Linear-in-temperature resistivity for optimally superconducting (Nd,Sr)NiO2.

The occurrence of superconductivity in proximity to various strongly correlated phases of matter has drawn extensive focus on their normal state properties, to develop an understanding of the state from which superconductivity emerges1-4. The recent finding of superconductivity in layered nickelates raises similar interests5-8. However, transport measurements of doped infinite-layer nickelate thin films have been hampered by materials limitations of these metastable compounds: in particular, a high density of extended defects9-11. Here, by moving to a substrate (LaAlO3)0.3(Sr2TaAlO6)0.7 that better stabilizes the growth and reduction conditions, we can synthesize the doping series of Nd1-xSrxNiO2 essentially free from extended defects. In their absence, the normal state resistivity shows a low-temperature upturn in the underdoped regime, linear behaviour near optimal doping and quadratic temperature dependence for overdoping. This is phenomenologically similar to the copper oxides2,12 despite key distinctions-namely, the absence of an insulating parent compound5,6,9,10, multiband electronic structure13,14 and a Mott-Hubbard orbital alignment rather than the charge-transfer insulator of the copper oxides15,16. We further observe an enhancement of superconductivity, both in terms of transition temperature and range of doping. These results indicate a convergence in the electronic properties of both superconducting families as the scale of disorder in the nickelates is reduced.

Effects of rare-earth magnetism on the superconducting upper critical field in infinite-layer nickelates.

The search for superconductivity in infinite-layer nickelates was motivated by analogy to the cuprates, and this perspective has framed much of the initial consideration of this material. However, a growing number of studies have highlighted the involvement of rare-earth orbitals; in that context, the consequences of varying the rare-earth element in the superconducting nickelates have been much debated. Here, we show notable differences in the magnitude and anisotropy of the superconducting upper critical field across the La-, Pr-, and Nd-nickelates. These distinctions originate from the 4f electron characteristics of the rare-earth ions in the lattice: They are absent for La3+, nonmagnetic for the Pr3+ singlet ground state, and magnetic for the Nd3+ Kramer's doublet. The unique polar and azimuthal angle-dependent magnetoresistance found in the Nd-nickelates can be understood to arise from the magnetic contribution of the Nd3+ 4f moments. Such robust and tunable superconductivity suggests potential in future high-field applications.

Resolving the polar interface of infinite-layer nickelate thin films.

Nickel-based superconductors provide a long-awaited experimental platform to explore possible cuprate-like superconductivity. Despite similar crystal structure and d electron filling, however, superconductivity in nickelates has thus far only been stabilized in thin-film geometry, raising questions about the polar interface between substrate and thin film. Here we conduct a detailed experimental and theoretical study of the prototypical interface between Nd1-xSrxNiO2 and SrTiO3. Atomic-resolution electron energy loss spectroscopy in the scanning transmission electron microscope reveals the formation of a single intermediate Nd(Ti,Ni)O3 layer. Density functional theory calculations with a Hubbard U term show how the observed structure alleviates the polar discontinuity. We explore the effects of oxygen occupancy, hole doping and cation structure to disentangle the contributions of each for reducing interface charge density. Resolving the non-trivial interface structure will be instructive for future synthesis of nickelate films on other substrates and in vertical heterostructures.

Geometric frustration of Jahn-Teller order in the infinite-layer lattice.

The Jahn-Teller effect, in which electronic configurations with energetically degenerate orbitals induce lattice distortions to lift this degeneracy, has a key role in many symmetry-lowering crystal deformations1. Lattices of Jahn-Teller ions can induce a cooperative distortion, as exemplified by LaMnO3 (refs. 2,3). Although many examples occur in octahedrally4 or tetrahedrally5 coordinated transition metal oxides due to their high orbital degeneracy, this effect has yet to be manifested for square-planar anion coordination, as found in infinite-layer copper6,7, nickel8,9, iron10,11 and manganese oxides12. Here we synthesize single-crystal CaCoO2 thin films by topotactic reduction of the brownmillerite CaCoO2.5 phase. We observe a markedly distorted infinite-layer structure, with ångström-scale displacements of the cations from their high-symmetry positions. This can be understood to originate from the Jahn-Teller degeneracy of the dxz and dyz orbitals in the d7 electronic configuration along with substantial ligand-transition metal mixing. A complex pattern of distortions arises in a [Formula: see text] tetragonal supercell, reflecting the competition between an ordered Jahn-Teller effect on the CoO2 sublattice and the geometric frustration of the associated displacements of the Ca sublattice, which are strongly coupled in the absence of apical oxygen. As a result of this competition, the CaCoO2 structure forms an extended two-in-two-out type of Co distortion following 'ice rules'13.

Nickelate Superconductivity without Rare-Earth Magnetism: (La,Sr)NiO2.

