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Superconductivity in a quintuple-layer square-planar nickelate

Nature Materials volume 21, pages 160–164 (2022)Cite this article

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Abstract

Since the discovery of high-temperature superconductivity in copper oxide materials1, there have been sustained efforts to both understand the origins of this phase and discover new cuprate-like superconducting materials2. One prime materials platform has been the rare-earth nickelates and, indeed, superconductivity was recently discovered in the doped compound Nd0.8Sr0.2NiO2 (ref. 3). Undoped NdNiO2 belongs to a series of layered square-planar nickelates with chemical formula Ndn+1NinO2n+2 and is known as the ‘infinite-layer’ (n = ∞) nickelate. Here we report the synthesis of the quintuple-layer (n = 5) member of this series, Nd6Ni5O12, in which optimal cuprate-like electron filling (d8.8) is achieved without chemical doping. We observe a superconducting transition beginning at ~13 K. Electronic structure calculations, in tandem with magnetoresistive and spectroscopic measurements, suggest that Nd6Ni5O12 interpolates between cuprate-like and infinite-layer nickelate-like behaviour. In engineering a distinct superconducting nickelate, we identify the square-planar nickelates as a new family of superconductors that can be tuned via both doping and dimensionality.

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Fig. 1: Electronic phase diagram and structural description of the layered nickelates.
Fig. 2: Structural characterization of the layered nickelates.
Fig. 3: Transport properties of the layered nickelate thin films.
Fig. 4: Electronic structure description of the layered nickelates.

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Data availability

The data supporting the findings of this study are available from the corresponding authors upon reasonable request. Source data for Figs. 2–4 are provided with this paper.

References

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

    Article  CAS  Google Scholar 

  2. Keimer, B., Kivelson, S. A., Norman, M. R., Uchida, S. & Zaanen, J. From quantum matter to high-temperature superconductivity in copper oxides. Nature 518, 179–186 (2015).

    Article  CAS  Google Scholar 

  3. Li, D. et al. Superconductivity in an infinite-layer nickelate. Nature 572, 624–627 (2019).

    Article  CAS  Google Scholar 

  4. Anisimov, V. I., Bukhvalov, D. & Rice, T. M. Electronic structure of possible nickelate analogs to the cuprates. Phys. Rev. B 59, 7901–7906 (1999).

    Article  CAS  Google Scholar 

  5. Chaloupka, J. & Khaliullin, G. Orbital order and possible superconductivity in LaNiO3/LaMO3 superlattices. Phys. Rev. Lett. 100, 016404 (2008).

    Article  Google Scholar 

  6. Emery, V. J., Kivelson, S. A. & Tranquada, J. M. Stripe phases in high-temperature superconductors. Proc. Natl Acad. Sci. USA 96, 8814–8817 (1999).

    Article  CAS  Google Scholar 

  7. Li, D. et al. Superconducting dome in Nd1−xSrxNiO2 infinite layer films. Phys. Rev. Lett. 125, 027001 (2020).

    Article  CAS  Google Scholar 

  8. Zeng, S. et al. Phase diagram and superconducting dome of infinite-layer Nd1−xSrxNiO2 thin films. Phys. Rev. Lett. 125, 147003 (2020).

    Article  CAS  Google Scholar 

  9. Lee, K.-W. & Pickett, W. E. Infinite-layer LaNiO2: Ni1+ is not Cu2+. Phys. Rev. B 70, 165109 (2004).

    Article  Google Scholar 

  10. Botana, A. S. & Norman, M. R. Similarities and differences between LaNiO2 and CaCuO2 and implications for superconductivity. Phys. Rev. X 10, 011024 (2020).

    CAS  Google Scholar 

  11. Hepting, M. et al. Electronic structure of the parent compound of superconducting infinite-layer nickelates. Nat. Mater. 19, 381–385 (2020).

    Article  CAS  Google Scholar 

  12. Goodge, B. H. et al. Doping evolution of the Mott–Hubbard landscape in infinite-layer nickelates. Proc. Natl Acad. Sci. USA 118, e2007683118 (2021).

    Article  CAS  Google Scholar 

  13. Lee, K. et al. Aspects of the synthesis of thin film superconducting infinite-layer nickelates. APL Mater. 8, 041107 (2020).

    Article  CAS  Google Scholar 

  14. Gu, Q. et al. Single particle tunneling spectrum of superconducting Nd1−xSrxNiO2 thin films. Nat. Commun. 11, 6027 (2020).

    Article  CAS  Google Scholar 

  15. Li, Q. et al. Absence of superconductivity in bulk Nd1−xSrxNiO2. Commun. Mater. 1, 16 (2020).

    Article  Google Scholar 

  16. Wang, B.-X. et al. Synthesis and characterization of bulk Nd1−xSrxNiO2 and Nd1−xSrxNiO3. Phys. Rev. Mater. 4, 084409 (2020).

