Growth and Electronic Structure of Copper Oxide Monolayer Epitaxial Films.

Copper-based high-temperature superconductors share a common feature in their crystal structure, which is the presence of a CuO2 plane, where superconductivity takes place. Therefore, important questions arise as to whether superconductivity can exist in a single layer of the CuO2 plane and, if so, how such superconductivity in a single CuO2 plane differs from that in a bulk cuprate system. To answer these questions, studies of the superconductivity in cuprate monolayers are necessary. In this study, we constructed a heterostructure system with a La2-xSrxCuO4 (LSCO) monolayer containing a single CuO2 plane and measured the resulting electronic structures. Monolayer LSCO has metallic and bulk-like electronic structures. The hole doping ratio of the monolayer LSCO is found to depend on the underlying buffer layer due to the interface effect. Our work will provide a platform for research into ideal two-dimensional cuprate systems.

Extended Oxygen Octahedral Tilt Proximity near Oxide Heterostructures.

The oxide interfaces between materials with different structural symmetries have been actively studied due to their novel physical properties. However, the investigation of intriguing interfacial phenomena caused by the oxygen octahedral tilt (OOT) proximity effect has not been fully exploited, as there is still no clear understanding of what determines the proximity length and what the underlying control mechanism is. Here, we achieved scalability of the OOT proximity effect in SrRuO3 (SRO) by epitaxial strain near the SRO/SrTiO3 heterointerface. We demonstrated that the OOT proximity length scale of SRO is extended from 4 unit cells to 14 unit cells by employing advanced scanning transmission electron microscopy. We also suggest that this variation may originate from changes in phonon dispersions due to electron-phonon coupling in SRO. This study will provide in-depth insights into the structural gradients of correlated systems and facilitate potential device applications.

Sign-tunable anomalous Hall effect induced by two-dimensional symmetry-protected nodal structures in ferromagnetic perovskite thin films.

Magnetism and spin-orbit coupling are two quintessential ingredients underlying topological transport phenomena in itinerant ferromagnets. When spin-polarized bands support nodal points/lines with band degeneracy that can be lifted by spin-orbit coupling, the nodal structures become a source of Berry curvature, leading to a large anomalous Hall effect. However, two-dimensional systems can possess stable nodal structures only when proper crystalline symmetry exists. Here we show that two-dimensional spin-polarized band structures of perovskite oxides generally support symmetry-protected nodal lines and points that govern both the sign and the magnitude of the anomalous Hall effect. To demonstrate this, we performed angle-resolved photoemission studies of ultrathin films of SrRuO3, a representative metallic ferromagnet with spin-orbit coupling. We show that the sign-changing anomalous Hall effect upon variation in the film thickness, magnetization and chemical potential can be well explained by theoretical models. Our work may facilitate new switchable devices based on ferromagnetic ultrathin films.

Flexoelectricity-Driven Mechanical Switching of Polarization in Metastable Ferroelectrics.

Flexoelectricity-based mechanical switching of ferroelectric polarization has recently emerged as a fascinating alternative to conventional polarization switching using electric fields. Here, we demonstrate hyperefficient mechanical switching of polarization exploiting metastable ferroelectricity that inherently holds a unique mechanical response. We theoretically predict that mechanical forces markedly reduce the coercivity of metastable ferroelectricity, thus greatly bolstering flexoelectricity-driven mechanical polarization switching. As predicted, we experimentally confirm the mechanical polarization switching via an unusually low mechanical force (100 nN) in metastable ferroelectric CaTiO_{3}. Furthermore, the use of low mechanical forces narrows the width of mechanically writable nanodomains to sub-10 nm, suggesting an ultrahigh data storage density of ≥1 Tbit cm^{-2}. This Letter sheds light on the mechanical switching of ferroelectric polarization as a viable key element for next-generation efficient nanoelectronics and nanoelectromechanics.

In Situ Cryogenic HAADF-STEM Observation of Spontaneous Transition of Ferroelectric Polarization Domain Structures at Low Temperatures.

Precise determination of atomic structures in ferroelectric thin films and their evolution with temperature is crucial for fundamental study and design of functional materials. However, this has been impeded by the lack of techniques applicable to a thin-film geometry. Here we use cryogenic scanning transmission electron microscopy (STEM) to observe the atomic structure of a BaTiO3 film on a (111)-SrTiO3 substrate under varying temperatures. Our study explicitly proves a structure transition from a complex polymorphic nanodomain configuration at room temperature transitioning to a homogeneous ground-state rhombohedral structure of BaTiO3 below ∼250 K, which was predicted by phase-field simulation. More importantly, another unexpected transition is revealed, a transition to complex nanodomains below ∼105 K caused by an altered mechanical boundary condition due to the antiferrodistortive phase transition of the SrTiO3 substrate. This study demonstrates the power of cryogenic STEM in elucidating structure-property relationships in numerous functional materials at low temperatures.

Superconducting Sr2RuO4 Thin Films without Out-of-Phase Boundaries by Higher-Order Ruddlesden-Popper Intergrowth.

