Abstract
Vanadium dioxide is a strongly correlated material1,2,3,4 that undergoes a metal–insulator transition5 from a high-temperature, rutile metal to a monoclinic insulating state at 67 °C. In recent years, experiments on single-crystal vanadium-dioxide nanowires grown by physical vapour deposition6 have shed light on the crucial role of strain in the structural and electronic phase diagram of this material7,8,9,10, including evidence for a new M2 phase11,12, but the detailed physics of this material is still not fully understood. The transition temperature can be reduced by doping with tungsten8,13, but this process is not reversible. Here, we show that the metal–insulator transition in nanoscale beams of vanadium dioxide can be strongly modified by doping with atomic hydrogen14 using the catalytic spillover method15. We also show that this process is completely reversible, and that the metal–insulator transition eventually vanishes when the doping exceeds a threshold value. Raman and conventional optical microscopy, electron diffraction and transmission electron microscopy provide evidence that the structure of the metallic post-hydrogenation state is similar to that of the rutile state. First-principles electronic structure calculations confirm that a distorted rutile structure is energetically favoured following hydrogenation, and also that such doping favours metallicity from both the Mott and Peierls perspectives. We anticipate that hydrogen doping will be a powerful tool for examining the metal–insulator transition and for engineering the properties of vanadium dioxide.
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Acknowledgements
The authors acknowledge support from the US Department of Energy (DE-FG02-06ER46337). J.W. acknowledges support from the Evans Attwell/Robert A. Welch Postdoctoral Fellowship, overseen by the R. E. Smalley Institute for Nanoscale Science and Technology at Rice University. The authors acknowledge very useful conversations with E. Morosan, C-W. Chen, M. S. Wong, J. Velazquez, L. Pretzer, N. Soultanidis, S. L. Biswal and M. Thakur. The authors also thank Yu Zhu and Bo Chen for help with XPS measurements.
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J.W. and H.J. fabricated the samples and performed SEM and electronic measurements. J.W. performed the optical measurements and J.W. and W.G. performed TEM measurements. A.H.N. performed and analysed the electronic structure calculations. D.N. actively guided the work. J.W., D.N. and A.H.N. wrote the manuscript.
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Wei, J., Ji, H., Guo, W. et al. Hydrogen stabilization of metallic vanadium dioxide in single-crystal nanobeams. Nature Nanotech 7, 357–362 (2012). https://doi.org/10.1038/nnano.2012.70
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DOI: https://doi.org/10.1038/nnano.2012.70
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