- Physical Review Journals
All JournalsPhysics Magazine

Physical Review Research

Reuse & Permissions

It is not necessary to obtain permission to reuse this article or its components as it is available under the terms of the Creative Commons Attribution 4.0 International license. This license permits unrestricted use, distribution, and reproduction in any medium, provided attribution to the author(s) and the published article's title, journal citation, and DOI are maintained. Please note that some figures may have been included with permission from other third parties. It is your responsibility to obtain the proper permission from the rights holder directly for these figures.

Export citation

Export citation

Choose format for download:

Download Citation
  • Letter
  • Open Access

Prediction of a strong polarizing field in thin film paraelectrics

Chiara Gattinoni*

Nicola A. Spaldin†

  • Department of Chemical and Energy Engineering, London South Bank University, London SE1 0AA, United Kingdom

  • Department of Materials, ETH Zurich, CH-8093 Zürich, Switzerland

  • *gattinoc@lsbu.ac.uk
  • †nicola.spaldin@mat.ethz.ch
PDF

Phys. Rev. Research 4, L032020 – Published 5 August, 2022

DOI: https://doi.org/10.1103/PhysRevResearch.4.L032020

Abstract

We demonstrate the existence of a polarizing field in thin films of insulators with charged ionic layers. The polarizing field derives from the same physics as the well-known depolarizing field that suppresses ferroelectric polarization in thin-film ferroelectrics, but instead drives thin films of materials that are centrosymmetric and paraelectric in their bulk form into a noncentrosymmetric, polar state. We illustrate the behavior using density-functional computations for perovskite-structure potassium tantalate, KTaO3, which is of considerable interest for its high dielectric constant, proximity to a quantum critical point, and superconductivity. We then provide a simple recipe to identify whether a particular material and film orientation will exhibit the effect and develop an electrostatic model to estimate the critical thickness of the induced polarization in terms of basic material parameters. Our results provide practical guidelines for exploiting the electrostatic properties of thin-film ionic insulators to engineer novel functionalities for nanoscale devices.

View figure in article

Physics Subject Headings (PhySH)

Article Text

Supplemental Material

References (37)

  1. P. Wurfel and I. P. Batra, Depolarization-field-induced instability in thin ferroelectric films—Experiment and theory, Phys. Rev. B 8, 5126 (1973).
  2. M. Dawber, K. M. Rabe, and J. F. Scott, Physics of thin-film ferroelectric oxides, Rev. Mod. Phys. 77, 1083 (2005).
  3. C. Lichtensteiger, M. Dawber, N. Stucki, J.-M. Triscone, J. Hoffman, J.-B. Yau, C. H. Ahn, L. Despont, and P. Aebi, Monodomain to polydomain transition in ferroelectric PbTiO3 thin films with La0.67Sr0.3MnO3 electrodes, Appl. Phys. Lett. 90, 052907 (2007).
  4. J. Junquera and P. Ghosez, Critical thickness for ferroelectricity in perovskite ultrathin films, Nature (London) 422, 506 (2003).
  5. J. A. Mundy, B. F. Grosso, C. A. Heikes, D. F. Segedin, Z. Wang, Y.-T. Shao, C. Dai, B. H. Goodge, Q. N. Meier, C. T. Nelson, B. Prasad, F. Xue, S. Ganschow, D. A. Muller, L. F. Kourkoutis, L.-Q. Chen, W. D. Ratcliff, N. A. Spaldin, R. Ramesh, and D. G. Schlom, Liberating a hidden antiferroelectric phase with interfacial electrostatic engineering, Sci. Adv. 8, eabg5860 (2022).
  6. M. Stengel, Electrostatic stability of insulating surfaces: Theory and applications, Phys. Rev. B 84, 205432 (2011).
  7. A. Ohtomo and H. Y. Hwang, A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface, Nature (London) 427, 423 (2004).
  8. H. Y. Hwang, Tuning interface states, Science 313, 1895 (2006).
  9. N. Nakagawa, H. Y. Hwang, and D. A. Muller, Why some interfaces cannot be sharp, Nat. Mater. 5, 204 (2006).
  10. S. M. Yang, A. N. Morozovska, R. Kumar, E. A. Eliseev, Y. Cao, L. Mazet, N. Balke, S. Jesse, R. K. Vasudevan, C. Dubourdieu, and S. V. Kalinin, Mixed electrochemical-ferroelectric states in nanoscale ferroelectrics, Nat. Phys. 13, 812 (2017).
  11. I. Efe, N. A. Spaldin, and C. Gattinoni, On the happiness of ferroelectric surfaces and its role in water dissociation: The example of bismuth ferrite, J. Chem. Phys. 154, 024702 (2021).
  12. N. A. Spaldin, I. Efe, M. Rossell, and C. Gattinoni, Layer and spontaneous polarizations in perovskite oxides and their interplay in multiferroic bismuth ferrite, J. Chem. Phys. 154, 154702 (2021).
  13. D. E. E. Deacon-Smith, D. O. Scanlon, C. R. A. Catlow, A. A. Sokol, and S. M. Woodley, Interlayer cation exchange stabilizes polar perovskite surfaces, Adv. Mater. 26, 7252 (2014).
  14. M. Setvin, M. Reticcioli, F. Poelzleitner, J. Hulva, M. Schmid, L. A. Boatner, C. Franchini, and U. Diebold, Polarity compensation mechanisms on the perovskite surface KTa O3(001), Science 359, 572 (2018).
  15. Y. Wang, J. Cheng, M. Behtash, W. Tang, J. Luo, and K. Yang, First-principles studies of polar perovskite KTaO3 surfaces: Structural reconstruction, charge compensation, and stability diagram, Phys. Chem. Chem. Phys. 20, 18515 (2018).
  16. X. Zhao and A. Selloni, Structure and stability of NaTaO3(001) and KTaO3(001) surfaces, Phys. Rev. Mater. 3, 015801 (2019).
  17. P. D. C. King, R. H. He, T. Eknapakul, P. Buaphet, S.-K. Mo, Y. Kaneko, S. Harashima, Y. Hikita, M. S. Bahramy, C. Bell, Z. Hussain, Y. Tokura, Z.-X. Shen, H. Y. Hwang, F. Baumberger, and W. Meevasana, Subband Structure of a Two-Dimensional Electron Gas Formed at the Polar Surface of the Strong Spin-Orbit Perovskite KTaO3, Phys. Rev. Lett. 108, 117602 (2012).
  18. A. F. Santander-Syro, C. Bareille, F. Fortuna, O. Copie, M. Gabay, F. Bertran, A. Taleb-Ibrahimi, P. Le Fèvre, G. Herranz, N. Reyren, M. Bibes, A. Barthélémy, P. Lecoeur, J. Guevara, and M. J. Rozenberg, Orbital symmetry reconstruction and strong mass renormalization in the two-dimensional electron gas at the surface of KTaO3, Phys. Rev. B 86, 121107(R) (2012).
  19. K. Ueno, S. Nakamura, H. Shimotani, H. T. Yuan, N. Kimura, T. Nojima, H. Aoki, Y. Iwasa, and M. Kawasaki, Two-dimensional superconductivity and anisotropic transport at KTaO3(111) interfaces, Nat. Nanotechnol. 6, 408 (2011).
  20. Z. Chen, Z. Liu, Y. Sun, X. Chen, Y. Liu, H. Zhang, H. Li, M. Zhang, S. Hong, T. Ren, C. Zhang, H. Tian, Y. Zhou, J. Sun, and Y. Xie, Two-Dimensional Superconductivity at the LaAlO3/ KTaO3(110) Heterointerface, Phys. Rev. Lett. 126, 026802 (2021).
