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Nano Research 2024, 17(3): 2195-2203 https://doi.org/10.1007/s12274-024-6445-4
Research Article | Issue | Published: 25 January 2024

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

Show Author's Information Yongqiang Qiao1,  Sen Zhang1,  Peixian Zhang1,  Juan Guo1,  Andrea Sanson2,  Xi Zhen1,  Kaiyue Zhao1,  Qilong Gao1( ),  Jun Chen3( )
Key Laboratory of Materials Physics of Ministry of Education, and School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, China
Department of Physics and Astronomy, University of Padova, Padova I-35131, Italy
Beijing Advanced Innovation Center for Materials Genome Engineering, Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, China
Keywords:
chemical synthesis, negative thermal expansion, fluorides, nanosheet structure, first principles calculations
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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 Research, 2024, 17(3): 2195-2203. https://doi.org/10.1007/s12274-024-6445-4
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Abstract Full text Electronic supplementary material About this article

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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About this article

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

Show Author's information Yongqiang Qiao1, Sen Zhang1, Peixian Zhang1, Juan Guo1, Andrea Sanson2, Xi Zhen1, Kaiyue Zhao1, Qilong Gao1( ), Jun Chen3( )
Key Laboratory of Materials Physics of Ministry of Education, and School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, China
Department of Physics and Astronomy, University of Padova, Padova I-35131, Italy
Beijing Advanced Innovation Center for Materials Genome Engineering, Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, China

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.

Keywords: chemical synthesis, negative thermal expansion, fluorides, nanosheet structure, first principles calculations

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Publication history
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Acknowledgements

Publication history

Received: 07 November 2023
Revised: 11 December 2023
Accepted: 22 December 2023
Published: 25 January 2024
Issue date: March 2024

Copyright

© Tsinghua University Press 2024

Acknowledgements

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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