Transition-metal oxynitrides with perovskite-type structures are an emerging class of materials with optical, photocatalytic, dielectric and magnetoresistive properties that may be sensitive to oxide–nitride order, but the anion-ordering principles were unclear. Here we report an investigation of the representative compounds SrMO2N (M = Nb, Ta) using neutron and electron diffraction. This revealed a robust 1O/2(O0.5N0.5) partial anion order (up to at least 750 °C in the apparently cubic high-temperature phases) that directs the rotations of MO4N2 octahedra in the room-temperature superstructure. The anion distribution is consistent with local cis-ordering of the two nitrides in each octahedron driven by covalency, which results in disordered zigzag M–N chains in planes within the perovskite lattice. Local structures for the full range of oxynitride perovskites are predicted and a future challenge is to tune properties by controlling the order and dimensionality of the anion chains and networks.
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We thank M. Senn and C. Ritter for assistance with the neutron experiment at ILL. This work was supported by the Ministerio de Ciencia e Innovación (grants MAT2008-04587 and PR2008-0164), the Generalitat de Catalunya, the Engineering and Physical Science Research Council, the Science and Technology Facilities Council, the Royal Society, the Chemistry Research School of Edinburgh and St Andrews Universities and the Leverhulme Trust. We acknowledge the use of the Chemical Database Service at Daresbury.
The authors declare no competing financial interests.
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Yang, M., Oró-Solé, J., Rodgers, J. et al. Anion order in perovskite oxynitrides. Nature Chem 3, 47–52 (2011). https://doi.org/10.1038/nchem.908
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