Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Conflicting evidence for ferroelectricity

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

Subjects

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

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

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

References

  1. Tayi, A. S. et al. Room-temperature ferroelectricity in supramolecular networks of charge-transfer complexes. Nature 488, 485–489 (2012)

    Article  CAS  ADS  Google Scholar 

  2. Tayi, A. S., Kaeser, A., Matsumoto, M., Aida, T. & Stupp, S. I. Supramolecular ferroelectrics. Nat. Chem. 7, 281–294 (2015)

    Article  CAS  Google Scholar 

  3. Blackburn, A. K. et al. Lock-arm supramolecular ordering: a molecular construction set for cocrystallizing organic charge transfer complexes. J. Am. Chem. Soc. 136, 17224–17235 (2014)

    Article  CAS  Google Scholar 

  4. Horiuchi, S. & Tokura, Y. Organic ferroelectrics. Nat. Mater. 7, 357–366 (2008)

    Article  CAS  ADS  Google Scholar 

  5. Kobayashi, K. et al. Electronic ferroelectricity in a molecular crystal with large polarization directing antiparallel to ionic displacement. Phys. Rev. Lett. 108, 237601 (2012)

    Article  ADS  Google Scholar 

  6. Pecile, C., Painelli, A. & Girlando, A. Studies of organic semiconductors for 40 years—V. Mol. Cryst. Liq. Cryst. 171, 69–87 (1989)

    Google Scholar 

  7. Colthup, N. B., Daly, L. H. & Wiberly, S. E. Introduction to Infrared and Raman Spectrocopy 90 (Academic Press, 1990)

  8. Ranzieri, P., Masino, M. & Girlando, A. Charge-sensitive vibrations in p-chloranil: the strange case of the CC antisymmetric stretching. J. Phys. Chem. B 111, 12844–12848 (2007)

    Article  CAS  Google Scholar 

  9. Ranzieri, P., Masino, M., Girlando, A. & Lemée-Cailleau, M. H. Temperature-induced valence and structural instability in DMTTF-CA: single-crystal Raman and infrared measurements. Phys. Rev. B 76, 134115 (2007)

    Article  ADS  Google Scholar 

  10. D’Avino, G. & Verstraete, M. J. Are hydrogen-bonded charge transfer crystals room temperature ferroelectrics? Phys. Rev. Lett. 113, 237602 (2014)

    Article  ADS  Google Scholar 

  11. D’Avino, G., Girlando, A. & Painelli, A. Anomalous dispersion of optical phonons at the neutral-ionic transition: evidence from diffuse X-ray scattering. Phys. Rev. Lett. 99, 156407 (2007)

    Article  ADS  Google Scholar 

  12. Giovannetti, G., Kumar, S., Stroppa, A., Van Den Brink, J. & Picozzi, S. Multiferroicity in TTF-CA organic molecular crystals predicted through ab initio calculations. Phys. Rev. Lett. 103, 266401 (2009)

    Article  ADS  Google Scholar 

  13. Horiuchi, S. et al. Above-room-temperature ferroelectricity in a single-component molecular crystal. Nature 463, 789–792 (2010)

    Article  CAS  ADS  Google Scholar 

  14. Lunkenheimer, P. et al. Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism. Nat. Mater. 11, 755–758 (2012)

    Article  CAS  ADS  Google Scholar 

  15. Scott, J. F. Ferroelectrics go bananas. J. Phys. Condens. Matter 20, 021001 (2007)

    Article  ADS  Google Scholar 

Download references

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
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Manuel Souto
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Matteo Masino
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jonas K. H. Fischer
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Imma Ratera
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Xavier Fontrodona
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Gianluca Giovannetti
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Matthieu J. Verstraete
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Anna Painelli
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Peter Lunkenheimer
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Jaume Veciana
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Alberto Girlando
    View author publications

    You can also search for this author in PubMed Google Scholar

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.

Ethics declarations

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)

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature22801

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing