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Directionally tunable and mechanically deformable ferroelectric crystals from rotating polar globular ionic molecules

Nature Chemistry volume 8, pages 946–952 (2016)Cite this article

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Abstract

Ferroelectrics are used in a wide range of applications, including memory elements, capacitors and sensors. Recently, molecular ferroelectric crystals have attracted interest as viable alternatives to conventional ceramic ferroelectrics because of their solution processability and lack of toxicity. Here we show that a class of molecular compounds—known as plastic crystals—can exhibit ferroelectricity if the constituents are judiciously chosen from polar ionic molecules. The intrinsic features of plastic crystals, for example, the rotational motion of molecules and phase transitions with lattice-symmetry changes, provide the crystals with unique ferroelectric properties relative to those of conventional molecular crystals. This allows a flexible alteration of the polarization axis direction in a grown crystal by applying an electric field. Owing to the tunable nature of the crystal orientation, together with mechanical deformability, this type of molecular crystal represents an attractive functional material that could find use in a diverse range of applications.

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Figure 1: Molecular and crystal structures.
Figure 2: Ferroelectric properties.
Figure 3: Direction of the crystal orientation.
Figure 4: Polarization enhancement by the application of an electric field.
Figure 5: Phase-dependent pressure-induced morphology changes of crystals of 1.

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Acknowledgements

This work was partly supported by JSPS KAKENHI Grant no. 26620054 and a Grant-in-Aid for Scientific Research on Innovative Areas ‘π-System Figuration: Control of Electron and Structural Dynamism for Innovative Functions’ (Grant no. 15H00980) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. The authors thank A. Kobayashi (Hokkaido University) for access to a Bruker D8 ADVANCE powder X-ray diffractometer.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, 060-0810, Japan

    Jun Harada, Hiroyuki Hasegawa, Yukihiro Takahashi & Tamotsu Inabe

  2. Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-0810, Japan

    Jun Harada, Takafumi Shimojo, Hideaki Oyamaguchi, Yukihiro Takahashi & Tamotsu Inabe

  3. Graduate School of Medicine, Yamaguchi University, Yamaguchi, 753-8512, Japan

    Koichiro Satomi, Yasutaka Suzuki & Jun Kawamata

Authors
  1. Jun Harada
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  2. Takafumi Shimojo
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Contributions

J.H. conceived and designed the study, performed the crystallographic studies and wrote the manuscript. T.S. and H.O. prepared the samples and performed the hysteresis experiments. T.S. carried out the dielectric measurements and thermal analysis. Y.T. assisted with the hysteresis and dielectric experiments. H.H. and H.O. carried out the SEM. K.S., Y.S. and J.K. conducted the SHG measurements. T.I. contributed to the design of the study and supervised the project.

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Correspondence to Jun Harada or Tamotsu Inabe.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 969 kb)

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Crystallographic data for compound 1 at 300 K. (CIF 226 kb)

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Crystallographic data for compound 1 at 350 K. (CIF 131 kb)

Supplementary information

Crystallographic data for compound 1 at 380 K. (CIF 128 kb)

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Harada, J., Shimojo, T., Oyamaguchi, H. et al. Directionally tunable and mechanically deformable ferroelectric crystals from rotating polar globular ionic molecules. Nature Chem 8, 946–952 (2016). https://doi.org/10.1038/nchem.2567

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