Compositional dependence of crystallization in Ge-Sb-Se glasses relevant to optical fiber making

For fiber-optic mid-infrared bio- and chemical-sensing, Ge-Sb-Se glass optical fibers are more attractive than Ge-As-Se because of: (i) lowered toxicity and (ii) lower phonon energy and hence transmission to longer wavelengths, with potential to reach the spectral "fingerprint region" for molecular sensing. There is little previous work on Ge-Sb-Se fibers. Here, fibers are fabricated from two glass compositions in the GexSb10Se90-x atomic (at.) % series. Both glass compositions are of similar mean-coordination-number, lying in the overconstrained region, yet of different chemical composition: stoichiometric Ge25Sb10Se65 at. % and non-stoichiometric Ge20Sb10Se70 at. %. Thermal analysis on bulk glasses has previously shown that the former exhibited the maximum glass stability of the series. However, during fiber-drawing of Ge25Sb10Se65 at. %, the preform tip is found to undergo surface-devitrification to monoclinic GeSe2 alone, the primary phase, no matter if the preform is an annealed, as-melted rod or annealed, extruded rod. The heating rate of the preform-tip to the fiber-drawing temperature is estimated to be up to similar to 100 degrees C/min to similar to 490 degrees C. Lower heating rates of 10 degrees C/min using thermal analysis, in contrast, encourage crystallization of both Sb2Se3 and GeSe2. The non-stoichiometric: Ge20Sb10Se70 at. % composition drew successfully to low optical loss fiber, no matter whether the preform was an annealed, as-melted rod or annealed, extruded rod.