Letter | Published:

Freestanding crystalline oxide perovskites down to the monolayer limit

Abstract

Two-dimensional (2D) materials such as graphene and transition-metal dichalcogenides reveal the electronic phases that emerge when a bulk crystal is reduced to a monolayer1,2,3,4. Transition-metal oxide perovskites host a variety of correlated electronic phases5,6,7,8,9,10,11,12, so similar behaviour in monolayer materials based on transition-metal oxide perovskites would open the door to a rich spectrum of exotic 2D correlated phases that have not yet been explored. Here we report the fabrication of freestanding perovskite films with high crystalline quality almost down to a single unit cell. Using a recently developed method based on water-soluble Sr3Al2O6 as the sacrificial buffer layer13,14 we synthesize freestanding SrTiO3 and BiFeO3 ultrathin films by reactive molecular beam epitaxy and transfer them to diverse substrates, in particular crystalline silicon wafers and holey carbon films. We find that freestanding BiFeO3 films exhibit unexpected and giant tetragonality and polarization when approaching the 2D limit. Our results demonstrate the absence of a critical thickness for stabilizing the crystalline order in the freestanding ultrathin oxide films. The ability to synthesize and transfer crystalline freestanding perovskite films without any thickness limitation onto any desired substrate creates opportunities for research into 2D correlated phases and interfacial phenomena that have not previously been technically possible.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding authors upon reasonable request.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

References

  1. 1.

    Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).

  2. 2.

    Radisavljevic, B., Radenovic, A., Brivio, J., Giacometti, V. & Kis, A. Single-layer MoS2 transistors. Nat. Nanotechnol. 6, 147–150 (2011).

  3. 3.

    Lopez-Sanchez, O., Lembke, D., Kayci, M., Radenovic, A. & Kis, A. Ultrasensitive photodetectors based on monolayer MoS2. Nat. Nanotechnol. 8, 497–501 (2013).

  4. 4.

    Mak, K. F., He, K., Shan, J. & Heinz, T. F. Control of valley polarization in monolayer MoS2 by optical helicity. Nat. Nanotechnol. 7, 494–498 (2012).

  5. 5.

    Bednorz, J. G. & Müller, K. A. Possible high T c superconductivity in the Ba–La–Cu–O system. Z. Phys. B 64, 189–193 (1986).

  6. 6.

    Dagotto, E. Correlated electrons in high-temperature superconductors. Rev. Mod. Phys. 66, 763–840 (1994).

  7. 7.

    Jin, S. et al. Thousandfold change in resistivity in magnetoresistive La–Ca–Mn–O films. Science 264, 413–415 (1994).

  8. 8.

    Tokura, Y. & Tomioka, Y. Colossal magnetoresistive manganites. J. Magn. Magn. Mater. 200, 1–23 (1999).

  9. 9.

    Imada, M., Fujimori, A. & Tokura, Y. Metal-insulator transitions. Rev. Mod. Phys. 70, 1039–1263 (1998).

  10. 10.

    Ahn, K. H., Lookman, T. & Bishop, A. R. Strain-induced metal–insulator phase coexistence in perovskite manganites. Nature 428, 401–404 (2004).

  11. 11.

    Ramesh, R. & Spaldin, N. A. Multiferroics: progress and prospects in thin films. Nat. Mater. 6, 21–29 (2007).

  12. 12.

    Cheong, S.-W. & Mostovoy, M. Multiferroics: a magnetic twist for ferroelectricity. Nat. Mater. 6, 13–20 (2007).

  13. 13.

    Lu, D. et al. Synthesis of freestanding single-crystal perovskite films and heterostructures by etching of sacrificial water-soluble layers. Nat. Mater. 15, 1255–1260 (2016).

  14. 14.

    Hong, S. S. et al. Two-dimensional limit of crystalline order in perovskite membrane films. Sci. Adv. 3, eaao5173 (2017).

  15. 15.

    Bakaul, S. R. et al. Single crystal functional oxides on silicon. Nat. Commun. 7, 10547 (2016).

  16. 16.

    Paskiewicz, D. M., Sichel-Tissot, R., Karapetrova, E., Stan, L. & Fong, D. D. Single-crystalline SrRuO3 nanomembranes: a platform for flexible oxide electronics. Nano Lett. 16, 534–542 (2016).

  17. 17.

    Matthews, J. W. Growth of face-centered-cubic metals on sodium chloride substrates. J. Vac. Sci. Technol. 3, 133–145 (1966).

  18. 18.

    Wong, W. S., Sands, T. & Cheung, N. W. Damage-free separation of GaN thin films from sapphire substrates. Appl. Phys. Lett. 72, 599–601 (1998).

