Abstract

Designing materials to function in harsh environments, such as conductive aqueous media, is a problem of broad interest to a range of technologies, including energy, ocean monitoring and biological applications1,2,3,4. The main challenge is to retain the stability and morphology of the material as it interacts dynamically with the surrounding environment. Materials that respond to mild stimuli through collective phase transitions and amplify signals could open up new avenues for sensing. Here we present the discovery of an electric-field-driven, water-mediated reversible phase change in a perovskite-structured nickelate, SmNiO35,6,7. This prototypical strongly correlated quantum material is stable in salt water, does not corrode, and allows exchange of protons with the surrounding water at ambient temperature, with the concurrent modification in electrical resistance and optical properties being capable of multi-modal readout. Besides operating both as thermistors and pH sensors, devices made of this material can detect sub-volt electric potentials in salt water. We postulate that such devices could be used in oceanic environments for monitoring electrical signals from various maritime vessels and sea creatures.

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Acknowledgements

S.R. thanks K. Catania (Vanderbilt University) for discussions on bioelectric fields in marine organisms and B. Robinson and K. Benoit-Bird of the Monterey Bay Aquarium Research Institute for technical discussions on electroreception in sharks. We acknowledge financial support from the Army Research Office (W911NF-16-1-0289, W911NF-16-1-0042), National Science Foundation (DMR-1609898, DMR-1610215), Defense Advanced Research Projects Agency (grant D15AP00111), Office of Naval Research (grants N00014-16-1-2442 and N00014-12-1040) and Air Force Office of Scientific Research (grants FA9550-16-1-0159 and FA9550-14-1-0389). Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the US Department of Energy (DOE), the Office of Science, Office of Basic Energy Sciences under contract number DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, a US DOE Office of Science User Facility operated by Argonne National Laboratory under contract number DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the US DOE under contract number DE-AC02-05CH11231. An award of computer time was provided by the Innovative and Novel Computational Impact on Theory and Experiment (INCITE) programme. This research used resources of the Argonne Leadership Computing Facility at Argonne National Laboratory, which is supported by the Office of Science of the US DOE under contract DE-AC02-06CH11357. S.S.N. acknowledges support from the University of Massachusetts-Amherst through start-up funding. Part of the research described in this paper was performed at the Canadian Light Source, which is supported by the Canada Foundation for Innovation, Natural Sciences and Engineering Research Council of Canada, the University of Saskatchewan, the Government of Saskatchewan, Western Economic Diversification Canada, the National Research Council Canada and the Canadian Institutes of Health Research.

Author information

Author notes

    • Badri Narayanan

    Present address: Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, USA.

    • Zhen Zhang
    •  & Derek Schwanz

    These authors contributed equally to this work.

Affiliations

  1. School of Materials Engineering, Purdue University, West Lafayette, Indiana 47907, USA

    • Zhen Zhang
    • , Derek Schwanz
    • , Yifei Sun
    • , Koushik Ramadoss
    •  & Shriram Ramanathan
  2. Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, USA

    • Badri Narayanan
    • , Mathew Cherukara
    •  & Subramanian K. R. S. Sankaranarayanan
  3. Department of Physics and Astronomy, Rutgers University, Piscataway, New Jersey 08854, USA

    • Michele Kotiuga
    •  & Karin M. Rabe
  4. NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA

    • Joseph A. Dura
  5. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA

    • Hua Zhou
    •  & John W. Freeland
  6. Department of Physics, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    • Jiarui Li
    •  & Riccardo Comin
  7. Canadian Light Source, University of Saskatchewan, Saskatoon, Saskatchewan S7N 2V3, Canada

    • Ronny Sutarto
    •  & Feizhou He
  8. Department of Applied Physics and Applied Mathematics, Columbia University, New York 10027, USA

    • Chongzhao Wu
    •  & Nanfang Yu
  9. Department of Mechanical and Industrial Engineering, University of Massachusetts – Amherst, Amherst, Massachusetts 01003, USA

    • Jiaxin Zhu
    •  & Stephen S. Nonnenmann

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Contributions

Z.Z., D.S. and S.R. conceived the study. Z.Z. and D.S. fabricated the SNO thin-film devices and performed the electrical, stability, sensing and electrochemical experiments. B.N., M.C. and S.K.R.S.S. performed the AIMD simulations and the nudged elastic band calculations to compute activation barriers. M.K. and K.M.R. performed first-principles electronic structure calculations. D.S. and J.A.D. performed neutron reflectivity measurements. Y.S., D.S. and H.Z. performed X-ray diffraction and X-ray reflectivity measurements. J.W.F., J.L., R.S., F.H. and R.C. performed X-ray absorption measurements. C.W. and N.Y. performed optical measurements and analysis. J.Z. and S.S.N. performed cross-sectional conducting AFM studies. K.R. and Z.Z. performed in-plane conducting AFM studies. Z.Z., D.S., B.N., S.K.R.S.S. and S.R. wrote the manuscript. All authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Shriram Ramanathan.

Reviewer Information Nature thanks M. Lyons and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Supplementary information

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  1. 1.

    Supplementary Information

    This file contains supplementary text 1 – 7, supplementary tables 1 – 3 and references.

Videos

  1. 1.

    AIMD video showing the interaction of SNO surface with water molecules at 300 K.

    MD trajectory highlights the dissociation of water molecules near the oxide-water interface into free protons and OH- ions. A fraction of the protons migrates to the oxide surface and binds to surface oxygen of the SNO. The spheres shown here represent nickel (green), samarium (purple), oxygen (red), and hydrogen (cyan) atoms.

  2. 2.

    AIMD video showing the interaction of SNO surface with water molecules at 500 K.

    The mechanism of protonation of the SNO surface is similar to that observed at 300 K. Note that the surface of SNO maintains its structural integrity even at elevated temperatures. The spheres shown here represent nickel (green), samarium (purple), oxygen (red), and hydrogen (cyan) atoms.

  3. 3.

    AIMD video showing proton hopping between two neighboring O atoms belonging to a NiO6 octahedron in bulk SNO at 300 K.

    Only a selected region of bulk SNO is shown, wherein proton hopping occurs within ~1.5 ps. The spheres shown here represent nickel (green), samarium (purple), oxygen (red), and hydrogen (cyan) atoms.

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