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Anisotropic Structural Collapse of Mg3Sb2 and Mg3Bi2 at High Pressure
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    Anisotropic Structural Collapse of Mg3Sb2 and Mg3Bi2 at High Pressure
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    • Mario Calderón-Cueva
      Mario Calderón-Cueva
      Chemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United States
    • Wanyue Peng
      Wanyue Peng
      Chemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United States
      More by Wanyue Peng
    • Samantha M. Clarke
      Samantha M. Clarke
      Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, California 94550, United States
    • Jingxuan Ding
      Jingxuan Ding
      Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United States
    • Benjamin L. Brugman
      Benjamin L. Brugman
      Department of Earth and Environmental Sciences, Michigan State University, East Lansing, Michigan 48824, United States
    • Gill Levental
      Gill Levental
      Chemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United States
    • Ashiwini Balodhi
      Ashiwini Balodhi
      Chemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United States
    • Megan Rylko
      Megan Rylko
      Chemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United States
      More by Megan Rylko
    • Olivier Delaire
      Olivier Delaire
      Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United States
    • James P. S. Walsh
      James P. S. Walsh
      Department of Chemistry, University of Massachusetts Amherst, Amherst, Massachusetts 01003, United States
    • Susannah M. Dorfman
      Susannah M. Dorfman
      Department of Earth and Environmental Sciences, Michigan State University, East Lansing, Michigan 48824, United States
    • Alexandra Zevalkink*
      Alexandra Zevalkink
      Chemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United States
      *Email: [email protected]
    Other Access OptionsSupporting Information (2)

    Chemistry of Materials

    Cite this: Chem. Mater. 2021, 33, 2, 567–573
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    https://doi.org/10.1021/acs.chemmater.0c03678
    Published January 12, 2021
    Copyright © 2021 American Chemical Society

    Abstract

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    Alloys between Mg3Sb2 and Mg3Bi2 have recently been shown to be exceptional thermoelectric materials due in part to their anomalously low thermal conductivity. In the present study, in situ high-pressure synchrotron X-ray diffraction was used to investigate the structure and bonding in Mg3Sb2 and Mg3Bi2 at pressures up to 50 GPa. Our results confirm prior predictions of isotropic in-plane and out-of-plane compressibility but reveal large disparities between the bond strength of the two distinct Mg sites. Using single-crystal diffraction, we show that the octahedral Mg–Sb bonds are significantly more compressible than the tetrahedral Mg–Sb bonds in Mg3Sb2, which lends support to prior arguments that the weaker octahedral Mg bonds are responsible for the anomalous thermal properties of Mg3Sb2 and Mg3Bi2. Further, we report the discovery of a displacive and reversible phase transition in both Mg3Sb2 and Mg3Bi2 above 7.8 and 4.0 GPa, respectively. The transition to the high-pressure structure involves a highly anisotropic volume collapse, in which the out-of-plane axis compresses significantly more than the in-plane axes. Single-crystal diffraction at high pressure was used to solve the monoclinic high-pressure structure (C2/m), which is a distorted variant of the ambient-pressure structure containing four unique Mg coordination environments.

    Copyright © 2021 American Chemical Society

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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.0c03678.

    • Crystallographic details (CIF)

    • Optical microscopy of as-grown mass of Mg3Sb2 crystals; parameters from the second- and third-order Birch–Murnaghan EOS; octahedra in Mg3Sb2 and CaMg2Bi2 at ambient pressure; pressure dependence of individual and octahedral bond lengths; summary of uncertainties for polyhedral volume (PDF)

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    This article is cited by 17 publications.

