Abstract
Although high-transition-temperature (high-Tc) superconductivity in cuprates has been known for more than three decades, the underlying mechanism remains unknown1,2,3,4. Cuprates are the only unconventional superconductors that exhibit bulk superconductivity with Tc above the liquid-nitrogen boiling temperature of 77 K. Here we observe that high-pressure resistance and mutual inductive magnetic susceptibility measurements showed signatures of superconductivity in single crystals of La3Ni2O7 with maximum Tc of 80 K at pressures between 14.0 GPa and 43.5 GPa. The superconducting phase under high pressure has an orthorhombic structure of Fmmm space group with the \(3{d}_{{x}^{2}-{y}^{2}}\) and \(3{d}_{{z}^{2}}\) orbitals of Ni cations strongly mixing with oxygen 2p orbitals. Our density functional theory calculations indicate that the superconductivity emerges coincidently with the metallization of the σ-bonding bands under the Fermi level, consisting of the \(3{d}_{{z}^{2}}\) orbitals with the apical oxygen ions connecting the Ni–O bilayers. Thus, our discoveries provide not only important clues for the high-Tc superconductivity in this Ruddlesden–Popper double-layered perovskite nickelates but also a previously unknown family of compounds to investigate the high-Tc superconductivity mechanism.
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Acknowledgements
M.W. acknowledges the support of the National Natural Science Foundation of China (grant no. 12174454), the Guangdong Basic and Applied Basic Research Funds (grant no. 2021B1515120015) and the Guangdong Provincial Key Laboratory of Magnetoelectric Physics and Devices (grant no. 2022B1212010008). H.S. acknowledges the support of the Guangzhou Basic and Applied Basic Research Funds (grant no. 202201011123). D.-X.Y. is supported by NKRDPC-2022YFA1402802, NKRDPC-2018YFA0306001, NSFC-92165204, NSFC-11974432 and the Shenzhen International Quantum Academy. P.Y., B.W. and J.C. are supported by the National Natural Science Foundation of China (grant nos 12025408 and 11921004), the Beijing Natural Science Foundation (grant no. Z190008), the National Key R&D Program of China (grant no. 2021YFA1400200) and the Strategic Priority Research Program of CAS (grant no. XDB33000000). A portion of this work was carried out at the Synergetic Extreme Condition User Facility. High-pressure synchrotron X-ray measurements were performed at the 4W2 High-Pressure Station, Beijing Synchrotron Radiation Facility, which is supported by the Chinese Academy of Sciences (grant nos. KJCX2-SW-N20 and KJCX2-SW-N03).
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M.W. designed the project; Z.L. and M.H. grew the single crystals; H.S., M.H. and J.L. performed the resistance measurements at varying pressures; H.S. performed the synchrotron XRD measurements; H.S. and J.L. conducted the high-pressure susceptibility measurements with the support of L.T. and Z.M.; magnetic susceptibility for pressures below 14 GPa (data not shown) was measured with the support of P.Y., B.W. and J.C.; H.S., Y.H. and M.H. conducted the structural analysis; D.-X.Y. and X.H. performed the DFT calculations. G.-M.Z. proposed a relevant physical picture to understand both the numerical and experimental results. M.W. and G.-M.Z. wrote the paper with inputs from all co-authors.
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Extended data figures and tables
Extended Data Fig. 1 Ni-O distances in the NiO6 octahedra of La3Ni2O7 under pressure.
a, Ni-O distances against pressure. The lattice constants are refined from synchrotron X-ray diffraction. The Ni-O distances are determined from optimization by the density functional theory and used in the calculations. b, Sketch of the NiO6 octahedra. The d1, d2, d3, and d4 label the corresponding Ni-O distances.
Extended Data Fig. 2 Density functional theory calculations for La3Ni2O7 at 1.6 and 29.5 GPa.
a–f, Orbital-decomposed band structures of La3Ni2O7 at a–d 1.6 GPa and e–f 29.5GPa. i, The total density of states at 1.6 and 29.5 GPa near the Fermi level. j, Schematic of the three-dimensional reciprocal unit cell. The red lines correspond to the paths of the electronic bands. k, Calculated two-dimensional Fermi surfaces of La3Ni2O7 in a Brillouin zone at 1.6 GPa marked by a black square. The Fermi surfaces consist of electrons bands (α1,2) and a hole band (β1). l, Two-dimensional Fermi surfaces of La3Ni2O7 at 29.5 GPa. Additional hole bands (Ni \(3{d}_{{z}^{2}}\)) cross the Fermi level.
Extended Data Fig. 3 Resistance measurements of La3Ni2O7 single crystals under pressure acquired in different runs.
a–c, Resistance curves obtained from: a, Run 1, b, Run 3, and c, Run 4 measured with a gasket of cubic boron nitride without a pressure-transmitting medium. The vertical dashed lines indicate the onset superconducting transition temperature Tc. The inset in a is a photo showing the electrodes for the high-pressure measurements. A current of 10 μA was used for the measurements.
Extended Data Fig. 4 Suppression of superconductivity of La3Ni2O7 by external magnetic fields.
a,b, Resistance measured at a, 29.1 GPa and b, 43.5 GPa in the Run 2 with KBr as the pressure transmitting medium. The horizontal dashed lines mark 0.9 × R(Tconset), where R(Tconset) is the resistance at the onset Tc.
Extended Data Fig. 5 Diamagnetic response measurements of La3Ni2O7 under pressure using the magnetic inductive technique.
a–c, Raw data of the real part of the ac susceptibility showing a prominent diamagnetic response at 28.7 GPa with a current magnitude of 50 mA and frequency of a 373, b 393, c 423 Hz. d–f, Identical measurements at 25.2 GPa. The red dashed lines are fitted backgrounds following the trend above the superconducting transitions. Insets in a–f show the diamagnetic signals obtained by subtracting the fitted linear backgrounds. The transition temperature shifts because the pressure changes for each measurement. g, h, Diamagnetic response measurements at 5.3 GPa measured during the decompressing process with a 373 and 393 Hz frequency current, respectively. i, The background measurement of the diamagnetic response of the cell without a sample. The inset in i is an image of the experimental set-up for the ac susceptibility measurements in a diamond-anvil cell, with a signal coil around the diamond anvils and a neighbor compensating coil.
Extended Data Fig. 6 Magnetic susceptibility of La3Ni2O7 measured at 13.0 GPa with the palm-type cubit anvil cell.
The sharp drop at 3.6 K corresponds to the superconducting transition of Pb, which is used to calibrate the pressure. No other obvious transitions are reflected from the magnetic susceptibility.
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Sun, H., Huo, M., Hu, X. et al. Signatures of superconductivity near 80 K in a nickelate under high pressure. Nature 621, 493–498 (2023). https://doi.org/10.1038/s41586-023-06408-7
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DOI: https://doi.org/10.1038/s41586-023-06408-7
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