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Ferroelastic-switching-driven large shear strain and piezoelectricity in a hybrid ferroelectric

Nature Materials volume 20, pages 612–617 (2021)Cite this article

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A Publisher Correction to this article was published on 18 January 2021

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Abstract

Materials that can produce large controllable strains are widely used in shape memory devices, actuators and sensors1,2, and great efforts have been made to improve the strain output3,4,5,6. Among them, ferroelastic transitions underpin giant reversible strains in electrically driven ferroelectrics or piezoelectrics and thermally or magnetically driven shape memory alloys7,8. However, large-strain ferroelastic switching in conventional ferroelectrics is very challenging, while magnetic and thermal controls are not desirable for practical applications. Here we demonstrate a large shear strain of up to 21.5% in a hybrid ferroelectric, C6H5N(CH3)3CdCl3, which is two orders of magnitude greater than that in conventional ferroelectric polymers and oxides. It is achieved by inorganic bond switching and facilitated by structural confinement of the large organic moieties, which prevents undesired 180° polarization switching. Furthermore, Br substitution can soften the bonds, allowing a sizable shear piezoelectric coefficient (d35 ≈ 4,830 pm V−1) at the Br-rich end of the solid solution, C6H5N(CH3)3CdBr3xCl3(1−x). The electromechanical properties of these compounds suggest their potential in lightweight and high-energy-density devices, and the strategy described here could inspire the development of next-generation piezoelectrics and electroactive materials based on hybrid ferroelectrics.

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Fig. 1: Crystal structures and photos of (PTMA)CdCl3 in two different ferroelastic states.
Fig. 2: Ferroelectric and ferroelastic properties of (PTMA)CdBr3xCl3(1−x).
Fig. 3: Large-signal piezoelectric properties of (PTMA)CdBr3xCl3(1−x).
Fig. 4: Calculated switching barriers of (PTMA)CdBr3 and (PTMA)CdCl3.

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Data availability

The data supporting the findings of this study are available within the article and its Supplementary Information or on figshare.com, https://doi.org/10.6084/m9.figshare.13227434.

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Acknowledgements

We acknowledge the Facility for Analysis, Characterisation, Testing and Simulation (FACTS) at Nanyang Technological University, Singapore, for access to the XRD facilities, X. R. Zhou (School of Materials Science and Engineering, Nanyang Technological University) for assistance in the piezoelectric measurements and F. Li (Xi’an Jiaotong University) for discussions on piezoelectric resonance measurements. L.Y. and B.X. acknowledge the startup funds from Soochow University and the support from Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions. L.Y. also acknowledges the support from National Natural Science Foundation of China (12074278) and Key University Science Research Project of Jiangsu Province (20KJA140001). B.X. also acknowledges the support from National Natural Science Foundation of China under grant no. 12074277 and Natural Science Foundation of Jiangsu Province (BK20201404). H.J.F. acknowledges the support from AME Individual Research Grant (A1883c0004), Agency for Science, Technology, and Research (A*STAR). J.W. acknowledges the support from the Ministry of Education, Singapore (AcRF Tier 1 118/17 and 189/18) and the startup grant from Southern University of Science and Technology (SUSTech), China.

Author information

Author notes

  1. These authors contributed equally: Yuzhong Hu, Lu You, Bin Xu.

Authors and Affiliations

  1. School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore

    Yuzhong Hu & Hong Jin Fan

  2. School of Materials Science and Engineering, Nanyang Technological University, Singapore, Singapore

    Yuzhong Hu, Tao Li, Pooi See Lee & Junling Wang

  3. Jiangsu Key Laboratory of Thin Films, School of Physical Science and Technology, Soochow University, Suzhou, China

    Lu You, Bin Xu, Yehui Zhang & Xin Wang

  4. Facility for Analysis, Characterisation, Testing and Simulation (FACTS), Nanyang Technological University, Singapore, Singapore

    Samuel Alexander Morris

  5. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore

    Yongxin Li

  6. Department of Physics, Southern University of Science and Technology, Shenzhen, China

    Junling Wang

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Contributions

Y.H., L.Y., H.J.F. and J.W. conceived the idea and designed the project. Y.H. grew the single crystals and performed the powder XRD measurements. S.A.M. and Y.H. conducted the powder XRD analysis. Y.L. and S.A.M. performed the single-crystal XRD characterization and analysis. Y.H. prepared the devices and carried out the PFM, ferroelectric, piezoelectric, dielectric, TGA and DSC measurements, and analysed the results with L.Y., J.W. and H.J.F. Y.H., T.L. and P.S.L. conducted the shear strain characterizations. B.X., Y.Z. and X.W. carried out the DFT calculations. Y.H., L.Y., H.J.F. and J.W. wrote the manuscript with input from all the authors.

Corresponding authors

Correspondence to Hong Jin Fan or Junling Wang.

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The authors declare no competing interests.

Additional information

Peer review information Nature Materials thanks Gustau Catalan, Damien Thompson and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Text 1–3, Figs. 1–11, Tables 1–4, captions for Videos 1–5 and refs. 1–47.

Supplementary Video 1

Real-time video of the ferroelastic switching cycle of the bulk (PTMA)CdBr0.45Cl2.55 single crystal at a frequency of 1 Hz (starting from left tilt to right tilt and back to left tilt).

Supplementary Video 2

Real-time video of the ferroelastic switching cycle of the bulk (PTMA)CdBr0.45Cl2.55 single crystal at a frequency of 1 Hz (starting from right tilt to left tilt and back to right tilt).

Supplementary Video 3

Real-time video of the ferroelastic switching cycles of the bulk (PTMA)CdBr2.7Cl0.3 single crystal at frequencies ranging from 0.5 to 20 Hz.

Supplementary Video 4

Sequential structural evolution of (PTMA)CdCl3 during the ferroelastic switching as derived from the switching path calculation.

Supplementary Video 5

Sequential structural evolution of (PTMA)CdBr3 during the ferroelastic switching as derived from the switching path calculation.

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Hu, Y., You, L., Xu, B. et al. Ferroelastic-switching-driven large shear strain and piezoelectricity in a hybrid ferroelectric. Nat. Mater. 20, 612–617 (2021). https://doi.org/10.1038/s41563-020-00875-3

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