    Article  CAS  Google Scholar 

  17. Zhang, J. et al. Large orbital polarization in a metallic square-planar nickelate. Nat. Phys. 13, 864–869 (2017).

    Article  CAS  Google Scholar 

  18. Lin, J. Q. et al. Strong superexchange in a d9−δ nickelate revealed by resonant inelastic X-ray scattering. Phys. Rev. Lett. 126, 087001 (2021).

    Article  CAS  Google Scholar 

  19. Mukuda, H., Shimizu, S., Iyo, A. & Kitaoka, Y. High-Tc superconductivity and antiferromagnetism in multilayered copper oxides—a new paradigm of superconducting mechanism. J. Phys. Soc. Jpn 81, 011008 (2012).

    Article  Google Scholar 

  20. Greenblatt, M. Ruddlesden–Popper \({{{{\rm{Ln}}}}}_{n+1}{{{{\rm{Ni}}}}}_{n}{{{{\rm{O}}}}}_{3n+1}\) nickelates: structure and properties. Curr. Opin. Solid State Mater. Sci. 2, 174–183 (1997).

    Article  CAS  Google Scholar 

  21. Li, Q. et al. Contrasting physical properties of the trilayer nickelates Nd4Ni3O10 and Nd4Ni3O8. Sci. China Phys. Mech. Astron. 64, 227411 (2020).

    Article  Google Scholar 

  22. Abbate, M. et al. Electronic structure and metal-insulator transition in LaNiO3−δ. Phys. Rev. B 65, 155101 (2002).

    Article  Google Scholar 

  23. Miyatake, T. et al. Chemical substitution effect of high-Tc superconductor candidate R4Ni3O8 (R: rare-earth). JPS Conf. Proc. 30, 011061 (2020).

    Google Scholar 

  24. Wang, B. Y. et al. Isotropic Pauli-limited superconductivity in the infinite-layer nickelate Nd0.775Sr0.225NiO2. Nat. Phys. 17, 473–477 (2021).

    Article  CAS  Google Scholar 

  25. Osada, M. et al. A superconducting praseodymium nickelate with infinite layer structure. Nano Lett. 20, 5735–5740 (2020).

    Article  CAS  Google Scholar 

  26. Zeng, S. et al. Observation of perfect diamagnetism and interfacial effect on the electronic structures in Nd0.8Sr0.2NiO2 superconducting infinite layers. Preprint at https://arxiv.org/abs/2104.14195 (2021).

  27. Osada, M. et al. Nickelate superconductivity without rare-earth magnetism: (La, Sr)NiO2. Adv. Mater. https://doi.org/10.1002/adma.202104083 (2021).

  28. Zeng, S. et al. Superconductivity in infinite-layer lanthanide nickelates. Preprint at https://arxiv.org/abs/2105.13492 (2021).

  29. Takagi, H. et al. Superconductor-to-nonsuperconductor transition in \({({{{{\rm{La}}}}}_{1-x}{{{{\rm{Sr}}}}}_{x})}_{2}{{{{\rm{CuO}}}}}_{4}\) as investigated by transport and magnetic measurements. Phys. Rev. B 40, 2254 (1989).

    Article  CAS  Google Scholar 

  30. Wu, X. et al. Robust \({d}_{{x}^{2}-{y}^{2}}\)-wave superconductivity of infinite-layer nickelates. Phys. Rev. B 101, 060504(R) (2020).

    Article  Google Scholar 

  31. Karp, J. et al. Comparative many-body study of Pr4Ni3O8 and NdNiO2. Phys. Rev. B 102, 245130 (2020).

    Article  CAS  Google Scholar 

  32. LaBollita, H. & Botana, A. S. Electronic structure and magnetic properties of higher-order layered nickelates: Lan+1NinO2n+2 (n = 4−6). Phys. Rev. B 104, 035148 (2021).

    Article  CAS  Google Scholar 

  33. Sakakibara, H. et al. Orbital mixture effect on the Fermi-surface–Tc correlation in the cuprate superconductors: bilayer vs. single layer. Phys. Rev. B 89, 224505 (2014).

    Article  Google Scholar 

  34. Zhang, F. C. & Rice, T. M. Effective Hamiltonian for the superconducting Cu oxides. Phys. Rev. B 37, 3759(R) (1988).

    Article  Google Scholar 

  35. Nica, E. M. et al. Theoretical investigation of superconductivity in trilayer square-planar nickelates. Phys. Rev. B 102, 020504(R) (2020).

    Article  Google Scholar 

  36. Suntivich, J. et al. Estimating hybridization of transition metal and oxygen states in perovskites from O K-edge X-ray absorption spectroscopy. J. Phys. Chem. C 118, 1856–1863 (2014).

    Article  CAS  Google Scholar 

  37. Li, Y. et al. Impact of cation stoichiometry on the crystalline structure and superconductivity in nickelates. Front. Phys. 9, 719534 (2021).

    Article  Google Scholar 

  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 (1996).

