Glass formation and the nature of the chemical interaction in the As₂Se₃–Tl₂Te₃ system were studied by differential-thermal (DTA), X-ray phase (XRD), microstructural (MSA) analysis. Based on the performed experiments T-x phase diagram is constructed. It is established that the phase diagram of the system is a partially quasi-binary section of the quaternary system Tl,As//Se,Te. Eutectic equilibrium and peritectic transformation process occur in the system. When the ratio of As₂Se₃ and Tl₂Te₃ components is 1:1, a new quaternary compound Tl₂As₂Se₃Te₃ is formed. It has been established that the Tl₂As₂Se₃Te₃ compound melts with an open maximum at 568K and crystallizes in a hexagonal symmetry. In the system, under normal cooling, the glass formation area reaches −80mol.% Tl₂Te₃, and in the mode of quenching in liquid nitrogen up to −100mol.% T1₂Te₃. The photoelectric properties of glassy alloys (As₂Se $_{3})_{1 - x}$ (Tl₂Te $_{3})_{x}$ ( $x = 0.01$ ; 0.3; 0.05) have been studied. Depending on the Tl₂Te₃ concentration of the system, the observed changes in the photoelectric properties and calculated parameters are presented.

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