  19. 19.

    Bruel, M. Application of hydrogen ion beams to silicon on insulator material technology. Nucl. Instrum. Methods Phys. Res. B 108, 313–319 (1996).

  20. 20.

    Meyer, J. C. et al. The structure of suspended graphene sheets. Nature 446, 60 (2007).

  21. 21.

    Jang, H. W. et al. Strain-induced polarization rotation in epitaxial (001) BiFeO3 thin films. Phys. Rev. Lett. 101, 107602 (2008).

  22. 22.

    Béa, H. et al. Evidence for room-temperature multiferroicity in a compound with a giant axial ratio. Phys. Rev. Lett. 102, 217603 (2009).

  23. 23.

    Yang, J. C. et al. Orthorhombic BiFeO3. Phys. Rev. Lett. 109, 247606 (2012).

  24. 24.

    Xu, G. et al. Low symmetry phase in (001) BiFeO3 epitaxial constrained thin films. Appl. Phys. Lett. 86, 182905 (2005).

  25. 25.

    Xu, G., Li, J. & Viehland, D. Ground state monoclinic (M b) phase in (110)c BiFeO3 epitaxial thin films. Appl. Phys. Lett. 89, 222901 (2006).

  26. 26.

    Yan, L., Cao, H., Li, J. F. & Viehland, D. Triclinic phase in tilted (001) oriented BiFeO3 epitaxial thin films. Appl. Phys. Lett. 94, 132901 (2009).

  27. 27.

    Ricinschi, D., Yun, K. Y. & Okuyama, M. First-principles study of BiFeO3 films with giant polarization and its dependence on structural parameters. Ferroelectrics 335, 181–190 (2006).

  28. 28.

    Zhang, J. X. et al. Microscopic origin of the giant ferroelectric polarization in tetragonal-like BiFeO3. Phys. Rev. Lett. 107, 147602 (2011).

  29. 29.

    Ederer, C. & Spaldin, N. Effect of epitaxial strain on the spontaneous polarization of thin film ferroelectrics. Phys. Rev. Lett. 95, 257601 (2005).

  30. 30.

    Lebeugle, D., Colson, D., Forget, A. & Viret, M. Very large spontaneous electric polarization in BiFeO3 single crystals at room temperature and its evolution under cycling fields. Appl. Phys. Lett. 91, 022907 (2007).

  31. 31.

    Wang, H. et al. Direct observation of room-temperature out-of-plane ferroelectricity and tunneling electroresistance at the two-dimensional limit. Nat. Commun. 9, 3319 (2018).

  32. 32.

    Cao, Y. et al. Unconventional superconductivity in magic-angle graphene superlattices. Nature 556, 43–50 (2018).

  33. 33.

    Cao, Y. et al. Correlated insulator behaviour at half-filling in magic-angle graphene superlattices. Nature 556, 80–84 (2018).

  34. 34.

    Neaton, J., Ederer, C., Waghmare, U., Spaldin, N. & Rabe, K. First-principles study of spontaneous polarization in multiferroic BiFeO3. Phys. Rev. B 71, 014113 (2005).

  35. 35.

    Nelson, C. T. et al. Domain dynamics during ferroelectric switching. Science 334, 968–971 (2011).

  36. 36.

    Tang, Y. L. et al. Observation of a periodic array of flux-closure quadrants in strained ferroelectric PbTiO3 films. Science 348, 547–551 (2015).

  37. 37.

    Yadav, A. K. et al. Observation of polar vortices in oxide superlattices. Nature 530, 198–201 (2016).

  38. 38.

    Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

  39. 39.

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

  40. 40.

    Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

  41. 41.

    Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).

  42. 42.

    Paudel, T. R., Jaswal, S. S. & Tsymbal, E. Y. Intrinsic defects in multiferroic BiFeO3 and their effect on magnetism. Phys. Rev. B 85, 104409 (2012).

  43. 43.

    Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA+U study. Phys. Rev. B 57, 1505–1509 (1998).

Download references

Acknowledgements

This paper is dedicated to the memory of N. B. Ming, who supported the Center for Microstructure of Quantum Materials at Nanjing University. This work was supported by the National Basic Research Program of China (grant 2015CB654901), the National Natural Science Foundation of China (grants 11574135, 51772143, 11474147, 51672125, 11774153 and 11874199), the Fundamental Research Funds for the Central Universities (grant 0213-14380058), and the National Natural Science Foundation of China/The Research Grants Council of Hong Kong (NSFC/RGC, grant 11861161004). Y.N. and P.W. are supported by the National Thousand-Young-Talents Program and the Program for High-Level Entrepreneurial and Innovative Talents Introduction, Jiangsu Province. S.C. is supported by Program A for Outstanding Ph.D. candidate of Nanjing University (grant 201801A013) and the Postgraduate Research and Practice Innovation Program of Jiangsu Province (grant KYCX18_0045). TEM work at the University of California, Irvine used the facilities of the Irvine Materials Research Institute (IMRI) and was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under grant DE-SC0014430. The research at the University of Nebraska–Lincoln is supported by the National Science Foundation (NSF) under the Nebraska MRSEC programme (grant DMR-1420645). Y.N. acknowledges discussions with H. Hwang, D. Li and S. S. Hong.

