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Size-driven phase evolution in ultrathin relaxor films

Nature Nanotechnology volume 20, pages 478–486 (2025)Cite this article

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Abstract

Relaxor ferroelectrics (relaxors) are a special class of ferroelectrics with polar nanodomains (PNDs), which present characteristics such as slim hysteresis loops and strong dielectric relaxation. Applications such as nanoelectromechanical systems, capacitive-energy storage and pyroelectric-energy harvesters require thin-film relaxors. Hence, understanding relaxor behaviour in the ultrathin limit is of both fundamental and technological importance. Here the evolution of relaxor phases and PNDs with thickness is explored in prototypical thin relaxor films. Epitaxial 0.68PbMg1/3Nb2/3O3-0.32PbTiO3 films of various nanometre thicknesses are grown by pulsed-laser deposition and characterized by ferroelectric and dielectric measurements, temperature-dependent synchrotron X-ray diffuse scattering, scanning transmission electron microscopy and molecular dynamics simulations. As the film thickness approaches the length of the long axis of the PNDs (25–30 nm), electrostatically driven phase instabilities induce their rotation towards the plane of the films, stabilize the relaxor behaviour and give rise to anisotropic phase evolution along the out-of-plane and in-plane directions. The complex anisotropic evolution of relaxor properties ends in a collapse of the relaxor behaviour when the film thickness reaches the smallest dimension of the PNDs (6–10 nm). These findings establish that PNDs define the critical length scale for the evolution of relaxor behaviour at the nanoscale.

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Fig. 1: Out-of-plane ferroelectric properties.
Fig. 2: Out-of-plane dielectric properties.
Fig. 3: X-ray diffuse-scattering studies.
Fig. 4: STEM characterizations.
Fig. 5: MD simulations.
Fig. 6: In-plane dielectric properties and anisotropic phase evolution upon size reduction.

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Data availability

All data supporting the findings of this study are available within the Article and its Supplementary Information. The datasets used in the Supplementary Information are available via Zenodo at https://doi.org/10.5281/zenodo.14510532 (ref. 57). Source data are provided with this paper.

Code availability

Custom Python scripts used to analyse STEM images are available from the corresponding author upon request.

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Acknowledgements

J.K. acknowledges support from the Army Research Office under grant W911NF-21-1-0118. Y.Q. acknowledges support from the Office of Naval Research grant under N00014-24-1-2500 and National Science Foundation EPSCoR RII-Track-1 Cooperative Agreement 'Future Technologies and Enabling Plasma Processes’ OIA-2148653. H.T. acknowledges support from the Office of Naval Research grant under N00014-24-1-2500. Y.L.T. acknowledges support from the National Natural Science Foundation of China under grant 51922100. Y.L.T. acknowledges support from the Youth Innovation Promotion Association CAS under grant no. Y202048. R.R., J.M.L., A.M.R. and L.W.M. acknowledge that this research was sponsored by the Army Research Laboratory and was accomplished under cooperative agreement number W911NF-24-2-0100. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressed or implied, of the Army Research Laboratory or the US Government. The US Government is authorized to reproduce and distribute reprints for Government purposes notwithstanding any copyright notation herein. L.W.M. acknowledges additional support by the Air Force Office of Scientific Research under award number FA9550-24-1-0266. Any opinions, findings and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the US Air Force. This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357.

Author information

Author notes

  1. Zishen Tian

    Present address: Rice Advanced Materials Institute, Rice University, Houston, TX, USA

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of California Berkeley, Berkeley, CA, USA

    Jieun Kim, Yun-Long Tang, Zishen Tian & Ramamoorthy Ramesh

  2. Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, Daejeon, Republic of Korea

    Jieun Kim

  3. Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA

    Yubo Qi & Andrew M. Rappe

  4. Department of Physics, University of Alabama at Birmingham, Birmingham, AL, USA

    Yubo Qi

  5. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Abinash Kumar, Michael Xu, Menglin Zhu & James M. LeBeau

  6. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Yun-Long Tang & Lane W. Martin

  7. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, China

    Yun-Long Tang

  8. Department of Chemistry and Biochemistry, University of California Santa Cruz, Santa Cruz, CA, USA

    Hiroyuki Takenaka

  9. Department of Physics, University of California Berkeley, Berkeley, CA, USA

    Ramamoorthy Ramesh

  10. Department of Materials Science and Nanoengineering, Rice University, Houston, TX, USA

    Ramamoorthy Ramesh & Lane W. Martin

  11. Department of Physics and Astronomy, Rice University, Houston, TX, USA

    Ramamoorthy Ramesh & Lane W. Martin

  12. Rice Advanced Materials Institute, Rice University, Houston, TX, USA

    Ramamoorthy Ramesh & Lane W. Martin

  13. Department of Chemistry, Rice University, Houston, TX, USA

    Lane W. Martin

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Contributions

J.K. and L.W.M. conceived this study. J.K. synthesized the films. J.K. performed electrical characterizations. J.K. performed structural characterizations. J.K. performed synchrotron diffraction. A.K., Y.-L.T, M.X., M.Z., J.M.L. and R.R. performed the STEM studies. Y.Q., H.T. and A.M.R. performed the MD simulations studies. J.K, Y.Q., A.K., H.T., J.M.L., A.M.R. and L.W.M. performed the formal analysis of the results. J.K. wrote the initial draft of the manuscript. J.K., Y.Q., A.K., J.M.L., A.M.R. and L.W.M. revised the manuscript. All authors discussed the results and edited the manuscript.

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Correspondence to Lane W. Martin.

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Nature Nanotechnology thanks Fei Li, Yuan-Hua Lin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Kim, J., Qi, Y., Kumar, A. et al. Size-driven phase evolution in ultrathin relaxor films. Nat. Nanotechnol. 20, 478–486 (2025). https://doi.org/10.1038/s41565-025-01863-x

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