Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Manipulating the insulator–metal transition through tip-induced hydrogenation


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.

This is a preview of subscription content, access via your institution

Access options

Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

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.


  1. Imada, M., Fujimori, A. & Tokura, Y. Metal-insulator transitions. Rev. Mod. Phys. 70, 1039–1263 (1998).

    Article  CAS  Google Scholar 

  2. Zhou, Y. & Ramanathan, S. Mott memory and neuromorphic devices. Proc. IEEE 103, 1289–1310 (2015).

    Article  CAS  Google Scholar 

  3. Ji, H., Wei, J. & Natelson, D. Modulation of the electrical properties of VO2 nanobeams using an ionic liquid as a gating medium. Nano Lett. 12, 2988–2992 (2012).

    Article  CAS  Google Scholar 

  4. Lu, N. et al. Electric-field control of tri-state phase transformation with a selective dual-ion switch. Nature 546, 124–128 (2017).

    Article  CAS  Google Scholar 

  5. Li, S. et al. Large transport gap modulation in graphene via electric-field-controlled reversible hydrogenation. Nat. Electron. 4, 254–260 (2021).

    Article  CAS  Google Scholar 

  6. Altendorf, S. G. et al. Facet-independent electric-field-induced volume metallization of tungsten trioxide films. Adv. Mater. 28, 5284–5292 (2016).

    Article  CAS  Google Scholar 

  7. Ohta, H. et al. Field-induced water electrolysis switches an oxide semiconductor from an insulator to a metal. Nat. Commun. 1, 118 (2010).

    Article  Google Scholar 

  8. Katase, T., Endo, K., Tohei, T., Ikuhara, Y. & Ohta, H. Room-temperature-protonation-driven on-demand metal–insulator conversion of a transition metal oxide. Adv. Electron. Mater. 1, 1500063 (2015).

    Article  Google Scholar 

  9. Chen, S. et al. Gate-controlled VO2 phase transition for high-performance smart windows. Sci. Adv. 5, eaav6815 (2019).

    Article  CAS  Google Scholar 

  10. Lee, D. et al. Isostructural metal-insulator transition in VO2. Science 362, 1037–1040 (2018).

    Article  CAS  Google Scholar 

  11. Liu, M. et al. Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial. Nature 487, 345–348 (2012).

    Article  CAS  Google Scholar 

  12. Jeong, J. et al. Suppression of metal-insulator transition in VO2 by electric field–induced oxygen vacancy formation. Science 339, 1402–1405 (2013).

    Article  CAS  Google Scholar 

  13. Nakano, M. et al. Collective bulk carrier delocalization driven by electrostatic surface charge accumulation. Nature 487, 459–462 (2012).

    Article  CAS  Google Scholar 

  14. Liu, K., Lee, S., Yang, S., Delaire, O. & Wu, J. Recent progresses on physics and applications of vanadium dioxide. Mater. Today 21, 875–896 (2018).

    Article  CAS  Google Scholar 

  15. Leighton, C. Electrolyte-based ionic control of functional oxides. Nat. Mater. 18, 13–18 (2019).

    Article  CAS  Google Scholar 

  16. Zhang, H.-T. et al. Reconfigurable perovskite nickelate electronics for artificial intelligence. Science 375, 533–539 (2022).

    Article  CAS  Google Scholar 

  17. Tan, A. J. et al. Magneto-ionic control of magnetism using a solid-state proton pump. Nat. Mater. 18, 35–41 (2019).

    Article  CAS  Google Scholar 

  18. Huang, M. et al. Voltage control of ferrimagnetic order and voltage-assisted writing of ferrimagnetic spin textures. Nat. Nanotechnol. 16, 981–988 (2021).

    Article  CAS  Google Scholar 

  19. Kreuer, K. D. Proton-conducting oxides. Annu. Rev. Mater. Res. 33, 333–359 (2003).

    Article  CAS  Google Scholar 

  20. Sood, A. et al. Electrochemical ion insertion from the atomic to the device scale. Nat. Rev. Mater. 6, 847–867 (2021).

    Article  CAS  Google Scholar 

  21. Wei, J., Ji, H., Guo, W., Nevidomskyy, A. H. & Natelson, D. Hydrogen stabilization of metallic vanadium dioxide in single-crystal nanobeams. Nat. Nanotechnol. 7, 357–362 (2012).

    Article  CAS  Google Scholar 

  22. Yoon, H. et al. Reversible phase modulation and hydrogen storage in multivalent VO2 epitaxial thin films. Nat. Mater. 15, 1113–1119 (2016).

    Article  CAS  Google Scholar 

  23. Bonnell, D. A., Kalinin, S. V., Kholkin, A. L. & Gruverman, A. Piezoresponse force microscopy: a window into electromechanical behavior at the nanoscale. MRS Bull. 34, 648–657 (2009).

    Article  CAS  Google Scholar 

  24. Giridharagopal, R. et al. Electrochemical strain microscopy probes morphology-induced variations in ion uptake and performance in organic electrochemical transistors. Nat. Mater. 16, 737–742 (2017).

    Article  CAS  Google Scholar 

  25. Garcia, R., Knoll, A. W. & Riedo, E. Advanced scanning probe lithography. Nat. Nanotechnol. 9, 577–587 (2014).

    Article  CAS  Google Scholar 

  26. Evans, D. M. et al. Conductivity control via minimally invasive anti-Frenkel defects in a functional oxide. Nat. Mater. 19, 1195–1200 (2020).

    Article  CAS  Google Scholar 

  27. Cen, C. et al. Nanoscale control of an interfacial metal–insulator transition at room temperature. Nat. Mater. 7, 298–302 (2008).

    Article  CAS  Google Scholar 

  28. Bi, F. et al. ‘Water-cycle’ mechanism for writing and erasing nanostructures at the LaAlO3/SrTiO3 interface. Appl. Phys. Lett. 97, 2012–2015 (2010).

    Article  Google Scholar 

  29. Xie, Y., Bell, C., Yajima, T., Hikita, Y. & Hwang, H. Y. Charge writing at the LaAlO3/SrTiO3 surface. Nano Lett. 10, 2588–2591 (2010).

    Article  CAS  Google Scholar 

  30. Henderson, M. The interaction of water with solid surfaces: fundamental aspects revisited. Surf. Sci. Rep. 46, 1–308 (2002).

    Article  CAS  Google Scholar 

Download references


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.

Author information

Authors and Affiliations



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.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

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

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

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

Source data

Source Data Fig. 1

Statistical source data.

Source Data Fig. 2

Statistical source data.

Source Data Fig. 3

Statistical source data.

Source Data Fig. 4

Statistical source data.

Rights and permissions

Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Li, L., Wang, M., Zhou, Y. et al. Manipulating the insulator–metal transition through tip-induced hydrogenation. Nat. Mater. 21, 1246–1251 (2022).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing