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Since the discovery of high-temperature superconductivity in copper oxide materials, there have been sustained efforts to both understand the origins of this phase and discover new cuprate-like superconducting materials. One prime materials platform has been the rare-earth nickelates and, indeed, superconductivity was recently discovered in the doped compound NdSrNiO (ref. ). Undoped NdNiO belongs to a series of layered square-planar nickelates with chemical formula NdNiO and is known as the 'infinite-layer' (n = ∞) nickelate. Here we report the synthesis of the quintuple-layer (n = 5) member of this series, NdNiO, in which optimal cuprate-like electron filling (d) 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 NdNiO 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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http://dx.doi.org/10.1038/s41563-021-01142-9 | DOI Listing |
Adv Mater
April 2025
Universitè de Strasbourg, CNRS, IPCMS UMR 7504, Strasbourg, F-67034, France.
Several reports about infinite-layer nickelate thin films suggest that the superconducting critical temperature versus chemical doping phase diagram has a dome-like shape, similar to cuprates. Here, a highly reproducible superconducting state in undoped PrNiO thin films grown on SrTiO are demonstrated. Scanning transmission electron microscopy measurements show coherent infinite-layer phase with no visible stacking-fault defects, an overall high structural quality where possible unintentional chemical doping or interstitial oxygen, if present, sum well below the measurable threshold of the technique.
View Article and Find Full Text PDFChem Sci
March 2025
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany
The coordination chemistry of carbene-CS adducts of selected NHCs and cAACs and their redox active nature in nickel complexes is reported. These azolium-2-dithiocarboxylate ligands can be considered as 1,1-isomeric dithiolene analogues bearing a 2π electron reservoir. Depending on the co-ligands attached to nickel, square planar mono- or bis-(carbene-CS) complexes of the types [Ni(IPr)(carbene-CS)] (2a-g) (carbene = cAAC, IDipp, IMes, BIMe, BIPr, IPr, and IPr) and [Ni(carbene-CS)] (3a-c) (carbene = cAAC, IDipp, and IMes) are accessible by alkene substitution using [Ni(IPr)(ƞ-CH)] or [Ni(COD)] as the starting material (cAAC = 1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene, IR = 1,3-diorganylimidazolin-2-ylidene, IR = 1,3-diorganyl-4,5-dimethylimidazolin-2-ylidene, and BIR = 1,3-diorganylbenzimidazolin-2-ylidene).
View Article and Find Full Text PDFSci Adv
January 2025
Materials Science Division, Argonne National Laboratory, Lemont, IL 60439, USA.
We report the appearance of superconductivity in single-unit-cell NdNiO, exhibiting a transition temperature similar to that of thicker films. In situ synchrotron x-ray scattering performed during growth of the parent phase, NdNiO, shows that the necessary layer-by-layer deposition sequence does not follow the sequence of the formula unit but an alternate order due to the relative stability of the perovskite unit cell. We exploit this insight to grow ultrathin NdNiO heterostructures and conduct in situ studies of topotactic reduction, finding that formation of the square-planar phase occurs rapidly and is highly sensitive to reduction temperature, with small deviations from the optimum condition leading to inhomogeneity and the loss of superconductivity.
View Article and Find Full Text PDFAdv Mater
October 2024
X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, IL, 60439, USA.
Nat Commun
August 2024
NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD, 20899, USA.