The recent observation of superconductivity in Nd$_{0.8}$Sr$_{0.2}$NiO$_{2}$ calls for further investigation and optimization of the synthesis of this metastable infinite-layer nickelate structure. Here, we present our current understanding of important aspects of the growth of the parent perovskite compound via pulsed laser deposition on SrTiO$_{3}$ (001) substrates, and the subsequent topotactic reduction. We find that to achieve single-crystalline, single-phase superconducting Nd$_{0.8}$Sr$_{0.2}$NiO$_{2}$, it is essential that the precursor perovskite Nd$_{0.8}$Sr$_{0.2}$NiO$_{3}$ thin film is stabilized with high crystallinity and no impurity phases; in particular, a Ruddlesden-Popper-type secondary phase is often observed. We have further investigated the evolution of the soft-chemistry topotactic reduction conditions to realize full transformation to the infinite-layer structure with no film decomposition or formation of other phases. We find that capping the nickelate film with a subsequent SrTiO$_{3}$ layer provides an epitaxial template to the top region of the nickelate film, much like the substrate. Thus, for currently optimized growth conditions, we can stabilize superconducting single-phase Nd$_{0.8}$Sr$_{0.2}$NiO$_{2}$ (001) epitaxial thin films up to ~ 10 nm.
The discovery of superconductivity in infinite-layer nickelates has attracted much attention due to their association to the high-$T_c$ cuprates. Cuprate superconductivity was first demonstrated in bulk samples and subsequently in thin films. In the nickelates, however, the situation has been reversed: although surging as a bulk phenomenon, nickelate superconductivity has only been reported in thin films so far. At the same time, the specifics of infinite-layer nickelates yield distinct interface and surface effects that determine their bulk vs thin-film behavior. In this paper, we provide an …
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…
Motivated by recent reports of superconductivity in Sr-doped NdNiO$_2$ films on SrTiO$_3$(001) [Nature (London) 572, 624 (2019)], we explore the role of the polar interface on the structural and electronic properties of NdNiO$_n$/SrTiO$_3$(001) ($n=2,3$) by performing first-principles calculations including a Coulomb repulsion term. For infinite-layer nickelate films ($n=2$), electronic reconstruction drives the surprising emergence of a two-dimensional electron gas (2DEG) at the interface involving a strong occupation of the Ti $3d$ states. This effect is more pronounced than in LaAlO$_3$/SrT…
Achieving superconductivity in infinite-layer nickelate thin films by aluminum sputtering deposition
Laboratoire Albert Fert, CNRS, Thales, Université Paris-Saclay（阿尔伯特·费尔特实验室，法国国家科学研究中心，泰雷兹集团，巴黎萨克雷大学）；Laboratoire de Physique des Solides, CNRS, Université Paris-Saclay（固体物理实验室，法国国家科学研究中心，巴黎萨克雷大学）；Synchrotron SOLEIL（索莱尔同步辐射中心）
The recent discovery of superconductivity in infinite-layer nickelate films has aroused great interest since it provides a new platform to explore the mechanism of high-temperature superconductivity. However, superconductivity only appears in the thin film form and synthesizing superconducting nickelate films is extremely challenging, limiting the in-depth studies on this compound. Here, we explore the critical parameters in the growth of high quality nickelate films using molecular beam epitaxy (MBE). We found that stoichiometry is crucial in optimizing the crystalline structure and realizing…
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…
We report the phase diagram of infinite layer Pr$_{1-x}$Sr$_{x}$NiO$_2$ thin films synthesized via topotactic reduction from the perovskite precursor phase using CaH$_2$. Based on the electrical transport properties, we find a doping-dependent superconducting dome extending between $x$ = 0.12 and 0.28, with a maximum superconducting transition temperature $T_{\rm{c}}$ of 14 K at $x$ = 0.18, bounded by weakly insulating behavior on both sides. In contrast to the narrower dome observed in Nd$_{1-x}$Sr$_{x}$NiO$_2$, a local $T_{\rm{c}}$ suppression near $x$ = 0.2 was not observed for the Pr$_{1-x…