    Article  CAS  Google Scholar 

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Acknowledgements

We thank M. R. Norman and M. Mitrano for discussions. We also thank K. Lee and H. Y. Hwang for discussions and technical guidance in reduction experiments; D. Erdosy, J. Lee, N. Pappas, S. Thapa and M. Wenny for continued support in reductions; H. Hijazi at the Rutgers University Laboratory of Surface Modification for assistance in Rutherford backscattering spectrometry; and J. MacArthur for electronics support. This research was funded in part by the Gordon and Betty Moore Foundation’s EPiQS Initiative, grant no. GBMF6760 to J. A. Mundy. Materials growth and electron microscopy were supported in part by the Platform for the Accelerated Realization, Analysis, and Discovery of Interface Materials (PARADIM) under NSF Cooperative Agreement no. DMR-2039380. Electron microscopy made use of the Cornell Center for Materials Research (CCMR) Shared Facilities, which are supported through the NSF MRSEC Program (no. DMR-1719875). The Thermo Fisher Spectra 300 X-CFEG was acquired with support from PARADIM, an NSF MIP (DMR-2039380) and Cornell University. Nanofabrication work was performed in part at Harvard University’s Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Coordinated Infrastructure Network (NNCI), supported by the National Science Foundation under NSF grant no. 1541959, and in part at the University of Michigan Lurie Nanofabrication Facility. This research used resources of the Advanced Light Source, a US DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. G.A.P. acknowledges support from the Paul & Daisy Soros Fellowship for New Americans and from the NSF Graduate Research Fellowship grant no. DGE-1745303. G.A.P. and D.F.S. acknowledge support from US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under award no. DE-SC0021925. Q.S., S.D. and D.C.C. were supported by the STC Center for Integrated Quantum Materials, NSF grant no. DMR-1231319. B.H.G., H.P. and L.F.K. acknowledge support by PARADIM, NSF no. DMR-2039380. A.T.P. acknowledges support from the Department of Defense through the National Defense Science and Engineering Graduate Fellowship (NDSEG) Program. J. A. Mason acknowledges support from the Arnold and Mabel Beckman Foundation through a Beckman Young Investigator grant. O.E. acknowledges support from NSF grant no. DMR-1904716. A.S.B. and H.L. acknowledge NSF grant no. DMR-2045826 and the ASU Research Computing Center for HPC resources. J. A. Mundy acknowledges support from the Packard Foundation.

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Authors and Affiliations

  1. Department of Physics, Harvard University, Cambridge, MA, USA

    Grace A. Pan, Dan Ferenc Segedin, Qi Song, Andrew T. Pierce, Spencer Doyle, Denisse Córdova Carrizales, Amir Yacoby, Charles M. Brooks & Julia A. Mundy

  2. Department of Physics, Arizona State University, Tempe, AZ, USA

    Harrison LaBollita, Emilian M. Nica, Onur Erten & Antia S. Botana

  3. School of Applied and Engineering Physics, Cornell University, Ithaca, NY, USA

    Berit H. Goodge & Lena F. Kourkoutis

  4. Kavli Institute at Cornell for Nanoscale Science, Cornell University, Ithaca, NY, USA

    Berit H. Goodge & Lena F. Kourkoutis

  5. Department of Physics, University of Michigan, Ann Arbor, MI, USA

    Steve Novakov

  6. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Alpha T. N’Diaye & Padraic Shafer

  7. Platform for the Accelerated Realization, Analysis, and Discovery of Interface Materials (PARADIM), Cornell University, Ithaca, NY, USA

    Hanjong Paik

  8. Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI, USA

    John T. Heron

  9. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA

    Jarad A. Mason

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Contributions

G.A.P., Q.S., C.M.B. and J. A. Mundy synthesized the thin films with assistance from H.P. G.A.P., D.F.S. and S.D. conducted the reductions with guidance from J. A. Mason. B.H.G. and L.F.K. characterized the samples with scanning transmission electron microscopy. G.A.P., A.T.P. and A.Y. performed transport measurements using fabrication assistance from S.N. and J.T.H. G.A.P., D.F.S., Q.S., D.C.C., A.T.N. and P.S. performed X-ray absorption spectroscopy. H.L. and A.S.B. performed density functional theory calculations. E.M.N., O.E. and A.S.B. constructed the t−J model. A.S.B. and J. A. Mundy conceived and guided the study. G.A.P., A.S.B. and J. A. Mundy wrote the manuscript with discussion and contributions from all authors.

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Correspondence to Antia S. Botana or Julia A. Mundy.

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Peer review information Nature Materials thanks Hai-Hu Wen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary information

Supplementary Table 1, Figs. 1–15 and Notes 1–6.

Source Data Fig. 2

X-ray diffraction spectra.

Source Data Fig. 3

Temperature dependence of electrical resistivities and Hall coefficients.

Source Data Fig. 4

Band structure diagrams.

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Pan, G.A., Ferenc Segedin, D., LaBollita, H. et al. Superconductivity in a quintuple-layer square-planar nickelate. Nat. Mater. 21, 160–164 (2022). https://doi.org/10.1038/s41563-021-01142-9

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