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Thermo-kinetic behaviour of Ge20Te75I5 glass for infrared optics

ABSTRACT The iodine-doped GeTe4 infrared chalcogenide glass was studied by means of differential scanning calorimetry DSC, X-ray diffraction XRD, Raman spectroscopy and infrared microscopy. Extensive non-isothermal thermo-kinetic characterisation of the glass transition, crystallisation and melting phenomena was performed in dependence on the particle size. The Tool–Narayanaswamy–Moynihan model was applied to describe the enthalpy relaxation processes: the compositional evolution of the relaxation parameters was then explained in terms of the structural changes and movements of the characteristic structural units. Mathematic deconvolution was applied to treat the complex crystallization kinetics – two crystal growth sub-processes were identified and described in terms of the autocatalytic Šesták-Berggren model. Based on the XRD and microscopic analyses the following crystallization mechanisms were revealed: initial precipitation of tellurium (surface-located) followed by a combined surface- and bulk-located formation of GeTe and GeI4 phases. Based on the DSC results obtained for fine powders, the presence of mechanically induced defects was found to accelerate the Te precipitation, the consequences of which are discussed with regard to the performance of nowadays glass stability criteria.