Ruddlesden-Popper (RP) phases (An+1BnO3n+1, n = 1, 2,···) have attracted intensive research with diverse functionalities for device applications. However, the realization of a high-quality RP-phase film is hindered by the formation of out-of-phase boundaries (OPBs) that occur at terrace edges, originating from lattice mismatch in the c-axis direction with the A'B'O3 (n = ∞) substrate. Here, using strontium ruthenate RP-phase Sr2RuO4 (n = 1) as a model system, an experimental approach for suppressing OPBs was developed. By tuning the growth parameters, the Sr3Ru2O7 (n = 2) phase was formed in a controlled manner near the film-substrate interface. This higher-order RP-phase then blocked the subsequent formation of OPBs, resulting in nearly defect-free Sr2RuO4 layer at the upper region of the film. Consequently, the Sr2RuO4 thin films exhibited superconductivity up to 1.15 K, which is the highest among Sr2RuO4 films grown by pulsed laser deposition. This work paves the way for synthesizing pristine RP-phase heterostructures and exploring their unique physical properties.

Bulk Metamaterials Exhibiting Chemically Tunable Hyperbolic Responses.

Extraordinary properties of traditional hyperbolic metamaterials, not found in nature, arise from their man-made subwavelength structures causing unique light-matter interactions. However, their preparation requiring nanofabrication processes is highly challenging and merely provides nanoscale two-dimensional structures. Stabilizing their bulk forms via scalable procedures has been a sought-goal for broad applications of this technology. Herein, we report a new strategy of designing and realizing bulk metamaterials with finely tunable hyperbolic responses. We develop a facile two-step process: (1) self-assembly to obtain heterostructured nanohybrids of building blocks and (2) consolidation to convert nanohybrid powders to dense bulk pellets. Our samples have centimeter-scale dimensions typically, readily further scalable. Importantly, the thickness of building blocks and their relative concentration in bulk materials serve as a delicate means of controlling hyperbolic responses. The resulting new bulk heterostructured material system consists of the alternating h-BN and graphite/graphene nanolayers and exhibits significant modulation in both type-I and type-II hyperbolic resonance modes. It is the first example of real bulk hyperbolic metamaterials, consequently displaying the capability of tuning their responses along both in-plane and out-of-plane directions of the materials for the first time. It also distinctly interacts with unpolarized and polarized transverse magnetic and electronic beams to give unique hyperbolic responses. Our achievement can be a new platform to create various bulk metamaterials without complicated nanofabrication techniques. Our facile synthesis method using common laboratory techniques can open doors to broad-range researchers for active interdisciplinary studies for this otherwise hardly accessible technology.

Observation of Spin-Dependent Dual Ferromagnetism in Perovskite Ruthenates.

We performed in situ angle-resolved photoemission spectroscopy (ARPES) and spin-resolved ARPES (SARPES) experiments to investigate the relationship between electronic band structures and ferromagnetism in SrRuO_{3} (SRO) thin films. Our high quality ARPES and SARPES results show clear spin-lifted band structures. The spin polarization is strongly dependent on momentum around the Fermi level, whereas it becomes less dependent at high-binding energies. This experimental observation matches our dynamical mean-field theory results very well. As temperature increases from low to the Curie temperature, spin-splitting gap decreases and band dispersions become incoherent. Based on the ARPES study and theoretical calculation results, we found that SRO possesses spin-dependent electron correlations in which majority and minority spins are localized and itinerant, respectively. Our finding explains how ferromagnetism and electronic structure are connected, which has been under debate for decades in SRO.

Controllable Thickness Inhomogeneity and Berry Curvature Engineering of Anomalous Hall Effect in SrRuO3 Ultrathin Films.

In quantum matters hosting electron-electron correlation and spin-orbit coupling, spatial inhomogeneities, arising from competing ground states, can be essential for understanding exotic topological properties. A prominent example is Hall anomalies observed in SrRuO3 films, which were interpreted in terms of either magnetic skyrmion-induced topological Hall effect or inhomogeneous anomalous Hall effect (AHE). To clarify this ambiguity, we systematically investigated the evolution of AHE with controllable inhomogeneities in SrRuO3 film thickness (tSRO). By exploiting the step-flow growth of SrRuO3 films, we induced a microscopically ordered stripe pattern with one-unit-cell differences in tSRO. The associated spatial distribution of momentum-space Berry curvatures enables a two-channel AHE with hump-like Hall anomalies, which can be continuously engineered according to non-integer tSRO. We further microscopically characterized the stripe-like ferromagnetic domains and two-step magnetic switching behavior in the inhomogeneous SrRuO3 film. These unique features can be utilized to identify the two-channel AHE model and understand its microscopic origin.

Polar Metal Phase Induced by Oxygen Octahedral Network Relaxation in Oxide Thin Films.

