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Understanding the complex ground state of van der Waals (vdW) magnets is essential for designing new materials and devices that leverage these platforms. Here, we investigate a two-dimensional vdW ferromagnet -- Fe$_5$GeTe$_2$-- with one of the highest reported Curie temperatures, to elucidate its magnetic excitations and charge order. Using Fe $L_3 - $edge resonant inelastic x-ray scattering, we find the dual character of magnetic excitations, consisting of a coherent magnon and a continuum, similar to what is reported for its sister compound Fe$_3$GeTe$_2$. The magnon has an energy of $\approx$ 36 meV at the maximum in-plane momentum transfer ($-$0.35 r.l.u.) allowed at Fe $L_3 - $edge. A broad and non-dispersive continuum extends up to 150 meV, 50$\%$ higher energy than in Fe$_3$GeTe$_2$. Its intensity is sinusoidally modulated along the $L$ direction, with a period matching the inter-slab distance. Our findings suggest that while the unconventional dual character of magnetic excitations is generic to ternary Fe-Ge-Te vdW magnets, the correlation length of the out-of-plane magnetic interaction increases in Fe$_5$GeTe$_2$ as compared to Fe$_3$GeTe$_2$, supporting a stronger three-dimensional character for the former. Furthermore, by investigating the $\pm$(1/3, 1/3, $L$) peaks by resonant x-ray diffraction, we conclude these to have structural origin rather than charge order -- as previously reported -- and suggest doubling of the structural unit cell along the $c-$axis., Comment: 17 pages, 3 figures

Erbium-doped \ch{TiO2} materials are promising candidates for advancing quantum technologies, necessitating a thorough understanding of their electronic and crystal structures to tailor their properties and enhance coherence times. This study explored epitaxial erbium-doped rutile \ch{TiO2} films deposited on r-sapphire substrates using molecular beam epitaxy. Photoluminescence excitation spectroscopy demonstrated decreasing fluorescence lifetimes with erbium doping, indicating limited coherence times. Lattice distortions associated with \ch{Er^{3+}} were probed by X-ray absorption spectroscopy, indicating that erbium primarily occupies \ch{Ti^{4+}} sites and influences oxygen vacancies. Significant lattice distortions in the higher-order shells and full coordination around erbium suggest that additional defects are likely prevalent in these regions. These findings indicate that defects contribute to limited coherence times by introducing alternative decay pathways, leading to shorter fluorescence lifetimes., Comment: 8 pages, 13 figures, 3 tables

A central paradigm of non-equilibrium physics concerns the dynamics of heterogeneity and disorder, impacting processes ranging from the behavior of glasses to the emergent functionality of active matter. Understanding these complex mesoscopic systems requires probing the microscopic trajectories associated with irreversible processes, the role of fluctuations and entropy growth, and the timescales on which non-equilibrium responses are ultimately maintained. Approaches that illuminate these processes in model systems may enable a more general understanding of other heterogeneous non-equilibrium phenomena, and potentially define ultimate speed and energy cost limits for information processing technologies. Here, we apply ultrafast single shot x-ray photon correlation spectroscopy to resolve the non-equilibrium, heterogeneous, and irreversible mesoscale dynamics during a light-induced phase transition. This approach defines a new way of capturing the nucleation of the induced phase, the formation of transient mesoscale defects at the boundaries of the nuclei, and the eventual annihilation of these defects, even in systems with complex polarization topologies. A non-equilibrium response spanning >10 orders of magnitude in timescales is observed, with multistep behavior similar to the plateaus observed in supercooled liquids and glasses. We show how the observed time-dependent long-time correlations can be understood in terms of the stochastic dynamics of domain walls, encoded in effective waiting-time distributions with power-law tails. This work defines new possibilities for probing the non-equilibrium and correlated dynamics of disordered and heterogeneous media.

$RE$NiO$_3$ is a negative charge transfer energy system and exhibits a temperature-driven metal-insulator transition (MIT), which is also accompanied by a bond disproportionation (BD) transition. In order to explore how hole doping affects the BD transition, we have investigated the electronic structure of single-crystalline thin films of Nd$_{1-x}$Ca$_x$NiO$_3$ by synchrotron based experiments and {\it ab-initio} calculations. For a small value of $x$, we find that the doped holes are localized on one or more Ni sites around the dopant Ca$^{2+}$ ions, while the BD state for the rest of the lattice remains intact. The effective charge transfer energy ($\Delta$) increases with Ca concentration and the formation of BD phase is not favored above a critical $x$, suppressing the insulating phase. Our present study firmly demonstrates that the appearance of BD mode is essential for the MIT and settles a long-standing debate about the role of structural distortions for the MIT of the $RE$NiO$_3$ series., Comment: 4 Figures

The Mott-insulating rare-earth titanates (RTiO$_3$, R being a rare-earth ion) are an important class of materials that encompasses interesting spin-orbital phases as well as ferromagnet-antiferromagnet and insulator-metal transitions. The growth of these materials has been plagued by difficulties related to overoxidation, which arises from a strong tendency of Ti$^{3+}$ to oxidize to Ti$^{4+}$. We describe our efforts to grow sizable single crystals of YTiO$_3$ and its La-substituted and Ca-doped variants with the optical travelling-solvent floating-zone technique. We present sample characterization $via$ chemical composition analysis, magnetometry, charge transport, neutron scattering, x-ray absorption spectroscopy and x-ray magnetic circular dichroism to understand macroscopic physical property variations associated with overoxidation. Furthermore, we demonstrate a good signal-to-noise ratio in inelastic magnetic neutron scattering measurements of spin-wave excitations. A superconducting impurity phase, found to appear in Ca-doped samples at high doping levels, is identified as TiO.

