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We present a study of emission, absorption and vibrational properties of Sm³⁺ doped lead fluoroborate glasses (PbO–PbF₂–B₂O₃–Sm₂O₃) as a function of the Sm³⁺ content. Changes in the position and the intensity parameters of the transitions are closely related to structural changes in the glass network. A Judd–Ofelt scheme was used to estimate the intensity parameters Ω_λ and radiative properties for Sm³⁺ in the glass. The behaviour of Ω₂ and Ω₆ parameters suggested a decrease in the asymmetry degree of the local ligand field at Sm³⁺ sites and an increase in the covalency of Sm–O bond, respectively. This hypothesis was verified by analysing the structural role of Sm₂O₃ through Raman and infrared spectroscopy measurements.