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Manipulating the insulator–metal transition through tip-induced hydrogenation

Abstract

Manipulating the insulator–metal transition in strongly correlated materials has attracted a broad range of research activity due to its promising applications in, for example, memories, electrochromic windows and optical modulators1,2. Electric-field-controlled hydrogenation using ionic liquids3,4,5,6 and solid electrolytes7,8,9 is a useful strategy to obtain the insulator–metal transition with corresponding electron filling, but faces technical challenges for miniaturization due to the complicated device architecture. Here we demonstrate reversible electric-field control of nanoscale hydrogenation into VO2 with a tunable insulator–metal transition using a scanning probe. The Pt-coated probe serves as an efficient catalyst to split hydrogen molecules, while the positive-biased voltage accelerates hydrogen ions between the tip and sample surface to facilitate their incorporation, leading to non-volatile transformation from insulating VO2 into conducting HxVO2. Remarkably, a negative-biased voltage triggers dehydrogenation to restore the insulating VO2. This work demonstrates a local and reversible electric-field-controlled insulator–metal transition through hydrogen evolution and presents a versatile pathway to exploit multiple functional devices at the nanoscale.

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Fig. 1: IMT of VO2 thin films through hydrogenation.
Fig. 2: Manipulation of the hydrogenation into VO2 with scanning probe.
Fig. 3: Manipulation of the IMT through tip-induced hydrogenation.
Fig. 4: Reversibility and spatially resolved tests for the tip-induced hydrogenation.

Data availability

All data are available in the main text or the Supplementary Information. Other data relevant to this paper are available from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This research was supported by the Basic Science Center Program of the National Natural Science Foundation of China (grant no. 51788104); the National Basic Research Program of China (grant nos 2021YFE0107900 and 2021YFA1400300); the National Natural Science Foundation of China (grant nos 52025024 and 51872155); the Beijing Nature Science Foundation (grant no. Z200007); and the Beijing Advanced Innovation Center for Future Chip. L.L. acknowledges support from the Postdoctoral Innovative Talent Support Program. Y.D. acknowledges support by the US Department of Energy, Office of Science, Office of Basic Science, Early Career Research Program under award no. 68278. A portion of the research was performed using the Environmental Molecular Sciences Laboratory, a US Department of Energy User Facility sponsored by the Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory under contract no. DE-AC05-76RL01830. This research used the resources of the Beijing National Center for Electron Microscopy at Tsinghua University.

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Authors and Affiliations

Authors

Contributions

P.Y. and L.L. conceived the study. M.W. and Y. Wu prepared the VO2 thin films and performed the catalytic experiments. L.L. performed the SPM-based hydrogenation, transport, Raman and cAFM experiments and data analysis with help from F.Z., H.P. and S.S.; Y. Zhou., Y.D. and Z.Z. carried out the SIMS measurements. Y. Wang and Y.L. performed the synchrotron microscopic XANES measurements. N.L. and G.W. performed the X-ray diffraction measurements. Y. Zhang. carried out the transmission electron microscopy measurements. L.L. and P.Y. wrote the paper with suggestions from C.-W.N. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Pu Yu.

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The authors declare no competing interests.

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Nature Materials thanks Jeremy Levy, Chan-Ho Yang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–14, Notes 1–5 and refs. 1–10.

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Statistical source data.

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Statistical source data.

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Li, L., Wang, M., Zhou, Y. et al. Manipulating the insulator–metal transition through tip-induced hydrogenation. Nat. Mater. 21, 1246–1251 (2022). https://doi.org/10.1038/s41563-022-01373-4

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