The occurrence of unconventional superconductivity in cuprates has long motivated the search for manifestations in other layered transition metal oxides. Recently, superconductivity is found in infinite-layer nickelate (Nd,Sr)NiO2 and (Pr,Sr)NiO2 thin films, formed by topotactic reduction from the perovskite precursor phase. A topic of much current interest is whether rare-earth moments are essential for superconductivity in this system. In this study, it is found that with significant materials optimization, substantial portions of the La1- x Srx NiO2 phase diagram can enter the regime of coherent low-temperature transport (x = 0.14 - 0.20), with subsequent superconducting transitions and a maximum onset of ≈9 K at x = 0.20. Additionally, the unexpected indication of a superconducting ground state in undoped LaNiO2 is observed, which likely reflects the self-doped nature of the electronic structure. Combining the results of (La/Pr/Nd)1- x Srx NiO2 reveals a generalized superconducting dome, characterized by systematic shifts in the unit cell volume and in the relative electron-hole populations across the lanthanides.

Doping evolution of the Mott-Hubbard landscape in infinite-layer nickelates.

The recent observation of superconductivity in [Formula: see text] has raised fundamental questions about the hierarchy of the underlying electronic structure. Calculations suggest that this system falls in the Mott-Hubbard regime, rather than the charge-transfer configuration of other nickel oxides and the superconducting cuprates. Here, we use state-of-the-art, locally resolved electron energy-loss spectroscopy to directly probe the Mott-Hubbard character of [Formula: see text] Upon doping, we observe emergent hybridization reminiscent of the Zhang-Rice singlet via the oxygen-projected states, modification of the Nd 5d states, and the systematic evolution of Ni 3d hybridization and filling. These experimental data provide direct evidence for the multiband electronic structure of the superconducting infinite-layer nickelates, particularly via the effects of hole doping on not only the oxygen but also nickel and rare-earth bands.

Superconducting Dome in Nd_{1-x}Sr_{x}NiO_{2} Infinite Layer Films.

We report the phase diagram of Nd_{1-x}Sr_{x}NiO_{2} infinite layer thin films grown on SrTiO_{3}. A superconducting dome spanning 0.125

A Superconducting Praseodymium Nickelate with Infinite Layer Structure.

A variety of nickel oxide compounds have long been studied for their manifestation of various correlated electron phenomena. Recently, superconductivity was observed in nanoscale infinite layer nickelate thin films of Nd0.8Sr0.2NiO2, epitaxially stabilized on SrTiO3 substrates via topotactic reduction from the perovskite precursor phase. Here, we present the synthesis and properties of PrNiO2 thin films on SrTiO3. Upon doping in Pr0.8Sr0.2NiO2, we observe superconductivity with a transition temperature of 7-12 K and robust critical current density at 2 K of 334 kA/cm2. These findings indicate that superconductivity in the infinite layer nickelates is relatively insensitive to the details of the rare earth 4f configuration. Furthermore, they motivate the exploration of a broader family of compounds based on two-dimensional NiO2 planes, which will enable systematic investigation of the superconducting and normal state properties and their underlying mechanisms.

Superconductivity in an infinite-layer nickelate.

The discovery of unconventional superconductivity in (La,Ba)2CuO4 (ref. 1) has motivated the study of compounds with similar crystal and electronic structure, with the aim of finding additional superconductors and understanding the origins of copper oxide superconductivity. Isostructural examples include bulk superconducting Sr2RuO4 (ref. 2) and surface-electron-doped Sr2IrO4, which exhibits spectroscopic signatures consistent with a superconducting gap3,4, although a zero-resistance state has not yet been observed. This approach has also led to the theoretical investigation of nickelates5,6, as well as thin-film heterostructures designed to host superconductivity. One such structure is the LaAlO3/LaNiO3 superlattice7-9, which has been recently proposed for the creation of an artificially layered nickelate heterostructure with a singly occupied [Formula: see text] band. The absence of superconductivity observed in previous related experiments has been attributed, at least in part, to incomplete polarization of the eg orbitals10. Here we report the observation of superconductivity in an infinite-layer nickelate that is isostructural to infinite-layer copper oxides11-13. Using soft-chemistry topotactic reduction14-20, NdNiO2 and Nd0.8Sr0.2NiO2 single-crystal thin films are synthesized by reducing the perovskite precursor phase. Whereas NdNiO2 exhibits a resistive upturn at low temperature, measurements of the resistivity, critical current density and magnetic-field response of Nd0.8Sr0.2NiO2 indicate a superconducting transition temperature of about 9 to 15 kelvin. Because this compound is a member of a series of reduced layered nickelate crystal structures21-23, these results suggest the possibility of a family of nickelate superconductors analogous to copper oxides24 and pnictides25.

Oxygen Evolution Reaction Activity in IrO x/SrIrO3 Catalysts: Correlations between Structural Parameters and the Catalytic Activity.

Understanding how structural properties affect the oxygen evolution reaction (OER) of a catalyst can reveal important information not only on the catalytic mechanism but also on the general design strategy of OER catalysts. We report a variation of ∼0.15 V in the overpotential of the recently discovered IrO x/SrIrO3 OER catalysts, which directly correlates with the structural parameters of the as-synthesized SrIrO3 epitaxial films. This variation is caused by both extrinsic area enhancement and intrinsic electronic structure modification driven by defect formation. These correlations not only indicate that microscopic film defects play an important role in the activity of the IrO x/SrIrO3 catalyst but also provide readily accessible parameters predictive of the activity post-transformation to IrO x/SrIrO3. Establishing strong associations between the catalytic activity and key structural and electronic parameters, rather than synthetic variables, provides important guidance to control and study these complex catalysts independent of the synthetic technique.