The layered square-planar nickelates, Nd$_{n+1}$Ni$_{n}$O$_{2n+2}$, are an appealing system to tune the electronic properties of square-planar nickelates via dimensionality; indeed, superconductivity was recently observed in Nd$_{6}$Ni$_{5}$O$_{12}$ thin films. Here, we investigate the role of epitaxial strain in the competing requirements for the synthesis of the $n=3$ Ruddlesden-Popper compound, Nd$_{4}$Ni$_{3}$O$_{10}$, and subsequent reduction to the square-planar phase, Nd$_{4}$Ni$_{3}$O$_{8}$. We synthesize our highest quality Nd$_{4}$Ni$_{3}$O$_{10}$ films under compressive strain on La…
Electronic structures across superconductor-insulator transition in Ruddlesden-Popper bilayer nickelate films
University of Science and Technology of China（中国科学技术大学）；Hefei National Laboratory, University of Science and Technology of China（合肥国家实验室，中国科学技术大学）；Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China（微观尺度物理科学合肥国家研究中心，中国科学技术大学）；Southern University of Science and Technology（南方科技大学）；Quantum Science Center of Guangdong-Hong Kong-Macao Greater Bay Area（粤港澳大湾区量子科学中心）；Nanjing University（南京大学）；Shanghai Jiao Tong University（上海交通大学）；Tsinghua University（清华大学）
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…
Rare-earth nickelates are strongly correlated oxides displaying a metal-to-insulator transition at a temperature tunable by the rare-earth ionic radius. In PrNiO$_3$ and NdNiO$_3$, the transition is very sharp and shows an hysteretic behavior akin to a first-order transition. Both the temperature at which the transition occurs and the associated resistivity change are extremely sensitive to doping and therefore to off-stoichiometry issues that may arise during thin film growth. Here we report that strong deviations in the transport properties of NdNiO$_3$ films can arise in films grown consecu…
Nickelate films have recently attracted broad attention due to the observation of superconductivity in the infinite layer phase of $Nd_{0.8}Sr_{0.2}NiO_2$ (obtained by reducing Sr doped $NdNiO_3$ films) and their similarity to the cuprates high temperature superconductors. Here we report on the observation of a new type of transport in oxygen poor $Nd_{0.8}Sr_{0.2}NiO_{3-δ}$ films. At high temperatures, variable range hopping is observed while at low temperatures a novel tunneling behavior is found where Josephson-like tunneling junction characteristic with serial resistance is revealed. We at…
High-field-stabilized reentrant superconductivity in infinite-layer nickelate thin films
National High Magnetic Field Laboratory, Los Alamos National Laboratory（洛斯阿拉莫斯国家实验室高磁场实验室）；Department of Physics, Faculty of Science, National University of Singapore（新加坡国立大学理学院物理系）；Center for Integrated Nanotechnologies, Los Alamos National Laboratory（洛斯阿拉莫斯国家实验室集成纳米技术中心）；Department of Physics, Faculty of Science and Technology, Universitas Airlangga（艾尔朗加大学理学院物理系）；Singapore Synchrotron Light Source (SSLS), National University of Singapore（新加坡国立大学新加坡同步辐射光源）；Department of Physics, The Chinese University of Hong Kong（香港中文大学物理系）
We report a temperature-dependent Raman scattering investigation of thin film rare earth nickelates SmNiO3, NdNiO3 and Sm0.60Nd0.40NiO3, which present a metal-to-insulator (MI) transition at TMI and an antiferromagnetic-paramagnetic Neel transition at TN. Our results provide evidence that all investigated samples present a structural phase transition at TMI but the Raman signature across TMI is significantly different for NdNiO3 (TMI = TN) compared to SmNiO3 and Sm0.60Nd0.40NiO3 (TMI =/ TN). It is namely observed that the paramagnetic-insulator phase (TN < T < TMI) in SmNiO3 and Sm0.60Nd0.40Ni…
Although rare earth nickelates (ReNiO3) exhibit abundant electronic phases and widely adjustable metal to insulator electronic transition properties, their practical electronic applications are largely impeded by their intrinsic meta stability. Apart from elevating oxygen reaction pressures, heterogeneous nucleation is expected as an alternative strategy that enables the crystallization of ReNiO3 at low meta stability. In this work, the respective roles of high oxygen pressure and heterogeneous interface in triggering ReNiO3 thin films growth at metastable state are revealed. The ReNiO3 (Re:Nd…
Persistent structural distortions and absent superconductivity in trilayer nickelate thin films
