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Direct mapping of Li-enabled octahedral tilt ordering and associated strain in nanostructured perovskites

Nature Materials volume 14, pages 1142–1149 (2015)Cite this article

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Abstract

Self-assembled nanostructures with periodic phase separation hold great promise for creating two- and three-dimensional superlattices with extraordinary physical properties. Understanding the mechanism(s) driving the formation of such superlattices demands an understanding of their underlying atomic structure. However, the nanoscale structural fluctuations intrinsic to these superlattices pose a new challenge for structure determination methods. Here we develop an optimized atomic-level imaging condition to measure TiO6 octahedral tilt angles, unit-cell-by-unit-cell, in perovskite-based Li0.5−3xNd0.5+xTiO3, and thereby determine the mathematical formula governing this nanoscale superstructure. We obtain a direct real-space correlation of the octahedral tilt modulation with the superstructure geometry and lattice-parameter variations. This reveals a composition-dependent, self-ordered octahedral superlattice. Amazingly, we observe a reversible annihilation/reconstruction of the octahedral superlattice correlated with the delithiation/lithiation process in this promising Li-ion conductor. This approach to quantify local octahedral tilt and correlate it with strain can be applied to characterize complex octahedral behaviours in other advanced oxide systems.

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Figure 1: Mapping modulated [001] octahedral tilting in Li0.38Nd0.54TiO3 using optimized BF-STEM.
Figure 2: Quantitative fitting of the measured octahedral tilt modulation to determine its mathematical form in Li0.38Nd0.54TiO3.
Figure 3: Correlated maps of lattice spacing and octahedral tilt angle in Li0.38Nd0.54TiO3.
Figure 4: Mapping modulated c+ octahedral tilting in Li0.215Nd0.595TiO3 using optimized BF-STEM.
Figure 5: Li%-dependent relaxation/annihilation and recovery of the ordered-domain pattern in [001]-oriented Li0.38Nd0.54TiO3.

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Acknowledgements

This work was supported by the Australian Research Council (ARC) grants DP110104734 and DP150104483 and a Monash University IDR grant. The FEI Titan3 80-300 S/TEM at Monash Centre for Electron Microscopy was funded by the ARC Grant LE0454166. The authors are grateful to M. Weyland for optimizing the Titan microscope and to L. Noren for synthesizing the materials. R.L.W. acknowledges support from ARC grant number DP110100618. C.D. acknowledges the support of the Ernst Ruska Centre at Forschungszentrum Juelich.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Monash University, Victoria 3800, Australia

    Ye Zhu, Laure Bourgeois & Joanne Etheridge

  2. Research School of Chemistry, College of Physical and Mathematical Sciences, The Australian National University, Canberra, Australian Capital Territory 0200, Australia

    Ray L. Withers

  3. Monash Centre for Electron Microscopy, Monash University, Victoria 3800, Australia

    Laure Bourgeois & Joanne Etheridge

  4. Department of Physics, Arizona State University, Tempe, Arizona 85287, USA

    Christian Dwyer

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  1. Ye Zhu
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Contributions

Y.Z. and J.E. designed the experiments. Y.Z. developed the optimized BF-STEM imaging mode, performed the BF-STEM measurements, and analysed the data. R.L.W. developed mathematics to describe the modulated structure with higher-order harmonics and carried out bond-valence sum calculations. L.B. prepared TEM samples and initiated the TEM/STEM observations. Y.Z. and C.D. performed multislice image simulations. J.E. supervised the project. Y.Z. and J.E. wrote the manuscript. All authors reviewed and edited the manuscript.

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Correspondence to Ye Zhu or Joanne Etheridge.

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Zhu, Y., Withers, R., Bourgeois, L. et al. Direct mapping of Li-enabled octahedral tilt ordering and associated strain in nanostructured perovskites. Nature Mater 14, 1142–1149 (2015). https://doi.org/10.1038/nmat4390

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