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Planar negative thermal expansion in the layered hybrid network material ZnB2(CN)8

Junbiao Guo1, Guanqun Cai1, Kaiyue Zhao2, Ben Durham3, Keith Refson4, and Martin T Dove5,1,6,*

  • 1Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, Sichuan 610065, China
  • 2Key Laboratory of Materials Physics of Ministry of Education, and School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, China
  • 3School of Physics, Engineering and Technology, University of York, Heslington, York YO10 5DD, United Kingdom
  • 4ISIS Facility, Science and Technology Facilities Council, Harwell Campus, Chilton, Didcot, Oxon OX11, United Kingdom
  • 5School of Mechanical Engineering, Guizhou University of Engineering Science, Bijie, Guizhou 551700, China
  • 6School of Physical and Chemical Sciences, Queen Mary University of London, Mile End Road, London, E1 4NS, United Kingdom

  • *Contact author: martin.dove@icloud.com
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Phys. Rev. B 113, 064108 – Published 11 February, 2026

DOI: https://doi.org/10.1103/gc3b-h3c2

Abstract

We report a computational study of thermal expansion in the hybrid layer structure ZnB2(CN)8 using density functional theory (DFT) methods. The crystal structure has a trigonal lattice, with a larger positive thermal expansion in the axial direction (c axis) and a very small negative thermal expansion within the layer normal to the axial axis (the a−b plane). The results of the DFT calculations for the structure, lattice dynamics and thermal expansion are consistent with experimental data, and, together with a flexibility analysis, it is possible to explain the large difference between axial and area thermal expansivities. We argue from some general features that the difference between the two expansivities is an inevitable consequence of a combination of the elasticity being stiffer within the layers than between the layers, and of the existence of a tension effect operating within the layers, which lowers the values of the area-strain Grüneisen parameters relative to the axial ones. These two factors combine in a way to enhance the axial expansivity but cancel in the calculation of the area expansivity. This is likely to be a general case for any layer structure in which the layers can be described as a partly flexible network.

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See Also

Biaxial zero thermal expansion in zinc tetracyanoborate

Qilong Gao, Shibo Zhao, Sabine Lorenzen, Kaiyue Zhao, Qiang Sun, Maik Finze, Guanqun Cai, Shogo Kawaguchi, ErJun Liang, and Jun Chen
Phys. Rev. B 113, 064107 (2026)

Article Text

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Phys. Rev. B 113, 064108– Published 11 February, 2026
  • Received 30 August 2025
  • Revised 4 November 2025
  • Accepted 19 November 2025
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