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Heterostructure engineering provides an efficient way to obtain several emergent phases of LaNiO3, as demonstrated in recent studies. In this work, a new class of short-periodic superlattice, consisting of LaNiO3 and EuNiO3, has been grown by pulsed laser interval deposition to investigate the effect of structural symmetry mismatch on the electronic and magnetic behaviors. Using synchrotron-based soft and hard x-ray resonant scattering experiments, we have found that these heterostructures undergo simultaneous electronic and magnetic transitions. Most importantly, LaNiO3 within these artificial structures exhibits a new antiferromagnetic, charge ordered insulating phase, which may be a potential candidate to achieve high temperature superconductivity.

Materials that combine metallic behaviour with stable electric polarization are scarce despite being proposed in the 1960s. Here the authors engineer a perovskite heterostructure where 2D polar metallic behavior coexists with built-in electric polarization from the displacement of B-site titanium cations.

Interfaces between two dissimilar transition metal oxides can exhibit emergent strongly correlated electronic and magnetic states due to charge transfer and electronic reconfiguration. Here, the authors synthesize and investigate an exotic Mott ground state in LaTiO3+δ/LaNiO3heterostructures.

The relativistic Mott insulator Sr _2 IrO _4 driven by large spin–orbit interaction is known for the ${J}_{\mathrm{eff}}=1/2$ antiferromagnetic state which closely resembles the electronic structure of parent compounds of superconducting cuprates. Here, we report the realization of hole-doped Sr _2 IrO _4 by means of interfacial charge transfer in Sr _2 IrO _4 /LaNiO _3 heterostructures. X-ray photoelectron spectroscopy on Ir 4 f edge along with the x-ray absorption spectroscopy at Ni L _2 edge confirmed that 5 d electrons from Ir sites are transferred onto Ni sites, leading to markedly electronic reconstruction at the interface. Although the Sr _2 IrO _4 /LaNiO _3 heterostructure remains non-metallic, we reveal that the transport behavior is no longer described by the Mott variable range hopping mode, but by the Efros–Shklovskii model. These findings highlight a powerful utility of interfaces to realize emerging electronic states of the Ruddlesden–Popper phases of Ir-based oxides.

Probing the emergent excitations in a range of is fundamentally important to understand a variety of emergent phenomena in quantum materials, however, the characterization techniques of which are very limited at present. Here, we take high-temperature superconducting YBa2Cu3O7−δ films () as an archetype to demonstrate the powerful capabilities of middle-energy electron energy loss spectroscopy (EELS) in determining the emergent excitations. Three dominative features (2.9, 12.9, and 25 eV) are observed in the EELS spectra, one of which is a newly observed peak near 2.9 eV resulting from excitations between the Zhang-Rice state and the upper Hubbard band. Moreover, incident energy-dependent EELS spectra indicate that the signals of these three features are strongly dependent on the energy of incident electrons. Our work provides a route to probe emergent excitations in the energy range with utilizing high-resolution two-dimensional energy and momentum mapping. [ABSTRACT FROM AUTHOR]

Emergent magnetic phenomena at interfaces represent a frontier in materials science, pivotal for advancing technologies in spintronics and magnetic storage. In this Letter, we utilize a suite of advanced X-ray spectroscopic and scattering techniques to investigate emergent interfacial ferromagnetism in oxide superlattices composed of antiferromagnetic CaMnO 3 and paramagnetic CaRuO 3 . Our findings demonstrate that ferromagnetism exhibits an asymmetric profile and may extend beyond the interfacial layer into multiple unit cells of CaMnO 3 . Complementary density functional calculations reveal that the interfacial ferromagnetism is driven by the double exchange mechanism, facilitated by charge transfer from Ru to Mn ions. Additionally, defect chemistry, particularly the presence of oxygen vacancies, can play a crucial role in modifying the magnetic moments at the interface, possibly leading to the observed asymmetry between the top and bottom CaMnO 3 interfacial magnetic layers. Our findings underscore the potential of manipulating interfacial ferromagnetism through point defect engineering.