One of the major puzzles in condensed matter physics has been the observation of a Mott-insulating state away from half-filling. The filling-controlled Mott insulator-metal transition, induced via charge-carrier doping, has been extensively researched, but its governing mechanisms have yet to be fully understood. Several theoretical proposals aimed to elucidate the nature of the transition have been put forth, a notable one being phase separation and an associated percolation-induced transition. In the present work, we study the prototypical doped Mott-insulating rare-earth titanate YTiO$_3$, in which the insulating state survives up to a large hole concentration of 35%. Single crystals of Y$_{1-x}$Ca$_x$TiO$_3$ with $0 \leq x \leq 0.5$, spanning the insulator-metal transition, are grown and investigated. Using x-ray absorption spectroscopy, a powerful technique capable of probing element-specific electronic states, we find that the primary effect of hole doping is to induce electronic phase separation into hole-rich and hole-poor regions. The data reveal the formation of electronic states within the Mott-Hubbard gap, near the Fermi level, which increase in spectral weight with increasing doping. From a comparison with DFT+$U$ calculations, we infer that the hole-poor and hole-rich components have charge densities that correspond to the Mott-insulating $x = 0$ and metallic $x \sim 0.5$ states, respectively, and that the new electronic states arise from the metallic component. Our results indicate that the hole-doping-induced insulator-metal transition in Y$_{1-x}$Ca$_x$TiO$_3$ is indeed percolative in nature, and thus of inherent first-order character., Comment: 15 pages, supplementary material included

We explore the magnetically-ordered ground state of the isovalently-substituted Mott-insulator Y$_{1-x}$La$_{x}$TiO$_{3}$ for $x$ $\leq$ 0.3 via single crystal growth, magnetometry, neutron diffraction, x-ray magnetic circular dichroism (XMCD), muon spin rotation ($\mu$SR) and small-angle neutron scattering (SANS). We find that the decrease in the magnetic transition temperature on approaching the ferromagnetic (FM) - antiferromagnetic (AFM) phase boundary at the La concentration $x_c$ $\approx$ 0.3 is accompanied by a strong suppression of both bulk and local ordered magnetic moments, along with a volume-wise separation into magnetically-ordered and paramagnetic regions. The thermal phase transition does not show conventional second-order behavior, since neither a clear signature of dynamic critical behavior nor a power-law divergence of the magnetic correlation length is found for the studied substitution range; this finding becomes increasingly obvious with substitution. Finally, from SANS and magnetometry measurements, we discern a crossover from easy-axis to easy-plane magneto-crystalline anisotropy with increasing La substitution. These results indicate complex changes in magnetic structure upon approaching the phase boundary., Comment: 16 pages, 16 figures

The quantum spin liquid (QSL) is an exotic phase of magnetic materials where the spins continue to fluctuate without any symmetry breaking down to zero temperature. Among the handful reports of QSL with spin $S\ge$1, examples with magnetic ions on a three-dimensional magnetic lattice are extremely rare since both larger spin and higher dimension tend to suppress quantum fluctuations. In this work, we offer a new strategy to achieve 3-D QSL with high spin by utilizing two types of transition metal ions, both are magnetically active but located at crystallographically inequivalent positions. We design a 3-D magnetic system Ba$_3$NiIr$_2$O$_9$ consisting of interconnected corner shared NiO$_6$ octahedra and face shared Ir$_2$O$_9$ dimer, both having triangular arrangements in \textit{a-b} plane. X-ray absorption spectroscopy measurements confirm the presence of Ni$^{2+}$ ($S$=1). Our detailed thermodynamic and magnetic measurements reveal that this compound is a realization of gapless QSL state down to at least 100 mK. Ab-initio calculations find a strong magnetic exchange between Ir and Ni sublattices and in-plane antiferromagnetic coupling between the dimers, resulting in dynamically fluctuating magnetic moments on both the Ir and Ni sublattice., Comment: 4 Figures

