Abstract
125Te-Mössbauer spectroscopy has been used to verify whether the observed ionic transport crossover for the Ag–As–Se–Te glasses with a silver content of 15 at.% at approximately equimolar Se/Te ratio is accompanied by variations in the hyperfine interaction parameters produced by corresponding changes in the microstructural organization of the glass network. We found that an unusual decrease of the quadrupole splitting with decreasing tellurium fraction, r=Te/(Se+Te)<0.5, is caused by the combined effect of increasing Te–Ag(As) interatomic distances and a non-random substitution of multiple Se sites by Te with a preferential occupation of those with at least one Ag nearest neighbour. The latter process leads also to a step-like decrease in the isomer shift at r⩽0.35. The assumed expansion of the glass network at smaller r and the contrasting network contraction for the Te-rich glasses are consistent with the ionic transport crossover.
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