Laser-excited fluorescence of rare earth elements in fluorite: Initial observations with a laser Raman microprobe

Details Laser-excited fluorescence of rare earth elements in fluorite: Initial observations with a laser Raman microprobe Laser-excited fluorescence of rare earth elements in fluorite: Initial observations with a laser Raman microprobe

Jul 1992

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1992gecoa..56.2713b&link_type=abstract

Geochimica et Cosmochimica Acta, vol. 56, Issue 7, pp.2713-2723

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Fluorescence emission spectra of three samples of fluorite containing 226-867 ppm total rare earth elements (REE) were excited by visible and ultraviolet wavelength lines of an argon ion laser and recorded with a Raman microprobe spectrometer system. Narrow emission lines (< 1 nm) due to 4f-4f electron transitions in individual trivalent REE (Pr, Nd, Sm, Eu?, Tb, Dy, Ho, Er, Tm) were observed in the wavelength range of 400-900 nm. Emission from individual REE occur in bands of overlapping lines in the wavelength intervals of 470-495 nm, 535-560 nm, 565-580 nm, 585-620 nm, 640-643 nm, 671.4 nm, and 758.2 nm. A broad band at 419 nm excited by the 363.8-nm ultraviolet line of the laser is due to a 4f-5 d transition in Eu 2+ . Two bands of enigmatic origin are a narrow line at 682.8 nm present at all excitation wavelengths in only one sample and a broad band at 720 nm. We have tentatively assigned individual REE to specific lines in each emission band based on selection rules for strongly and weakly allowed 4f-4f transitions and the position of absorption and emission bands documented in the literature for REE in CaF 2 and LaF 3 host crystals. Working curves of integrated peak intensity of emission from Er 3+ and Eu 2+ vs. ppm measured by ICP-MS give linear log-log fits with R 2 > 0.9 for Eu 2+ and 0.99 for Er 3+ . Detection limits for three micrometer spots are about 0.01 ppm Eu 2+ and 0.07 ppm Er 3+ . These limits are less than chondrite abundance for Eu and Er, demonstrating the potential microprobe analytical applications of laser-excited fluorescence of REE in fluorite. However, application of this technique to common rock-forming minerals may be hampered by competition between fluorescence emission and radiationless energy transfer processes involving lattice phonons.

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