Abstract
The Ruddlesden–Popper (R–P) bilayer nickelate, La3Ni2O7, was recently found to show signatures of high-temperature superconductivity (HTSC) at pressures above 14 GPa (ref. 1). Subsequent investigations achieved zero resistance in single-crystalline and polycrystalline samples under hydrostatic pressure conditions2,3,4. Yet, obvious diamagnetic signals, the other hallmark of superconductors, are still lacking owing to the filamentary nature with low superconducting volume fraction2,4,5. The presence of a new 1313 polymorph and competing R–P phases obscured proper identification of the phase for HTSC6,7,8,9. Thus, achieving bulk HTSC and identifying the phase at play are the most prominent tasks. Here we address these issues in the praseodymium (Pr)-doped La2PrNi2O7 polycrystalline samples. We find that substitutions of Pr for La effectively inhibit the intergrowth of different R–P phases, resulting in a nearly pure bilayer structure. For La2PrNi2O7, pressure-induced orthorhombic to tetragonal structural transition takes place at Pc ≈ 11 GPa, above which HTSC emerges gradually on further compression. The superconducting transition temperatures at 18–20 GPa reach \({T}_{{\rm{c}}}^{{\rm{onset}}}=82.5\,{\rm{K}}\) and \({T}_{{\rm{c}}}^{{\rm{zero}}}=60\,{\rm{K}}\), which are the highest values, to our knowledge, among known nickelate superconductors. Importantly, bulk HTSC was testified by detecting clear diamagnetic signals below about 75 K with appreciable superconducting shielding volume fractions at a pressure of above 15 GPa. Our results not only resolve the existing controversies but also provide directions for exploring bulk HTSC in the bilayer nickelates.
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Acknowledgements
This work is supported by the National Key Research and Development Program of China (2023YFA1406100, 2021YFA1400200, 2023YFA1607400 and 2022YFA1403402), National Natural Science Foundation of China (12025408, 11921004, U23A6003, U22A6005, 12174424, 12374142, 12304170, 12074414 and 12304075), the Strategic Priority Research Program of CAS (XDB33000000), the Specific Research Assistant Funding Program of CAS (E3VP011X61), the Postdoctoral Fellowship Program of China Postdoctoral Science Foundation (GZB20230828), the China Postdoctoral Science Foundation (2023M743740), CAS PIFI program (2024PG0003) and the Outstanding member of Youth Promotion Association of CAS (Y2022004). J. Hu was supported by the New Cornerstone Investigator Program. J. Yan was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Division of Materials Sciences and Engineering. The high-pressure transport and the NQR experiments were, respectively, performed at the Cubic Anvil Cell station and the High Field Nuclear Magnetic Resonance station of Synergic Extreme Condition User Facility. High-pressure synchrotron XRD measurements were performed at the 4W2 High Pressure Station, Beijing Synchrotron Radiation Facility and the BL15U1 station of Shanghai Synchrotron Radiation Facility. This research used resources at the High Flux Isotope Reactor, a US DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.
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J.C. designed and supervised this project. N.W. and G.W. synthesized the materials and characterized their structure using XRD and EDX; N.W., G.W., Y.L., H.Z. and X.D. measured the physical properties at ambient pressure; N.W., G.W. and J. Hou performed high-pressure resistivity measurements by using the cubic anvil cell apparatus with the support of H.M., P.Y., Z.L., J.S. and B.W.; N.W., G.W. and L.S. performed high-pressure SXRD measurements; X.S. J. Hou, S.N., K.K. and Y.U. performed high-pressure resistivity and a.c. magnetic susceptibility measurements by using the multianvil apparatus; N.W., G.W. and J.C. analysed all the collected data; J.L., J.D., J.F., J.Y. and R.Z. carried out the NQR measurements; R.Z. analysed the NQR data; X.M. and H.Y. performed the HAADF-STEM measurements and data analyses; Y.S. and Z.R. measured the TGA data; S.C. and J. Yan measured and analysed the NPD data; Y.W., K.J. and J. Hu gave advice from a theoretical perspective; J.C., N.W., G.W. and R.Z. wrote the paper with inputs from all co-authors.
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Extended data figures and tables
Extended Data Fig. 1 139La-NQR spectrum for the La3Ni2O7-δ sample at 188 K.
Four distinct pairs of resonance peaks are observed, denoted by four sets of arrows, indicating the existence of four unique La(2) sites within the sample. Owing to a broader linewidth, only one resonance peak corresponding to 7/2 – 5/2 transition is observed in the spectrum for the La(1) site. The solid lines represent fits obtained using Lorentz functions.
