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Ferroelastically protected reversible orthorhombic to monoclinic-like phase transition in ZrO2 nanocrystals

Nature Materials (2024)Cite this article

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Abstract

Robust ferroelectricity in nanoscale fluorite oxide-based thin films enables promising applications in silicon-compatible non-volatile memories and logic devices. However, the polar orthorhombic (O) phase of fluorite oxides is a metastable phase that is prone to transforming into the ground-state non-polar monoclinic (M) phase, leading to macroscopic ferroelectric degradation. Here we investigate the reversibility of the O–M phase transition in ZrO2 nanocrystals via in situ visualization of the martensitic transformation at the atomic scale. We reveal that the reversible shear deformation pathway from the O phase to the monoclinic-like (M′) state, a compressive-strained M phase, is protected by 90° ferroelectric–ferroelastic switching. Nevertheless, as the M′ state gradually accumulates localized strain, a critical tensile strain can pin the ferroelastic domain, resulting in an irreversible M′–M strain relaxation and the loss of ferroelectricity. These findings demonstrate the key role of ferroelastic switching in the reversibility of phase transition and also provide a tensile-strain threshold for stabilizing the metastable ferroelectric phase in fluorite oxide thin films.

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Fig. 1: Reversible 90° ferroelectric–ferroelastic switching and O–M′ martensitic transformation in ZrO2.
Fig. 2: The in-plane strain distributions in shear deformation.
Fig. 3: Multilayer accumulated strain-induced irreversible Mʹ–M transformation.
Fig. 4: Strain comparison between reversible O–M′ and irreversible M′–M martensitic transformations.
Fig. 5: The influence of strain on the O–M martensitic transformation and ferroelastic switching according to first-principles calculations.

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Data availability

The data generated in figures and calculated structures from this study are available via Figshare at https://doi.org/10.6084/m9.figshare.25286494 (ref. 54). All data in this article are available from the corresponding authors upon request. Source data are provided with this paper.

Code availability

The computer code used for data analysis is available from the corresponding author upon request.

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Acknowledgements

We are grateful for funding support from the National Natural Science Foundation of China (52322212, 52250402, 52025025, 52072400, 51991344, 12074416 and 12222414), the National Key R&D Program of China (no. 2019YFA0308500) and the Youth Innovation Promotion Association of the Chinese Academy of Sciences (no. Y2022003).

Author information

Author notes

  1. These authors contributed equally: Xinyan Li, Zhuohui Liu, Ang Gao.

Authors and Affiliations

  1. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Xinyan Li, Zhuohui Liu, Qinghua Zhang, Hai Zhong, Ting Lin, Shiyu Wang, Dong Su, Kuijuan Jin & Chen Ge

  2. College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, China

    Xinyan Li & Zhuohui Liu

  3. Beijing National Center for Electron Microscopy and Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing, China

    Ang Gao & Lin Gu

  4. School of Physical Sciences, University of Chinese Academy of Sciences, Beijing, China

    Hai Zhong, Ting Lin, Shiyu Wang, Kuijuan Jin & Chen Ge

  5. School of Materials Science and Engineering, Peking University, Beijing, China

    Fanqi Meng

  6. Songshan Lake Materials Laboratory, Dongguan, China

    Kuijuan Jin

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Contributions

L.G., C.G. and Q.Z. conceived the idea of the work. X.L. and Q.Z. designed the research. Z.L. and H.Z. fabricated the thin films. A.G. and X.L. performed the theoretical calculations and interpreted the calculation results. X.L., Q.Z., T.L., F.M. and S.W. performed and analysed the in situ STEM experiments. X.L. and Q.Z. prepared the manuscript with contributions from the other authors. All authors contributed to the discussion and provided feedback on the manuscript. L.G., C.G., Q.Z., D.S. and K.J. guided the project.

Corresponding authors

Correspondence to Qinghua Zhang, Chen Ge or Lin Gu.

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Nature Materials thanks Ignasi Fina and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Plan-view imaging and transfer methods of ZrO2 thin film.

(a) Schematic of plan-view imaging. Different areas with different colors represent [111] or [010] crystal orientations of ZrO2 grains in the film. In this work, we focus on the imaging of O-[010] grains to visualize the 90° switching and the transition between O and M phases. (b) Transfer method of ZrO2 thin films: PLD growth of ZrO2/LSMO/STO; LSMO layer is etched by acid solution; ZrO2 film is released and transferred to TEM Cu grid for plan-view imaging.

Extended Data Fig. 2 Lattice parameter analysis of Fig. 1c, d.

(a, b) Lattice plane spacing mapping of Fig. 1c along the x-axis (a) and y-axis (b). The vertical stripes in (a) indicate the vertical polarization direction of O-phase ZrO2. (c, d) Lattice plane spacing mapping of Fig. 1d along the x-axis (c) and y-axis (d). The horizontal stripes in (d) indicate the horizontal polarization direction.

Extended Data Fig. 3 Inversed ABF-STEM images of M phase (a) and monolayer shear deformation (b) within O phase.

Scale bars: 1 nm.

Extended Data Fig. 4 (a) ABF-STEM images of ZrO2 nanocrystal. (b,c) Multilayer (b) and monolayer shear deformation (c) within O phase in Fig. 1e.

Scale bars: 5 nm in (a) and 1 nm in (b,c).

Extended Data Fig. 5 The HAADF-STEM image of ZrO2 (a) and 90° domain wall structure (b) of white rectangular region in Fig. 3d.

The M phase is marked by red dots and the yellow dashed lines represent the 90° domain walls. Scale bars: 5 nm in (a) and 1 nm in (b).

Extended Data Fig. 6 The averaged in-plane strain of the Zr layers in Fig. 4a, b.

Error bars represent the standard deviations of in-plane strain from neighboring Zr atoms in each layer (~100 atoms per layer) and the data are presented as mean values of in-plane strain ± standard deviation.

Source data

Extended Data Fig. 7 The observed coexistence of [001] and [010] ferroelectric-ferroelastic domains in another nanocrystal.

The light blue dashed region denotes a [001] domain with out-of-plane polarization direction. Two ferroelastic domain walls are cb/bc and ab/ac, corresponding to Type 5 and Type 9 boundaries as defined in reference31. It is worth noting that the axis in this figure differs from the reference because of the distinct space group definitions. Scale bar: 5 nm.

Extended Data Fig. 8 (a,b) Two cases of polarization order evolution during 90° switching.

The polarization direction in each polar layer can be reorganized after ferroelastic switching. The polarization direction is indicated by the shifting of polarized oxygen ions. The orange and cyan arrows represent two reversed polarization states along the in-plane direction. Scale bars: 3 nm.

Supplementary information

Supplementary Information

Supplementary Note, Tables S1 and S2, Caption to Video 1 and refs. 1–17.

Supplementary Video 1

Movie sequentially showing the step-by-step HAADF-STEM images of the ZrO2 nanocrystal at the speed of 1 s per frame.

Source data

Source Data Fig. 2

In-plane strain data plotted in Fig. 2c–e.

Source Data Fig. 5

Calculated total energy data plotted in Fig. 5a, energy barrier data plotted in Fig. 5b and interface energy plotted in Fig. 5e.

Source Data Extended Data Fig. 6

Mean in-plane strain data and standard deviations plotted in Extended Data Fig. 6.

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Li, X., Liu, Z., Gao, A. et al. Ferroelastically protected reversible orthorhombic to monoclinic-like phase transition in ZrO2 nanocrystals. Nat. Mater. (2024). https://doi.org/10.1038/s41563-024-01853-9

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