John A. Paulson School of Engineering and Applied Sciences, Harvard University（哈佛大学生物工程与应用科学学院）；Department of Physics, Harvard University（哈佛大学物理系）；Department of Electrical Engineering & Computer Science, Massachusetts Institute of Technology（麻省理工学院电气与计算机科学系）；School of Applied & Engineering Physics, Cornell University（康奈尔大学应用与工程物理学院）；Department of Physics, Arizona State University（亚利桑那州立大学物理系）；Cornell High Energy Synchrotron Source, Cornell University（康奈尔大学高能同步辐射光源）；Advanced Photon Source, Argonne National Laboratory（阿贡国家实验室先进光子源）
After the reward of more than two decades of pursuit on the high-Tc cuprate analog with the hope to obtain a better understanding of the mechanism of high-Tc superconductivity, the discovery of superconductivity in the infinite-layer nickelate brings more mystery to the picture than expected. Tops in the list of questions are perhaps (1) absence of superconductivity in the bulk nickelate and limited thickness of the infinite-layer phase in thin film, (2) absence of superconductivity in the La-nickelate despite it being the earliest studied rare-earth nickelate, and the role of 4f orbital in th…
Observation of flat-bottom U-shaped energy gap in high-Tc nickelate (La,Pr)3Ni2O7 thin films
Peking University（北京大学）；Hefei National Laboratory（合肥国家实验室）；Quantum Science Center of Guangdong-Hong Kong-Macao Greater Bay Area（粤港澳大湾区量子科学中心）；Boston College（波士顿学院）；Collaborative Innovation Center of Quantum Matter（量子物质协同创新中心）
Rare earth nickelates RENiO3 which attract interest due to their sharp metal-insulator phase transition, are instable in bulk form due to the necessity of an important oxygen pressure to stabilize Ni in its 3+ state of oxidation. Here, we report the stabilization of rare earth nickelates in [(SmNiO3)t/(NdNiO3)t]n thin film multilayers, t being the thickness of layers alternated n times. Both bilayers and multilayers have been deposited by Metal-Organic Chemical Vapour Deposition. The multilayer structure and the presence of the metastable phases SmNiO3 and NdNiO3 are evidenced from by X-ray an…
The recent discovery of a zero-resistance state in nickel-based compounds has generated a re-excitement about the long-standing problem in condensed matter of high-critical-temperature superconductivity, in light of the analogies between infinite-layer nickelates and cuprates. However, despite some formal valence and crystal symmetry analogies, the electronic properties of infinite-layer nickelates are remarkably original accounting, among other properties, of a unique Nd5d-Ni3d hybridization. This designates infinite-layer nickelates as a new class of oxide superconductors which should be con…
Resistances that exceed the Mott-Ioffe-Regel limit, known as bad metal behavior, and non-Fermi liquid behavior are ubiquitous features of the normal state of many strongly correlated materials. Here we establish the conditions that lead to bad metal and non-Fermi liquid phases in NdNiO3, which exhibits a prototype, bandwidth-controlled metal-insulator transition. We show that resistance saturation is determined by the magnitude of the Ni eg orbital splitting, which can be tuned by strain in epitaxial films, causing the appearance of bad metal behavior under certain conditions. The results shed…
The rare-earth nickelates possess a diverse set of collective phenomena including metal-to-insulator transitions, magnetic phase transitions, and, upon chemical reduction, superconductivity. Here, we demonstrate epitaxial stabilization of layered nickelates in the Ruddlesden-Popper form, Nd$_{n+1}$Ni$_n$O$_{3n+1}$, using molecular beam epitaxy. By optimizing the stoichiometry of the parent perovskite NdNiO$_3$, we can reproducibly synthesize the $n = 1 - 5$ member compounds. X-ray absorption spectroscopy at the O $K$ and Ni $L$ edges indicate systematic changes in both the nickel-oxygen hybrid…
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）
Atomically resolved intrinsic superconducting gap in (La,Pr)3Ni2O7 films
Southern University of Science and Technology（南方科技大学）；Quantum Science Center of Guangdong-Hong Kong-Macao Greater Bay Area（粤港澳大湾区量子科学中心）；Shanghai Jiao Tong University（上海交通大学）；Tsinghua University（清华大学）
