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Conflicting evidence for ferroelectricity

Nature volume 547, pages E9–E10 (2017)Cite this article

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Arising from S. A. Tayi et al. Nature 488, 485–489 (2012); doi:10.1038/nature11395

Organic ferroelectric materials operating at room temperature are in demand in the emerging field of lightweight, flexible and environmentally friendly electronics. Tayi et al.1 reported room-temperature ferroelectricity in organic mixed-stack charge-transfer crystals, produced using a supramolecular design concept—the lock-arm supramolecular ordering (LASO)—that synergistically combines intermolecular charge transfer and hydrogen bonds2,3. Here we present an independent experimental investigation that found no evidence for ferroelectricity in one of the LASO compounds described in ref. 1 and, together with theoretical calculations, demonstrates that a possible ferroelectric behaviour is not of electronic origin as proposed in ref. 1. We therefore question the reproducibility of the room-temperature ferroelectricity claimed for LASO systems1. There is a Reply to this Comment by Tayi, S. A. et al. Nature 547, 10.1038/nature22802 (2017).

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Figure 1: Vibrational spectra of LASO compound 1·2.
Figure 2: Dielectric measurements for LASO compound 1·2.

References

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Author information

Authors and Affiliations

  1. nanomat/QMAT/CESAM, Université de Liège, and European Theoretical Spectroscopy Facility, Liège, B-4000, Belgium

    Gabriele D’Avino & Matthieu J. Verstraete

  2. Institut Néel, CNRS and Grenoble Alpes University, Grenoble, F-38042, France

    Gabriele D’Avino

  3. Laboratory for the Chemistry of Novel Materials, University of Mons, Mons, 7000, Belgium

    Gabriele D’Avino

  4. Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Cerdanyola del Vallès, E-08193, Spain

    Manuel Souto, Imma Ratera & Jaume Veciana

  5. Department of Chemistry, Life Science and Environmental Sustainability, Parma University and INSTM-UdR Parma, Parma, 43124, Italy

    Matteo Masino, Anna Painelli & Alberto Girlando

  6. Experimental Physics V, Center for Electronic Correlations and Magnetism, University of Augsburg, Augsburg, 86159, Germany

    Jonas K. H. Fischer & Peter Lunkenheimer

  7. Serveis Científico-Tècnics, Campus de Montilivi, University of Girona, Girona, E-17071, Spain

    Xavier Fontrodona

  8. CNR-IOM-Democritos National Simulation Centre and International School for Advanced Studies (SISSA), Trieste, I-34136, Italy

    Gianluca Giovannetti

Authors
  1. Gabriele D’Avino
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  2. Manuel Souto
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  3. Matteo Masino
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  4. Jonas K. H. Fischer
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  5. Imma Ratera
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  6. Xavier Fontrodona
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  7. Gianluca Giovannetti
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  8. Matthieu J. Verstraete
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  9. Anna Painelli
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  10. Peter Lunkenheimer
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  11. Jaume Veciana
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  12. Alberto Girlando
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Contributions

G.D. and A.G. designed the research and wrote the Comment with contributions from the other authors. Experimental work was performed by M.S. and I.R. (materials synthesis and crystallization), X.F. (X-ray diffraction), M.M. (vibrational spectra) and J.K.H.F. (dielectric measurements). G.D. and G.G. performed DFT calculations. All authors discussed the results and contributed to data analysis.

Corresponding author

Correspondence to Gabriele D’Avino.

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Competing interests

The authors declare no competing financial interests.

Extended data figures and tables

Extended Data Figure 1 Raman spectra of compounds 1, 2 and 1·2.

The negligible frequency variation of the C=O mode between 1 and 1·2 further confirms the very small charge transfer (ρ ≈ 0) in the co-crystal, as is also evident from the infrared spectra in Fig. 1c. Raman intensity is given in counts per second per mW of laser power.

Extended Data Figure 2 Additional electric measurements for LASO compound 1·2.

a, Picture of two of the single crystals of 1·2 after removal of the contacts. The measured crystals are of good quality, with smooth surfaces and no branching or splintering. b, Electric-field-dependent polarization of 1·2 at 7 K (circles). c, d, Room-temperature time-dependent excitation field (c) and current response (d) of the positive-up, negative-down measurements. The responses of pulses I and II are identical, just as the responses of pulses III and IV are identical, indicating the absence of polar order.

Extended Data Table 1 DFT calculations for the three LASO crystals of ref. 1
Full size table

Supplementary information

Supplementary Information

This file contains Supplementary Text, Supplementary Figures 1-5, Supplementary Table 1 and Supplementary References. (PDF 1258 kb)

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D’Avino, G., Souto, M., Masino, M. et al. Conflicting evidence for ferroelectricity. Nature 547, E9–E10 (2017). https://doi.org/10.1038/nature22801

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