The discovery of superconductivity in a $d^{9-{\delta}}$ nickelate has inspired disparate theoretical perspectives regarding the essential physics of this class of materials. A key issue is the magnitude of the magnetic superexchange, which relates to whether cuprate-like high-temperature nickelate superconductivity could be realized. We address this question using Ni L-edge and O K-edge spectroscopy of the reduced trilayer nickelate $d^{9-1/3}$ La4Ni3O8 and associated theoretical modeling. A magnon energy scale of ~80 meV resulting from a nearest-neighbor magnetic exchange of $J = 69(4)4$ meV is observed, proving that $d^{9-{\delta}}$ nickelates can host a large superexchange. This value, along with that of the Ni-O hybridization estimated from our O K-edge data, implies that trilayer nickelates represent an intermediate case between the infinite-layer nickelates and the cuprates, and suggests that they represent a promising route towards higher-temperature nickelate superconductivity., Comment: 7 pages not including supplmentary material; To appear in Physical Review Letters

The observation of metallic interface between band insulators LaAlO$_3$ and SrTiO$_3$ has led to massive efforts to understand the origin of the phenomenon as well as to search for other systems hosting such two dimensional electron gases (2-DEG). However, the understanding of the origin of the 2-DEG is very often hindered as several possible mechanisms such as polar catastrophe, cationic intermixing and oxygen vacancy (OV) etc. can be operative simultaneously. The presence of a heavy element makes KTaO$_3$ (KTO) based 2-DEG a potential platform to investigate spin orbit coupling driven novel electronic and magnetic phenomena. In this work, we investigate the sole effect of the OV, which makes KTO metallic. Our detailed \textit{ab initio} calculations not only find partially filled conduction bands in the presence of an OV but also predict a highly localized mid-gap state due to the linear clustering of OVs around Ta. Photoluminescence measurements indeed reveal the existence of such mid-gap state and O $K$-edge X-ray absorption spectroscopy finds electron doping in Ta $t_{2g}^*$ antibonding states. This present work suggests that one should be cautious about the possible presence of OVs within KTO substrate in interpreting metallic behavior of KTO based 2-DEG., Comment: 4 figures

Ultrashort x-ray pulses can be used to disentangle magnetic and structural dynamics and are accordingly utilized here to study the photoexcitation of NdNiO$_3$ (NNO), a model nickelate exhibiting structural and magnetic dynamics that conspire to induce an IMT. During the course of the photoinduced insulator to metal transition (IMT) with above gap excitation, we observe an ultrafast ($<$ 180 fs) quenching of magnetic order followed by a time delayed collapse of the insulating phase probed by X-ray absorption and THz transmission (~ 450 fs) that correlates with the slowest optical phonon mode involved in the structural transition. A simultaneous order-disorder response at the Ni site and displacive response at the Nd site coexist in the ultrafast magnetic response. Crucially, we observe the optical phonon through its coherent coupling with Nd magnetic order, demonstrating that the magnetic and structural degrees of freedom both contribute in driving the IMT. Density functional theory (DFT) calculations reveal a consistent scenario where optically driven inter-site charge transfer (ICT) drives a collapse of antiferromagnetic order that in turn destabilizes the charge-ordered phase resulting in an IMT. These experiments provide new modalities for control of electronic phase transitions in quantum materials based on ultrafast interplay between structural and magnetic orders created by femtosecond photoexcitation., Comment: 9 pages, 5 figures, major revision and title change from previous version

Transition metal based oxide heterostructures exhibit diverse emergent phenomena e.g. two dimensional electron gas, superconductivity, non-collinear magnetic phase, ferroelectricity, polar vortices, topological Hall effect etc., which are absent in the constituent bulk oxides. The microscopic understandings of these properties in such nanometer thick materials are extremely challenging. Synchrotron x-ray based techniques such as x-ray diffraction, x-ray absorption spectroscopy (XAS), resonant x-ray scattering (RXS), resonant inelastic x-ray scattering (RIXS), x-ray photoemission spectroscopy, etc. are essential to elucidating the response of lattice, charge, orbital, and spin degrees of freedoms to the heterostructuring. As a prototypical case of complex behavior, rare-earth nickelates (RENiO3 with RE=La, Pr, Nd, Sm, Eu, Lu) based thin films and heterostructures have been investigated quite extensively in recent years. An extensive body of literature about these systems exists and for an overview of the field, we refer the interested readers to the recent reviews Annual Review of Materials Research 46, 305 (2016) and Reports on Progress in Physics 81, 046501 (2018). In the present article, we give a brief review that concentrates on the use of synchrotron based techniques to investigate a specific set of EuNiO3/LaNiO3 superlattices, specifically designed to solve a long-standing puzzle about the origin of simultaneous electronic, magnetic and structural transitions of the RENiO3 series., Comment: Invited Review Article

High entropy oxides (HEOs) are a class of materials, containing equimolar portions of five or more transition metal and/or rare-earth elements. We report here about the layer-by-layer growth of HEO [(La$_{0.2}$Pr$_{0.2}$Nd$_{0.2}$Sm$_{0.2}$Eu$_{0.2}$)NiO$_3$] thin films on NdGaO$_3$ substrates by pulsed laser deposition. The combined characterizations with in-situ reflection high energy electron diffraction, atomic force microscopy, and X-ray diffraction affirm the single crystalline nature of the film with smooth surface morphology. The desired +3 oxidation of Ni has been confirmed by an element sensitive X-ray absorption spectroscopy measurement. Temperature dependent electrical transport measurements revealed a first order metal-insulator transition with the transition temperature very similar to the undoped NdNiO$_3$. Since both of these systems have a comparable tolerance factor, this work demonstrates that the electronic behaviors of $A$-site disordered perovskite-HEOs are primarily controlled by the average tolerance factor., Comment: 4 figures