Extended Data Fig. 2 Rietveld refinements on the La3-xPrxNi2O7-δ (x = 0, 0.3, 1.0) samples.
a,b, Refinement results of XRD and NPD patterns with the space group Amam. c,d, The obtained unit-cell parameters and volume as a function of the Pr-content x from the NPD data. e,f, Ni-O bond lengths and Ni-O-Ni bond angles as a function of the Pr-content x from the NPD data. According to the NPD refinement results, no site preference for Pr was detected and the oxygen vacancies at the inner apical O1 sites decrease gradually with increasing the Pr content.
Extended Data Fig. 3 ρ(T) of La3-xPrxNi2O7-δ at ambient pressure.
Temperature dependence of ρ(T) increases gradually with increasing the Pr-content x in the La3-xPrxNi2O7-δ (x = 0, 0.3, 1.0) samples.
Extended Data Fig. 4 EDX and TGA results of the La2PrNi2O7 sample.
a–d, EDX mapping patterns showing the uniform distribution of La, Pr, and Ni elements. Each colour represents a specific element; the mapping image illustrates the spatial distribution of elements within the sample. e,f, Analysis of the TGA data revealed a negligible oxygen deficiency with δ ≈ 0.02(1) for La2PrNi2O7-δ, which is smaller than the δ ≈ 0.07 for La3Ni2O7-δ prepared in the similar conditions. The thermal decomposition behaviour is similar to that in La3Ni2O7-δ.
Extended Data Fig. 5 Refinement results on HP SXRD of La2PrNi2O7.
a,b, Rietveld refinements on the HP SXRD patterns of La2PrNi2O7 by using orthorhombic Fmmm and tetragonal I4/mmm space group under (a) 17.3 GPa and (b) 19.5 GPa. c, Comparison of the obtained lattice parameters (a and b) as a function of the pressure. Although both space groups can refine the data equally well, the refinement results using the orthorhombic Fmmm space group at higher pressures show that a and b merge together, indicating the symmetry of the crystal structure has changed.
Extended Data Fig. 6 Effects of magnetic field and electrical current on the superconducting transition of La2PrNi2O7 under high pressures.
a, The low-temperature ρ(T) at 15 GPa under various magnetic fields up to 8.5 T. b, Temperature dependence of the upper critical field μ0Hc2(T) at 15 GPa. The solid line is the fitting curve by using the formula Hc2 = Hc2(0)(1 − t2)/(1 + t2), where t = T/Tc. c, The low-temperature ρ(T) at 19 GPa of sample #2 measured with different currents, which shows that Tczero can be gradually inhibited by increasing electrical currents.
Extended Data Fig. 7 Ac magnetic susceptibility χ′(T) of FeSe single crystal and La2PrNi2O7 sample #4.
a, The χ′(T) data of the FeSe single crystals together with a piece of Pb measured at ambient pressure (Run1) and b, under hydrostatic pressures up to 12 GP with the mutual induction method in CAC (Run2). The inset of a shows the photo of the pick-up coil filled with FeSe and Pb for Run1. c, The χ′(T) of La2PrNi2O7 sample #4 together with a piece of FeSe single crystals measured under hydrostatic pressures up to 20 GP with the mutual induction method in MA. Note that the fsc ~ 57(6)% at 20 GPa observed for this sample is smaller than ~97(10)% at 19 GPa for sample #3. In addition, the superconducting diamagnetic responses of χ′(T) around Tc for these two samples show distinct behaviours. Although these observations indicate some sample-dependent behaviours for the La2PrNi2O7 polycrystalline samples, the appreciable fsc values for these two independent measurements confirm the bulk nature of observed HTSC.
Extended Data Fig. 8 T-P phase diagram.
Pressure dependence of Tc for the La2PrNi2O7 in comparison with that of La3Ni2O7-δ polycrystalline samples. The open and filled symbols represent the onset and zero-resistance superconducting transition temperatures of La2PrNi2O7 determined from the ρ(T) measurements in CAC and MA. The marks for La3Ni2O7-δ are taken from our previous study4. The initial slope of dTczero/dP ~ 10 K/GPa for La2PrNi2O7 is much larger than that of ~ 4.5 K/GPa for La3Ni2O7-δ.
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Wang, N., Wang, G., Shen, X. et al. Bulk high-temperature superconductivity in pressurized tetragonal La2PrNi2O7. Nature (2024). https://doi.org/10.1038/s41586-024-07996-8
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DOI: https://doi.org/10.1038/s41586-024-07996-8
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