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Engineering interfacial polarization switching in van der Waals multilayers

Nature Nanotechnology (2024)Cite this article

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Abstract

In conventional ferroelectric materials, polarization is an intrinsic property limited by bulk crystallographic structure and symmetry. Recently, it has been demonstrated that polar order can also be accessed using inherently non-polar van der Waals materials through layer-by-layer assembly into heterostructures, wherein interfacial interactions can generate spontaneous, switchable polarization. Here we show that deliberate interlayer rotations in multilayer van der Waals heterostructures modulate both the spatial ordering and switching dynamics of polar domains. The engendered tunability is unparalleled in conventional bulk ferroelectrics or polar bilayers. By means of operando transmission electron microscopy we show how alterations of the relative rotations of three WSe2 layers produce structural polytypes with distinct arrangements of polar domains with either a global or localized switching response. Furthermore, the presence of uniaxial strain generates structural anisotropy that yields a range of switching behaviours, coercivities and even tunable biased responses. We also provide evidence of mechanical coupling between the two interfaces of the trilayer, a key consideration for the control of switching dynamics in polar multilayer structures more broadly.

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Fig. 1: TTL-WSe2 polytypes and assignment of polar domains.
Fig. 2: Polar domain dynamics in AtA′ WSe2.
Fig. 3: Biased polarization from heterostrain gradients in the AtA′ polytype.
Fig. 4: Polarization switching in the tAB′ polytype.
Fig. 5: Design principles for tuning polarization-switching dynamics in twisted WSe2 trilayers.

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Data availability

All data shown in this work are available on Zenodo at https://doi.org/10.5281/zenodo.10697962 (ref. 54).

Code availability

Scripts used for multislice simulations are available on Zenodo at https://doi.org/10.5281/zenodo.10697962 (ref. 54).

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Acknowledgements

This work was supported by the US National Science Foundation (NSF) under award number DMR-2238196 (D.K.B.). M.V. acknowledges support from a University of California, Berkeley Philomathia Graduate Fellowship. I.M.C. acknowledges support from a National Defense Science and Engineering Graduate (NDSEG) Fellowship under contract FA9550-21-F-0003 sponsored by the Air Force Research Laboratory (AFRL), the Office of Naval Research (ONR) and the Army Research Office (ARO). Work at the Molecular Foundry, LBNL was supported by the Office of Science, Office of Basic Energy Sciences, of the US DOE under contract number DE-AC02-05CH11231. Other instrumentation used in this work was supported by grants from the Gordon and Betty Moore Foundation EPiQS Initiative (award number 10637, D.K.B.), the Canadian Institute for Advanced Research (CIFAR-Azrieli Global Scholar, award number GS21-011, D.K.B.) and the 3M Foundation through the 3M Non-Tenured Faculty Award (number 67507585, D.K.B.). K.W. and T.T. acknowledge support from the JSPS KAKENHI (grant numbers 20H00354 and 23H02052) and the World Premier International Research Center Initiative (WPI), MEXT, Japan.

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Authors and Affiliations

  1. Department of Chemistry, University of California, Berkeley, Berkeley, CA, USA

    Madeline Van Winkle, Nikita Dowlatshahi, Nikta Khaloo, Mrinalni Iyer, Isaac M. Craig & D. Kwabena Bediako

  2. Department of Chemistry, University of Minnesota, Minneapolis, MN, USA

    Mrinalni Iyer

  3. Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Rohan Dhall

  4. Research Center for Materials Nanoarchitectonics, National Institute for Materials Science, Tsukuba, Japan

    Takashi Taniguchi

  5. Research Center for Electronic and Optical Materials, National Institute for Materials Science, Tsukuba, Japan

    Kenji Watanabe

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

    D. Kwabena Bediako

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  1. Madeline Van Winkle
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Contributions

M.V.W. and D.K.B. conceived the study. M.V.W., N.D. and N.K. designed and fabricated the samples. M.V.W. and R.D. acquired TEM and 4D-STEM data. M.I. performed multislice simulations with input from I.M.C. I.M.C. wrote the code used for generation of colour-coded virtual DF images. T.T. and K.W. provided the bulk hBN crystals. M.V.W. processed and analysed the data. M.V.W. and D.K.B. wrote the manuscript with input from all coauthors.

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Correspondence to D. Kwabena Bediako.

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Nature Nanotechnology thanks Ondrej Dyck 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 sections 1–8, Figs. 1–16 and Tables 1 and 2.

Supplementary Video 1

DF-TEM video of an AtA′-type WSe2 trilayer during application of an out-of-plane electric field. The region outlined in yellow in the first frame was analysed in Fig. 2a,b. The region outlined in blue in the first frame was analysed in Fig. 3a,c,e. Images generated using the \([10{\bar1}0]\) Bragg reflection.

Supplementary Video 2

DF-TEM video of an AtA′-type WSe2 trilayer with heterostrain-induced polar domain walls during application of an out-of-plane electric field. Images generated using the \([10{\bar1}0]\) Bragg reflection and analysed in Fig. 2c–h and Fig. 3b,d,f–i. Specific regions of interest outlined in Supplementary Fig. 13.

Supplementary Video 3

DF-TEM video of an AtA′-type WSe2 trilayer with heterostrain-induced polar domain walls during two additional biasing cycles. Images generated using the \([10{\bar1}0]\) Bragg reflection and analysed in Fig. 3f. Specific regions of interest outlined in Supplementary Fig. 13. Images in Supplementary Videos 2 and 3 were collected on separate days, leading to a difference in sample tilt and change in observed domain contrast.

Supplementary Video 4

DF-TEM video of an AtA′-type WSe2 trilayer with heterostrain-induced polar domain walls during application of an out-of-plane electric field. Images generated using the \([{\bar 1}2{\bar 1}0]\) Bragg reflection and analysed in Fig. 2h. Specific regions of interest outlined in Supplementary Fig. 13.

Supplementary Video 5

DF-TEM video of a tAB′-type WSe2 trilayer during application of an out-of-plane electric field. The twisted trilayer region outlined in yellow in the first frame was analysed in Fig. 4a,b (TTL12, θ < 0.05°). The twisted bilayer region outlined in blue in the first frame was analysed in Fig. 4b (TBL, θ ≈ 0.31°). Images generated using the \([10{\bar1}0]\) Bragg reflection.

Supplementary Video 6

DF-TEM video of a tAB′-type WSe2 trilayer during application of an out-of-plane electric field over three cycles. The region outlined in yellow in the first frame was analysed in Fig. 4c–g. The region outlined in blue in the first frame was analysed in Fig. 4b (TTL23, θ ≈ 0.25°). Images generated using the \([1{\bar 1}00]\) Bragg reflection. Images in cycle 1 and 2/3 were collected on separate days, leading to a difference in sample tilt and change in observed domain contrast.

Supplementary Video 7

DF-TEM video of twisted bilayer (TBL) WSe2 during application of an out-of-plane electric field. The region outlined in yellow in the first frame was analysed in Fig. 4b (TBL, θ ≈ 0.03°). Images generated using the \([10{\bar1}0]\) Bragg reflection.

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Van Winkle, M., Dowlatshahi, N., Khaloo, N. et al. Engineering interfacial polarization switching in van der Waals multilayers. Nat. Nanotechnol. (2024). https://doi.org/10.1038/s41565-024-01642-0

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