The recent observation of superconductivity in Nd$_{0.8}$Sr$_{0.2}$NiO$_2$ 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 Nd$_{1-x}$Sr$_x$NiO$_2$. Upon doping, we observe emergent hybridization reminiscent of the Zhang-Rice singlet via the oxygen-projected states, modification of the Nd 5$d$ states, and the systematic evolution of Ni 3$d$ hybridization and filling. These results clearly evidence the multiband nature of this system and the distinct electronic landscape for infinite-layer nickelates despite their formal similarity to the cuprates.
The interplay between superconductivity and charge density waves (CDWs) under hole doping in cuprates is one of the central phenomena in condensed matter physics. Recently, CDWs are also observed in CaCuO$_2$-analogous nickelates RNiO$_2$ (R = La, Nd) but exhibit fundamentally different hole-doping-dependent behaviors compared to that in cuprates, raising a challenging question on its origin. In this article, we propose that electronic instability (EI) and moment-dependent electron-phonon coupling (MEPC), mainly contributed by Ni 3dx2-y2 and R 5dz2, respectively, may be the possible reasons fo…
Based on first-principles calculations including a Coulomb repulsion term, we identify trends in the electronic reconstruction of $A$NiO$_2$/SrTiO$_3$(001) ($A=$ Pr, La) and $A$CuO$_2$/SrTiO$_3$(001) ($A=$ Ca, Sr). Common to all cases is the emergence of a quasi-two-dimensional electron gas (q2DEG) in SrTiO$_3$(001), albeit the higher polarity mismatch at the interface of nickelates vs. cuprates to the nonpolar SrTiO$_3(001)$ substrate (${3+}/0$ vs. ${2+}/0$) results in an enhanced q2DEG carrier density. The simulations reveal a significant dependence of the interfacial Ti $3d_{xy}$ band bendi…
The correlated electronic structure of the infinite-layer compounds NdNiO$_2$ and SrCuO$_2$ at stoichiometry and with finite hole doping is compared. Key differences are elucidated from an advanced first-principles many-body perspective. Contrary to the charge-transfer insulating cuprate, the self-doped nickelate remains non-insulating even for large interaction strength, though the Ni-$d_{x^2-y^2}$ spectral weight is also gapped in that limit. Hybridization between Ni$(3d)$ and Nd$(5d)$ is crucial for the appearance of the self-doping band. Upon realistic hole doping, Sr$_{1-y}$CuO$_2$ shows …
The recent discovery of high-T$_{c}$ superconductivity (HTS) in Sr-doped NdNiO$_2$ has sparked a renewed interest in investigating nickelates as cuprate counterparts. Parent cuprates [Cu$^{2+}$: d$^9$] are antiferromagnetic charge-transfer insulators with the involvement of a single d$_{x^2-y^2}$ band around the Fermi level and strong $p-d$ hybridization. In contrast, isoelectronic NdNiO$_2$ [Ni$^+$: d$^9$] is metallic with a d$_{x^2-y^2}$ band self-doped by Nd-d states. Using first-principles calculations, we study the effect of Sr-doping in the electronic and magnetic properties of infinite-…
We give a brief review of the Mott-Kondo scenario and its consequence in the recently-discovered infinite-layer nickelate superconductors. We argue that the parent state is a self-doped Mott insulator and propose an effective $t$-$J$-$K$ model to account for its low-energy properties. At small doping, the model describes a low carrier density Kondo system with incoherent Kondo scattering at finite temperatures, in good agreement with experimental observation of the logarithmic temperature dependence of electric resistivity. Upon increasing Sr doping, the model predicts a breakdown of the Kondo…
We propose the parent compound of the newly discovered superconducting nickelate Nd$_{1-x}$Sr$_{x}$NiO$_{2}$ as a self-doped Mott insulator, in which the low-density Nd-$5d$ conduction electrons couple to localized Ni-3$% d_{x^{2}-y^{2}}$ electrons to form Kondo spin singlets at low temperatures. This proposal is motivated with our analyses of the reported resistivity and Hall coefficient data in the normal state, showing logarithmic temperature dependence at low temperatures. In the strong Kondo coupling limit, we derive a generalized $t$-$J$ model with both Kondo singlets and nickel holons m…