On a lattice composed of triangular plaquettes where antiferromagnetic exchange interactions between localized spins cannot be simultaneously satisfied, the system becomes geometrically frustrated with magnetically disordered phases remarkably different from a simple paramagnet. Spin liquid belongs to one of these exotic states, in which a macroscopic degeneracy of the ground state gives rise to the rich spectrum of collective phenomena. Here, we report on the discovery of a new magnetic state in the heterostructures derived from a single unit cell (111)-oriented spinel CoCr2O4 sandwiched between nonmagnetic Al2O3 spacers. The artificial quasi-two-dimensional material composed of three triangle and one kagome atomic planes shows a degree of magnetic frustration which is almost two orders of magnitude enlarged compared to the bulk crystals. Combined resonant X-ray absorption and torque magnetometry measurements confirm that the designer system exhibits no sign of spin ordering down to 30 mK, implying a possible realization of a quantum spin liquid state in the two dimensional limit.

We report on the emergent magnetic state of (111)-oriented CoCr2O4 ultrathin films sandwiched by Al2O3 in the 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 (XMCD) demonstrates the appearance of long-range ferromagnetic ordering of spins on both Co and Cr sublattices. Brillouin function analyses further corroborates that the observed phenomena are due to the strongly altered magnetic frustration, manifested by the onset of a Yafet-Kittel type ordering as the new ground state in the ultrathin limit, which is unattainable in the bulk.

The relativistic Mott insulator Sr2IrO4 driven by large spin-orbit interaction is known for the Jeff = 1/2 antiferromagnetic state which closely resembles the electronic structure of parent compounds of superconducting cuprates. Here, we report the realization of hole-doped Sr2IrO4 by means of interfacial charge transfer in Sr2IrO4/LaNiO3 heterostructures. X-ray photoelectron spectroscopy on Ir 4f edge along with the X-ray absorption spectroscopy at Ni L2 edge confirmed that 5d electrons from Ir sites are transferred onto Ni sites, leading to markedly electronic reconstruction at the interface. Although the Sr2IrO4/LaNiO3 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., Comment: 9 pages including 3 figures and references

We report for the first time the magnetic structure of the high entropy oxide $(Mg_{0.2}Co_{0.2}Ni_{0.2}Cu_{0.2}Zn_{0.2})O$ using neutron powder diffraction. This material exhibits a sluggish magnetic transition but possesses a long-range ordered antiferromagnetic ground state, as revealed by DC and AC magnetic susceptibility, elastic and inelastic neutron scattering measurements. The magnetic propagation wavevector is k=(1/2, 1/2, 1/2) based on the cubic structure Fm-3m, and the magnetic structure consists of ferromagnetic sheets in the (111) planes with spins antiparallel between two neighboring planes. Inelastic neutron scattering reveals strong magnetic excitations at 100 K that survive up to room temperature. This work demonstrates that entropy-stabilized oxides represent a unique platform to study long range magnetic order with extreme chemical disorder., Comment: 13 pages, 4 figures, supplemental material is upon request

Perovskite nickelate heterostructure consisting of single unit cell of EuNiO$_3$ and LaNiO$_3$ have been grown on a set of single crystalline substrates by pulsed laser interval deposition to investigate the effect of epitaxial strain on electronic and magnetic properties at the extreme interface limit. Despite the variation of substrate in-plane lattice constants and lattice symmetry, the structural response to heterostructuring is primarily controlled by the presence of EuNiO$_3$ layer. In sharp contrast to bulk LaNiO$_3$ or EuNiO$_3$, the superlattices grown under tensile strains exhibit metal to insulator transition (MIT) below room temperature. The onset of magnetic and electronic transitions associated with the MIT can be further separated by application of large tensile strain. Furthermore, these transitions can be entirely suppressed by very small compressive strain. X-ray resonant absorption spectroscopy measurements reveal that such strain-controlled MIT is directly linked to strain induced self-doping effect without any chemical doping., Comment: Accepted in Phys. Rev. B

Samarium hexaboride is a topological Kondo insulator, with metallic surface states manifesting from its insulating band structure. Since the insulating bulk itself is driven by strong correlations, both the bulk and surface host compelling magnetic and electronic phenomena. We employed X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) at the Sm M$_{4,5}$ edges to measure surface and bulk magnetic properties of Sm$^{2+}$ and Sm$^{3+}$ within SmB$_6$. We observed anti-alignment to the applied field of the Sm$^{3+}$ magnetic dipole moment below $T = 75$ K and of the total orbital moment of samarium below 30 K. The induced Sm$^{3+}$ moment at the cleaved surface at 8 K and 6 T implies 1.5% of the total Sm as magnetized Sm$^{3+}$. The field dependence of the Sm$^{3+}$ XMCD dichorism at 8 K is diamagnetic and approximately linear. The bulk magnetization at 2 K is however driven by Sm$^{2+}$ Van Vleck susceptibility as well as 1% paramagnetic impurities with $\mu_{\rm Eff} = 5.2(1)~\mu_{\rm B}$. This indicates diamagnetic Sm$^{3+}$ is compensated within the bulk. The XAS and XMCD spectra are weakly affected by Sm vacancies and carbon doping while XAS is strongly affected by polishing.

