Clustering of rare earths in GeAs sulfide glass

Abstract

Clustering of rare-earth dopants in GeAs sulfide glasses was studied by fluorescence spectroscopy of Pr-doped glasses and by EPR measurements of Gd-doped samples. The linewidth of the g ∼ 2 resonance of Gd 3+, as well as the relative intensity of emission from the 1D 2 level of Pr 3+, was used as a relative measure of rare-earth clustering. Rare earths were found to have low solubility in uncodoped GeAs sulfide glasses, which also displayed poor fluorescence efficiency due to severe clustering. Codoping such glasses with Ga greatly enhanced rare-earth solubility and dispersal, particularly for Ga:rare earth ratios ≥ 10:1, as evidenced by the narrower EPR resonances and more intense luminescence of Gd- and Pr-doped glasses, respectively. In, P and Sn were also observed to ‘decluster’ rare earths, although less efficiently than Ga, whereas codoping with I was found to have no effect on clustering. These phenomena are explained by a structural model in which (1) rare-earth dopants and codopants are spatially associated and (2) rare-earth dispersal is accomplished by a statistical distribution of codopants in tetrahedral network sites.