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Ferroelectricity in hafnia controlled via surface electrochemical state

Nature Materials volume 22, pages 1144–1151 (2023)Cite this article

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Abstract

Ferroelectricity in binary oxides including hafnia and zirconia has riveted the attention of the scientific community due to the highly unconventional physical mechanisms and the potential for the integration of these materials into semiconductor workflows. Over the last decade, it has been argued that behaviours such as wake-up phenomena and an extreme sensitivity to electrode and processing conditions suggest that ferroelectricity in these materials is strongly influenced by other factors, including electrochemical boundary conditions and strain. Here we argue that the properties of these materials emerge due to the interplay between the bulk competition between ferroelectric and structural instabilities, similar to that in classical antiferroelectrics, coupled with non-local screening mediated by the finite density of states at surfaces and internal interfaces. Via the decoupling of electrochemical and electrostatic controls, realized via environmental and ultra-high vacuum piezoresponse force microscopy, we show that these materials demonstrate a rich spectrum of ferroic behaviours including partial-pressure-induced and temperature-induced transitions between ferroelectric and antiferroelectric behaviours. These behaviours are consistent with an antiferroionic model and suggest strategies for hafnia-based device optimization.

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Fig. 1: Structural and chemical characterization of HZO.
Fig. 2: BE-PFM ferroelectric poling.
Fig. 3: BEPS hysteresis loops.
Fig. 4: Phenomenological Landau-type modelling.
Fig. 5: Temperature-dependent BEPS.

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Data availability

The data that support the findings of this study are available from the corresponding authors upon request. Data supporting the theoretical results were visualized in Mathematica 12.2 (https://www.wolfram.com/mathematica) and can be found at the Notebook Archive (https://github.com/SergeiVKalinin/SergeiVKalinin-Hafnia_NatureMaterials2023/blob/main/arxiv_org_abs_HZO-2023_ANM.nb). Source data are provided with this paper.

Code availability

Detailed information related to the codes used in this manuscript is available in the Supplementary Information files or from the corresponding authors upon request.

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Acknowledgements

This effort (K.P.K., Y.L., S.S.F., S.T.J., T.M., J.F.I., S.C., E.C.D. and S.V.K.) was supported as part of the Center for 3D Ferroelectric Microelectronics (3DFeM), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences under award number DE-SC0021118. The scanning probe microscopy research was performed and partially supported at Oak Ridge National Laboratory’s Center for Nanophase Materials Sciences, a US Department of Energy, Office of Science User Facility. S.T.J. acknowledges support from the US National Science Foundation’s Graduate Research Fellowship Program via grant number DGE-1842490. A.N.M. received funding from the National Academy of Sciences of Ukraine (grant N 4.8/23-II, ‘Innovative materials and systems with magnetic and/or electrodipole ordering for the needs of using spintronics and nanoelectronics in strategically important issues of new technology’, fund 1230) and was also supported by the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 778070. Some authors (S.C. and E.C.D.) acknowledge the use of the Materials Characterization Facility at Carnegie Mellon University, supported by MCF-677785.

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Authors and Affiliations

  1. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Kyle P. Kelley & Yongtao Liu

  2. Institute of Physics, National Academy of Sciences of Ukraine, Kyiv, Ukraine

    Anna N. Morozovska

  3. Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, Kyiv, Ukraine

    Eugene A. Eliseev

  4. Department of Materials Science and Engineering, University of Virginia, Charlottesville, VA, USA

    Shelby S. Fields, Samantha T. Jaszewski, Takanori Mimura & Jon F. Ihlefeld

  5. Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, PA, USA

    Sebastian Calderon & Elizabeth C. Dickey

  6. Charles L. Brown Department of Electrical and Computer Engineering, University of Virginia, Charlottesville, VA, USA

    Jon F. Ihlefeld

  7. Materials Science and Engineering Department, University of Tennessee, Knoxville, Knoxville, TN, USA

    Sergei V. Kalinin

  8. Joint Institute for Advanced Materials, Department of Materials Science and Engineering, University of Tennessee, Knoxville, Knoxville, TN, USA

    Sergei V. Kalinin

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  1. Kyle P. Kelley
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Contributions

K.P.K. performed and conceived experiments; A.N.M. and E.A.E. performed theoretical calculations; Y.L. performed ambient PFM measurements; S.T.J., S.S.F., T.M. and J.F.I. grew samples and performed bulk characterization; S.C. and E.C.D. performed STEM and analysis; and K.P.K. and S.V.K conceived the project. All authors contributed to discussions and the final manuscript.

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Correspondence to Kyle P. Kelley or Sergei V. Kalinin.

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Nature Materials thanks Thomas Mikolajick, Bo Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–16, Tables 1–3, Discussion and References 1–20.

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Kelley, K.P., Morozovska, A.N., Eliseev, E.A. et al. Ferroelectricity in hafnia controlled via surface electrochemical state. Nat. Mater. 22, 1144–1151 (2023). https://doi.org/10.1038/s41563-023-01619-9

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