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Direct observation of geometric and sliding ferroelectricity in an amphidynamic crystal

Abstract

Sliding ferroelectricity is a recently observed polarity existing in two-dimensional materials. However, due to the weak polarization and poor electrical insulation in these materials, existing experimental evidences are indirect and mostly based on nanoscale transport properties or piezoresponse force microscopy. We report the direct observation of sliding ferroelectricity, using a high-quality amphidynamic single crystal (15-crown-5)Cd3Cl6, which possesses a large bandgap and so allows direct measurement of polarization–electric field hysteresis. This coordination polymer is a van der Waals material, which is composed of inorganic stators and organic rotators as determined by X-ray diffraction and NMR characterization. From density functional theory calculations, we find that after freezing the rotators, an electric dipole is generated in each layer driven by the geometric mechanism, while a comparable ferroelectric polarization originates from the interlayer sliding. The net polarization of these two components can be directly measured and manipulated. Our finding provides insight into low-dimensional ferroelectrics, especially control of the synchronous dynamics of rotating molecules and sliding layers in solids.

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Fig. 1: Structure of CCC.
Fig. 2: Characterization of ferroelectricity.
Fig. 3: PFM characterization and manipulation of ferroelectric domains.
Fig. 4: Schematic of geometric ferroelectricity.
Fig. 5: Schematic of sliding ferroelectricity.

Data availability

The experimental cif files can be found in CCDC (1875017-1875018 and 2160711-2160716). The experimental and DFT optimized structural files were also uploaded as supplementary files. Source data for figures in main text and supplemental information of this paper are available at https://figshare.com/articles/dataset/Direct_observation_of_geometric_and_sliding_ferroelectricity_in_an_amphidynamic_crystal/20102213. Other data supporting these findings are available from the corresponding authors upon request. Source data are provided with this paper.

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Acknowledgements

We thank D.-W. Fu and H.-F. Lu for their suggestions on project conception and structural analysis, and X. Liu, Z. Sheng and M. Liu for their kind help on SHG analysis and Rietveld refinement. Y.Z. acknowledges support from the National Key Research and Development Program of China (grant number 2017YFA0204800) and the Open Project of Shanghai Key Laboratory of Magnetic Resonance (grant number 2018004). S.D. acknowledges support from National Natural Science Foundation of China (grant number 11834002). L.-P.M. acknowledges support from the Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry (grant number 20212BCD42018). Y.-F.Y. acknowledges support from the Xing-Fu-Zhi-Hua Foundation of ECNU. We thank the Big Data Center of Southeast University for providing the facility support on the numerical calculations.

Author information

Authors and Affiliations

Authors

Contributions

Y.Z. and S.D. conceived the project. Y.Z. designed the experiments. S.D. proposed the theoretical mechanisms. L.-P.M. prepared the samples and performed the DSC and SHG measurements. N.W. contributed to PFM measurements. C.S. and H.-Y.Y. contributed to single-crystal measurement and analysis. Y.-F.Y. performed the NMR measurement and analysis. N.D. performed the DFT calculations guided by S.D. L.L. contributed to the analysis of PFM. S.D. and Y.Z. wrote the manuscript, with inputs from all other authors.

Corresponding authors

Correspondence to Shuai Dong or Yi Zhang.

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Nature Materials thanks Sarah Guerin 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 Notes 1–3, Figs. 1–14, Tables 1–5 and references 1 and 2

Crystallographic Data 1

Crystal structures of CCC form 253 K to 343 K by experiment

Crystallographic Data 1

CheckCIF/PLATON report

Computational Data 1

Crystal structure of “0+” state by DFT calculation

Computational Data 2

Crystal structure of “+P” state by DFT calculation

Computational Data 3

Crystal structure of “monolayer A” state by DFT calculation

Computational Data 4

Crystal structure of “monolayer B” state by DFT calculation

Computational Data 5

Crystal structure of “0-” state by DFT calculation

Computational Data 6

Crystal structure of “-P” state by DFT calculation

Source data

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Miao, LP., Ding, N., Wang, N. et al. Direct observation of geometric and sliding ferroelectricity in an amphidynamic crystal. Nat. Mater. (2022). https://doi.org/10.1038/s41563-022-01322-1

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