Abstract
The pursuit of discovering new high-temperature superconductors that diverge from the copper-based model1,2,3 has profound implications for explaining mechanisms behind superconductivity and may also enable new applications4,5,6,7,8. Here our investigation shows that the application of pressure effectively suppresses the spin–charge order in trilayer nickelate La4Ni3O10−δ single crystals, leading to the emergence of superconductivity with a maximum critical temperature (Tc) of around 30 K at 69.0 GPa. The d.c. susceptibility measurements confirm a substantial diamagnetic response below Tc, indicating the presence of bulk superconductivity with a volume fraction exceeding 80%. In the normal state, we observe a strange metal behaviour, characterized by a linear temperature-dependent resistance extending up to 300 K. Furthermore, the layer-dependent superconductivity observed hints at a unique interlayer coupling mechanism specific to nickelates, setting them apart from cuprates in this regard. Our findings provide crucial insights into the fundamental mechanisms underpinning superconductivity, while also introducing a new material platform to explore the intricate interplay between the spin–charge order, flat band structures, interlayer coupling, strange metal behaviour and high-temperature superconductivity.
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Acknowledgements
This work was supported by the Key Program of the National Natural Science Foundation of China (grant no. 12234006), the National Key R&D Program of China (grant no. 2022YFA1403202), the Innovation Program for Quantum Science and Technology (grant no. 2024ZD0300103), the Beijing Natural Science Foundation (grant no. Z200005) and the Shanghai Municipal Science and Technology Major Project (grant no. 2019SHZDZX01). Y.Z. was supported by the Youth Foundation of the National Natural Science Foundation of China (grant no. 12304173). H.W. was supported by the Youth Foundation of the National Natural Science Foundation of China (grant no. 12204108). B.P. was supported by the Natural Science Foundation of Shandong Province (grant no. ZR2020YQ03). D.P. and Q.Z. acknowledge the financial support from the Shanghai Science and Technology Committee (no. 22JC1410300) and Shanghai Key Laboratory of Material Frontiers Research in Extreme Environments (no. 22dz2260800). A portion of this work was carried out at the Synergetic Extreme Condition User Facility (SECUF). A portion of this research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. A portion of this research used resources at the beamline 15U1 of Shanghai synchrotron radiation facility.
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J.Z. planned the project; Y.Z., E.Z. and L.C. synthesized the single-crystal samples; Y.Z., F. Liu, E.Z., L.C., H.W., Yiqing Gu and Yimeng Gu performed the thermodynamic and transport measurements at ambient conditions; E.Z., B.P., Xu Chen, D.P., W.W. and J.W. performed the resistance measurements under pressure with the support of J.G., Q.Z., L.J. and J.Z.; H.R., T.Y., Xiaolong Chen and Y.S. assisted the resistance measurement under pressure. D.P. and Z.X. conducted the susceptibility measurements under pressure with the support of Q.Z.; N.L., Y.Z., D.P. and F. Lan performed the synchrotron XRD measurements and analysis with the support of W.Y. and Q.Z.; J.H. and Y.Z. conducted the S/TEM characterization with the support of C.Z.; D.J., Y.Z. and Y.H. performed the in-house powder and single-crystal diffraction measurements under pressure and data analysis with the support of H.G., H.C. and J.Z.; Y.H. performed the neutron single-crystal diffraction measurements and data analysis; J.Z., Y.Z. and F. Liu analysed the data; and J.Z., B.P. and Y.Z. wrote the paper. All authors provided comments on the paper.
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Extended data figures and tables
Extended Data Fig. 1 XRD measurements of La4Ni3O10-δ single crystals and powdered single crystals.
a, XRD measurements of a La4Ni3O10-δ single crystal along the ab plane, revealing no detectable impurity phases. The measurements were carried out on a Bruker D8 Discover diffractometer, utilizing Cu Kα radiation. The inset displays a photograph of a La4Ni3O10-δ single crystal, grown using the high-pressure floating-zone method. b, Rietveld refinement of synchrotron-based powder XRD pattern of La4Ni3O10-δ at ambient pressure and room temperature. The olive solid lines and red circles represent the fitted and experimental data, respectively. The blue solid lines indicate the intensity difference between the data and calculations. The short vertical bars indicate the Bragg peak positions. The data can be well described with the space group P21/a. The data were collected using a powdered La4Ni3O10-δ single crystal. The refinement parameters are summarized in Supplementary Table 3.
Extended Data Fig. 2 Lab-based XRD measurements of a powdered La4Ni3O10-δ single crystal at various pressures at room temperature.
a, XRD measurements at various indicated pressures. The black arrows indicate the intensities from stainless steel. Upon releasing pressure to ambient condition, the diffraction pattern (black solid line) remains essentially unaltered in comparison to the data obtained prior to applying pressure, indicating that the process is reversible and the sample is stable against pressure. The structural transition observed in synchrotron-based XRD was not resolved in this measurement due to limited resolution. b, Measurements of empty cell with stainless steel gasket at indicated pressures at room temperature.
Extended Data Fig. 3 Synchrotron-based XRD measurements of powdered La4Ni3O10-δ single crystals under various pressures, using a helium DAC at room temperature.
a, XRD measurements under various pressures. b, An enlarge view of diffraction peaks within the range of 12.5° < 2θ < 14°, illustrating the merging of the monoclinic (0 2 0)M and (−2 0 1)M peaks into the tetragonal (1 1 0)T peak, a clear indication of the structural phase transition from monoclinic to tetragonal. c, Rietveld refinement of XRD pattern of La4Ni3O10-δ at 2.5 GPa. d, Rietveld refinement of XRD pattern of La4Ni3O10-δ at 34.0 GPa. The refinement parameters are summarized in Supplementary Table 3.
