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The effect of chloride and/or bromide ions on the redox equilibrium of rare-earth ions, Sm and Yb, was investigated in an AlF3-based YABC glass system. The large absorption bands of 4f-5d transition of Sm2+ and Yb2+ ions were found in the chlorine-doped samples in the visible and ultra-violet regions, respectively. Their intensities increased with the degree of incorporation. Change in the redox equilibrium of Yb ions was found to be a function of both the quantity and type of non-fluoride halide ions used as dopants. Br- was about 6 times more efficient than Cl- and co-doping resulted in a greater number of divalent Yb2+ ions. X-ray photoelectron spectra of Y3d and the thermodynamics data of various halide compounds and molecules reveal that the direct bond formation between rare-earth ions and non-fluoride ions and the lower free energies of mixed halide molecules would play key roles in the formation of divalent rare-earth ions in the glass melts.

Redox Equilibrium of Rare-Earth Ions in Chlorine- and Bromine-Doped Fluoroaluminate Glasses