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Emergent high-Tc ferroelectric ordering of strongly correlated and frustrated protons in a heteroepitaxial ice film

Nature Physics volume 12, pages 1063–1068 (2016)Cite this article

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Abstract

Materials containing strong correlation and frustration have the potential to respond to external perturbations in an unusual way. In the case of common water ice, protons in the hydrogen-bond network are strongly correlated and highly frustrated under Pauling’s ice rules. At low temperature, the strongly correlated protons lose ergodicity, and little is understood about the cooperative thermodynamic and electric response to external stimuli. Here, using a model platinum substrate, we demonstrate emergent high-Tc ferroelectric proton ordering in a heteroepitaxial ice film. Such proton ordering is thermodynamically stable and has an extremely high critical temperature of ∼175 K. We found that anisotropy and protolysis driven by the electrostatistics at the heterointerface are key factors in stimulating this novel exotic ordering in the many-body correlated proton system. The significant increase in Tc due to the heterointerface suggests the ubiquity of ferroelectric ice in nature—specifically, in space and the polar stratosphere.

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Figure 1: Schematic illustration of in situ infrared–visible sum-frequency generation (SFG) spectroscopy of a heteroepitaxial ice film.
Figure 2: Infrared–visible sum-frequency generation spectroscopy of crystalline-ice films on Pt(111).
Figure 3: Growth model of crystalline-ice films, the propagation of net-H-down proton ordering, and partial violation of the ice rules on Pt(111).
Figure 4: Effect of ice-rules violation on high-Tc proton ordering.

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Acknowledgements

We are grateful to N. Okumura, K. Harada, F. Kato and H. Takakuwa for assistance with the experiments; K.-I. Inoue, Y. Miyamoto, S. Hatta and T. Aruga for assistance with the apparatus development; T. Hama, A. Kouchi, N. Watanabe, H. Hidaka, H. Kato, S. Yamamoto, Y. Nagata, E. H. G. Backus, M. Bonn, K. Ando, C. Michioka, T. Ishiyama and A. Morita for fruitful discussions. This work was supported by MEXT KAKENHI: Grant-in-Aid for Scientific Research on Innovative Areas, No. 26108508 and 16H00937; JSPS KAKENHI Grant-in-Aid for Young Scientists (B), No. 26810006; Grant-in-Aid for Young Scientists (A), No. 16H06029; Grant-in-Aid for Scientific Research (A), No. 25248006 and 16H02249.

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  1. Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan

    Toshiki Sugimoto, Norihiro Aiga, Yuji Otsuki, Kazuya Watanabe & Yoshiyasu Matsumoto

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  1. Toshiki Sugimoto
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Contributions

T.S. planned and Y.M. organized the project; K.W. developed the experimental system; T.S., N.A. and Y.O. improved the experimental system and conducted measurements, T.S. analysed the data and wrote the manuscript; all authors discussed the results and commented on the manuscript.

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Correspondence to Toshiki Sugimoto or Yoshiyasu Matsumoto.

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Sugimoto, T., Aiga, N., Otsuki, Y. et al. Emergent high-Tc ferroelectric ordering of strongly correlated and frustrated protons in a heteroepitaxial ice film. Nature Phys 12, 1063–1068 (2016). https://doi.org/10.1038/nphys3820

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