earth mineralization in the deposit. With the exception of one Pb-poor sample showing an appreciable positive shift in 208Pb/204Pb value (~39.2), the Bear Lodge carbonatites are remarkably uniform in their Nd, Sr and Pb isotopic composition: (143Nd/144Nd)i=0.512591-0.512608; εNd=0.2-0.6; (87Sr/86Sr)i=0.704555-0.704639; εSr=-1.5-2.7; (206Pb/204Pb)i=18.071-18.320; (207Pb/204Pb)i=15.543-15.593; (208Pb/204Pb)i=38.045-39.165. These isotopic characteristics indicate that the source of the carbonatitic magma was in the subcontinental lithospheric mantle, and modified by subduction-related metasomatism. Carbonatites are interpreted to be generated from small degrees of partial melt that may have been produced via interaction of upwelling asthenosphere giving a small depleted MORB component, with an EM1 component likely derived from subducted Farallon crust.

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