  21. C. Liu, X. Yan, D. Jin, Y. Ma, H.-W. Hsiao, Y. Lin, T. M. Bretz-Sullivan, X. Zhou, J. Pearson, B. Fisher, J. S. Jiang, W. Han, J.-M. Zuo, J. Wen, D. D. Fong, J. Sun, H. Zhou, and A. Bhattacharya, Two-dimensional superconductivity and anisotropic transport at KTaO3(111) interfaces, Science 371, 716 (2021).
  22. J. H. Barrett, Dielectric constant in perovskite type crystals, Phys. Rev. 86, 118 (1952).
  23. S. H. Wemple, Some transport properties of oxygen-deficient single-crystal potassium tantalate (KTaO3), Phys. Rev. 137, A1575 (1965).
  24. S. E. Rowley, L. J. Spalek, R. P. Smith, M. P. M. Dean, M. Itoh, J. F. Scott, G. G. Lonzarich, and S. S. Saxena, Ferroelectric quantum criticality, Nat. Phys. 10, 367 (2014).
  25. P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, G. L. Chiarotti, M. Cococcioni, I. Dabo, A. D. Corso, S. de Gironcoli, S. Fabris, G. Fratesi, R. Gebauer, U. Gerstmann, C. Gougoussis, A. Kokalj, M. Lazzeri, L. Martin-Samos et al., QUANTUM ESPRESSO: A modular and open-source software project for quantum simulations of materials, J. Phys.: Condens. Matter 21, 395502 (2009).
  26. J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple, Phys. Rev. Lett. 77, 3865 (1996).
  27. K. F. Garrity, J. W. Bennett, K. M. Rabe, and D. Vanderbilt, Pseudopotentials for high-throughput DFT calculations, Comput. Mater. Sci. 81, 446 (2014).
  28. S. Cabuk, Ab initio volume-dependent elastic and lattice dynamics properties of KTaO3, Phys. Status Solidi B 247, 93 (2010).
  29. See Supplemental Material at http://link.aps.org/supplemental/10.1103/PhysRevResearch.4.L032020 for detailed calculations of bulk and slab KTaO3, the polarization-energy profile of LaAlO3, and the detailed solution and code for Eq. (6)
  30. Note that changes in the details of the calculation, such as using the lattice parameter of the paraelectric unit cell, or relaxing the lattice axis in the direction of the polar distortion lead to small changes in the shape of the double well. The exact procedure does not, however, affect our findings.
  31. T. Esswein and N. A. Spaldin, Ferroelectric, quantum paraelectric or paraelectric? Calculating the evolution from BaTiO3 to SrTiO3 to KTaO3 using a single-particle quantum-mechanical description of the ions, Phys. Rev. Research, 4, 033020 (2022).
  32. A. R. Akbarzadeh, L. Bellaiche, K. Leung, J. Íñiguez, and D. Vanderbilt, Atomistic simulations of the incipient ferroelectric KTaO3, Phys. Rev. B 70, 054103 (2004).
  33. M. V. Abrashev,  A. P. Litvinchuk, M. N. Iliev, R. L. Meng, V. N. Popov, V. G. Ivanov, R. A. Chakalov, and C. Thomsen, Comparative study of optical phonons in the rhombohedrally distorted perovskites LaAlO3 and LaMnO3, Phys. Rev. B 59, 4146 (1999).
  34. We note that previous DFT calculations of SrTiO3−LaAlO3 heterostructures overestimated the polarizability of the LaAlO3 as a result of disabling its large octahedral rotations [37]; this considerably softens the polar mode leading to an underestimation of the energy cost to polarize (see SM [29]). In spite of this, the LaAlO3 still showed considerable band bending, and charge transfer across the gap, even in the ultra-thin limit.
  35. F. Y. Bruno, S. McKeown Walker, S. Ricco, A. de la Torre, Z. Wang, A. Tamai, T. K. Kim, M. Hoesch, M. S. Bahramy, and F. Baumberger, Band structure and spinorbital texture of the (111)-KTaO3 2D electron gas, Adv. Electron. Mater. 5, 1800860 (2019).
  36. C. Bareille, F. Fortuna, T. C. Rödel, F. Bertran, M. Gabay, O. H. Cubelos, A. Taleb-Ibrahimi, P. L. Fèvre, M. Bibes, A. Barthélémy, T. Maroutian, P. Lecoeur, M. J. Rozenberg, and A. F. Santander-Syro, Two-dimensional electron gas with six-fold symmetry at the (111) surface of KTaO3, Sci. Rep. 4, 3586 (2015).
  37. R. Pentcheva and W. E. Pickett, Avoiding the Polarization Catastrophe in LaAlO3 Overlayers on SrTiO3(001) through Polar Distortion, Phys. Rev. Lett. 102, 107602 (2009).

Outline

Information

Phys. Rev. Research 4, L032020– Published 5 August, 2022
  • Received 6 January 2022
  • Revised 10 May 2022
  • Accepted 6 July 2022
Crossmark - Check for updates button
Creative Commons Logo

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

Published by the American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation