EPR and optical absorption studies of Cr³⁺ ions in alkaline earth alumino borate glasses

Abstract

Electron paramagnetic resonance (EPR) and optical absorption spectra of Cr³⁺ ions in Calcium alumino borate (CaAB) glasses have been studied. The EPR spectra exhibit weak resonance signal at g ≈ 4.50 and intense resonance signal at g ≈ 1.98. A sharp resonance signal at g ≈ 1.97 was also observed at lower concentrations of chromium. The concentration dependence of the linewidth of the resonance signal at g ≈ 1.98 suggests the formation of Cr³⁺ ion clusters by magnetic superexchange interactions. The temperature dependence of the peak to peak intensity and the linewidth of the resonance signal at g ≈ 1.98 suggests that the exchange interactions between Cr³⁺ ions in the present sample were antiferromagnetic in nature with Néel temperature, T_N = 233 K. From the number of spins participating in the resonance at g ≈ 1.98, the paramagnetic susceptibility (χ) was calculated at different temperatures (233–295 K). A plot of 1/χ and T was found to obey Curie-Weiss law with negative Curie temperature. By measuring the relative intensities of the resonance signal at g ≈ 1.98, at different temperatures, the value of antiferromagnetic coupling constant (J) has been estimated. The optical absorption spectrum of chromium doped CaAB glass exhibits four bands, characteristic of Cr³⁺ ions, in nearly octahedral symmetry. From the band positions, the crystal field splitting parameter, Dq and the Racah interelectronic repulsion parameters, B and C were evaluated. The optical band gap (E_opt) and the Urbach energy (ΔE) were calculated from the ultraviolet absorption edges.