Controlling phase transitions in transition metal oxides remains a central feature of both technological and fundamental scientific relevance. A well-known example is the metal–insulator transition, which has been shown to be highly controllable. However, the length scale over which these phases can be established is not yet well understood. To gain insight into this issue, we atomically engineered an artificially phase-separated system through fabricating epitaxial superlattices that consist of SmNiO3 and NdNiO3, two materials that undergo a metal-to-insulator transition at different temperatures. We demonstrate that the length scale of the interfacial coupling between metal and insulator phases is determined by balancing the energy cost of the boundary between a metal and an insulator and the bulk phase energies. Notably, we show that the length scale of this effect exceeds that of the physical coupling of structural motifs, which introduces a new framework for interface-engineering properties at temperatures against the bulk energetics.
This is a preview of subscription content
Subscribe to Nature+
Get immediate online access to the entire Nature family of 50+ journals
Subscribe to Journal
Get full journal access for 1 year
only $8.25 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
The data that support the findings of this study are available from the corresponding author upon reasonable request.
The computer codes and algorithm used to generate the results reported in the Article are available from the corresponding author upon reasonable request.
Khomskii, D. I. Transition Metal Compounds (Cambridge Univ. Press, 2014).
Lee, D. et al. Isostructural metal–insulator transition in VO2. Science 362, 1037–1040 (2018).
Cen, C. et al. Nanoscale control of an interfacial metal–insulator transition at room temperature. Nat. Mater. 7, 298–302 (2008).
Thiel, S., Hammerl, G., Schmehl, A., Schneider, C. W. & Mannhart, J. Tunable quasi-two-dimensional electron gases in oxide heterostructures. Science 313, 1942–1945 (2006).
Zubko, P., Gariglio, S., Gabay, M., Ghosez, P. & Triscone, J.-M. Interface physics in complex oxide heterostructures. Annu. Rev. Condens. Matter Phys. 2, 141–165 (2011).
Mattoni, G. et al. Striped nanoscale phase separation at the metal–insulator transition of heteroepitaxial nickelates. Nat. Commun. 7, 13141 (2016).
Post, K. W. et al. Coexisting first- and second-order electronic phase transitions in a correlated oxide. Nat. Phys. 14, 1056–1071 (2018).
Lacorre, P. et al. Synthesis, crystal structure, and properties of metallic PrNiO3: comparison with metallic NdNiO3 and semiconducting SmNiO3. J. Solid State Chem. 91, 225–237 (1991).
Torrance, J., Lacorre, P., Nazzal, A., Ansaldo, E. & Niedermayer, C. Systematic study of insulator–metal transitions in perovskites RNiO3 (R = Pr, Nd, Sm, Eu) due to closing of charge-transfer gap. Phys. Rev. B 45, 8209–8212 (1992).
Middey, S. et al. Physics of ultrathin films and heterostructures of rare-earth nickelates. Annu. Rev. Mater. Res. 46, 305–334 (2016).
Catalano, S. et al. Rare-earth nickelates RNiO3: thin films and heterostructures. Rep. Prog. Phys. 81, 046501 (2017).
Medarde, M. L. Structural, magnetic and electronic properties of RNiO3 perovskites (R = rare earth). J. Condens. Matter Phys. 9, 1679–1707 (1997).
Catalan, G. Progress in perovskite nickelate research. Phase Transit. 81, 729–749 (2008).
Mercy, A., Bieder, J., Íñiguez, J. & Ghosez, P. Structurally triggered metal–insulator transition in rare-earth nickelates. Nat. Commun. 8, 1677 (2017).
Alonso, J. A. et al. Charge disproportionation in RNiO3 perovskites: simultaneous metal–insulator and structural transition in YNiO3. Phys. Rev. Lett. 82, 3871–3874 (1999).
Scherwitzl, R. et al. Electric-field control of the metal–insulator transition in ultrathin NdNiO3 films. Adv. Mater. 22, 5517–5520 (2010).
May, S. J. et al. Control of octahedral rotations in (LaNiO3)n/(SrMnO3)m superlattices. Phys. Rev. B 83, 153411 (2011).
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).
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).
Chakhalian, J., Millis, A. J. & Rondinelli, J. Whither the oxide interface. Nat. Mater. 11, 92–94 (2012).
Moon, E. J. et al. Spatial control of functional properties via octahedral modulations in complex oxide superlattices. Nat. Commun. 5, 5710 (2014).
Aso, R., Kan, D., Shimakawa, Y. & Kurata, H. Atomic level observation of octahedral distortions at the perovskite oxide heterointerface. Sci. Rep. 3, 2214 (2013).
Liao, Z. et al. Controlled lateral anisotropy in correlated manganite heterostructures by interface-engineered oxygen octahedral coupling. Nat. Mater. 15, 425–431 (2016).
Liao, Z. et al. Metal–insulator-transition engineering by modulation tilt-control in perovskite nickelates for room temperature optical switching. Proc. Natl Acad. Sci. USA 115, 9515–9520 (2018).
