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Simple chemical synthesis and isotropic negative thermal expansion in MHfF6 (M = Ca, Mn, Fe, and Co)

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Abstract

The rapid progress of modern technologies has accelerated the prominence of thermal expansion mismatch between materials, and tunable thermal expansion materials will be a powerful safeguard against this challenge. Here, isotropic MHfF6 (M = Ca, Mn, Fe, and Co) compounds with tunable thermal expansion have been produced via a low-cost synthetic method and investigated. By utilizing temperature dependent X-ray diffraction (XRD) and Raman spectroscopy, combined with first principles calculations, it was revealed that the transverse thermal vibrations of the F atoms are dominated by low-frequency phonons with negative Grüneisen parameters and are therefore the origin of the negative thermal expansion (NTE). Very interestingly, with the increase of the M atomic number, the metal⋯F atomic linkages become stiffer, reducing the number of vibrational modes with negative Grüneisen parameters, so that the strong NTE can be gradually adjusted to moderate NTE and to near zero thermal expansion. The present study achieves the tunable thermal expansion in a new compound family and shed light on the internal mechanism from the perspective of lattice vibrational dynamics.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 22071221 and 21905252) and Natural Science Foundation of Henan Province (Nos. 212300410086, 222301420040 and 222300420325). All calculations were supported by the National Supercomputing Center in Zhengzhou.

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Authors and Affiliations

  1. Key Laboratory of Materials Physics of Ministry of Education, and School of Physics and Microelectronics, Zhengzhou University, Zhengzhou, 450052, China

    Yongqiang Qiao, Sen Zhang, Peixian Zhang, Juan Guo, Xi Zhen, Kaiyue Zhao & Qilong Gao

  2. Department of Physics and Astronomy, University of Padova, Padova, I-35131, Italy

    Andrea Sanson

  3. Beijing Advanced Innovation Center for Materials Genome Engineering, Department of Physical Chemistry, University of Science and Technology Beijing, Beijing, 100083, China

    Jun Chen

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  1. Yongqiang Qiao
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  2. Sen Zhang
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  6. Xi Zhen
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Correspondence to Qilong Gao or Jun Chen.

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Qiao, Y., Zhang, S., Zhang, P. et al. Simple chemical synthesis and isotropic negative thermal expansion in MHfF6 (M = Ca, Mn, Fe, and Co). Nano Res. 17, 2195–2203 (2024). https://doi.org/10.1007/s12274-024-6445-4

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