Reviewer information

Nature thanks Gertjan Koster and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Author information

X.P., Y.N. and P.W. conceived and directed the project. Y.N. and Z.G. supervised the synthesis of epitaxial and freestanding films. H.S. developed the process for growing SAO and grew and transferred the STO freestanding films. D.J. grew and transferred the BFO freestanding films (with the help of Y. Zang and W. Guo). P.W. and X.P. supervised the STEM characterizations. S.C. prepared the TEM cross-sectional samples using the focused ion beam technique. S.C., D.J., C.Z., Y.W., M.G., W. Gao and H.H. carried out STEM experiments and data analysis. T.R.P., with E.Y.T., performed the theoretical calculations and analysed results. L.H. and D.J. performed the PFM measurements and data analysis (with the help of Y. Zhang and D.W.). Y.N., D.J., P.W., X.P., S.C., T.R.P., E.Y.T., H.S. and Y. Zang wrote and edited the manuscript. All authors discussed the data and contributed to the manuscript.

Competing interests

The authors declare no competing interests.

Correspondence to Peng Wang or Yuefeng Nie or Xiaoqing Pan.

Extended data figures and tables

Extended Data Fig. 1 Growth and transfer of freestanding SrTiO3 films.

a–d, The growth and surface morphology of ultrathin STO films of thickness four unit cells (a), three unit cells (b), two unit cells (c) and one unit cell (u.c.) (d) on six-unit-cell-thick SAO-buffered STO substrates. The RHEED intensity oscillations (red curves) exhibit four intensity oscillation periods in the growth of one-unit-cell-thick SAO (especially near the SAO surface). Insets, the RHEED diffraction patterns show clear fourfold reconstructed diffraction patterns. The atomic force microscopy (AFM) images (right panels) show clear steps and terraces, indicating the smooth film surfaces. e, High-resolution XRD ω scans of a three-layered heterostructure consisting of an STO film (60 unit cells thick) on an SAO (four unit cells thick) on an STO substrate heterostructure and the corresponding freestanding STO film and STO substrate after releasing the sample. The asterisk denotes the background diffraction peak from the PDMS tape. f, Optical image of the freestanding 60-unit-cell-thick STO transferred onto PDMS with the support of a glass slide. g, Magnification of the ω scans around the STO(002) substrate peak show clear thickness fringes, indicating the smooth surfaces of both the as-grown and freestanding films.

Extended Data Fig. 2 Synthesis of ultrathin freestanding BFO films.

ac, Cross-sectional HAADF images (a), SAED patterns (b), and plan-view HAADF images (c) of ultrathin freestanding BFO films of various unit-cell thicknesses (four, three, two and one) below the reported 2D limit. Scale bars, 2 nm (a); 2 nm−1 (b); and 5 nm (c). All BFO films were suspended on holey carbon grids. As the one-unit-cell-thick freestanding film is extremely sensitive to the electron beam, it can survive only at low-dose SAED measurements.

Extended Data Fig. 3 SAED measurements on a one-unit-cell-thick freestanding BFO film.

a, b, SAED measurements on a one-unit-cell-thick freestanding BFO film taken at the same region in a sequence showing clear broadening of the diffraction spots. Scale bars, 2 nm−1. c, The fitted full-width at half-maximum (FWHM) of the diffraction spots (red and green dashed boxes in a and b) show a FWHM of 0.2 nm−1 and 0.39 nm−1, indicating that the real-space crystalline lattice domain size decreases by almost half between these two measurements.

Extended Data Fig. 4 PFM measurements on BFO films with different thicknesses.

a, Topography, b, out-of-plane PFM phase images, c, in-plane PFM phase images, and d, in-plane PFM amplitude images of freestanding BFO films. Scale bars, 500 nm. All freestanding films exhibit a single out-of-plane domain. Only the freestanding films thicker than four unit cells show in-plane polarizations, which is consistent with the R-phase to T-phase transition observed in the atomically resolved HAADF images, as discussed in the main text. e, The corresponding local out-of-plane PFM hysteresis loops show the switchable out-of-plane polarizations in all ultrathin films. The asymmetry of the coercive field is probably due to asymmetric electrostatic boundary conditions and a self-poling effect, which arises at the interface between BFO and the conductive silicon substrate employed in the measurements.

