Optical and EPR spectroscopy of manganese doped LiNaGe4O9 single crystals

Abstract

The paper presents data on the study of optical absorption, photoluminescence and EPR of lithium-sodium tetragermanate crystals (LiNaGe4O9) doped with Mn ions. Optical spectra were measured in the range 11000–45000 cm−1 and temperatures 77–300 K. They are attributed to manganese in the +4 charge state. From the analysis of optical spectra, the crystal field strength Dq = 2175.2 cm−1 and Racah parameters A = 4065 cm−1, B = 813 cm−1, C = 3239 cm−1 were determined for the Mn4+ ions. The value of the Huang-Rhys factor SFHR = 17.56 indicates a strong electron-phonon interaction of the Mn4+ ion. The presence of Mn4+ ions was further confirmed by measurement of EPR spectra at microwave frequencies 8.9 and 320 GHz. EPR data show that Mn4+ ions occupy two structurally nonequivalent lattice sites with the formation of two Mn4+ centers: Mn1 and Mn2. From the angular dependences of the EPR spectra, the components of the g factor and the hyperfine interaction tensor A, the parameters of the axial D and rhombic E crystal field were determined for both centers. The axial constant D is large for both centers: 0.644 and 0.560 cm−1, respectively. Analysis of optical and EPR spectroscopic data testifies that Mn4+ ions replace the Ge4+ ions in oxygen octahedrons within the host. Structurally nonequivalent centers are attributed to manganese ions located in undistorted lattice sites (Mn1) and in sites perturbed by the LiNa antisite defect (Mn2).