    1. Harshada Suryawanshi, Bharti Agrawal, Nirma Kumari, Titas Dasgupta. Developing a Multiband Electronic Band Structure Model and Predictive Maps for Bismuth-Rich Mg3(Sb1–xBix)2 Thermoelectric Materials. ACS Applied Materials & Interfaces 2024, 16 (2) , 2263-2269. https://doi.org/10.1021/acsami.3c15019
    2. Xinghai Han, Guihong Song, Di Luo, Yusheng Wu, Junhua You. Influence of modulation period on thermoelectric properties for Mg3Bi2/Mg/Mg2Sn multilayer films. Journal of Materials Science: Materials in Electronics 2025, 36 (1) https://doi.org/10.1007/s10854-024-14096-w
    3. Nagendra Singh Chauhan, Takao Mori. Alloying induced superionic β-phase formation in Mg 3 Sb 2 based Zintl compounds. Journal of Materials Chemistry A 2024, 12 (47) , 32703-32711. https://doi.org/10.1039/D4TA06173J
    4. G.X. Yin, K.-T. Wang, H.-L. Cui. Electronic, Mechanical, Vibrational and Piezoelectric Properties of Mg 3 X 2 (X = As, Sb) Monolayers. Acta Physica Polonica A 2024, 146 (2) , 186-194. https://doi.org/10.12693/APhysPolA.146.186
    5. Weiwei Dong, Wei Xu, Zhiying Guo, Weishu Liu, Yu Pan, Satishkumar Kulkarni, Xiaodong Li, Konstantin Glazyrin. Assessing structure of Mg3Bi2−Sb (0 ≤ x ≤ 2) at pressures below 40 GPa. Journal of Materiomics 2024, 10 (4) , 837-844. https://doi.org/10.1016/j.jmat.2023.10.004
    6. Yaoming Shao, Pingping Zheng, Tianhao Dong, Lianghuan Wei, Haifei Wu, Jianxiao Si. High thermoelectric performance of n-type Mg3Bi2 films deposited by magnetron sputtering. Vacuum 2024, 220 , 112791. https://doi.org/10.1016/j.vacuum.2023.112791
    7. He Zhang, Cunyin Zhang, Duncan H Gregory, Zhanxiang Yin, Yaqiang Wang, Pan He, Xin Guo. A review of pressure manipulating structure and performance in thermoelectrics. Journal of Physics D: Applied Physics 2023, 56 (18) , 183001. https://doi.org/10.1088/1361-6463/acbec1
    8. Eleonora Isotta, Wanyue Peng, Ashiwini Balodhi, Alexandra Zevalkink. Elastic Moduli: a Tool for Understanding Chemical Bonding and Thermal Transport in Thermoelectric Materials. Angewandte Chemie 2023, 135 (12) https://doi.org/10.1002/ange.202213649
    9. Eleonora Isotta, Wanyue Peng, Ashiwini Balodhi, Alexandra Zevalkink. Elastic Moduli: a Tool for Understanding Chemical Bonding and Thermal Transport in Thermoelectric Materials. Angewandte Chemie International Edition 2023, 62 (12) https://doi.org/10.1002/anie.202213649
    10. Madison K. Brod, Shashwat Anand, G. Jeffrey Snyder. The Importance of Mg–Sb Interactions in Achieving High Conduction Band Degeneracy in Mg3Sb2 for High n-Type Thermoelectric Performance. Materials Today Physics 2023, 31 , 100959. https://doi.org/10.1016/j.mtphys.2022.100959
    11. Ni Ma, Hailong Zhu, Qi Jiang, Benrui Huang, Kaiyi Li, Hongping Mei, Mao Ye, Shan Qiao, Ang Li. Experimental Realization of Spin‐Polarized States on Mg 3 Bi 2 Surface. physica status solidi (RRL) – Rapid Research Letters 2023, 17 (1) https://doi.org/10.1002/pssr.202200250
    12. Sen Xie, Yujie Ouyang, Wei Liu, Fan Yan, Jiangfan Luo, Xianda Li, Ziyu Wang, Yong Liu, Xinfeng Tang. Temperature-Driven Twin Structure Formation and Electronic Structure of Epitaxially Grown Mg3Sb2 Films on Mismatched Substrates. Nanomaterials 2022, 12 (24) , 4429. https://doi.org/10.3390/nano12244429
    13. Y. Zhu, J. Liu, B. Wei, S. Xu, Y. Song, X. Wang, T.-L. Xia, J. Chen, G.J. Snyder, J. Hong. Giant phonon anharmonicity driven by the asymmetric lone pairs in Mg3Bi2. Materials Today Physics 2022, 27 , 100791. https://doi.org/10.1016/j.mtphys.2022.100791
    14. Suiting Ning, Shan Huang, Ziye Zhang, Ning Qi, Man Jiang, Zhiquan Chen, Xinfeng Tang. Band convergence boosted high thermoelectric performance of Zintl compound Mg3Sb2 achieved by biaxial strains. Journal of Materiomics 2022, 8 (5) , 1086-1094. https://doi.org/10.1016/j.jmat.2022.02.001
    15. Veera Prabu Kannan, Immanuel Paulraj, Vinothkumar Lourdhusamy, Chia-Jyi Liu, Sridharan Madanagurusamy. Electronic transport of ZnSnSb2 for thermoelectric application. Materials Today: Proceedings 2022, 49 , 2761-2764. https://doi.org/10.1016/j.matpr.2021.09.301
    16. Juan Li, Shuai Zhang, Kai Han, Bing Sun, Lianzhen Cao. Large improvement in thermoelectric performance of pressure-tuned Mg 3 Sb 2. RSC Advances 2021, 12 (2) , 1149-1156. https://doi.org/10.1039/D1RA08930G
    17. Jingxuan Ding, Tyson Lanigan-Atkins, Mario Calderón-Cueva, Arnab Banerjee, Douglas L. Abernathy, Ayman Said, Alexandra Zevalkink, Olivier Delaire. Soft anharmonic phonons and ultralow thermal conductivity in Mg 3 (Sb, Bi) 2 thermoelectrics. Science Advances 2021, 7 (21) https://doi.org/10.1126/sciadv.abg1449

    Chemistry of Materials

    Cite this: Chem. Mater. 2021, 33, 2, 567–573
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.0c03678
    Published January 12, 2021
    Copyright © 2021 American Chemical Society

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