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Ferroelectricity near room temperature in co-crystals of nonpolar organic molecules

A Corrigendum to this article was published on 01 November 2008

Abstract

The research on ferroelectric materials—mostly inorganic compounds or organic polymers1,2,3—is increasingly motivated by both basic scientific concerns and the potential for practical applications in electronics and optics. Ferroelectricity in organic solids would be important for the development of all-organic electronic and photonic devices. The conventional approach to making organic ferroelectrics is based on the use of polar molecules. Here we report that through supramolecular assembly of nonpolar conjugated molecules, a remarkable ferroelectric response can be obtained in co-crystals of low-molecular-weight organic compounds. Co-crystals of phenazine and chloranilic acid reveal large spontaneous polarization and sizable room-temperature dielectric constants exceeding 100. The present findings provide an approach to making potentially useful organic ferroelectric materials.

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Figure 1: Chemical formulae and crystal structures of co-crystals of phenazine and 2,5-dihalo-3,6-dihydroxy-p-benzoquinones (Phz-H2xa).
Figure 2: Temperature dependence of dielectric constant ε measured at 1 MHz.
Figure 3: Effects of hydrostatic pressure or chemical substitution on the Phz-H2xa co-crystals.
Figure 4: Polarization reversal of the Phz-H2ca crystal.

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References

  1. Samara, G. A. in Solid State Physics (ed. Ehrenreich, H. & Spaepen, F.) 239–458 (Academic, San Diego, 2001).

    Google Scholar 

  2. Furukawa, T. Ferroelectric properties of vinylidene fluoride copolymers. Phase Trans. 18, 143–211 (1989).

    Article  CAS  Google Scholar 

  3. Ferroelectric and Related Substances in Group III: Crystal and Solid State Physics Vols 16 and 28 (eds Mitsui, T. & Nakamura, E.) (Landolt–Börnstein Numerical Data and Functional Relationships in Science and Technology Series, Springer, Berlin, 1982 and 1990).

  4. Fousek, J. Ferroelectricity: remarks on historical aspects and recent trends. Ferroelectrics 113, 3–20 (1991).

    Article  CAS  Google Scholar 

  5. Sworakowski, J. Ferroelectricity and related properties of molecular solids. Ferroelectrics 128, 295–306 (1992).

    Article  CAS  Google Scholar 

  6. Goldsmith, G. J. & White, J. G. Ferroelectric behavior of thiourea. J. Chem. Phys. 31, 1175–1187 (1959).

    Article  CAS  Google Scholar 

  7. Bordeaux, D. et al. New ferroelastic-ferroelectric compound: tanane. Phys. Rev. Lett. 31, 314–317 (1973).

    Article  Google Scholar 

  8. Lipscomb, G. F., Garito, A. F. & Wei, T. S. An apparent ferroelectric transition in an organic diacetylene solid. Ferroelectrics 23, 161–172 (1980).

    Article  CAS  Google Scholar 

  9. Kamishima, Y., Akishige, Y. & Hashimoto, M. Ferroelectricity activity in organic crystal trichloroacetamide. J. Phys. Soc. Jpn 60, 2147–2150 (1991).

    Article  Google Scholar 

  10. Kroupa, J. et al. Dielectric and optical properties of weak ferroelectric cyclohexan-1,1′-diacetic acid. Ferroelectrics 202, 229–234 (1997).

    Article  CAS  Google Scholar 

  11. Tokura, Y. et al. Domain-wall dynamics in organic charge-transfer compounds with one-dimensional ferroelectricity. Phys. Rev. Lett. 63, 2405–2408 (1989).

    Article  CAS  Google Scholar 

  12. Okamoto, H. et al. Anomalous dielectric response in tetrathiafulvalene-p-chloranil as observed in temperature- and pressure-induced neutral-to-ionic phase transition. Phys. Rev. B 43, 8224–8232 (1991).

    Article  CAS  Google Scholar 

  13. Horiuchi, S. et al. Neutral-ionic phase separation and one-dimensional ferroelectricity in organic relaxors. Phys. Rev. Lett. 85, 5210–5213 (2000).

    Article  CAS  Google Scholar 

  14. Lehn, J.-M. Supramolecular Chemistry: Concepts and Perspectives (VCH, Weinheim, 1995).

    Book  Google Scholar 

  15. Zaman, M. B., Tomura, M. & Yamashita, Y. Crystal engineering using anilic acids and dipyridyl compounds through a new supramolecular synthon. J. Org. Chem. 66, 5987–5995 (2001).

    Article  CAS  Google Scholar 

  16. Andersen, E. K. The crystal and molecular structure of hydroxyquinones and salts of hydroxyquinones. I. Chloranilic acid. Acta Cryst. 22, 188–191 (1967).

    Article  Google Scholar 

  17. Samara, G. A., Sakudo, T. & Yoshimitsu, K. Important generalization concerning the role of competing forces in displacive phase transitions. Phys. Rev. Lett. 35, 1767–1769 (1975).

    Article  CAS  Google Scholar 

  18. Moritomo, Y. et al. Quantum paraelectricity and subsequent disappearance of bond alternation of molecule caused by proton dynamics in squaric acid crystal. Phys. Rev. Lett. 67, 2041–2044 (1991).

    Article  CAS  Google Scholar 

  19. Sugawara, T. et al. Organic paraelectrics resulting from tautomerization coupled with proton-transfer. Solid State Commun. 83, 665–668 (1992).

    Article  CAS  Google Scholar 

  20. Andersen, E. K. The crystal and molecular structure of hydroxyquinones and salts of hydroxyquinones. III. Ammonium chloranilate monohydrate. Acta Cryst. 22, 196–201 (1967).

    Article  Google Scholar 

  21. Tokunaga, M. Two different mechanisms of the Curie–Weiss dielectric susceptibility in ferroelectrics. J. Phys. Soc. Jpn 57, 4275–4283 (1988).

    Article  Google Scholar 

  22. King-Smith, R. D. & Vanderbilt, D. Theory of polarization of crystalline solids. Phys. Rev. B 47, 1651–1654 (1993).

    Article  CAS  Google Scholar 

  23. Cohen, R. E. Origin of ferroelectricity in perovskite oxides. Nature 358, 136–138 (1992).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors would like to thank K. Terakura, S. Ishibashi, T. Hasegawa, and Y. Abe for enlightening discussions.

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Correspondence to Sachio Horiuchi.

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Horiuchi, S., Ishii, F., Kumai, R. et al. Ferroelectricity near room temperature in co-crystals of nonpolar organic molecules. Nature Mater 4, 163–166 (2005). https://doi.org/10.1038/nmat1298

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