Site symmetry and crystal field splittings of Ce 3+ in LiLuF 4 and LiSr 0.8 Ca 0.2 AlF 6

Electron paramagnetic resonance (EPR) spectra of Ce 3+ in LiLuF 4 (LLF) and LiSr 0.8 Ca 0.2 AlF 6 (LSCAF) observed at low temperatures (<20 v K) show that the Ce 3+ centers have tetragonal and pseudo-trigonal symmetry with ( g , g )=(2.751, 1.467) and (2.14, 0.80), respectively. The EPR lines of Ce 3+ in LSCAF are inhomogeneously broadened by different Ce 3+ configurations which correspond to the random occupation of the second nearest neighbor cation sites by Ca 2+ and Sr 2+ and/or charge compensators. These EPR results indicate that the Ce 3+ centers in LLF and LSCAF are associated with substitution of Ce 3+ for Lu 3+ with eight-fold coordination and Sr 2+ /Ca 2+ with six-fold coordination, respectively. Fourier transform infrared absorption has been used to measure transitions between the 2 F 5/2 ground state and the 2 F 7/2 multiplet of Ce 3+ in LLF at 10 v K. The optical absorption and luminescence of Ce 3+ :LLF and Ce 3+ :LSCAF in the UV range are strongly polarized. The energy levels and polarization dependence of the optical transitions can be accounted for in terms of the crystal field potential experienced by the Ce 3+ ions under the action of the different point group symmetries.