Coupled transitions between distinct ordered phases are important aspects behind the rich phase complexity of correlated oxides that hinders 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 ultra-short period superlattices, which allow one to disentangle the simultaneous orderings in $RE$NiO$_3$. 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., Comment: Accepted in Phys. Rev. Lett

High temperature cuprate superconductivity remains a defining problem in condensed matter physics. Among myriad approaches to addressing this problem has been the study of alternative transition metal oxides with similar structures and 3d electron count that are suggested as proxies for cuprate physics. None of these analogs has been superconducting, and few are even metallic. Here, we report that the low-valent, quasi-two-dimensional trilayer compound, Pr4Ni3O8 avoids a charge-stripe ordered phase previously reported for La4Ni3O8, leading to a metallic ground state. By combining x-ray absorption spectroscopy and density functional theory calculations, we further find that metallic Pr4Ni3O8 exhibits a low-spin configuration and significant orbital polarization of the unoccupied eg states with pronounced dx2-y2 character near the Fermi energy, both hallmarks of the cuprate superconductors. Belonging to a regime of 3d electron count found for hole-doped cuprates, Pr4Ni3O8 thus represents one of the closest analogies to cuprates yet reported and a singularly promising candidate for high-Tc superconductivity if appropriately doped., Comment: 20 pages, 4 figures

The dynamical processes associated with electric field manipulation of the polarization in a ferroelectric remain largely unknown but fundamentally determine the speed and functionality of ferroelectric materials and devices. Here we apply sub-picosecond duration, single-cycle terahertz pulses as an ultrafast electric field bias to prototypical BaTiO$_3$ ferroelectric thin films with the atomic-scale response probed by femtosecond x-ray scattering techniques. We show that electric fields applied perpendicular to the ferroelectric polarization drive large amplitude displacements of the titanium atoms along the ferroelectric polarization axis, comparable to that of the built-in displacements associated with the intrinsic polarization and incoherent across unit cells. This effect is associated with a dynamic rotation of the ferroelectric polarization switching on and then off on picosecond timescales. These transient polarization modulations are followed by long-lived vibrational heating effects driven by resonant excitation of the ferroelectric soft mode, as reflected in changes in the c-axis tetragonality. The ultrafast structural characterization described here enables direct comparison with first-principles-based molecular dynamics simulations, with good agreement obtained.

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 $T_c$ superconductor YBa$_2$Cu$_3$O$_7$ (YBCO) and colossal magnetoresistance ferromagnet La$_{0.67}$Ca$_{0.33}$MnO$_3$ (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 response 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 $T_c$ 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., Comment: Accepted in Scientific Reports

The electronic structure of transition metal oxides featuring correlated electrons can be rationalized within the Zaanen-Sawatzky-Allen framework. Following a brief description of the present paradigms of electronic behavior, we focus on the physics of rare earth nickelates as an archetype of complexity emerging within the charge transfer regime. The intriguing prospect of realizing the physics of high $T_c$ cuprates through heterostructuring resulted in a massive endeavor to epitaxially stabilize these materials in ultra-thin form. A plethora of new phenomena unfolded in such artificial structures due to the effect of epitaxial strain, quantum confinement, and interfacial charge transfer. Here we review the present status of artificial rare-earth nickelates in an effort to uncover the interconnection between the electronic and magnetic behavior and the underlying crystal structure. We conclude by discussing future directions to disentangle the puzzle regarding the origin of the metal-insulator transition, the role of oxygen holes, and the true nature of the antiferromagnetic spin configuration in the ultra-thin limit., Comment: Invited review article (Annual Review of Materials Research)

Magnetic flux noise is a dominant source of dephasing and energy relaxation in superconducting qubits. The noise power spectral density varies with frequency as $1/f^\alpha$ with $\alpha \sim 1$ and spans 13 orders of magnitude. Recent work indicates that the noise is from unpaired magnetic defects on the surfaces of the superconducting devices. Here, we demonstrate that adsorbed molecular O$_2$ is the dominant contributor to magnetism in superconducting thin films. We show that this magnetism can be suppressed by appropriate surface treatment or improvement in the sample vacuum environment. We observe a suppression of static spin susceptibility by more than an order of magnitude and a suppression of $1/f$ magnetic flux noise power spectral density by more than a factor of 5. These advances open the door to realization of superconducting qubits with improved quantum coherence., Comment: Main text: 5 pages, 4 figures. Supplement: 8 pages, 6 figures

We report on the phase diagram of competing magnetic interactions at nanoscale in engineered ultra-thin 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 tunable two-dimensional $d$-electron Kondo lattice, and potential spin Hall applications.

Vanadium dioxide, an archetypal correlated-electron material, undergoes an insulator-metal transition near room temperature that exhibits electron-correlation-driven and structurally-driven physics. Using ultrafast optical spectroscopy and x-ray scattering we show that these processes can be disentangled in the time domain. Specifically, following intense sub-picosecond electric-field excitation, a partial collapse of the insulating gap occurs within the first ps. Subsequently, this electronic reconfiguration initiates a change in lattice symmetry taking place on a slower timescale. We identify the kinetic energy increase of electrons tunneling in the strong electric field as the driving force, illustrating a novel method to control electronic interactions in correlated materials on an ultrafast timescale.

We present a comparison of the in-plane length scale over which charge and magnetism are correlated in (La0.4Pr0.6)1-xCaxMnO3 films with x = 0.33 and 0.375, across the metal to insulator transition (MIT) temperature. We combine electrical transport (resistance) measurements, x-ray absorption spectroscopy (XAS), x-ray magnetic circular dichroism (XMCD), and specular/off-specular x-ray resonant magnetic scattering (XRMS) measurements as a function of temperature to elucidate relationships between electronic, magnetic and morphological structure of the thin films. Using off-specular XRMS we obtained the charge-charge and charge-magnetic correlation length of these LPCMO films near the MIT. The charge-magnetic correlation length (~ 12000 {\AA}) for x = 0.33 was much larger (~4 times) than the charge-charge correlation length (~ 3200 {\AA}) at 20 K. Whereas for x = 0.375 the charge-magnetic correlation length (~ 7500 {\AA}) was smaller than the charge-charge correlation length (~ 9000 {\AA}).

High-quality (001)-oriented (pseudo-cubic notation) ferromagnetic YTiO$_3$ thin films were epitaxially synthesized in a layer-by-layer way by pulsed laser deposition. Structural, magnetic and electronic properties were characterized by reflection-high-energy-electron-diffraction, X-ray diffraction, vibrating sample magnetometry, and element-resolved resonant soft X-ray absorption spectroscopy. To reveal ferromagnetism of the constituent titanium ions, X-ray magnetic circular dichroism spectroscopy was carried out using four detection modes probing complimentary spatial scale, which overcomes a challenge of probing ferromagnetic titanium with pure Ti3+(3d$^1$). Our work provides a pathway to distinguish between the roles of titanium and A-site magnetic rare-earth cations in determining the magnetism in rare-earth titanates thin films and heterostructures.

In response to Lu et al, (arXiv:1506.02787v1), here we present a detailed writeup concerning the questions raised in their comment on our eprint (arXiv:1505.07451). The key question raised by Lu et al was if the bulk-like charge ordered state becomes indetectable with resonant scattering due to ultrathin film thickness. In this reply, we first detail the relation of our work to past work on the same compound by Staub et al to demonstrate that the presented data are indeed sufficient to support our claims of no charge order on ultra thin films of NdNiO3 (NNO) on NdGaO3 (NGO). Further, we demonstrate that if a well defined charge ordered phase exists in ultra thin films, it is indeed resolvable such as that in EuNiO3 (ENO)., Comment: 7 pages, 1 figure

In complex materials observed electronic phases and transitions between them often involves 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 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 a purely electronic Mott metal-insulator transition., Comment: 16 pages, 4 Figures

Using a combination of X-ray absorption spectroscopy experiments with first principle calculations, we demonstrate that insulating KCuO_2 contains Cu in an unusually-high formal-3+ valence state, the ligand-to-metal (O to Cu) charge transfer energy is intriguingly negative (Delta~ -1.5 eV) and has a dominant (~60%) ligand-hole character in the ground state akin to the high Tc cuprate Zhang-Rice state. Unlike most other formal Cu^{3+} compounds, the Cu 2p XAS spectra of KCuO_2 exhibits pronounced 3d^8 (Cu^{3+}) multiplet structures, which accounts for ~40% of its ground state wave-function. Ab-initio calculations elucidate the origin of the band-gap in KCuO_2 as arising primarily from strong intra-cluster Cu 3d - O 2p hybridizations (t_{pd}); the value of the band-gap decreases with reduced value of t_{pd}. Further, unlike conventional negative charge-transfer insulators, the band-gap in KCuO_2 persists even for vanishing values of Coulomb repulsion U, underscoring the importance of single-particle band-structure effects connected to the one-dimensional nature of the compound.

In pursuit of creating cuprate-like electronic and orbital structures, artificial heterostructures based on LaNiO$_3$ 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 after 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 correlated metal LaNiO$_3$ and doped Mott insulator LaTiO$_{3+\delta}$, 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 $e_\textrm{g}$ 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., Comment: 4 figures

We demonstrate that magnetic properties of ultra-thin Co films adjacent to Gd2O3 gate oxides can be directly manipulated by voltage. The Co films can be reversibly changed from an optimally-oxidized state with a strong perpendicular magnetic anisotropy to a metallic state with an in-plane magnetic anisotropy, or to an oxidized state with nearly zero magnetization, depending on the polarity and time duration of the applied electric fields. Consequently, an unprecedentedly large change of magnetic anisotropy energy up to 0.73 erg/cm2 has been realized in a nonvolatile manner using gate voltages of only a few volts. These results open a new route to achieve ultra-low energy magnetization manipulation in spintronic devices., Comment: 12 pages, 9 figures, including supplemental materials. Phys. Rev. Lett., in press (Editors' Suggestion, featured in Physics)

Interfaces between correlated complex oxides are promising avenues to realize new forms of magnetism that arise as a result of charge transfer, proximity effects and locally broken symmetries. We report upon the discovery of a non-collinear magnetic structure in superlattices of the ferromagnetic metallic oxide La2/3Sr1/3MnO3 (LSMO) and the correlated metal LaNiO3 (LNO). The exchange interaction between LSMO layers is mediated by the intervening LNO, such that the angle between the magnetization of neighboring LSMO layers varies in an oscillatory manner with the thickness of the LNO layer. The magnetic field, temperature, and spacer thickness dependence of the non-collinear structure are inconsistent with the bilinear and biquadratic interactions that are used to model the magnetic structure in conventional metallic multilayers. A model that couples the LSMO layers to a helical spin state within the LNO fits the observed behavior. We propose that the spin-helix results from the interaction between a spatially varying spin susceptibility within the LNO and interfacial charge transfer that creates localized Ni2+ states. This provides a new approach to engineering non-collinear spin textures in metallic oxide heterostructures that can be exploited in devices based on both spin and charge transport.

Deterministic control over the periodic geometrical arrangement of the constituent atoms is the backbone of the material properties, that 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 pseudo cubic [111] direction. The resulting artificial graphene-like Mott crystal with magnetic 3$d$ electrons has antiferromagnetic correlations. In addition, a combination of resonant X-ray linear dichroism measurements and \textit{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., Comment: Text, Figures have been modified

We report on the fabrication of high quality (1 1 1)-oriented ferrimagnetic normal spinel CoCr2O4 epitaxial thin films on single crystal Al2O3 substrates. The structural, electronic and magnetic properties were characterized by in-situ reflection high energy electron diffraction, atomic force microscopy, X-ray diffraction, X-ray photoemission spectroscopy, SQUID magnetometry and element resolved resonant X-ray magnetic scattering. The comprehensive characterization reveals that no disorder in the cation distribution or multivalency issue is present in the samples. As a result, Kagome and triangular layers are naturally formed via this specific growth approach. These findings offer a pathway to fabricate two dimensional Kagome heterostructures with novel quantum many-body phenomena by means of geometrical design., Comment: 11 pages, 4 figures

With current research efforts shifting towards the 4$d$ and 5$d$ transition metal oxides, understanding the evolution of the electronic and magnetic structure as one moves away from 3$d$ materials is of critical importance. Here we perform X-ray spectroscopy and electronic structure calculations on $A$-site ordered perovskites with Cu in the $A$-site and the $B$-sites descending along the 9th group of the periodic table to elucidate the emerging properties as $d$-orbitals change from partially filled 3$d$, 4$d$, to 5$d$. The results show that when descending from Co to Ir the charge transfers from the cuprate like Zhang-Rice state on Cu to the t$_{2g}$ orbital of the B site. As the Cu $d$-orbital occupation approaches the Cu$^{2+}$ limit, a mixed-valence state in CaCu$_3$Rh$_4$O$_{12}$ and heavy fermion state in CaCu$_3$Ir$_4$O$_{12}$ are obtained. The investigated d-electron compounds are mapped onto the Doniach phase diagram of the competing RKKY and Kondo interactions developed for f-electron systems., Comment: 4 pages, 4 figures

Ultra-thin films of the electron doped manganite La$_{0.8}$Ce$_{0.2}$MnO$_3$ were grown in a layer-by-layer growth mode on SrTiO$_3$ (001) substrates by pulsed laser interval deposition. High structural quality and surface morphology was confirmed by a combination of synchrotron based x-ray diffraction and atomic force microscopy. Resonant X-ray absorption spectroscopy measurements confirm the presence of Ce$^{+4}$ and Mn$^{+2}$ ions. In addition, the electron doping signature was corroborated by Hall effect measurements. All grown films show ferromagnetic ground state as revealed by both XMCD and magnetoresistance measurements and remain insulating contrary to earlier reports of metal-insulator transition. Our results hint at the possibility of electron-hole asymmetry in the colossal magnetoresistive (CMR) manganite phase diagram akin to high-$T_c$ cuprates.

