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A labile hydride strategy for the synthesis of heavily nitridized BaTiO3

Nature Chemistry volume 7, pages 1017–1023 (2015)Cite this article

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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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Figure 1: Two-step synthesis of oxynitride BaTiO3−xN2x/3.
Figure 2: Anion compositions, cell parameters and magnetism of the NH3-treated oxyhydrides.
Figure 3: Structural refinement for BaTiO2.4N0.4.
Figure 4: Systematic evolution of transport properties from oxyhydride SrTiO2.75H0.25 to oxyhydride–nitride SrTiO2.75HzNy (y + z < 0.25) to oxynitride SrTiO2.75Ny (y ≈ 0.16).
Figure 5: Ferroelectric properties of BaTiO2.4N0.4.

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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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Authors and Affiliations

  1. Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, 615-8510, Kyoto, 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, 277-8581, Chiba, 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, 615-8510, Kyoto, Japan

    Koji Fujita & Katsuhisa Tanaka

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

    Craig M. Brown

  6. School of Physical Sciences, University of Kent, Canterbury, CT2 7NH, Kent, UK

    Mark A. Green

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

    Hiroshi Kageyama

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  1. Takeshi Yajima
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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.

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Correspondence to Hiroshi Kageyama.

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Yajima, T., Takeiri, F., Aidzu, K. et al. A labile hydride strategy for the synthesis of heavily nitridized BaTiO3. Nature Chem 7, 1017–1023 (2015). https://doi.org/10.1038/nchem.2370

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