Abstract
Strong correlations between electrons, spins and lattices—stemming from strong hybridization between transition metal d and oxygen p orbitals—are responsible for the functional properties of transition metal oxides. Artificial oxide heterostructures with chemically abrupt interfaces provide a platform for engineering bonding geometries that lead to emergent phenomena. Here we demonstrate the control of the oxygen coordination environment of the perovskite, SrRuO3, by heterostructuring it with Ca0.5Sr0.5TiO3 (0–4 monolayers thick) grown on a GdScO3 substrate. We found that a Ru–O–Ti bond angle of the SrRuO3 /Ca0.5Sr0.5TiO3 interface can be engineered by layer-by-layer control of the Ca0.5Sr0.5TiO3 layer thickness, and that the engineered Ru–O–Ti bond angle not only stabilizes a Ru–O–Ru bond angle never seen in bulk SrRuO3, but also tunes the magnetic anisotropy in the entire SrRuO3 layer. The results demonstrate that interface engineering of the oxygen coordination environment allows one to control additional degrees of freedom in functional oxide heterostructures.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Goodenough, J. B. Magnetism and the Chemical Bond (Interscience, 1963).
Choi, K. J. et al. Enhancement of ferroelectricity in strained BaTiO3 thin films. Science 306, 1005–1009 (2004).
Zeches, R. J. et al. A strain-driven morphotropic phase boundary in BiFeO3 . Science 326, 977–980 (2009).
Lee, J. H. et al. A strong ferroelectric ferromagnet created by means of spin-lattice coupling. Nature 466, 954–958 (2010).
Bhattacharya, A. & May, S. J. Magnetic oxide heterostructures. Annu. Rev. Mater. Res. 44, 65–90 (2014).
May, S. J. et al. Control of octahedral rotations in (LaNiO3)n/(SrMnO3)m superlattices. Phys. Rev. B 83, 153411 (2011).
Kim, Y.-M. et al. Interplay of octahedral tilts and polar order in BiFeO3 films. Adv. Mater. 25, 2497–2504 (2013).
Kan, D., Aso, R., Kurata, H. & Shimakawa, Y. Research Update: Interface-engineered oxygen octahedral tilts in perovskite oxide heterostructures. APL Mater. 3, 062302 (2015).
Rondinelli, J. M., May, S. J. & Freeland, J. W. Control of octahedral connectivity in perovskite oxide heterostructures: an emerging route to multifunctional materials discovery. MRS Bull. 37, 261–270 (2012).
Glazer, A. M. The classification of tilted octahedra in perovskites. Acta Crystallogr. B 28, 3384–3392 (1972).
Woodward, P. M. Octahedral tilting in perovskites. I. Geometrical considerations. Acta Crystallogr. B 53, 32–43 (1997).
Rondinelli, J. M. & Spaldin, N. A. Structure and properties of functional oxide thin films: insights from electronic-structure calculations. Adv. Mater. 23, 3363–3381 (2011).
Schlom, D. G. et al. Strain tuning of ferroelectric thin films. Annu. Rev. Mater. Res. 37, 589–626 (2007).
Vailionis, A. et al. Misfit strain accommodation in epitaxial ABO3 perovskites: lattice rotations and lattice modulations. Phys. Rev. B 83, 064101 (2011).
Rondinelli, J. M. & Coh, S. Large isosymmetric reorientation of oxygen octahedra rotation axes in epitaxially strained perovskites. Phys. Rev. Lett. 106, 235502 (2011).
Choi, K. J. et al. Phase-transition temperatures of strained single-crystal SrRuO3 thin films. Adv. Mater. 22, 759–762 (2010).
Moon, E. J. et al. Spatial control of functional properties via octahedral modulations in complex oxide superlattices. Nature Commun. 5, 5710 (2014).
Bousquet, E. et al. Improper ferroelectricity in perovskite oxide artificial superlattices. Nature 452, 732–736 (2008).
Chang, S. H. et al. Thickness-dependent structural phase transition of strained SrRuO3 ultrathin films: the role of octahedral tilt. Phys. Rev. B 84, 104101 (2011).
Biegalski, M. D. et al. Interrelation between structure–magnetic properties in La0.5Sr0.5CoO3 . Adv. Mater. Interfaces 1, 1400203 (2014).
Lu, W., Yang, P., Song, W. D., Chow, G. M. & Chen, J. S. Control of oxygen octahedral rotations and physical properties in SrRuO3 films. Phys. Rev. B 88, 214115 (2013).
Kan, D., Aso, R., Kurata, H. & Shimakawa, Y. Phase control of a perovskite transition-metal oxide through oxygen displacement at the heterointerface. Dalton Trans. 44, 10594–10607 (2015).
Aso, R., Kan, D., Shimakawa, Y. & Kurata, H. Control of structural distortions in transition-metal oxide films through oxygen displacement at the heterointerface. Adv. Funct. Mater. 24, 5177–5184 (2014).
Moon, E. J. et al. Effect of interfacial octahedral behavior in ultrathin manganite films. Nano Lett. 2014, 2509–2514 (2014).
Jang, H. W. et al. Metallic and insulating oxide interfaces controlled by electronic correlations. Science 331, 886–889 (2011).
Chen, Z. H., Damodaran, A. R., Xu, R., Lee, S. & Martin, L. W. Effect of “symmetry mismatch” on the domain structure of rhombohedral BiFeO3 thin films. Appl. Phys. Lett. 104, 182908 (2014).
Koster, G. et al. Structure, physical properties, and applications of SrRuO3 thin films. Rev. Mod. Phys. 84, 253–298 (2012).
