Crucial effect of melt homogenization on the fragility of non-stoichiometric chalcogenides.

The kinetics of homogenization of binary AsxSe100 - x melts in the As concentration range 0% < x < 50% are followed in Fourier Transform (FT)-Raman profiling experiments, and show that 2 g sized melts in the middle concentration range 20% < x < 30% take nearly two weeks to homogenize when starting materials are reacted at 700 °C. In glasses of proven homogeneity, we find molar volumes to vary non-monotonically with composition, and the fragility index M displays a broad global minimum in the 20% < x < 30% range of x wherein M < 20. We show that properly homogenized samples have a lower measured fragility when compared to larger under-reacted melts.