INTERACTIONS IN THE Tl2Se–Zn(Cd, Hg)Se–GeSe2 SYSTEMS
DOI:
https://doi.org/10.32782/pcsd-2025-1-6Keywords:
quasi-ternary system, isothermal section, polythermal section, phase equilibria, solid solutions, quaternary compoundsAbstract
The nature of the physicochemical interaction in the quasi-ternary Tl2Se–Zn(Cd, Hg)Se–GeSe2 systems was studied using X-ray diffraction, differential thermal analysis, and microstructural analysis. Five new quaternary compounds were discovered in these systems: Tl2ZnGe3Sе8, Tl2СdGeSе4, Tl2СdGe3Sе8, Tl2HgGeSе4, and Tl2HgGe3Sе8. The existence of 7 small single-phase regions on the isothermal section of the Tl2Se–ZnSe–GeSe2 system was established at 570 K. They correspond to α, β, γ, δ, ε, η – solid solutions based on Tl2Se, ZnSe, GeSe2, Tl4GeSe4, Tl2GeSe3, respectively, and on the Tl2ZnGe3Sе8 compound. These single-phase fields are separated by 12 two-phase fields, between which there are 6 three-phase regions (α–β–δ, δ–β–ε, ε–β–Tl2ZnGe3Se8, ε–Tl2ZnGe3Se8–η, η–Tl2ZnGe3Se8–γ, γ–Tl2ZnGe3Se8–β). The nature of the physicochemical interaction in the Tl2Se–ZnSe section has been established, and the type of phase diagram is categorized as peritectic (Lр + β ↔ a). The isothermal section of the Tl2Se–CdSe–GeSe2 system at 570 K contains 9 single-phase regions: α, β, γ, δ, ε, η, ζ, σ, and θ. These fields correspond to solid solutions based on the compounds Tl2Se, CdSe, GeSe2, Tl4GeSe4, Tl2GeSe3, Tl2Ge2Sе5, Cd4GeSе6, Tl2СdGeSе4, and Tl2СdGe3Sе8, respectively. They are separated by 17 two-phase equilibria, between which there are 9 three-phase regions (α–β–δ, δ–β–σ, δ–σ–ε, ε–σ–θ, ε–θ–η, η–θ–γ, γ–θ–ζ, θ–β–ζ, σ–β–θ). The Tl2Se–CdSe section belongs to a eutectic type (Le ↔ a + β) with negligible solubility. The concentration triangle of the quasi-ternary system Tl2Se–HgSe–GeSe2 at 520 K contains 10 single-phase fields: α-, β-, γ-solid solutions based on binary compounds Tl2Se, HgSe, GeSe2; δ-, ε-, η-solid solutions based on ternary compounds Tl4GeSe4, Tl2GeSe3, Tl2Ge2Sе5, respectively, and four more compounds: Tl2Hg3Sе4, Hg2GeSе4, Tl2HgGeSе4, Tl2HgGe3Sе8. They are divided by 19 two-phase equilibria (α–Tl2Hg3Sе4, Tl2Hg3Sе4–β, α–δ, δ–ε, ε–η, η–γ, γ–Hg2GeSе4, Hg2GeSе4–β, δ–Tl2Hg3Sе4, δ–β, δ–Tl2HgGeSе4, ε–Tl2HgGeSе4, η–Tl2HgGeSе4, η–Tl2HgGe3Sе8, Tl2HgGe3Sе8–γ, Tl2HgGeSе4–β, Tl2HgGe3Sе8–β, Tl2HgGe3Sе8–Hg2GeSе4, Tl2HgGeSе4–Tl2HgGe3Sе8), between which there are 10 threephase regions. The crystal structure of the Tl2ZnGe3Sе8 and Tl2HgGe3Sе8 quaternary compounds was investigated by X-ray powder diffraction. These chalcogenides are isostructural and crystallize in the orthorhombic system SG P212121 (ST Cs2CdGe3Se8).
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