Extended Data Fig. 5 Domain writing of a 20-unit-cell-thick freestanding BFO film.

The initial state contains a single out-of-plane domain and multiple in-plane domains. The initial out-of-plane domain with polarization pointing downwards can be switched and this domain-writing process also affects the in-plane domain orientation owing to the trailing field effect. The voltage was applied at the tip during the domain reading and writing. Scale bar, 500 nm.

Extended Data Fig. 6 Lattice distortion as a function of position for an eight-unit-cell-thick BFO slab.

Clear lattice distortions c driven by the surface electric field are found near the polar surface. l is the thickness of the slab and z is the distance from the surface. The dotted line is a guide to the eye.

Extended Data Fig. 7 Schematic of the workflow of the TEM cross-sectional sample preparation using focused ion beam.

a, Deposition of a Pt protection layer on the film surface by electron beam evaporation. b, Etching by gallium ion beam to form a sample lamella. c, Cutting off the lamella by gallium ion beam and pulling it out by in situ micro-manipulator. d, Adjusting the lamella position. e, Transfer of the lamella to a sample grid and detaching of the micro-manipulator. f, Thinning of the lamella to be electron-transparent and removing the superficial amorphous layers by ion-beam fine milling and polishing.

Extended Data Fig. 8 Ripples and roughening in ultrathin freestanding films.

ae, STEM-HAADF cross-sectional images of BFO freestanding films showing flat (ac) and buckled shape (d, e) in thicker (ten unit cells) and thinner (four unit cells) freestanding films, respectively. For thicker freestanding films, all atomic columns can be sharply resolved in a single image since their zone axes were well aligned with the beam direction (b) and a mistilt of the lattice of just 1° leads to a blurred image (c). For thinner freestanding films, higher-magnification images (e) taken with different tilting angles (1° per step) indicate that the film is a single crystal but twisted owing to the ripples. The scale bars in the low-magnification images (a, d) are 20 nm and the scale bars in the enlarged images (b, c, e) are 5 nm.

Extended Data Fig. 9 Quantitative estimation of the effect of mistilt on the analysis of c/a.

To quantitatively estimate the effect of the degree of mistilt on the analysis of c/a, we calculated the simulated HAADF-STEM images of a hypothetical cubic BiFeO3 crystal as a function of the tilting angle around the [100] axis (a), and [010] axis (b), respectively, using a multislice simulation code called QSTEM. The thickness of the BFO model was about 20 nm (50 unit cells). As shown in a and b, within a few degrees of the tilt, the atomic columns in STEM images are noticeably elongated along the direction perpendicular to the rotation axis. Using the same two-dimensional Gaussian fitting procedure as that one used for analysing the experimental data in Fig. 3, the deviations of the fitted lattice constants from the nominal ones are negligible (c). The maximum deviation of the calculated c/a ratio is less than 0.002, which is two orders of magnitude smaller than the increment of the c/a ratio (1.22) observed in the ultrathin freestanding BFO films. The electron energy was 300 kV, the probe convergence angle was 25 mrad, and the angular range of the HAADF detector was 79.5 mrad to 200 mrad in the simulation, values consistent with the experiment. The error bars represent the fitting error of the lattice constants.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark
Fig. 1: Growth and transfer of ultrathin freestanding SrTiO3 films.
Fig. 2: Synthesis of ultrathin freestanding STO films of high crystalline quality.
Fig. 3: Giant polarization and lattice distortion in ultrathin freestanding BFO films.
Fig. 4: Calculated giant polarization and lattice distortion in ultrathin freestanding BFO films.
Extended Data Fig. 1: Growth and transfer of freestanding SrTiO3 films.
Extended Data Fig. 2: Synthesis of ultrathin freestanding BFO films.
Extended Data Fig. 3: SAED measurements on a one-unit-cell-thick freestanding BFO film.
Extended Data Fig. 4: PFM measurements on BFO films with different thicknesses.
Extended Data Fig. 5: Domain writing of a 20-unit-cell-thick freestanding BFO film.
Extended Data Fig. 6: Lattice distortion as a function of position for an eight-unit-cell-thick BFO slab.
Extended Data Fig. 7: Schematic of the workflow of the TEM cross-sectional sample preparation using focused ion beam.
Extended Data Fig. 8: Ripples and roughening in ultrathin freestanding films.
Extended Data Fig. 9: Quantitative estimation of the effect of mistilt on the analysis of c/a.

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.