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Research Article

Synthesis, structure, and thermal expansion in CaZrF6 with two polymorphs

Peixian Zhang1,§, Yongqiang Qiao1,§, Kaiyue Zhao1, Qingjie Wang1, Huan Zhao1, Juan Guo1, Erjun Liang1, Tao Sun3, Jiangwei Zhang2,4( ), Qilong Gao1( )
Key Laboratory of Materials Physics of Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, China
College of Energy Materials and Chemistry, Inner Mongolia University, Hohhot 010021, China
First Affiliated Hospital of Dalian Medical University, 222 Zhongshan Road, Dalian 116011, China
Ordos Laboratory, Ordos 017000, China

§ Peixian Zhang and Yongqiang Qiao contributed equally to this work.

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Graphical Abstract

A new simple and low-cost synthesis path of CaZrF6 has been designed. We adopt to control the sintering temperature to obtain two polymorphs, that is, orthorhombic with positive thermal expansion and cubic with negative thermal expansion.

Abstract

Due to the high structural flexibility and controllable thermal expansion, cubic double ReO3-type negative thermal expansion (NTE) fluorides provide a solution for solving the prominent phenomenon of thermal expansion mismatch between materials. However, the expensive raw materials and complex synthesis steps limit its practical application. In this work, we have designed a more advantageous method for the synthesis of NTE material CaZrF6, and it is expected to be generalized to the synthesis of other double ReO3-fluorides. Intriguingly, a new orthorhombic phase CaZrF6 has been synthesized via this method in a lower temperature. Unlike the strong isotropic NTE of the cubic phase CaZrF6, the orthorhombic phase shows the strong anisotropic positive thermal expansion (PTE). The combined analysis of temperature-dependent X-ray diffraction (XRD), Raman spectra, and first-principles calculations shows that the low frequency phonon vibration mode with negative Grüneisen parameter in cubic CaZrF6 are strongly correlated with the transverse thermal vibration of F atoms and dominates the NTE of the material.

Keywords

negative thermal expansionpolymorphfluorideslattice dynamicsfirst principles calculations

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Nano Research
Volume 17 Issue 9,
September 2024
Pages 8618-8626
DOI: 10.1007/s12274-024-6832-x
Cite this article:
Zhang P, Qiao Y, Zhao K, et al. Synthesis, structure, and thermal expansion in CaZrF6 with two polymorphs. Nano Research, 2024, 17(9): 8618-8626. https://doi.org/10.1007/s12274-024-6832-x
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Received: 02 April 2024
Revised: 01 June 2024
Accepted: 17 June 2024
Published: 09 July 2024
© Tsinghua University Press 2024
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