Optical characterization of Cr3+ centers in LiNbO3

Abstract

Low-temperature luminescence spectra of stoichiometric Cr:LiNbO₃, congruent Cr:LiNbO₃ and congruent Cr,Mg:LiNbO₃ were studied. Dominant low-field and minor high-crystal-field optical centers are the Cr³⁺ impurity ions that preferentially occupy Li⁺ sites (Cr_Li) in the Cr:LiNbO₃ crystals. Low-field centers related to Cr³⁺ substitution of Nb⁵⁺ (Cr_Nb) occur in addition to Cr_Li in co-doped Cr,Mg:LiNbO₃ samples. Application of high hydrostatic pressure leads to the transformation of dominant Cr³⁺ centers from low- to high-field type due to strong pressure-induced blue shift of the ⁴ T ₂ state, resulting in its crossing with the ² E state of Cr³⁺. This level-crossing effect was observed for the dominant Cr³⁺ _Li and Cr³⁺ _Nb centers at pressures that correlate well with estimations based on the ⁴ T ₂-² Eenergy gap (230 cm^-1 and 1160 cm^-1) and on the rate of their pressure-induced change (14.35 and 11.4 cm^-1/kbar, respectively). We also studied inhomogeneous broadeningof the ² E?⁴ A ₂transitions at ambient pressure for the minor high-field “defect” Cr³⁺ _Li centers in congruent LiNbO₃. A fine structure in the spectral response of these centers was observed. The obtained results are discussed on the basis of a microscopic hierarchic model for perturbed Cr³⁺ ions in the LiNbO₃ lattice.