Spectroscopic studies of the Eu3+ and Er3+ ions in the fluorozirconate LaZr2F11 matrix

Abstract

An investigation by optical spectroscopy of the Eu3 + and Er3 + active ions in the crystallized fluorozirconate matrix LaZr2F11 is presented. The D-5(1) --> F-7(0-5) emission lines of Eu3 + are used to extract the F-7(0-5) energy scheme and the observed extinctions permit the deduction of irreducible representations (IRREPS) associated with corresponding sub-levels in the D-2 symmetry. The crystal field analysis was carried out on a 387 x 387 basis set, comprising the F-7, D-5(1,2,3) F-5(1,2), (5)G(1,2,3) and P-3(1,2,3,4,5,6) terms of the Eu-3 (+) 4f(6) configuration. The deviation and rms are 6.8 and 7.9 cm (-1), respectively for 38 levels and ten parameters. The experimental crystal field parameters are in good agreement with the ab-initio ones. Moreover, the relative intensities of the D-5(0) --> F-7(2,3,4) emissions are well reproduced by an 'ab-initio' calculation, except for three lines. The Er3 + ions introduced in LaZr2F11, microcrystals also lie in an unique crystallographic site. A total of 31 energy levels were recorded and the crystal field analysis led to 6.6 and 7.8 cm (-1) for the deviation and rms, respectively, for nine variable parameters taken into account. The experimental CF parameters for Er3 + and Eu3 + are very similar, which seems to show that the host lattice contracts around the smaller Er3 + ion. The informations given by both Eu3 + and Eu3 + optical probes in LaZr2F11 are very consistent with the structure previously determined for the isotypic PrZr2F11 fluoride. (C) 2000 Elsevier B.V. B.V. All rights reserved.