EPR study of chromium-doped forsterite crystals: Cr³⁺(M1) with and without associated nearest-neighbor Mg²⁺(M2) vacancy

Abstract

Electron paramagnetic resonance (EPR) study of single crystals of chromium-doped forsterite grown by the Czochralski method in two different research laboratories has revealed, apart from the known paramagnetic centers Cr³⁺(M1), Cr³⁺(M2) and Cr⁴⁺, a new center ${\text{Cr}}^{ 3+ } (M 1){-}V_{{{\text{Mg}}^{ 2+ } }} (M 2)$ formed by a Cr³⁺ ion substituting for Mg²⁺ at the M1 structural position with a nearest-neighbor Mg²⁺ vacancy at the M2 position. For this center, the conventional zero-field splitting parameters D and E and the principal g values and A values of the ⁵³Cr hyperfine splitting have been determined as follows: D = 33.95(3) GHz, E = 8.64(1) GHz, g = [1.9811(2), 1.9787(2), 1.9742(2)], A = [51(3), 52(2), 44(3)] MHz. The center has been identified by comparing EPR spectra with those of the charge-uncompensated ion Cr³⁺(M1) and the ion pair Cr³⁺(M1)–Li⁺(M2) observed in forsterite crystals codoped with chromium and lithium. It has been found that the concentration of the new center decreases to zero, whereas that of the Cr³⁺(M1) and Cr³⁺(M1)–Li⁺(M2) centers increases with an increase of the Li content from 0 up to ~0.03 wt% (at the same Cr content ~0.07 wt%) in the melt. The known low-temperature luminescence data pertinent to the centers under consideration are also discussed.