The interplay between electronic interactions and strong spin-orbit coupling is expected to create a plethora of fascinating correlated topological states of quantum matter. Of particular interest are magnetic Weyl semimetals originally proposed in the pyrochlore iridates, which are only expected to reveal their topological nature in thin film form. To date, however, direct experimental demonstrations of these exotic phases remain elusive, due to the lack of usable single crystals and the insufficient quality of available films. Here, we report on the discovery of signatures for the long-sought magnetic Weyl semimetallic phase in (111)-oriented Eu_{2}Ir_{2}O_{7} high-quality epitaxial thin films. We observed an intrinsic anomalous Hall effect with colossal coercivity but vanishing net magnetization, which emerges right below the onset of a peculiar magnetic phase with all-in-all-out (AIAO) antiferromagnetic ordering. The anomalous Hall conductivity obtained experimentally is consistent with the theoretical prediction, likely arising from the nonzero Berry curvature emanated by Weyl node pairs near the Fermi level that act as sources and sinks of Berry flux, activated by broken cubic crystal symmetry at the top and bottom terminations of the thin film.

Complementary to bulk synthesis, here we propose a designer lattice with extremely high magnetic frustration and demonstrate the possible realization of a quantum spin liquid state from both experiments and theoretical calculations. In an ultrathin (111) CoCr 2 O 4 slice composed of three triangular and one kagome cation planes, the absence of a spin ordering or freezing transition is demonstrated down to 0.03 K, in the presence of strong antiferromagnetic correlations in the energy scale of 30 K between Co and Cr sublattices, leading to the frustration factor of ∼1000. Persisting spin fluctuations are observed at low temperatures via low-energy muon spin relaxation. Our calculations further demonstrate the emergence of highly degenerate magnetic ground states at the 0 K limit, due to the competition among multiply altered exchange interactions. These results collectively indicate the realization of a proximate quantum spin liquid state on the synthetic lattice.

We report on the emergent magnetic state of (111)-oriented CoCr 2 O 4 ultrathin films sandwiched between Al 2 O 3 spacer layers in a quantum confined geometry. At the two-dimensional crossover, polarized neutron reflectometry reveals an anomalous enhancement of the total magnetization compared to the bulk value. Synchrotron X-ray magnetic circular dichroism measurements demonstrate the appearance of a long-range ferromagnetic ordering of spins on both Co and Cr sublattices. Brillouin function analyses and ab-initio density functional theory calculations further corroborate that the observed phenomena are due to the strongly altered magnetic frustration invoked by quantum confinement effects, manifested by the onset of a Yafet-Kittel-type ordering as the magnetic ground state in the ultrathin limit, which is unattainable in the bulk.

Artificial complex-oxide heterostructures containing ultrathin buried layers grown along the pseudocubic [111] direction have been predicted to host a plethora of exotic quantum states arising from the graphene-like lattice geometry and the interplay between strong electronic correlations and band topology. To date, however, electronic-structural investigations of such atomic layers remain an immense challenge due to the shortcomings of conventional surface-sensitive probes with typical information depths of a few angstroms. Here, we use a combination of bulk-sensitive soft X-ray angle-resolved photoelectron spectroscopy (SX-ARPES), hard X-ray photoelectron spectroscopy (HAXPES), and state-of-the-art first-principles calculations to demonstrate a direct and robust method for extracting momentum-resolved and angle-integrated valence-band electronic structure of an ultrathin buckled graphene-like layer of NdNiO 3 confined between two 4-unit cell-thick layers of insulating LaAlO 3 . The momentum-resolved dispersion of the buried Ni d states near the Fermi level obtained via SX-ARPES is in excellent agreement with the first-principles calculations and establishes the realization of an antiferro-orbital order in this artificial lattice. The HAXPES measurements reveal the presence of a valence-band bandgap of 265 meV. Our findings open a promising avenue for designing and investigating quantum states of matter with exotic order and topology in a few buried layers.

We investigate [Formula: see text]/[Formula: see text] superlattices in which we observe a full electron transfer at the interface from Ir to Ni, triggering a massive structural and electronic reconstruction. Through experimental characterization and first-principles calculations, we determine that a large crystal field splitting from the distorted interfacial [Formula: see text] octahedra surprisingly dominates over the spin-orbit coupling and together with the Hund's coupling results in the high-spin (S = 1) configurations on both the Ir and Ni sites. This demonstrates the power of interfacial charge transfer in coupling lattice, charge, orbital, and spin degrees of freedom, opening fresh avenues of investigation of quantum states in oxide superlattices., Competing Interests: The authors declare no conflict of interest.