We perform core-level X-ray photoemission spectroscopy (XPS) and electronic Raman scattering studies of electronic structures and spin fluctuations in the bulk samples of the nickelate oxide NdNiO$_2$. According to Nd $3d$ and O $1s$ XPS spectra, we conclude that NdNiO$_2$ has a large transfer energy. From the analysis of the main line of the Ni $2p_{3/2}$ XPS, we confirm the NiO$_2$ planes in NdNiO$_2$ are of Mott-Hubbard type in the Zaanen-Sawatzky-Allen scheme. The two-magnon peak in the Raman scattering provides direct evidence for the strong spin-fluctuation in NdNiO$_2$. The peak positio…
Magnetism and superconductivity are closely entangled, elucidating the magnetic interactions in nickelate superconductors is at the heart of understanding the pairing mechanism. Our first-principles and spin-wave theory calculations highlight that NdNiO$_2$ is in the vicinity of a transition between a quasi-two-dimensional (2D) antiferromagnetic (AFM) state and a three-dimensional (3D) C-AFM state. Both states could accurately reproduce the experimentally measured magnetic excitation spectra, which was previously explained in terms of a 2D model. We further reveal that hole doping stabilizes a…
To understand the superconductivity recently discovered in Nd$_{0.8}$Sr$_{0.2}$NiO$_2$, we carried out LDA+DMFT (local density approximation plus dynamical mean-field theory) and magnetic force response calculations. The on-site correlation in Ni-$3d$ orbitals causes notable changes in the electronic structure. The calculated temperature-dependent susceptibility exhibits the Curie-Weiss behavior, indicating the localized character of its moment. From the low-frequency behavior of self-energy, we conclude that the undoped phase of this nickelate is Fermi-liquid-like contrary to cuprates. Intere…
Motivated by the recent discovery of superconductivity in doped NdNiO$_2$, we study the magnetic exchange interaction $J$ in layered $d^9$ nickelates from first principles. The mother compounds of the high-$T_{\rm c}$ cuprates belong to the charge-transfer regime in the Zaanen-Sawatzky-Allen diagram and have $J$ larger than 100 meV. While this feature makes the cuprates very different from other transition metal oxides, it is of great interest whether layered $d^9$ nickelates can also have such a large $J$. However, one complexity is that NdNiO$_2$ is not a Mott insulator due to carrier doping…
Heterostructuring as Gateway to Electron Doping of Nickelate Superconductors
Northwest University（西北大学）；University of Hyogo（兵库大学）；Kyushu Institute of Technology（九州工业大学）；Soochow University（苏州大学）；Universität Würzburg（维尔茨堡大学）；Southeast University（东南大学）；University of Science and Technology of China（中国科学技术大学）；TU Wien（维也纳工业大学）
The recent observation of superconductivity in infinite-layer Nd$_{1-x}$Sr$_x$NiO$_2$ thin films has attracted a lot of attention, since this compound is electronically and structurally analogous to the superconducting cuprates. Due to the challenges in the phase stabilization upon chemical doping with Sr, we synthesized artificial superlattices of LaNiO$_3$ embedded in insulating LaGaO$_3$, and used layer-selective topotactic reactions to reduce the nickelate layers to LaNiO$_{2}$. Hole doping is achieved via interfacial oxygen atoms and tuned via the layer thickness. We used electrical trans…
Doping dependence of local moments in infinite layer nickelates
Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory（斯坦福材料与能源科学研究所，SLAC国家加速器实验室）；Stanford University（斯坦福大学）；PSI Center for Neutron and Muon Sciences（瑞士保罗谢勒研究所中子与μ子科学中心）；Northwestern University（西北大学）；Laboratoire de Physique des Solides, Université Paris-Saclay, CNRS UMR 8502（巴黎萨克雷大学固体物理实验室，CNRS UMR 8502）；Department of Applied Physics, Stanford University（斯坦福大学应用物理系）
Motivated by the recent discovery of superconductivity in the pentalayer nickelate Nd$_6$Ni$_5$O$_{12}$ [Nature Materials 10.1038], we calculate its electronic structure and superconducting critical temperature. We find that electronic correlations are essential for pushing Nd$_6$Ni$_5$O$_{12}$ into the superconducting doping range as they shift the electron pockets above the Fermi energy. As a consequence, Nd$_6$Ni$_5$O$_{12}$ can be described with a single $d_{x^2-y^2}$ orbital per Ni. Instead, for the bilayer nickelate Nd$_3$Ni$_2$O$_6$ we find correlations to drive the system into a three-…
We report theoretical predictions on the pairing symmetry of the newly discovered superconducting nickelate Nd$_{1-x}$Sr$_{x}$NiO$_{2}$ based on the renormalized mean-field theory for a generalized model Hamiltonian proposed in [Phys. Rev. B \textbf{101}, 020501(R)]. For practical values of the key parameters, we find a transition between a gapped ($d+is$)-wave pairing state in the small doping region to a gapless $d$-wave pairing state in the large doping region, accompanied by an abrupt Fermi surface change at the critical doping. Our overall phase diagram also shows the possibility of a ($d…
High temperature superconductivity in cuprates arises from doping a parent Mott insulator by electrons or holes. A central issue is how the Mott gap evolves and the low-energy states emerge with doping. Here we report angle-resolved photoemission spectroscopy measurements on a cuprate parent compound by sequential in situ electron doping. The chemical potential jumps to the bottom of the upper Hubbard band upon a slight electron doping, making it possible to directly visualize the charge transfer band and the full Mott gap region. With increasing doping, the Mott gap rapidly collapses due to t…
Since the discovery of high-temperature superconductivity in the copper oxide materials, there have been sustained efforts to both understand the origins of this phase and discover new cuprate-like superconducting materials. One prime materials platform has been the rare-earth nickelates and indeed superconductivity was recently discovered in the doped compound Nd$_{0.8}$Sr$_{0.2}$NiO$_2$. Undoped NdNiO$_2$ belongs to a series of layered square-planar nickelates with chemical formula Nd$_{n+1}$Ni$_n$O$_{2n+2}$ and is known as the 'infinite-layer' ($n = \infty$) nickelate. Here, we report the s…
Since the discovery of superconductivity in infinite-layer nickelates RNiO$_2$ (R=La, Pr, Nd), great research efforts have been paid to unveil its underlying superconducting mechanism. However, the physical origin of the intriguing hole-doped superconductivity phase diagram, characterized by a superconductivity dome sandwiched between two weak insulators, is still unclear. Here, we present a microscopic theory for electronic structure of nickelates from a fundamental model-based perspective. We found that the appearance of weak insulator phase in lightly and heavily hole-doped regime is domina…
We report the observation of superconductivity in infinite-layer Ca-doped LaNiO$_2$ (La$_{1-x}$Ca$_x$NiO$_2$) thin films and construct their phase diagram. Unlike the metal-insulator transition in Nd- and Pr-based nickelates, the undoped and underdoped La1-xCaxNiO2 thin films are entirely insulating from 300 K down to 2 K. A superconducting dome is observed at 0.15<x<0.3 with weakly insulating behavior at the overdoped regime. Moreover, the sign of the Hall coefficient $R_H$ changes at low temperature for samples with a higher doping level. However, distinct from the Nd- and Pr-based nickelate…
Motivated by the recent discovery of superconductivity in the Sr-doped layered nickelate NdNiO$_2$, we perform a systematic computational materials design of layered nickelates that are dynamically stable and whose electronic structure better mimics the electronic structure of high-$T_c$ cuprates than NdNiO$_2$. While the Ni $3d$ orbitals are self-doped from the $d^9$ configuration in NdNiO$_2$ and the Nd-layer states form Fermi pockets, we find more than 10 promising compounds for which the self-doping is almost or even completely suppressed. We derive effective single-band models for those m…
The discovery of superconductivity in infinite-layer nickelates has added a new family of materials to the fascinating growing class of unconventional superconductors. By incorporating the strongly correlated multi-orbital nature of the low-energy electronic degrees of freedom, we compute the leading superconducting instability from magnetic fluctuations relevant for infinite-layer nickelates. Specifically, by properly including the doping dependence of the Ni $d_{x^2-y^2}$ and $d_{z^2}$ orbitals as well as the self-doping band, we uncover a transition from $d$-wave pairing symmetry to nodal $…
The recent discovery of superconductivity in Nd$_{1-x}$Sr$_{x}$NiO$_2$ has drawn significant attention in the field. A key open question regards the evolution of the electronic structure with respect to hole doping. Here, we exploit x-ray absorption spectroscopy (XAS) and resonant inelastic x-ray scattering (RIXS) to probe the doping dependent electronic structure of the NiO$_2$ planes. Upon doping, a higher energy feature in Ni $L_3$ edge XAS develops in addition to the main absorption peak. By comparing our data to atomic multiplet calculations including $D_{4h}$ crystal field, the doping in…
