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Improper ferroelectricity in perovskite oxide artificial superlattices

Abstract

Ferroelectric thin films and superlattices are currently the subject of intensive research1,2 because of the interest they raise for technological applications and also because their properties are of fundamental scientific importance3,4,5. Ferroelectric superlattices6 allow the tuning of the ferroelectric properties while maintaining perfect crystal structure and a coherent strain, even throughout relatively thick samples. This tuning is achieved in practice by adjusting both the strain7,8,9,10, to enhance the polarization, and the composition, to interpolate between the properties of the combined compounds11,12,13,14,15. Here we show that superlattices with very short periods possess a new form of interface coupling, based on rotational distortions, which gives rise to ‘improper’ ferroelectricity. These observations suggest an approach, based on interface engineering, to produce artificial materials with unique properties. By considering ferroelectric/paraelectric PbTiO3/SrTiO3 multilayers, we first show from first principles that the ground-state of the system is not purely ferroelectric but also primarily involves antiferrodistortive rotations of the oxygen atoms in a way compatible with improper ferroelectricity. We then demonstrate experimentally that, in contrast to pure PbTiO3 and SrTiO3 compounds, the multilayer system indeed behaves like a prototypical improper ferroelectric and exhibits a very large dielectric constant of εr ≈ 600, which is also fairly temperature-independent. This behaviour, of practical interest for technological applications16, is distinct from that of normal ferroelectrics, for which the dielectric constant is typically large but strongly evolves around the phase transition temperature and also differs from that of previously known improper ferroelectrics that exhibit a temperature-independent but small dielectric constant only.

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Figure 1: Schematic view of the prototype P 4/ mmm unit cell of the 1/1 PbTiO 3 /SrTiO 3 superlattice and atomic motions associated to different energy lowering distortions.
Figure 2: Results of the first-principles calculations.
Figure 3: Experimental measurements of phase transition behaviour in normal and anomalous samples.

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Acknowledgements

P.G. thanks A. P. Levanyuk for discussions concerning improper ferroelectrics. We thank R. Černý for help with X-ray diffraction. This work was supported by the VolkswagenStiftung, the European Network of Excellence FAME, the European STREP MaCoMuFi, the Swiss National Science Foundation through the “National Center of Competence in Research Materials with Novel Electronic Properties—MaNEP” and Division II, and ESF(THIOX).

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Correspondence to Matthew Dawber or Philippe Ghosez.

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The file contains Supplementary Notes illustrated with Supplementary Table S1 and Supplementary Figures S1-S2. (PDF 508 kb)

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Bousquet, E., Dawber, M., Stucki, N. et al. Improper ferroelectricity in perovskite oxide artificial superlattices. Nature 452, 732–736 (2008). https://doi.org/10.1038/nature06817

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