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Domain-wall conduction in ferroelectric BiFeO3 controlled by accumulation of charged defects

Nature Materials volume 16, pages 322–327 (2017)Cite this article

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Abstract

Mobile charged defects, accumulated in the domain-wall region to screen polarization charges, have been proposed as the origin of the electrical conductivity at domain walls in ferroelectric materials. Despite theoretical and experimental efforts, this scenario has not been directly confirmed, leaving a gap in the understanding of the intriguing electrical properties of domain walls. Here, we provide atomic-scale chemical and structural analyses showing the accumulation of charged defects at domain walls in BiFeO3. The defects were identified as Fe4+ cations and bismuth vacancies, revealing p-type hopping conduction at domain walls caused by the presence of electron holes associated with Fe4+. In agreement with the p-type behaviour, we further show that the local domain-wall conductivity can be tailored by controlling the atmosphere during high-temperature annealing. This work has possible implications for engineering local conductivity in ferroelectrics and for devices based on domain walls.

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Figure 1: Off-centre Fe displacements and lattice strain across a 109° DW in polycrystalline BiFeO3.
Figure 2: Accumulation of charged defects (Fe4+ and bismuth vacancies) at a 109° DW in polycrystalline BiFeO3.
Figure 3: Control of local conductivity at DWs in polycrystalline BiFeO3 by post-annealing in nitrogen and oxygen atmosphere.

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Acknowledgements

This work was financed by the Slovenian Research Agency (programmes P2-0105 and P2-0393; projects J2-5483 and J2-6754). Centres of Excellence NAMASTE and CONOT are acknowledged for access to the AFM/PFM and STEM equipment. B. Kmet is acknowledged for TEM sample preparation. T.R. thanks T. Grande for fruitful discussions on the defect chemistry of BiFeO3.

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Authors and Affiliations

  1. Electronic Ceramics Department, Jozef Stefan Institute, 1000 Ljubljana, Slovenia

    Tadej Rojac, Andreja Bencan, Hana Ursic, Maja Makarovic, Julian Walker & Barbara Malic

  2. Department of Materials Chemistry, National Institute of Chemistry, 1000 Ljubljana, Slovenia

    Goran Drazic

  3. Research Institute of Electronics, Shizuoka University, 3-5-1 Johoku, Naka-ku, Hamamatsu-shi, 432-8561, Japan

    Naonori Sakamoto

  4. Advanced Materials Department, Jozef Stefan Institute, 1000 Ljubljana, Slovenia

    Bostjan Jancar

  5. Department of Inorganic Chemistry and Technology, Jozef Stefan Institute, 1000 Ljubljana, Slovenia

    Gasper Tavcar

  6. Jozef Stefan International Postgraduate School, 1000 Ljubljana, Slovenia

    Maja Makarovic

  7. Laboratory for Ferroelectrics and Functional Oxides, Swiss Federal Institute of Technology–EPFL, 1015 Lausanne, Switzerland

    Dragan Damjanovic

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Contributions

T.R. directed the project. A.B., G.D. and N.S. performed STEM and EELS measurements and analyses, and G.D. performed HAADF simulations. H.U. performed AFM/PFM analyses. B.J. and G.T. designed standard materials for EELS analysis. M.M. synthesized the BiFeO3 samples. B.M. supervised the project and D.D. contributed to the interpretation of the results. T.R., A.B., G.D., H.U., B.J., J.W. and D.D. wrote the manuscript. All authors reviewed and edited the manuscript.

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Correspondence to Tadej Rojac.

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Rojac, T., Bencan, A., Drazic, G. et al. Domain-wall conduction in ferroelectric BiFeO3 controlled by accumulation of charged defects. Nature Mater 16, 322–327 (2017). https://doi.org/10.1038/nmat4799

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