Generally, lattice distortions play a key role in determining the electronic ground states of materials. Although it is well known that trigonal distortions are generic to most two dimensional transition metal dichalcogenides, the impact of this structural distortion on the electronic structure and topological properties has not been understood conclusively. Here, by using a combination of polarization dependent X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS) and atomic multiplet cluster calculations, we have investigated the electronic structure of titanium dichalcogenides TiX 2 (X = S, Se, Te), where the magnitude of the trigonal distortion increase monotonically from S to Se and Te. Our results reveal the presence of an anomalously large crystal field splitting. This unusual kind of crystal field splitting is likely responsible for the unconventional electronic structure of TiX 2 compounds and ultimately controls the degree of the electronic phase protection. Our findings also indicate the drawback of the distorted crystal field picture in explaining the observed electronic ground state and emphasize the key importance of trigonal symmetry, metal-ligand hybridization and electron-electron correlations in defining the electronic structures at the Fermi energy.

Polar metals, commonly defined by the coexistence of polar crystal structure and metallicity, are thought to be scarce because the long-range electrostatic fields favoring the polar structure are expected to be fully screened by the conduction electrons of a metal. Moreover, reducing from three to two dimensions, it remains an open question whether a polar metal can exist. Here we report on the realization of a room temperature two-dimensional polar metal of the B-site type in tri-color (tri-layer) superlattices BaTiO 3 /SrTiO 3 /LaTiO 3 . A combination of atomic resolution scanning transmission electron microscopy with electron energy-loss spectroscopy, optical second harmonic generation, electrical transport, and first-principles calculations have revealed the microscopic mechanisms of periodic electric polarization, charge distribution, and orbital symmetry. Our results provide a route to creating all-oxide artificial non-centrosymmetric quasi-two-dimensional metals with exotic quantum states including coexisting ferroelectric, ferromagnetic, and superconducting phases.

Coupled transitions between distinct ordered phases are important aspects behind the rich phase complexity of correlated oxides that hinder our understanding of the underlying phenomena. For this reason, fundamental control over complex transitions has become a leading motivation of the designer approach to materials. We have devised a series of new superlattices by combining a Mott insulator and a correlated metal to form ultrashort period superlattices, which allow one to disentangle the simultaneous orderings in RENiO_{3}. Tailoring an incommensurate heterostructure period relative to the bulk charge ordering pattern suppresses the charge order transition while preserving metal-insulator and antiferromagnetic transitions. Such selective decoupling of the entangled phases resolves the long-standing puzzle about the driving force behind the metal-insulator transition and points to the site-selective Mott transition as the operative mechanism. This designer approach emphasizes the potential of heterointerfaces for selective control of simultaneous transitions in complex materials with entwined broken symmetries.

Combining dissimilar transition metal oxides (TMOs) into artificial heterostructures enables to create electronic interface systems with new electronic properties that do not exist in bulk. A detailed understanding of how such interfaces can be used to tailor physical properties requires characterization techniques capable to yield interface sensitive spectroscopic information with monolayer resolution. In this regard resonant x-ray reflectivity (RXR) provides a unique experimental tool to achieve exactly this. It yields the element specific electronic depth profiles in a non-destructive manner. Here, using a YBa 2 Cu 3 O 7-δ (YBCO) thin film, we demonstrate that RXR is further capable to deliver site selectivity. By applying a new analysis scheme to RXR, which takes the atomic structure of the material into account, together with information of the local charge anisotropy of the resonant ions, we obtained spectroscopic information from the different Cu sites (e.g., chain and plane) throughout the film profile. While most of the film behaves bulk-like, we observe that the Cu-chains at the surface show characteristics of electron doping, whereas the Cu-planes closest to the surface exhibit an orbital reconstruction similar to that observed at La 1-x Ca x MnO 3 /YBCO interfaces.