Extended Data Fig. 4 Temperature-dependent resistances of sample 4 (S4) in a helium DAC.
a, Temperature-dependent resistances of S4 under various pressures between 2 K and 300 K. b, Detailed resistance profile from 2 K to 150 K. Zero resistance below Tc is observed above 45 GPa. c, An enlarged view of the resistance curve below Tc, providing a closer examination of the zero-resistance state. The inset is a photograph depicting the electrodes used for the measurement.
Extended Data Fig. 5 Magnetic field effects on the superconducting transition in La4Ni3O10-δ in a KBr DAC.
a, Field dependences of electrical resistance at 57.3 GPa for sample S1. b, Field dependences of electrical resistance at 61.0 GPa for sample S2. c, Field dependences of electrical resistance at 69.0 GPa for sample S2. The green dashed lines depict the linear fit of the normal state resistances. d, The Ginzburg–Landau fittings of the upper critical fields at 57.3 (S1) and 69.0 GPa (S2). The magnetic fields are applied perpendicular to the ab plane.
Extended Data Fig. 6 STEM-HAADF and integrated differential phase contrast (iDPC) measurements of La4Ni3O10-δ crystals.
a, The cleavage plane of a La4Ni3O10-δ single crystal. b, The STEM-HAADF image of a La4Ni3O10-δ crystal along the [110] direction on the scale of 5 nm. c, Atomic EDX mapping results and STEM-HAADF image in the same region. d, The STEM-HAADF image of La4Ni3O10-δ sample along the [110] direction on the scale of 2 nm. e, iDPC result in the same region and f, an enlarged view of the iDPC image. The oxygen atoms are clearly revealed through the iDPC imaging, aligning well with the crystal structure of La4Ni3O10-δ determined by neutron diffraction and XRD measurements.
Extended Data Fig. 7 Single-crystal refinements using neutron and X-ray diffraction data for La4Ni3O10-δ.
a, Combined single-crystal refinement results using neutron and X-ray diffraction data for La4Ni3O10-δ. The integrated intensities of Bragg reflections from a La4Ni3O10-δ single crystal, collected at room temperature and ambient pressure, are plotted against their calculated counterparts. Details of the refined parameters are provided in Supplementary Table 1. b, Single-crystal refinements of X-ray diffraction data. Integrated intensities of the Bragg reflections collected on a La4Ni3O10-δ single crystal at room temperature and 19.5 GPa are plotted against their calculated counterparts. The refinement parameters are summarized in Supplementary Table 2. The refinements suggest a structural phase transition from monoclinic P21/a to tetragonal I4/mmm in La4Ni3O10-δ under pressure.
Extended Data Fig. 8 Temperature-dependendent d.c. susceptibilities of sample 5 (S5) under various pressures.
a, Temperature dependent magnetization curves at 38.0 GPa under a magnetic field of 20 Oe applied perpendicular to the ab plane using the zero-field-cooled (ZFC) and field-cooled (FC) modes. The inset shows the photo of the crystal in the nitrogen mini-DAC. b, 40.0 GPa and 10 Oe. c, 42.0 GPa and 20 Oe. d, 50.0 GPa and 10 Oe. The black arrows indicate the superconducting transition temperatures. The broadening of the superconducting transition with increasing pressure could be attributed to the gradual deterioration of hydrostaticity in the nitrogen pressure-transmitting medium. This broadening is less pronounced in a smaller sample (S6), which contains more pressure-transmitting medium and, consequently, exhibits improved hydrostaticity (Fig. 3f–i).
Extended Data Fig. 9 Temperature dependent superconducting volume fractions of La4Ni3O10-δ single crystals determined through d.c. susceptibility measurements in Fig. 3 (S6) and Extended Data Fig. 8 (S5).
Superconducting volume fractions for S6 under a, 40.0 GPa; b, 47.0 GPa; c, 50.0 GPa; d, 55.0 GPa. Superconducting volume fractions for S5 under e, 38.0 GPa; f, 40.0 GPa; g, 42.0 GPa; h, 50.0 GPa.
Extended Data Fig. 10 Temperature-dependendent magnetization curves of sample 7 (S7) under various pressures under a magnetic field applied perpendicular to the ab plane using the zero-field-cooled (ZFC) and field-cooled (FC) modes.
a, 2.0 GPa and10 Oe b, 2.0 GPa 20 Oe. Temperature dependent magnetization curves at 5.0 GPa under magnetic fields of c, 5.0 GPa and 20 Oe and d, 5.0 GPa and 50 Oe. e, 15.0 GPa and 5 Oe; f, 15.0 GPa and 20 Oe; g, 15.0 GPa and 50 Oe; h, 15.0 GPa and 100 Oe. i, 30.0 GPa and 5 Oe; j, 30.0 GPa and 20 Oe; k, 30.0 GPa and 50 Oe; l, 30.0 GPa and 100 Oe. m, 49.0 GPa and 5 Oe; n, 49.0 GPa and 10 Oe; o, 49.0 GPa and 20 Oe; p, 49.0 GPa and 100 Oe. The inset shows the photo of the crystal in the mini-DAC.
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Zhu, Y., Peng, D., Zhang, E. et al. Superconductivity in pressurized trilayer La4Ni3O10−δ single crystals. Nature 631, 531–536 (2024). https://doi.org/10.1038/s41586-024-07553-3
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DOI: https://doi.org/10.1038/s41586-024-07553-3
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