Yuan, Y. et al. Three-dimensional atomic scale electron density reconstruction of octahedral tilt epitaxy in functional perovskites. Nat. Commun. 9, 5220 (2018).
Zhang, J. Y., Hwang, J., Raghavan, S. & Stemmer, S. Symmetry lowering in extreme-electron-density perovskite quantum wells. Phys. Rev. Lett. 110, 256401 (2013).
Subedi, A., Peil, O. E. & Georges, A. Low-energy description of the metal–insulator transition in the rare-earth nickelates. Phys. Rev. B 91, 075128 (2015).
Seth, P. et al. Renormalization of effective interactions in a negative charge transfer insulator. Phys. Rev. B 96, 205139 (2017).
Peil, O. E., Hampel, A., Ederer, C. & Georges, A. Mechanism and control parameters of the coupled structural and metal–insulator transition in nickelates. Phys. Rev. B 99, 245127 (2019).
Georgescu, A. B., Peil, O. E., Disa, A. S., Georges, A. & Millis, A. J. Disentangling lattice and electronic contributions to the metal–insulator transition from bulk vs. layer confined RNiO3. Proc. Natl Acad. Sci. USA 116, 14434–14439 (2019).
Catalan, G. Metal–insulator transition in NdNiO3 thin films. Phys. Rev. B 62, 7892–7900 (2000).
Jones, L. et al. Smart Align—a new tool for robust non-rigid registration of scanning microscope data. Adv. Struct. Chem. Imag. 1, 8 (2015).
Nord, M., Vullum, P. E., MacLaren, I., Tybell, T. & Holmestad, R. Atomap: a new software tool for the automated analysis of atomic resolution images using two-dimensional Gaussian fitting. Adv. Struct. Chem. Imag. 3, 9 (2017).
Bosman, M., Watanabe, M., Alexander, D. T. & Keast, V. J. Mapping chemical and bonding information using multivariate analysis of electron energy-loss spectrum images. Ultramicroscopy 106, 1024–1032 (2006).
Lucas, G., Burdet, P., Cantoni, M. & Hebert, C. Multivariate statistical analysis as a tool for the segmentation of 3D spectral data. Micron 52–53, 49–56 (2013).
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).
Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
Perdew, J. P. et al. Restoring the density-gradient expansion for exchange in solids and surfaces. Phys. Rev. Lett. 100, 136406 (2008).
Varignon, J., Grisolia, M. N., Íñiguez, J., Barthélémy, A. & Bibes, M. Complete phase diagram of rare-earth nickelates from first-principles. npj Quantum Mater. 2, 21 (2017).
Hampel, A. & Ederer, C. Interplay between breathing mode distortion and magnetic order in rare-earth nickelates RNiO3 within DFT + U. Phys. Rev. B 96, 165130 (2017).
Loschen, C., Carrasco, J., Neyman, K. M. & Illas, F. First-principles LDA + U and GGA + U study of cerium oxides: dependence on the effective U parameter. Phys. Rev. B. 75, 035115 (2007).
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).
Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).
Momma, K. & Izumi, F. VESTA: a three-dimensional visualization system for electronic and structural analysis. J. Appl. Crystallogr. 41, 653–658 (2008).
We thank H. Strand and M. Zingl for fruitful discussions and acknowledge M. Lopes and S. Muller for their invaluable technical support. This work was partly supported by the Swiss National Science Foundation through Division II. The research leading to these results received funding from the European Research Council under the European Union’s Seventh Framework Program (FP7/2007-2013)/ERC Grant Agreement 319286 Q-MAC). The authors acknowledge access to the electron microscopy facilities at the Interdisciplinary Centre for Electron Microscopy, École Polytechnique Fédérale de Lausanne. The Flatiron Institute is a division of the Simons Foundation. P.G., Y.Z. and A.M. acknowledge support from ULiège (ARC project AIMED), F.R.S.-FNRS Belgium (FRIA grant No 1.E.122.18 and PDR PROMOSPAN grant no. T.0107.20) and M-ERA.NET project SIOX, as well as access to computational resources provided by the Consortium des Equipements de Calcul Intensif (CECI), funded by the Belgian F.R.S.-FNRS under grant no. 2.5020.11 and the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles funded by the Walloon Region of Belgium under grant no. 1117545. M.G. acknowledges support by the Swiss National Science Foundation under grant no. PP00P2_170564.
The authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Domínguez, C., Georgescu, A.B., Mundet, B. et al. Length scales of interfacial coupling between metal and insulator phases in oxides. Nat. Mater. 19, 1182–1187 (2020). https://doi.org/10.1038/s41563-020-0757-x
Communications Physics (2022)
From hidden metal-insulator transition to Planckian-like dissipation by tuning the oxygen content in a nickelate
npj Quantum Materials (2021)
Resonant tunneling driven metal-insulator transition in double quantum-well structures of strongly correlated oxide
Nature Communications (2021)