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Dynamic layer rearrangement during growth of layered oxide films by molecular beam epitaxy

Nature Materials volume 13, pages 879–883 (2014)Cite this article

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Abstract

The An+1BnO3n+1 Ruddlesden–Popper homologous series offers a wide variety of functionalities including dielectric, ferroelectric, magnetic and catalytic properties. Unfortunately, the synthesis of such layered oxides has been a major challenge owing to the occurrence of growth defects that result in poor materials behaviour in the higher-order members. To understand the fundamental physics of layered oxide growth, we have developed an oxide molecular beam epitaxy system with in situ synchrotron X-ray scattering capability. We present results demonstrating that layered oxide films can dynamically rearrange during growth, leading to structures that are highly unexpected on the basis of the intended layer sequencing. Theoretical calculations indicate that rearrangement can occur in many layered oxide systems and suggest a general approach that may be essential for the construction of metastable Ruddlesden–Popper phases. We demonstrate the utility of the new-found growth strategy by performing the first atomically controlled synthesis of single-crystalline La3Ni2O7.

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Figure 1: Layer swap during the growth of Sr2TiO4.
Figure 2: Energetics for different layer sequencing during growth.
Figure 3: Layer swapping in additional systems.
Figure 4: Synthesis of single-crystal La3Ni2O7.

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Acknowledgements

The authors acknowledge discussions with D. G. Schlom, K. Lee and Y. Nie, and support at the APS from H. Zhou and C. Schlepütz. S.H.C., J.A.E., A.B. and D.D.F. were supported by the US. Department of Energy, Office of Science, Materials Sciences and Engineering Division. Work performed at Argonne National Laboratory, including the Advanced Photon Source, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. The calculations were carried out on the Fusion Cluster of Argonne’s Laboratory Computing Resource Center, at NERSC (supported by DOE), and on Argonne’s Carbon Cluster under award CNM29783 and CNM35702. D.M. and G.L. were partially supported by University of Wisconsin Materials Research Science and Engineering Center (DMR-1121288).

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Author notes

  1. J. H. Lee

    Present address: Present address: Neutron Science Division, Korea Atomic Energy Research Institute, Daejeon 305-600, Republic of Korea.,

  2. J. H. Lee and G. Luo: These authors contributed equally to this work.

Authors and Affiliations

  1. X-ray Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    J. H. Lee, I. C. Tung, H. Hong & J. W. Freeland

  2. Department of Materials Science & Engineering, University of Wisconsin-Madison, 1509 University Avenue Madison, Wisconsin 53706, USA

    G. Luo, M. Gadre & D. Morgan

  3. Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, USA

    I. C. Tung

  4. Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    S. H. Chang, Z. Luo, A. Bhattacharya, J. A. Eastman & D. D. Fong

  5. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230026, China

    Z. Luo

  6. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    M. Malshe & J. Jellinek

  7. Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, USA

    A. Bhattacharya

  8. Department of Materials Science & Engineering, and Institute of Materials Science, University of Connecticut, Storrs, Connecticut 06269, USA

    S. M. Nakhmanson

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Contributions

J.H.L., Z.L., I.C.T., S.H.C., A.B., J.A.E., H.H., D.D.F. and J.W.F. developed the in situ oxide MBE system and participated in the real-time growth experiments. J.H.L., Z.L., I.C.T., D.D.F. and J.W.F. handled analysis of the experimental data. G.L., M.M., M.G., S.M.N., J.J. and D.M. were responsible for the detailed theoretical calculations related to the experiments. All authors participated in the discussion of data/analysis/conclusions and in the writing of the manuscript.

Corresponding authors

Correspondence to D. Morgan or J. W. Freeland.

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Lee, J., Luo, G., Tung, I. et al. Dynamic layer rearrangement during growth of layered oxide films by molecular beam epitaxy. Nature Mater 13, 879–883 (2014). https://doi.org/10.1038/nmat4039

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