A unified theory of thin film and bulk bilayer nickelates
School of Physics, Hangzhou Normal University（杭州师范大学物理学院）；Beijing National Laboratory for Condensed Matter Physics and Institute of Physics, Chinese Academy of Sciences（中国科学院物理研究所北京凝聚态物理国家研究中心）；School of Physical Sciences, University of Chinese Academy of Sciences（中国科学院大学物理科学学院）
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 Nd$_{0.8}$Sr$_{0.2}$NiO$_2$, epitaxially stabilized on SrTiO$_3$ substrates via topotactic reduction from the perovskite precursor phase. Here we present the synthesis and properties of PrNiO$_2$ thin films on SrTiO$_3$. Upon doping in Pr$_{0.8}$Sr$_{0.2}$NiO$_2$, we observe superconductivity with a transition temperature of 7-12 K, and robust critical current density at 2 K of 3…
The recent observation of superconductivity in infinite-layer nickelates has brought intense debate on the established knowledge of unconventional superconductivity based on the cuprates. Despite many similarities, the nickelates differ from the cuprates in many characteristics, the most notable one among which is the magnetism. Instead of a canonical antiferromagnetic Mott insulator as the undoped cuprates, from which the superconductivity is generally believed to arise upon doping, the undoped nickelates show no sign of magnetic ordering in experiments. Through a combined density functional …
We investigate the effect of Na intercalation in the layered Mott insulator TiOCl within the framework of density functional theory. We show that the system remains always insulating for all studied Na concentrations, and the evolution of the spectral weight upon Na doping is consistent with recent photoemission experiments. We predict the Na-doped superlattice structures, and show that substitutions of O by F, Cl by S, or Ti by V (or Sc), respectively, fail to metallize the system. We propose a description in terms of a multiorbital ionic Hubbard model in a quasi-two-dimensional lattice and d…
The recent discovery of superconductivity in Sr-doped NdNiO$_2$, with a critical temperature of $10-15$ K suggests the possibility of a new family of nickel-based high-temperature superconductors (HTS). NdNiO$_{2}$ is the $n=\infty$ member of a larger series of layered nickelates with chemical formula R$_{n+1}$Ni$_{n}$O$_{2n+2}$ (R $=$ La, Nd, Pr; $n = 2, 3, \dots, \infty$). The $n=3$ member has been experimentally and theoretically shown to be cuprate-like and a promising HTS candidate if electron doping could be achieved. The higher-order $n=4,5,$ and $6$ members of the series fall directly …
The recent discovery of superconductivity in hole-doped planar nickelates R1-xSrNiO2 (R=Pr,Nd) raises the foundational question of how the electronic structure and electronic correlations of these Ni1+ compounds compare to those of the Cu2+ cuprate superconductors. Here, we present an Angle-Resolved Photoemission Spectroscopy (ARPES) study of the trilayer nickelate Pr4Ni3O8, revealing an electronic structure and Fermi surface very similar to that of the hole-doped cuprates but with a few critical differences. Specifically, the main portions of the Fermi surface are extremely similar to that of…
Ni-O hybridization-driven electronic reconstruction across the superconducting dome in an infinite-layer nickelate
National University of Singapore（新加坡国立大学）；Agency for Science, Technology and Research (A*STAR)（科学与技术研究局）；Shanghai University（上海大学）；Southern University of Science and Technology（南方科技大学）
Strongly correlated materials often undergo a Mott metal-insulator transition, which is tipically first-order, as a function of control parameters like pressure. Upon doping, rich phase diagrams with competing instabilities are found. Yet, the conceptual link between the interaction-driven Mott transition and the finite-doping behavior lacks a clear connection with the theory of critical phenomena. In a prototypical case of a first-order Mott transition the surface associated with the equation of state for the homogeneous system is "folded" so that in a range of parameters stable metallic and …
From perovskite to infinite-layer nickelates: hole concentration from x-ray absorption
