Structural relaxation in IR transmitting (GeSe4)100-x(As2Se3)x glasses

Abstract

(GeSe4)100-x (As2Se3)x glasses in the GeSe4-As2Se3 pseudo-binary joint are prepared by the melt quenching method. In this tie-line, the entire composition 0 ≤ x ≤ 100 is characterized by fixed average network connectivity of 2.40, which is considered to be optimal connectivity as the number of constraints and the number degrees of freedom available to the atoms are balanced at this average connectivity. The glass forming ability of the glasses having this average connectivity of 2.40 is usually found to be maximum. Glass transition temperature (Tg) decreases till x = 30 and remains invariant in the range 40 ≤ x ≤ 70. For x > 70, Tg shows an increasing trend. The jump in specific heat capacity (ΔCp), non-reversing heat flow (ΔHnr), Tg and the optical bandgap (Eg) show a distinct change in the composition range 40 and 70 mol.% of As2Se3. The fragility index (m) lies in the range of 15 and 32 for all the prepared glasses, representing the strong nature of these glass forming melts in the (GeSe4)100-x (As2Se3)x glasses. The viscosity as a function of reduced temperature (Tg/T) shows almost an Arrhenius nature for 0 ≤ x ≤ 70 and for x > 70, a slight deviation from the Arrhenius behviour is observed. The structural network of these glasses primarily consists of GeSe4/2 and Se-Se chains for x ≤ 30. For 40 ≤ x ≤ 70, the network is dominated by AsSe3/2 pyramidal units and As-As homopolar bonds. For x > 70, the structural network is characterized by AsSe3/2 pyramidal units. All the prepared glasses are found to transmit infrared (IR) light over a wide wavelength range from 2 to 17 μm. The super strong nature of the melts indicates that optical devices can be easily made for IR applications.