Spectroscopic Properties of Tb3+ Ions in TbF3-Doped CaF2 Crystals

Tb³⁺-doped CaF₂ single crystals are attractive materials for green photonic applications due to their low phonon energy, high optical transparency, and efficient Tb³⁺ emission. In this work, CaF₂ single crystals doped with different TbF₃ concentrations (1, 5, and 10 mol%) were grown and systematically investigated in order to clarify the concentration-dependent spectroscopic behavior of Tb³⁺ ions in a fluorite host. Optical absorption spectroscopy, Judd-Ofelt analysis, steady-state and time-resolved photoluminescence, colorimetric evaluation, and emission cross-section and gain calculations were employed. Judd-Ofelt intensity parameters typical of fluoride hosts were obtained, enabling the calculation of radiative transition probabilities and lifetimes. The emission spectra are dominated by intense green luminescence from the ⁵D₄ → ⁷F₅ transition, while the absence of ⁵D₃ emission is attributed to efficient cross-relaxation processes. Fluorescence lifetimes in the millisecond range show slight changes with Tb³⁺ concentration. Quantum efficiency increases from low to intermediate concentrations and tends to saturate at higher doping levels. CIE 1931 chromaticity coordinates confirm stable green emission, while emission cross-sections and gain parameters reveal a highest value for orange emission of 10 mol% TbF₃-doped CaF₂ crystal. These results indicate that CaF₂:Tb³⁺ single crystals are promising materials for photonic applications.