Transition metal oxides are complex electronic systems that exhibit a multitude of collective phenomena. Two archetypal examples are VO 2 and NdNiO 3 , which undergo a metal-insulator phase transition (MIT), the origin of which is still under debate. Here this study reports the discovery of a memory effect in both systems, manifested through an increase of resistance at a specific temperature, which is set by reversing the temperature ramp from heating to cooling during the MIT. The characteristics of this ramp-reversal memory effect do not coincide with any previously reported history or memory effects in manganites, electron-glass or magnetic systems. From a broad range of experimental features, supported by theoretical modelling, it is found that the main ingredients for the effect to arise are the spatial phase separation of metallic and insulating regions during the MIT and the coupling of lattice strain to the local transition temperature of the phase transition. We conclude that the emergent memory effect originates from phase boundaries at the reversal temperature leaving "scars" in the underlying lattice structure, giving rise to a local increase in the transition temperature. The universality and robustness of the effect shed new light on the MIT in complex oxides., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The superconductor-to-insulator transition (SIT) induced by means such as external magnetic fields, disorder or spatial confinement is a vivid illustration of a quantum phase transition dramatically affecting the superconducting order parameter. In pursuit of a new realization of the SIT by interfacial charge transfer, we developed extremely thin superlattices composed of high Tc superconductor YBa2Cu3O7 (YBCO) and colossal magnetoresistance ferromagnet La0.67Ca0.33MnO3 (LCMO). By using linearly polarized resonant X-ray absorption spectroscopy and magnetic circular dichroism, combined with hard X-ray photoelectron spectroscopy, we derived a complete picture of the interfacial carrier doping in cuprate and manganite atomic layers, leading to the transition from superconducting to an unusual Mott insulating state emerging with the increase of LCMO layer thickness. In addition, contrary to the common perception that only transition metal ions may respond to the charge transfer process, we found that charge is also actively compensated by rare-earth and alkaline-earth metal ions of the interface. Such deterministic control of Tc by pure electronic doping without any hindering effects of chemical substitution is another promising route to disentangle the role of disorder on the pseudo-gap and charge density wave phases of underdoped cuprates.

In complex materials observed electronic phases and transitions between them often involve coupling between many degrees of freedom whose entanglement convolutes understanding of the instigating mechanism. Metal-insulator transitions are one such problem where coupling to the structural, orbital, charge, and magnetic order parameters frequently obscures the underlying physics. Here, we demonstrate a way to unravel this conundrum by heterostructuring a prototypical multi-ordered complex oxide NdNiO3 in ultra thin geometry, which preserves the metal-to-insulator transition and bulk-like magnetic order parameter, but entirely suppresses the symmetry lowering and long-range charge order parameter. These findings illustrate the utility of heterointerfaces as a powerful method for removing competing order parameters to gain greater insight into the nature of the transition, here revealing that the magnetic order generates the transition independently, leading to an exceptionally rare purely electronic metal-insulator transition with no symmetry change.

We report on the phase diagram of competing magnetic interactions at the nanoscale in engineered ultrathin trilayer heterostructures of LaTiO_{3}/SrTiO_{3}/YTiO_{3}, in which the interfacial inversion symmetry is explicitly broken. Combined atomic layer resolved scanning transmission electron microscopy with electron energy loss spectroscopy and electrical transport have confirmed the formation of a spatially separated two-dimensional electron liquid and high density two-dimensional localized magnetic moments at the LaTiO_{3}/SrTiO_{3} and SrTiO_{3}/YTiO_{3} interfaces, respectively. Resonant soft x-ray linear dichroism spectroscopy has demonstrated the presence of orbital polarization of the conductive LaTiO_{3}/SrTiO_{3} and localized SrTiO_{3}/YTiO_{3} electrons. Our results provide a route with prospects for exploring new magnetic interfaces, designing a tunable two-dimensional d-electron Kondo lattice, and potential spin Hall applications.

Deterministic control over the periodic geometrical arrangement of the constituent atoms is the backbone of the material properties, which, along with the interactions, define the electronic and magnetic ground state. Following this notion, a bilayer of a prototypical rare-earth nickelate, NdNiO_{3}, combined with a dielectric spacer, LaAlO_{3}, has been layered along the pseudocubic [111] direction. The resulting artificial graphenelike Mott crystal with magnetic 3d electrons has antiferromagnetic correlations. In addition, a combination of resonant X-ray linear dichroism measurements and ab initio calculations reveal the presence of an ordered orbital pattern, which is unattainable in either bulk nickelates or nickelate based heterostructures grown along the [001] direction. These findings highlight another promising venue towards designing new quantum many-body states by virtue of geometrical engineering.

In pursuit of creating cuprate-like electronic and orbital structures, artificial heterostructures based on LaNiO3 have inspired a wealth of exciting experimental and theoretical results. However, to date there is a very limited experimental understanding of the electronic and orbital states emerging from interfacial charge transfer and their connections to the modified band structure at the interface. Towards this goal, we have synthesized a prototypical superlattice composed of a correlated metal LaNiO3 and a doped Mott insulator LaTiO(3+δ), and investigated its electronic structure by resonant X-ray absorption spectroscopy combined with X-ray photoemission spectroscopy, electrical transport and theory calculations. The heterostructure exhibits interfacial charge transfer from Ti to Ni sites, giving rise to an insulating ground state with orbital polarization and e(g) orbital band splitting. Our findings demonstrate how the control over charge at the interface can be effectively used to create exotic electronic, orbital and spin states.

