Experimental study of phase equilibria in the Cu2SnSe3-Cu3SbSe4-Se ternary system

Elnara N. Ismayilova; Leyla F. Mashadiyeva; Ikhtiyar B. Bakhtiyarly; Vagif A. Gasymov; Ilahе F. Huseynova; Yasin Isa Jafarov

doi:10.17308/kcmf.2025.27/13298

Elnara N. Ismayilova Institute of Catalysis and Inorganic Chemistry n.a. M. Nagiyev, 113 H. Javid av., Baku Az1143, Azerbaijan https://orcid.org/0000-0002-1327-1753
Leyla F. Mashadiyeva Institute of Catalysis and Inorganic Chemistry n.a. M. Nagiyev, 113 H. Javid av., Baku Az1143, Azerbaijan https://orcid.org/0000-0003-2357-6195
Ikhtiyar B. Bakhtiyarly Institute of Catalysis and Inorganic Chemistry n.a. M. Nagiyev, 113 H. Javid av., Baku Az1143, Azerbaijan https://orcid.org/0000-0002-7765-0672
Vagif A. Gasymov Institute of Catalysis and Inorganic Chemistry n.a. M. Nagiyev, 113 H. Javid av., Baku Az1143, Azerbaijan https://orcid.org/0000-0001-6233-5840
Ilahе F. Huseynova Institute of Catalysis and Inorganic Chemistry n.a. M. Nagiyev, 113 H. Javid av., Baku Az1143, Azerbaijan https://orcid.org/0000-0002-1106-0207
Yasin Isa Jafarov Baku State University, 33 Zahida Khalilova av., Baku Az1148, Azerbaijan https://orcid.org/0000-0002-3968-8725

DOI: https://doi.org/10.17308/kcmf.2025.27/13298

Keywords: Copper-antimony-tin selenides, Phase diagram, Immiscibility region, Solid solutions

Abstract

Objectives: Copper-tin and copper-antimony chalcogenides are highly desirable for the creation of novel, affordable, and ecologically friendly thermoelectric materials. Due to the potential for improving their thermoelectric performance through different cationic and anionic substitutions, these compounds have recently attracted increased attention. The aim of the work was to establish the nature of the physicochemical interaction in the Cu₂SnSe₃-Cu₃SbSe₄-Se compositions region of the Cu-Sn-Sb-Se quaternary system by experimentally studying phase equilibria.

Experimental: Elemental components of high purity (≥ 99.999 %) from EVOCHEM Advanced Materials GmbH (Germany) were used for the synthesis of the ternary compounds. The synthesis was carried out in evacuated (~10-2 Pa) quartz ampoules at temperatures 50 °C above the melting points of the ternary compounds. Phase equilibria in the Cu₂SnSe₃*Cu₃SbSe₄-Se system were experimentally studied using differential thermal analysis (NETZSCH 404 F1 Pegasus system) and X-ray diffraction (diffractometer Bruker D2 PHASER). This paper presents the T-x diagram of the Cu₂SnSe₃-Cu₃SbSe₄ boundary system, the isothermal section at 300 K, the liquidus surface projection, as well as three polythermal sections of the phase diagram. The primary crystallization fields of the phases and the types and coordinates of non- and monovariant equilibria are also determined.

Conclusions: The Cu₂SnSe₃-Cu₃SbSe₄ system has been established to be a quasi-binary eutectic system. Eutectic equilibrium is established at 68 mol % Cu₃SbSe₄ and 727 K. The liquidus surface of the studied system consists of two wide regions of primary crystallization of the Cu₂SnSe₃ and Cu₃SbSe₄ phases and one degenerate region near the selenium corner of the concentration triangle. A wide immiscibility area of two liquid phases is observed in the system, which has the form of a continuous solid solutions between the corresponding regions of the Cu₂SnSe₃-Se and Cu₃SbSe₄-Se boundary systems.

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Author Biographies

Elnara N. Ismayilova, Institute of Catalysis and Inorganic Chemistry n.a. M. Nagiyev, 113 H. Javid av., Baku Az1143, Azerbaijan

postgraduate student, Researcher, Institute of Catalysis and Inorganic Chemistry of the Ministry of Science and Education of Azerbaijan (Baku, Azerbaijan)

Leyla F. Mashadiyeva, Institute of Catalysis and Inorganic Chemistry n.a. M. Nagiyev, 113 H. Javid av., Baku Az1143, Azerbaijan

PhD in Chemistry, Senior Researcher, Institute of Catalysis and InorganicChemistry of the Ministry of Science and Education of Azerbaijan (Baku, Azerbaijan)

Ikhtiyar B. Bakhtiyarly, Institute of Catalysis and Inorganic Chemistry n.a. M. Nagiyev, 113 H. Javid av., Baku Az1143, Azerbaijan

Dr. Sci. (Chem.), Professor, Head of Laboratory, Institute of Catalysis and Inorganic Chemistry of the Ministry of Science and Education of Azerbaijan (Baku, Azerbaijan)

Vagif A. Gasymov, Institute of Catalysis and Inorganic Chemistry n.a. M. Nagiyev, 113 H. Javid av., Baku Az1143, Azerbaijan

Cand. Sci. (Chem.), Associate Professor, Institute of Catalysis and Inorganic Chemistry of the Ministry of Science and Education of Azerbaijan (Baku, Azerbaijan)

Ilahе F. Huseynova, Institute of Catalysis and Inorganic Chemistry n.a. M. Nagiyev, 113 H. Javid av., Baku Az1143, Azerbaijan

PhD in Chemistry, Institute of Catalysis and Inorganic Chemistry of the Ministry of Science and Education of Azerbaijan (Baku, Azerbaijan)

Yasin Isa Jafarov, Baku State University, 33 Zahida Khalilova av., Baku Az1148, Azerbaijan

Dr. Sci. (Chem.), Associate Professor, Baku State University (Baku, Azerbaijan)

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