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Glass transition temperatures (T g ) and liquid fragilities are measured along a line of constant Ge content in the system Ge-As-Te, and contrasted with the lack of glass-forming ability in the twin system Ge-Sb-Te at the same Ge content. The one composition established as free of crystal contamination in the latter system shows a behavior opposite to that of more covalent system.Comparison of T g vs bond density in the three systems Ge-As-chalcogen differing in chalcogen i.e. S, Se, or Te, shows that as the chalcogen becomes more metallic, i.e. in the order S = 2.3.When the more metallic Sb replaces As at greater than 2.3, incipient metallicity rather than directional bond covalency apparently gains control of the physics. This leads us to an examination of the electronic conductivity and, then, semiconductor-to-metal (SC-M) transitions, with their associated thermodynamic manifestations, in relevant liquid alloys. The thermodynamic components, as seen previously, control liquid fragility and cause fragile-tostrong transitions during cooling. We tentatively conclude that liquid state behavior in phase change materials (PCMs) is controlled by liquid-liquid (SC-M) transitions that have become submerged below the liquidus surface. In the case of the Ge-Te binary, a crude extrapolation to GeTe stoichiometry indicates that the SC-M transition lies about 20% below the melting point, suggesting a parallel with the intensely researched "hidden liquid-liquid (LL) transition", in supercooled water. In the water case, superfast crystallization initiates in the high fragility domain some 4% above the T LL which is located at ~15% below the (ambient pressure) melting point.

The fraction of edge- and corner-sharing tetrahedra in liquid ZnCl is quantified as a function of temperature using Raman spectroscopy and ab initio molecular dynamic simulations. Two distinct regimes are found in the temperature dependence of the change in these structural units. This behavior is consistent with the existence of a fragile-to-strong transition in liquid ZnCl as suggested by calorimetric and viscosity measurements. The structural origin of this transition is rationalized in terms of a constraint counting formalism. It is suggested that the ratio of edge- to corner-sharing tetrahedra controls the configurational entropy and in turn the viscosity of the melt. The temperature dependence of this ratio above the melting point is also found to be qualitatively consistent with neutron diffraction data. The observation of a similar fragile-to-strong transition in the isostructural GeSe melt indicates that it may be a common feature of tetrahedral liquids.

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a b s t r a c tGlassy materials based on chalcogen elements are becoming increasingly prominent in the development of advanced infrared sensors. In particular, infrared fibers constitute a desirable sensing platform due to their high sensitivity and versatile remote collection capabilities for in-situ detection. Tailoring the transparency window of an optical material to the vibrational signature of a target molecule is important for the design of infrared sensor, and particularly for fiber evanescent wave spectroscopy. Here we review the basic principles and recent developments in the fabrication of chalcogenide glass infrared fibers for application as bio-chemical sensors. We emphasize the challenges in designing materials that combine good rheological properties with chemical stability and sufficiently wide optical windows for bio-chemical sensing. The limitation in optical transparency due to higher order overtones of the amorphous network vibrations is established for this family of glasses. It is shown that glasses with wide optical window suffer from higher order overtone absorptions. Compositional engineering with heavy elements such as iodine is shown to widen the optical window but at the cost of lower chemical stability. The optical attenuations of various families of chalcogenide glass fibers are presented and weighed for their applications as chemical sensors. It is then shown that long-wave infrared fibers can be designed to optimize the collection of selective signal from bio-molecules such as cells and tissues. Issues of toxicity and mechanical resistance in the context of bio-sensing are also discussed.