We address the fundamental issue of growth of perovskite ultra-thin films under the condition of a strong polar mismatch at the heterointerface exemplified by the growth of a correlated metal LaNiO3 on the band insulator SrTiO3 along the pseudo cubic [111] direction. While in general the metallic LaNiO3 film can effectively screen this polarity mismatch, we establish that in the ultra-thin limit, films are insulating in nature and require additional chemical and structural reconstruction to compensate for such mismatch. A combination of in-situ reflection high-energy electron diffraction recorded during the growth, X-ray diffraction, and synchrotron based resonant X-ray spectroscopy reveal the formation of a chemical phase La2Ni2O5 (Ni(2+)) for a few unit-cell thick films. First-principles layer-resolved calculations of the potential energy across the nominal LaNiO3/SrTiO3 interface confirm that the oxygen vacancies can efficiently reduce the electric field at the interface.

Mott physics is characterized by an interaction-driven metal-to-insulator transition in a partially filled band. In the resulting insulating state, antiferromagnetic orders of the local moments typically develop, but in rare situations no long-range magnetic order appears, even at zero temperature, rendering the system a quantum spin liquid. A fundamental and technologically critical question is whether one can tune the underlying energetic landscape to control both metal-to-insulator and Néel transitions, and even stabilize latent metastable phases, ideally on a platform suitable for applications. Here we demonstrate how to achieve this in ultrathin films of NdNiO3 with various degrees of lattice mismatch, and report on the quantum critical behaviours not reported in the bulk by transport measurements and resonant X-ray spectroscopy/scattering. In particular, on the decay of the antiferromagnetic Mott insulating state into a non-Fermi liquid, we find evidence of a quantum metal-to-insulator transition that spans a non-magnetic insulating phase.

The interplay between antagonistic superconductivity and ferromagnetism has been a interesting playground to explore the interaction between competing ground states. Although this effect in systems of conventional superconductors is better understood, the framework of the proximity effect at complex-oxide-based superconductor/ferromagnet interfaces is not so clear. The main difficulty originates from the lack of experimental tools capable of probing the interfaces directly with high spatial resolution. Here we harness cross-sectional scanning tunnelling microscopy and spectroscopy together with atomic-resolution electron microscopy to understand the buried interfaces between cuprate and manganite layers. The results show that the fundamental length scale of the electronic evolution between YBa2Cu3O(7-δ) (YBCO) and La2/3Ca1/3MnO3 (LCMO) is confined to the subnanometre range. Our findings provide a complete and direct microscopic picture of the electronic transition across the YBCO/LCMO interfaces, which is an important step towards understanding the competition between ferromagnetism and superconductivity in complex-oxide heterostructures.

The metal-insulator transition and the underlying electronic and orbital structure in e(g)(1) quantum wells based on NdNiO3 were investigated by dc transport and resonant soft x-ray absorption spectroscopy. By comparing quantum wells of the same dimension but with two different confinement structures, we explicitly demonstrate that the quantum well boundary condition of correlated electrons is critical to selecting the many-body ground state. In particular, the long-range orderings and the metal-insulator transition are found to be strongly enhanced under quantum confinement by sandwiching NdNiO(3) with the wide-gap dielectric LaAlO(3), while they are suppressed when one of the interfaces is replaced by a surface (interface with vacuum). Resonant spectroscopy reveals that the reduced charge fluctuations in the sandwich structure are supported by the enhanced propensity to charge ordering due to the suppressed e(g) orbital splitting when interfaced with the confining LaAlO3 layer.

An optical study of NdNiO(3) ultrathin films with insulating and metallic ground states reveals new aspects of the insulator-to-metal transition that point to Mott physics as the driving force. In contrast with the behavior of charge-ordered systems, we find that the emergence of the Drude resonance across the transition is linked to a spectral weight transfer over an energy range of the order of the Coulomb repulsion U, as the energy gap is filled with states instead of closing continuously., (© 2011 American Physical Society)

Using resonant x-ray spectroscopies combined with density functional calculations, we find an asymmetric biaxial strain-induced d-orbital response in ultrathin films of the correlated metal LaNiO3 which are not accessible in the bulk. The sign of the misfit strain governs the stability of an octahedral "breathing" distortion, which, in turn, produces an emergent charge-ordered ground state with an altered ligand-hole density and bond covalency. Control of this new mechanism opens a pathway to rational orbital engineering, providing a platform for artificially designed Mott materials.