Max Planck Institute for Solid State Research（马克斯·普朗克固体研究所）；Universite de Strasbourg, CNRS, IPCMS UMR 7504（斯特拉斯堡大学）；Helmholtz-Zentrum Berlin für Materialien und Energie（柏林亥姆霍兹材料与能源中心）；European Synchrotron Radiation Facility（欧洲同步辐射装置）；Karlsruhe Institute of Technology (KIT)（卡尔斯鲁厄理工学院）
Superconducting nickelates appear to be difficult to synthesize. Since the chemical reduction of ABO3 (A: rare earth; B transition metal) with CaH2 may result in both, ABO2 and ABO2H, we calculate the topotactic H binding energy by density functional theory (DFT). We find intercalating H is energetically favorable for LaNiO2 but not for Sr-doped NdNiO2. This has dramatic consequences for the electronic structure as determined by DFT+dynamical mean field theory: that of 3d9 LaNiO2 is similar to (doped) cuprates, 3d8 LaNiO2H is a two-orbital Mott insulator. Topotactical H might hence explain why…
The discovery of superconductivity in square-planar low valence nickelates has ignited a vigorous debate regarding their essential electronic properties: Do these materials have appreciable oxygen charge-transfer character akin to the cuprates, or are they in a distinct Mott-Hubbard regime where oxygen plays a minimal role? Here, we resolve this question using O $K$-edge resonant inelastic x-ray scattering (RIXS) measurements of the low valence nickelate La$_{4}$Ni$_{3}$O$_{8}$ and a prototypical cuprate La$_{2-x}$Sr$_{x}$CuO$_{4}$ ($x=0.35$). As expected, the cuprate lies deep in the charge-t…
We present a comparative density-functional theory plus dynamical mean-field theory (DFT+DMFT) study of the two known superconducting members of the rare-earth (R) layered nickelate family: hole-doped RNiO$_{2}$ ($n=\infty$) and R$_{6}$Ni$_{5}$O$_{12}$ ($n=5$). At the same nominal carrier concentration, these two materials exhibit nearly identical electronic structures and many-body correlations effects: mass enhancements, self-energies, and occupations. However, the fermiology of the quintuple-layer nickelate is more two-dimensional-like than its infinite-layer counterpart making this new sup…
Following the discovery of superconductivity in the cuprates and the seminal work by Anderson, the theoretical efforts to understand high-temperature superconductivity have been focusing to a large extent on a simple model: the one-band Hubbard model. However, superconducting cuprates need to be doped, and the doped holes go into the oxygen orbitals. This requires a more elaborate multi-band model such as the three-orbital Emery model. The recently discovered nickelate superconductors appear, at first glance, to be even more complicated multi-orbital systems. Here, we analyse this multi-orbita…
The discovery of superconductivity in Nd$_{0.8}$Sr$_{0.2}$NiO$_2$ [1] introduced a new family of layered nickelate superconductors that has now been extended to include a range of Sr-doping [2, 3], Pr or La in place of Nd [4-6], and the 5-layer Nd$_6$Ni$_5$O$_{12}$ [7]. A number of studies indicate that electron correlations are strong in these materials [8-14], and hence a central question is whether or not magnetism is present as a consequence of these interactions. Here we report muon spin rotation/relaxation studies of a series of superconducting infinite-layer nickelates. In all cases we …
We review the electronic structure of nickelate superconductors with and without effects of electronic correlations. As a minimal model we identify the one-band Hubbard model for the Ni 3$d_{x^2-y^2}$ orbital plus a pocket around the $A$-momentum. The latter however merely acts as a decoupled electron reservoir. This reservoir makes a careful translation from {nominal} Sr-doping to the doping of the one-band Hubbard model mandatory. Our dynamical mean-field theory calculations, in part already supported by experiment, indicate that the $Γ$ pocket, Nd 4$f$ orbitals, oxygen 2$p$ and {the} other …
The novel nickelate superconductors of infinite-layer type feature challenging electronic pecularities in the normal-state phase diagram with doping. Distinct many-body behavior and different dispersion regimes of the entangled $\{$Ni-$d_{z^2}$, Ni-$d_{x^2-y^2}$$\}$ orbital sector give rise to highly rich physics, which is here studied for the case of the NdNiO$_2$ system. An analysis based on advanced realistic dynamical mean-field theory unveils that the superconducting hole-doped region is the meeting place of a (self-)doped Mott insulator from the underdoped side, and a bad Hund metal from…
