Reversible phase modulation and hydrogen storage in multivalent VO2 epitaxial thin films

Abstract

Hydrogen, the smallest and the lightest atomic element, is reversibly incorporated into interstitial sites in vanadium dioxide (VO2), a correlated oxide with a 3d1 electronic configuration, and induces electronic phase modulation. It is widely reported that low hydrogen concentrations stabilize the metallic phase, but the understanding of hydrogen in the high doping regime is limited. Here, we demonstrate that as many as two hydrogen atoms can be incorporated into each VO2 unit cell, and that hydrogen is reversibly absorbed into, and released from, VO2 without destroying its lattice framework. This hydrogenation process allows us to elucidate electronic phase modulation of vanadium oxyhydride, demonstrating two-step insulator (VO2)–metal (HxVO2)–insulator (HVO2) phase modulation during inter-integer d-band filling. Our finding suggests the possibility of reversible and dynamic control of topotactic phase modulation in VO2 and opens up the potential application in proton-based Mottronics and novel hydrogen storage.

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Figure 1: Low-temperature hydrogenation of VO2.
Figure 2: Structural phase modulation by hydrogenation.
Figure 3: Dynamic resistivity modulation of HxVO2 by hydrogenation.
Figure 4: X-ray photoemission spectroscopy and NEXAFS of pristine VO2 and fully hydrogenated insulating HVO2.
Figure 5: Calculated structural and electronic modulation in HVO2.

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Acknowledgements

We thank J. B. Song for RBS and ERD measurement, Y. C. Park for STEM, and J. H. Lee and S. Lee for helpful discussion. H.Y. and J.S. acknowledge support for this work by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (2014R1A1A1035950), and the IT R&D programme of MOTIE/KEIT (10045226). M.C. acknowledges support for this work by the Basic Science Research Program through the NRF funded by the Ministry of Science, ICT & Future Planning (2015R1C1A1A02037595). M.C., T.-W. L. and S.-Y.C. were supported by the Global Frontier R&D Program (2013-073298) on Center for Hybrid Interface Materials (HIM) funded by the Ministry of Science, ICT & Future Planning (2013M3A6B1078872). In addition, this study was partially supported by the Fundamental Research Program of the Korean Institute of Materials Science (KIMS) and Brain Korea 21 PLUS project (Center for Creative Industrial Materials).

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M.C. and J.S. conceived the idea and designed the study. H.Y. performed the film growth, X-ray diffraction and synchrotron measurement under the supervision of J.S. H.Y. and H.K. carried out the in situ electrical measurement under the guidance of J.S. and J.-K.K. M.C. performed the electronic structure calculations. T.-W.L. and S.-Y.C. characterized the samples with scanning transmission electron microscopy. J.S. directed the research. H.Y., M.C. and J.S. wrote the manuscript and all authors commented on it.

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Correspondence to Junwoo Son.

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Yoon, H., Choi, M., Lim, T. et al. Reversible phase modulation and hydrogen storage in multivalent VO2 epitaxial thin films. Nature Mater 15, 1113–1119 (2016). https://doi.org/10.1038/nmat4692

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