Topological insulators are materials characterized by dissipationless, spin-polarized surface states resulting from non-trivial band topologies. Recent theoretical models and experiments suggest that SmB6 is the first topological Kondo insulator, in which the topologically non-trivial band structure results from electron-electron interactions via Kondo hybridization. Here, we report that the surface conductivity of SmB6 increases systematically with bulk carbon content. Further, addition of carbon is linked to an increase in n-type carriers, larger low temperature electronic contributions to the specific heat with a characteristic temperature scale of T* = 17 K, and a broadening of the crossover to the insulating state. Additionally, X-ray absorption spectroscopy shows a change in Sm valence at the surface. Our results highlight the importance of phonon dynamics in producing a Kondo insulating state and demonstrate a correlation between the bulk thermodynamic state and low temperature resistance of SmB6.

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 LaNiO$_3$ on the band insulator SrTiO$_3$ along the pseudo cubic [111] direction. While in general the metallic LaNiO$_3$ 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 La$_2$Ni$_2$O$_5$ (Ni$^{2+}$) for a few unit-cell thick films. First-principles layer-resolved calculations of the potential energy across the nominal LaNiO$_3$/SrTiO$_3$ interface confirm that the oxygen vacancies can efficiently reduce the electric field at the interface.

Octahedral distortion plays a key role in engineering the physical properties of heterostructures composed of perovskite oxides. We observe a strong in-plane uniaxial magnetic anisotropy in a strain-enabled multiferroic EuTiO3 thin film epitaxially grown on a (110)o DyScO3 substrate. First principles calculations show that the magnetic anisotropy is closely correlated with the uniaxial TiO6 octahedral tilting and the ferroelectric polarization of the film, indicating potential strong magnetoelectric coupling in the strain-engineered multiferroic system., Comment: Accepted by Phys. Rev. B

We report a strong effect of interface-induced magnetization on the transport properties of magnetic tunnel junctions consisting of ferromagnetic manganite La$_{0.7}$Ca$_{0.3}$MnO$_{3}$ and insulating cuprate PrBa$_{2}$Cu$_{3}$O$_{7}$. Contrary to the typically observed steady increase of the tunnel magnetoresistance with decreasing temperature, this system exhibits a sudden anomalous decrease at low temperatures. Interestingly, this anomalous behavior can be attributed to the competition between the positive spin polarization of the manganite contacts and the negative spin-filter effect from the interface-induced Cu magnetization., Comment: 5 pages, 4 figures, with supplemental materials (2 figures). Physical Review Letters, in press

Ultrathin epitaxial films of EuNiO3 were grown on a series of substrates traversing highly compressive (- 2.4%) to highly tensile (2.5%) lattice mismatch. X-ray diffraction measurements showed the expected c-lattice parameter shift for compressive strain, but no detectable shift for tensilely strained substrates, while reciprocal space mapping confirmed the tensile strained film maintained epitaxial coherence. Transport measurements showed a successively (from tensile to compressive) lower resistance and a complete suppression of the metalinsulator transition at highly compressive lattice mismatch. Corroborating these findings, X-ray absorption spectroscopy measurements revealed a strong multiplet splitting in the tensile samples that progressively weakens with increasing compressive strain that, combined with cluster calculations, showed enhanced covalence between Ni-d and O-p orbitals leads to the metallic state.

We report on a resonant soft X-ray spectroscopy study of the electronic and magnetic structure of the cuprate-manganite interface. Polarized X-ray spectroscopy measurements taken at the Cu L edge reveal up to a five-fold increase in the dichroic signal as compared to past experimental and theoretical values. Furthermore an increase in the degree of interlayer charge transfer up to 0.25e (where e is charge of an electron) per copper ion is observed leading to a profound reconstruction in the orbital scheme for these interfacial copper ions. It is inferred that these enhancement are related to an increase in TMI observed for manganite layers grown with rapidly modulated flux.

The epitaxial stabilization of a single layer or superlattice structures composed of complex oxide materials on polar (111) surfaces is severely burdened by reconstructions at the interface, that commonly arise to neutralize the polarity. We report on the synthesis of high quality LaNiO$_3$/mLaAlO$_3$ pseudo cubic (111) superlattices on polar (111)-oriented LaAlO$_3$, the proposed complex oxide candidate for a topological insulating behavior. Comprehensive X-Ray diffraction measurements, RHEED, and element specific resonant X-ray absorption spectroscopy affirm their high structural and chemical quality. The study offers an opportunity to fabricate interesting interface and topology controlled (111) oriented superlattices based on ortho-nickelates.

Magnetism in La$_{1-x}$Sr$_x$CoO$_3$ as a function of doping is investigated with X-ray absorption spectroscopy and X-ray magnetic circular dichroism at the O K edge, and corresponding first principles electronic structure calculations. For small x, the spectra are consistent with the formation of ferromagnetic clusters occurring within a nonmagnetic insulating matrix. Sr-induced, magnetic O-hole states form just above E$_F$ and grow with increasing Sr doping. Density functional calculations for x = 0 yield a nonmagnetic ground state with the observed rhombohedral distortion and indicates that doping introduces holes at the Fermi level in magnetic states with significant O 2p and Co t$_{2g}$ character for the undistorted pseudocubic structure. Supercell calculations show stronger magnetism on oxygen atoms having more Sr neighbors.