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Direct observation of ferroelectric field effect and vacancy-controlled screening at the BiFeO3/LaxSr1−xMnO3 interface

Nature Materials volume 13, pages 1019–1025 (2014)Cite this article

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Abstract

The development of interface-based magnetoelectric devices necessitates an understanding of polarization-mediated electronic phenomena and atomistic polarization screening mechanisms. In this work, the LSMO/BFO interface is studied on a single unit-cell level through a combination of direct order parameter mapping by scanning transmission electron microscopy and electron energy-loss spectroscopy. We demonstrate an unexpected ~5% lattice expansion for regions with negative polarization charge, with a concurrent anomalous decrease of the Mn valence and change in oxygen K-edge intensity. We interpret this behaviour as direct evidence for screening by oxygen vacancies. The vacancies are predominantly accumulated at the second atomic layer of BFO, reflecting the difference of ionic conductivity between the components. This vacancy exclusion from the interface leads to the formation of a tail-to-tail domain wall. At the same time, purely electronic screening is realized for positive polarization charge, with insignificant changes in lattice and electronic properties. These results underline the non-trivial role of electrochemical phenomena in determining the functional properties of oxide interfaces. Furthermore, these behaviours suggest that vacancy dynamics and exclusion play major roles in determining interface functionality in oxide multilayers, providing clear implications for novel functionalities in potential electronic devices.

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Figure 1: Lattice spacing and polarization changes at the BFO/LSMO interface.
Figure 2: Tracing the average valence states of B-site cations at the two interfaces.
Figure 3: Oxygen content and strain at the two interfaces.
Figure 4: Landau–Ginsburg–Devonshire modelling of the data.

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Acknowledgements

The work is supported in part (A.Y.B., Y-M.K., S.V.K., R.M. and S.T.P.) by the Materials Science and Engineering Division, Office of Basic Energy Sciences of the US DOE and through a user project supported by Oak Ridge National Laboratory’s Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy. M.P.O. acknowledges support from DOE grant DE-FG02-09ER46554. The authors thank P. Yu (Tsinghua University, Beijing, China), Y-H. Chu (National Chiao Tung University, Hsinchu, Taiwan) and R. Ramesh (University of California Berkeley) for providing BiFeO3 films for the study. A.M. and E.E. acknowledge support via a bilateral SFFR-NSF project, namely US National Science Foundation under NSF-DMR-1210588 and State Fund of Fundamental Research of Ukraine, grant UU48/002. This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the US Department of Energy under Contract No. DE-AC02-05CH11231.

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Authors and Affiliations

  1. Materials Sciences and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA

    Young-Min Kim, Mark P. Oxley, Rohan Mishra, S. T. Pantelides & Albina Y. Borisevich

  2. Division of Electron Microscopic Research, Korea Basic Science Institute, Daejeon 305-333, Korea

    Young-Min Kim

  3. Institute of Physics, National Academy of Sciences of Ukraine, 46, pr. Nauki, 03028 Kiev Ukraine,

    Anna Morozovska

  4. Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, 3, Krjijanovskogo, 03142 Kiev, Ukraine

    Eugene Eliseev

  5. Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37235, USA

    Mark P. Oxley, Rohan Mishra & S. T. Pantelides

  6. Department of Materials Science and Engineering, Norwegian University of Science and Technology, NO-7491 Trondheim, Norway

    Sverre M. Selbach & Tor Grande

  7. The Center for Nanophase Materials Sciences. Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA

    Sergei V. Kalinin

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Contributions

Y-M.K. conducted STEM/EELS study and data analysis; A.M. and E.E. carried out LGD modelling; M.P.O. carried out EELS profile simulations; R.M. and S.T.P. conducted first-principles calculations; S.M.S. and T.G. provided solid state chemistry reasoning; A.Y.B. and S.V.K. conceived and directed the project. All authors contributed to writing the paper.

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Correspondence to Albina Y. Borisevich.

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Kim, YM., Morozovska, A., Eliseev, E. et al. Direct observation of ferroelectric field effect and vacancy-controlled screening at the BiFeO3/LaxSr1−xMnO3 interface. Nature Mater 13, 1019–1025 (2014). https://doi.org/10.1038/nmat4058

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