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Disorder-Mediated Structural Transformation in the Cu4TiSe4–xSx (0 ≤ x ≤ 4) System and Its Effects on the Thermal Transport Property
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    Disorder-Mediated Structural Transformation in the Cu4TiSe4–xSx (0 ≤ x ≤ 4) System and Its Effects on the Thermal Transport Property
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    Chemistry of Materials

    Cite this: Chem. Mater. 2024, 36, 11, 5741–5752
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    https://doi.org/10.1021/acs.chemmater.4c00904
    Published May 28, 2024
    Copyright © 2024 American Chemical Society
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    Abstract

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    Copper-transition-metal chalcogenides can offer low-cost and environmentally benign solutions to trap heat and heat to electric energy conversion. In this report, we present the synthesis and characterization of Cu–Ti-based mixed chalcogenides, Cu4TiSe4–xSx (x = 0–4). At room temperature, Cu4TiSe4 adopts a sulvanite-type cubic structure (P4̅3m), whereas Cu4TiS4 crystallizes in a body-centered tetragonal space group (I4̅2m), where the lattice parameter is doubled along the c-direction w.r.t. the sulvanite. The structure of the S-analogue is completely ordered, while the Se-analogue hosts positional disorder distributed over two Cu-sites (1a and 4e Wyckoff sites). A systematic investigation of a series of compositions of Cu4TiSe4–xSx (0 ≤ x ≤ 4) indicates that S insertion in the Cu4TiSe4–xSx boosts the disordered 4e site to coalesce into the 1a site. Up to x ≈ 2.6, Cu4TiSe4–xSx forms the cubic phase similar to Cu4TiSe4, whereas, for x ≥ 3.5, the pure tetragonal phase related to Cu4TiS4 appears. Herein, the cubic-to-tetragonal phase transformation is rationalized by theoretical calculations. Thermal conductivity measurements show a significant increase in the lattice thermal conductivity (κL) values from the cubic (0.3–0.47 Wm–1 K–1) to the tetragonal (above 0.7 Wm–1 K–1) phases. Phonon band structure and phonon density of state calculations suggest that both Cu and Se atoms are responsible for the anharmonic scattering of the acoustic phonons in the Se-rich cubic phase, whereas Cu atoms primarily contribute to this scattering process in the S-rich tetragonal phase.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.4c00904.

    • EDS spectra and mapping of the single crystals, variation in bond lengths, cell parameters for different single-crystal compositions, COHP plots, experimentally measured band gaps, TGA data, electrical conductivity, refined PXRD patterns of sintered samples, Rietveld refinement results within the biphasic range (2.6 ≤ x ≤ 3.4), atomic coordinates, SOFs, ADPs, bond distances, and information on different models used for theoretical calculations (PDF)

    • Crystallographic data of SC1 (CIF)

    • Crystallographic data of SC2 (CIF)

    • Crystallographic data of SC3 (CIF)

    • Crystallographic data of SC4 (CIF)

    • Crystallographic data of SC5 (CIF)

    Disorder-Mediated Structural Transformation in the Cu4TiSe4–xSx (0 ≤ x ≤ 4) System and Its Effects on the Thermal Transport Property

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    1
    A Disorder-mediated structural transformation in the
    Cu4Ti Se4-
    xS
    x (0 ≤
    x ≤ 4) system and its effects on
    the thermal transport property
    Achintya Lakshan1, Biplab Koley1, Krishnendu Buxi1, Parul R. Raghuvanshi2, Jürgen Nuss3,
    Amrita Bhattacharya*2, Ritayan Chatterjee4, Ahin Roy5, Partha Pratim Jana*1
    1 Department of Chemistry, IIT Kharagpur, Kharagpur-721302, India
    2 Department of Metallurgical Engg. and Materials Science, IIT Bombay, 400076, India
    3 Max Planck Institute for Solid State Research, Heisenbergstrasse 1, Stuttgart 70569, Germany
    4 Department of Physics, Heritage Institute of Technology, Kolkata -700107, India
    5 Materials Science Centre, IIT Kharagpur, Kharagpur-721302, India
    *Email: ppj@chem.iitkgp.ac.in
    *Email: b_amrita@iitb.ac.in
    2
    EDS spectra and mapping:
    Figure S1. (a) SEM image, (b) EDX spectrum, and elemental mapping for (c) Cu, (d) Ti, (e) Se,
    and (f) S in SC1.
    Figure S2. (a) SEM image, (b) EDX spectrum, and elemental mapping for (c) Cu, (d) Ti, (e) Se,
    and (f) S in SC2.

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    This article is cited by 7 publications.

    1. Ayat Tassanov, Huiju Lee, Yi Xia, James M. Hodges. Rational Pathways to Ordered Multianion Chalcogenides Using Retrosynthetic Crystal Chemistry. Journal of the American Chemical Society 2024, 146 (47) , 32627-32639. https://doi.org/10.1021/jacs.4c11617
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    2. Achintya Lakshan, Krishnendu Buxi, Paribesh Acharyya, Kishor Das, Biplab Koley, Kapildeb Dolui, Christophe Candolfi, Carmelo Prestipino, Emmanuel Guilmeau, Ahin Roy, Partha Pratim Jana. Key Role of Positional Disorder and Soft Structural Framework for Lowering the Thermal Conductivity of Quaternary Ag1–xCu3+xTiSe4 (0 ≤ x ≤ 0.8) System to an Ultralow Limit. Chemistry of Materials 2024, 36 (21) , 10773-10785. https://doi.org/10.1021/acs.chemmater.4c02404
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    3. Arnab Dutta, Achintya Lakshan, Simon Steinberg, Igor Moudrakovski, Jürgen Nuss, Partha Pratim Jana. Ultralow Thermal Conductivity in Layered CuGe 2 Se 3. Angewandte Chemie International Edition 2025, 64 (51) https://doi.org/10.1002/anie.202509226
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    4. Arnab Dutta, Achintya Lakshan, Simon Steinberg, Igor Moudrakovski, Jürgen Nuss, Partha Pratim Jana. Ultralow Thermal Conductivity in Layered CuGe 2 Se 3. Angewandte Chemie 2025, 137 (51) https://doi.org/10.1002/ange.202509226
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    5. Guangfeng Zhang, Tonghan Yang, Wei He, Zhikai Zhu, Hui Luo, Shuohai Fang, Changzhong Liao. Novel strategy to prepare pure Cu 4 TiSe 4 and its high-pressure Raman and thermoelectric performance investigation. Inorganic Chemistry Frontiers 2025, 12 (20) , 6274-6285. https://doi.org/10.1039/D5QI00707K
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    6. Surabhi Suresh Nair, Nirpendra Singh. Mechanisms and design principles for optimizing lattice thermal conductivity in chalcogenides: A comprehensive review. Materials Today Physics 2025, 57 , 101785. https://doi.org/10.1016/j.mtphys.2025.101785
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    7. Ruihuan Cheng, Wenxuan Wang, Wei Wang, Xingyu Wang, Chen Wang, Siu Ting Tai, Niuchang Ouyang, Qi Liu, Yue Chen. Atomic hopping induced dynamic disorder phonon scattering and suppressed thermal transport in Cu4TiSe4. Newton 2025, 1 (4) , 100090. https://doi.org/10.1016/j.newton.2025.100090
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    Chemistry of Materials

    Cite this: Chem. Mater. 2024, 36, 11, 5741–5752
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.4c00904
    Published May 28, 2024
    Copyright © 2024 American Chemical Society
    Request reuse permissions

    Article Views

    1649

    Altmetric

    11

    Citations

    7
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.

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