Oxygen vacancies play a crucial role in the control of the electronic, magnetic, ionic, and transport properties of functional oxide perovskites. Rare earth nickelates (RENiO$_{3-x}$) have emerged over the years as a rich platform to study the interplay between the lattice, the electronic structure, and ordered magnetism. In this study, we investigate the evolution of the electronic and magnetic structure in thin films of RENiO$_{3-x}$, using a combination of X-ray absorption spectroscopy and imaging, resonant X-ray scattering, and extended multiplet ligand field theory modeling. We find that …
The recent observation of superconductivity in thin film infinite-layer nickelates$^{1-3}$ offers a different angle to investigate superconductivity in layered oxides$^{4}$. A wide range of candidate models have been proposed$^{5-10}$, emphasizing single- or multi-orbital electronic structure, Kondo or Hund's coupling, and analogies to cuprates. Clearly, further experimental characterization of the superconducting state is needed to develop a full understanding of the nickelates. Here we use magnetotransport measurements to probe the superconducting anisotropy in Nd$_{0.775}$Sr$_{0.225}$NiO$_{…
NiO6 octahedral tilts in the LaNiO3/SrTiO3 superlattices are quantified using position averaged convergent beam electron diffraction in scanning transmission electron microscopy. It is shown that maintaining oxygen octahedra connectivity across the interface controls the octahedral tilts in the LaNiO3 layers, their lattice parameters and their transport properties. Unlike films and layers that are connected on one side to the substrate, subsequent LaNiO3 layers in the superlattice exhibit a relaxation of octahedral tilts towards bulk values. This relaxation is facilitated by correlated tilts i…
The newly found superconductivity in infinite-layer nickelate superconducting films has attracted much attention, because their crystalline and electronic structures are similar to high-$T_c$ cuprate superconductors. The upper critical field can provide much information on superconductivity, but detailed experimental data are still lacking in these films. Here we present temperature and angle dependence of resistivity measured under different magnetic fields ($H$) in Nd$_{0.8}$Sr$_{0.2}$NiO$_{2}$ thin films. The onset superconducting transition occurs at about 16.2 K at 0 T. Temperature depend…
The observation of superconductivity in infinite layer nickelate (Nd,Sr)NiO$_{2}$ thin films has led to rapid theoretical and experimental investigations of these copper-oxide-analogue systems [1-15]. Superconductivity has also been found in (Pr,Sr)NiO$_{2}$ [16,17], but not previously in (La,Sr)NiO$_{2}$ [2], raising a fundamental question whether superconductivity is associated with the presence of rare-earth moments [18,19]. Here we show that with significant materials optimization, substantial portions of the La$_{1-x}$Sr$_{x}$NiO$_{2}$ phase diagram can enter the regime of coherent low-te…
We report the first single crystal growth of the correlated metal LaNiO3 using a high-pressure optical-image floating zone furnace. The crystals were studied using single crystal/powder x-ray diffraction, resistivity, specific heat, and magnetic susceptibility. The availability of bulk LaNiO3 crystals will (i) promote deep understanding in this correlated material, including the mechanism of enhanced paramagnetic susceptibility, and (ii) provide rich opportunities as a substrate for thin film growth such as important ferroelectric and/or multiferroic materials. This study demonstrates the powe…
Nickel-based complex oxides have served as a playground for decades in the quest for a copper-oxide analog of the high-temperature superconductivity. They may provide clues towards understanding the mechanism and an alternative route for high-temperature superconductors. The recent discovery of superconductivity in the infinite-layer nickelate thin films has fulfilled this pursuit. However, material synthesis remains challenging, direct demonstration of perfect diamagnetism is still missing, and understanding of the role of the interface and bulk to the superconducting properties is still lack…
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…