Jones, C. W., Battle, P. D., Lightfoot, P. & Harrison, W. T. A. The structure of SrRuO3 by time-of-flight neutron powder diffraction. Acta Crystallogr. C 45, 365–367 (1989).
Kennedy, B. J. & Hunter, B. A. High-temperature phases of SrRuO3 . Phys. Rev. B 58, 653–658 (1998).
Borisevich, A. Y. et al. Suppression of octahedral tilts and associated changes in electronic properties at epitaxial oxide heterostructure interfaces. Phys. Rev. Lett. 105, 087204 (2010).
Aso, R., Kan, D., Shimakawa, Y. & Kurata, H. Octahedral tilt propagation controlled by A-site cation size at perovskite oxide heterointerfaces. Cryst. Growth Design 14, 2128–2132 (2014).
Jia, C. L. et al. Oxygen octahedron reconstruction in the SrTiO3/LaAlO3 heterointerfaces investigated using aberration-corrected ultrahigh-resolution transmission electron microscopy. Phys. Rev. B 79, 081405 (2009).
Fister, T. T. et al. Octahedral rotations in strained LaAlO3/SrTiO3 (001) heterostructures. APL Mater. 2, 021102 (2014).
Yamanaka, T., Hirai, N. & Komatsu, Y. Structure change of Ca1−xSrxTiO3 perovskite with composition and pressure. Am. Mineral. 87, 1183–1189 (2002).
Schubert, J. et al. Structural and optical properties of epitaxial BaTiO3 thin films grown on GdScO3 (110). Appl. Phys. Lett. 82, 3460 (2003).
Biegalski, M. D. et al. Thermal expansion of the new perovskite substrates DyScO3 and GdScO3 . J. Mater. Res. 20, 952–958 (2011).
Kan, D., Aso, R., Kurata, H. & Shimakawa, Y. Thickness-dependent structure–property relationships in strained (110) SrRuO3 thin films. Adv. Funct. Mater. 23, 1129–1136 (2013).
Vailionis, A., Siemons, W. & Koster, G. Room temperature epitaxial stabilization of a tetragonal phase in ARuO3 (A = Ca and Sr) thin films. Appl. Phys. Lett. 93, 051909 (2008).
Goodenough, J. B. Electronic and ionic transport properties and other physical aspects of perovskites. Rep. Prog. Phys. 67, 1915–1993 (2004).
Goldschmidt, V. M. Die Gesetze der Krystallochemie. Naturwissenschaften 14, 477–485 (1926).
Kanbayasi, A. Magnetic properties of SrRuO3 single crystal. J. Phys. Soc. Jpn 41, 1876–1878 (1976).
Kanbayasi, A. Magnetic properties of SrRuO3 single crystal. II. J. Phys. Soc. Jpn 44, 89–95 (1978).
Cao, G., McCall, S., Shepard, M., Crow, J. E. & Guertin, R. P. Thermal, magnetic, and transport properties of single-crystal Sr1−xCaxRuO3 (0 x 1.0). Phys. Rev. B 56, 321–329 (1997).
Kats, Y., Genish, I., Klein, L., Reiner, J. W. & Beasley, M. R. Large anisotropy in the paramagnetic susceptibility of SrRuO3 films. Phys. Rev. B 71, 100403 (2005).
Allen, P. B. et al. Transport properties, thermodynamic properties, and electronic structure of SrRuO3 . Phys. Rev. B 53, 4393–4398 (1996).
Liao, Z. et al. Controlled lateral anisotropy in correlated manganite heterostructures by interface-engineered oxygen octahedral coupling. Nature Mater. http://dx.doi.org/10.1038/nmat4579 (2016).
Aso, R., Kan, D., Shimakawa, Y. & Kurata, H. Atomic level observation of octahedral distortions at the perovskite oxide heterointerface. Sci. Rep. 3, 2214 (2013).
Acknowledgements
This work was partially supported by the Core Research for Evolutional Science and Technology (CREST) programme of the Japan Science and Technology Agency. The work was also supported by a grant for the Joint Project of Chemical Synthesis Core Research Institutions from the Ministry of Education, Culture, Sports, Science and Technology of Japan.
Author information
Authors and Affiliations
Contributions
D.K. conceived the idea and initiated the project. D.K. and R.S. fabricated the samples and performed X-ray structural characterization and transport measurements. R.A. and M.H. collected and analysed the STEM data. H.K. and Y.S. supervised the project. All authors discussed the experimental data and co-wrote the manuscript.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary Information
Supplementary Information (PDF 1726 kb)
Rights and permissions
About this article
Cite this article
Kan, D., Aso, R., Sato, R. et al. Tuning magnetic anisotropy by interfacially engineering the oxygen coordination environment in a transition metal oxide. Nature Mater 15, 432–437 (2016). https://doi.org/10.1038/nmat4580
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nmat4580
This article is cited by
-
Tuning orbital-selective phase transitions in a two-dimensional Hund’s correlated system
Nature Communications (2023)
-
Emergent and robust ferromagnetic-insulating state in highly strained ferroelastic LaCoO3 thin films
Nature Communications (2023)
-
Field-free spin-orbit switching of perpendicular magnetization enabled by dislocation-induced in-plane symmetry breaking
Nature Communications (2023)
-
Atomic and electronic structures of correlated SrRuO3/SrTiO3 superlattices
Journal of the Korean Physical Society (2023)
-
Continuous manipulation of magnetic anisotropy in a van der Waals ferromagnet via electrical gating
Nature Electronics (2022)