Vibrational Analysis of the Elpasolites Cs2NaAlF6 and Cs2NaGaF6 Doped with Cr3+ Ions by Fluorescence Spectroscopy

Interest in 3d transition metal impurities in ionic crystals has increased due to their important role in the laser activity of these materials. Moreover, recent advances in tunable solid-state lasers and high-power semiconductor laser diode arrays have generated a strong interest in investigating new compounds that emit in the visible and near-infrared spectral regions. In particular, many optical studies have been devoted to Cr3+-doped fluoride crystals as a consequence of the high quality of some Cr3+-based laser materials. In the present investigation, the low-temperature emission spectra of Cr3+ ions in the hexagonal elpasolites Cs2NaAlF6 and Cs2NaGaF6 have been measured. Each compound has two crystallographically inequivalent octahedral sites for the Al3+ and Ga3+ ions that can be occupied by Cr3+ ions. For both materials, the luminescence spectrum presents two zero-phonon lines accompanied by a well-defined vibrational structure. The different peaks of the emission broad band are described in terms of phonons of the lattice and normal modes of the octahedral complex [CrF6]3−. A detailed analysis of the vibrational structure observed leads to the conclusion that the 2E and 4T2 excited states of the [CrF6]3− ion are displaced along the eg and a1g and probably the t2g coordinates.