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Clamping enables enhanced electromechanical responses in antiferroelectric thin films

Nature Materials volume 23, pages 944–950 (2024)Cite this article

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Abstract

Thin-film materials with large electromechanical responses are fundamental enablers of next-generation micro-/nano-electromechanical applications. Conventional electromechanical materials (for example, ferroelectrics and relaxors), however, exhibit severely degraded responses when scaled down to submicrometre-thick films due to substrate constraints (clamping). This limitation is overcome, and substantial electromechanical responses in antiferroelectric thin films are achieved through an unconventional coupling of the field-induced antiferroelectric-to-ferroelectric phase transition and the substrate constraints. A detilting of the oxygen octahedra and lattice-volume expansion in all dimensions are observed commensurate with the phase transition using operando electron microscopy, such that the in-plane clamping further enhances the out-of-plane expansion, as rationalized using first-principles calculations. In turn, a non-traditional thickness scaling is realized wherein an electromechanical strain (1.7%) is produced from a model antiferroelectric PbZrO3 film that is just 100 nm thick. The high performance and understanding of the mechanism provide a promising pathway to develop high-performance micro-/nano-electromechanical systems.

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Fig. 1: Electromechanical response of typical (relaxor) ferroelectric and antiferroelectric thin films.
Fig. 2: Enhanced electromechanical response in orientation-engineered PbZrO3 antiferroelectric thin films.
Fig. 3: Operando STEM studies of the phase transition and structural evolution in (004)O-oriented PbZrO3 thin films.
Fig. 4: Mechanism for the enhancement of electromechanical response and abnormal thickness scaling in antiferroelectric PbZrO3 thin films.

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All data supporting the findings of this study are available within the article and its Supplementary Information. Additional data are available from the corresponding author upon request.

Code availability

Detailed information related to the codes of the DFT calculations used in this study is available from the corresponding author upon request.

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Acknowledgements

We thank T.J. Lee and O. Ashour for fruitful discussions. This work was funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under contract no. DE-AC02-05CH11231 (Materials Project programme KC23MP) for the development of functional materials. H.P., B.H., J.E.S., J.M.L. and L.W.M. acknowledge the support of the Army Research Laboratory under Cooperative Agreements W911NF-19-2-0119 and W911NF-24-2-0100. J.K. acknowledges the support of the US Army Research Office under grant W911NF-21-1-0118. Z.T. acknowledges the support of the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under award no. DE-SC-0012375 for the development of complex oxide thin-film heterostructures. X.H. and I.H. acknowledge the support of the SRC-JUMP ASCENT centre. H.Z. acknowledges the support of the US Department of Defense, Air Force Office of Scientific Research under grant no. FA9550-18-1-0480. E.B. acknowledges support from the US National Science Foundation Graduate Research Fellowship under grant no. 1752814. Computational resources were provided by the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy, Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under contract no. DE-AC02-05CH11231. J.E.S. and L.W.M. acknowledge additional support from the Army Research Office under grant W911NF-21-1-0126.

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Author notes

  1. These authors contributed equally: Hao Pan, Menglin Zhu, Ella Banyas.

Authors and Affiliations

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

    Hao Pan, Megha Acharya, Hongrui Zhang, Jiyeob Kim, Xianzhe Chen, Xiaoxi Huang, Zishen Tian & Lane W. Martin

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

    Menglin Zhu, Michael Xu & James M. LeBeau

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

    Ella Banyas, Megha Acharya, Hongrui Zhang, Xianzhe Chen, Zishen Tian, Francesco Ricci, Jeffrey B. Neaton & Lane W. Martin

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

    Ella Banyas, Isaac Harris, Francesco Ricci & Jeffrey B. Neaton

  5. Thayer School of Engineering, Dartmouth College, Hanover, NH, USA

    Louis Alaerts & Geoffroy Hautier

  6. DEVCOM Army Research Laboratory, Adelphi, MD, USA

    Brendan Hanrahan

  7. Department of Mechanical Engineering and Mechanics, Materials Science and Engineering, and Physics, Drexel University, Philadelphia, PA, USA

    Jonathan E. Spanier

  8. Kavli Energy Nanosciences Institute, University of California, Berkeley, Berkeley, CA, USA

    Jeffrey B. Neaton

  9. Departments of Materials Science and NanoEngineering, Chemistry, and Physics and Astronomy, Rice University, Houston, TX, USA

    Lane W. Martin

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

    Lane W. Martin

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  1. Hao Pan
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Contributions

H.P. and L.W.M. conceived and designed this study. H.P., M.A., J.K. and I.H. deposited films. H.P., H.Z. and X.C. prepared the capacitor samples. H.P., X.H. and Z.T. performed the electrical and electromechanical measurements. M.Z., M.X. and J.M.L. conducted the STEM studies. E.B., L.A., F.R., G.H. and J.B.N. conducted the first-principles calculations. B.H. and J.E.S. provided feedback and insights on antiferroelectric materials and helped with analysis of the findings. The manuscript was written by H.P. and L.W.M., with contributions from all others. All authors discussed the results and revised the manuscript.

Corresponding author

Correspondence to Lane W. Martin.

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Nature Materials thanks Ying-Hao Chu, Ming-Min Yang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Notes 1–6, Figs. 1–20, Tables 1 and 2 and references.

Supplementary Video 1

Operando STEM of the reversible field-induced antiferroelectric-to-ferroelectric transition.

Supplementary Data 1

Atomic coordinates of DFT calculations.

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Pan, H., Zhu, M., Banyas, E. et al. Clamping enables enhanced electromechanical responses in antiferroelectric thin films. Nat. Mater. 23, 944–950 (2024). https://doi.org/10.1038/s41563-024-01907-y

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