Abstract

Oxynitrides have been explored extensively in the past decade because of their interesting properties, such as visible-light absorption, photocatalytic activity and high dielectric permittivity. Their synthesis typically requires high-temperature NH3 treatment (800–1,300 °C) of precursors, such as oxides, but the highly reducing conditions and the low mobility of N3− species in the lattice place significant constraints on the composition and structure—and hence the properties—of the resulting oxynitrides. Here we show a topochemical route that enables the preparation of an oxynitride at low temperatures (<500 °C), using a perovskite oxyhydride as a host. The lability of H in BaTiO3−xHx (x ≤ 0.6) allows H/N3− exchange to occur, and yields a room-temperature ferroelectric BaTiO3−xN2x/3. This anion exchange is accompanied by a metal-to-insulator crossover via mixed O–H–N intermediates. These findings suggest that this ‘labile hydride’ strategy can be used to explore various oxynitrides, and perhaps other mixed anionic compounds.

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Acknowledgements

This work is supported by FIRST and CREST programmes of the Japan Science and Technology Agency. H.A., S.L. and V.G. acknowledge support from the National Science Foundation grant numbers DMR-1420620 and DMR-1210588. H.A. acknowledges support from Japan Society for the Promotion of Science for Research Abroad (No. 25-185). The synchrotron radiation experiments were performed at the BL02B2 of SPring-8 with the approval of the JASRI.

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Affiliations

  1. Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan

    • Takeshi Yajima
    • , Fumitaka Takeiri
    • , Kohei Aidzu
    • , Wataru Yoshimune
    • , Masatoshi Ohkura
    • , Takafumi Yamamoto
    • , Yoji Kobayashi
    •  & Hiroshi Kageyama
  2. Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581, Japan

    • Takeshi Yajima
  3. Department of Materials Science and Engineering, Pennsylvania State University, University Park, Pennsylvania 16802, USA

    • Hirofumi Akamatsu
    • , Shiming Lei
    •  & Venkatraman Gopalan
  4. Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan

    • Koji Fujita
    •  & Katsuhisa Tanaka
  5. NIST Center for Neutron Research, National Institute of Standards and Technology, 100 Bureau Drive, MS 6100, Gaithersburg, Maryland 20899-6100, USA

    • Craig M. Brown
  6. School of Physical Sciences, University of Kent, Canterbury, Kent CT2 7NH, UK

    • Mark A. Green
  7. CREST, Japan Science and Technology Agency, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

    • Hiroshi Kageyama

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Contributions

T. Yajima and F.T. contributed equally. T. Yajima, F.T. and H.K. conceived and designed the study. F.T., K.A., M.O., W.Y. and T. Yajima performed the synthesis, laboratory PXRD, synchrotron PXRD, XPS and elemental analysis. T.Yam., C.M.B., M.A.G. and H.K. obtained the neutron data. The structural refinement was performed by K.A., T. Yamamoto and T. Yajima. W.Y. and T. Yajima fabricated the thin films. H.A., K.F., S.L., V.G. and K.T. conducted the SHG and PFM measurements and FEM simulations. All authors discussed the results. F.T. and H.K. wrote the manuscript, with contributions and feedback from all the authors, mainly T. Yajima, Y.K., H.A. and K.F.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Hiroshi Kageyama.

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DOI

https://doi.org/10.1038/nchem.2370

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