ABO3 perovskite materials and their derivatives have inherent structural flexibility due to the corner sharing network of the BO6 octahedron, and the large variety of possible structural distortions and strong coupling between lattice and charge/spin degrees of freedom have led to the emergence of intriguing properties, such as high-temperature superconductivity, colossal magnetoresistance, and improper ferroelectricity. Here, an unprecedented polar ferromagnetic metal phase in SrRuO3 (SRO) thin films is presented, arising from the strain-controlled oxygen octahedral rotation (OOR) pattern. For compressively strained SRO films grown on SrTiO3 substrate, oxygen octahedral network relaxation is accompanied by structural phase separation into strained tetragonal and bulk-like orthorhombic phases, and the asymmetric OOR evolution across the phase boundary allows formation of the polar phase, while bulk metallic and ferromagnetic properties are maintained. From the results, it is expected that other oxide perovskite thin films will also yield similar structural environments with variation of OOR patterns, and thereby provide promising opportunities for atomic scale control of material properties through strain engineering.

Phase Instability amid Dimensional Crossover in Artificial Oxide Crystal.

Artificial crystals synthesized by atomic-scale epitaxy provide the ability to control the dimensions of the quantum phases and associated phase transitions via precise thickness modulation. In particular, the reduction in dimensionality via quantized control of atomic layers is a powerful approach to revealing hidden electronic and magnetic phases. Here, we demonstrate a dimensionality-controlled and induced metal-insulator transition (MIT) in atomically designed superlattices by synthesizing a genuine two-dimensional (2D) SrRuO_{3} crystal with highly suppressed charge transfer. The tendency to ferromagnetically align the spins in an SrRuO_{3} layer diminishes in 2D as the interlayer exchange interaction vanishes, accompanying the 2D localization of electrons. Furthermore, electronic and magnetic instabilities in the two SrRuO_{3} unit cell layers induce a thermally driven MIT along with a metamagnetic transition.

Ferroelectrically tunable magnetic skyrmions in ultrathin oxide heterostructures.

Magnetic skyrmions are topologically protected whirling spin texture. Their nanoscale dimensions, topologically protected stability and solitonic nature, together are promising for future spintronics applications. To translate these compelling features into practical spintronic devices, a key challenge lies in achieving effective control of skyrmion properties, such as size, density and thermodynamic stability. Here, we report the discovery of ferroelectrically tunable skyrmions in ultrathin BaTiO3/SrRuO3 bilayer heterostructures. The ferroelectric proximity effect at the BaTiO3/SrRuO3 heterointerface triggers a sizeable Dzyaloshinskii-Moriya interaction, thus stabilizing robust skyrmions with diameters less than a hundred nanometres. Moreover, by manipulating the ferroelectric polarization of the BaTiO3 layer, we achieve local, switchable and nonvolatile control of both skyrmion density and thermodynamic stability. This ferroelectrically tunable skyrmion system can simultaneously enhance the integratability and addressability of skyrmion-based functional devices.

Charge Transfer in Iridate-Manganite Superlattices.

Charge transfer in superlattices consisting of SrIrO3 and SrMnO3 is investigated using density functional theory. Despite the nearly identical work function and nonpolar interfaces between SrIrO3 and SrMnO3, rather large charge transfer was experimentally reported at the interface between them. Here, we report a microscopic model that captures the mechanism behind this phenomenon, providing a qualitative understanding of the experimental observation. This leads to unique strain dependence of such charge transfer in iridate-manganite superlattices. The predicted behavior is consistently verified by experiment with soft X-ray and optical spectroscopy. Our work thus demonstrates a new route to control electronic states in nonpolar oxide heterostructures.

Spin-Orbit Coupling and Interband Transitions in the Optical Conductivity of Sr_{2}RhO_{4}.

The prototypical correlated metal Sr_{2}RhO_{4} was studied using optical and photoemission spectroscopy. At low energies and temperatures, the optical data reveal a complex, multicomponent response that on the surface points to an unconventional metallic state in this material. Via a comparison with photoemission, the anomalous optical response may be attributed to an unexpectedly strong interband transition near 180 meV between spin-orbit coupled bands that are nearly parallel along ΓX. This spin-orbit coupling effect is shown to occur in a number of related metallic ruthenates and explains the previously puzzling optical properties reported for these materials.

Overcoming the Fundamental Barrier Thickness Limits of Ferroelectric Tunnel Junctions through BaTiO3/SrTiO3 Composite Barriers.

Ferroelectric tunnel junctions (FTJs) have attracted increasing research interest as a promising candidate for nonvolatile memories. Recently, significant enhancements of tunneling electroresistance (TER) have been realized through modifications of electrode materials. However, direct control of the FTJ performance through modifying the tunneling barrier has not been adequately explored. Here, adding a new direction to FTJ research, we fabricated FTJs with BaTiO3 single barriers (SB-FTJs) and BaTiO3/SrTiO3 composite barriers (CB-FTJs) and reported a systematic study of FTJ performances by varying the barrier thicknesses and compositions. For the SB-FTJs, the TER is limited by pronounced leakage current for ultrathin barriers and extremely small tunneling current for thick barriers. For the CB-FTJs, the extra SrTiO3 barrier provides an additional degree of freedom to modulate the barrier potential and tunneling behavior. The resultant high tunability can be utilized to overcome the barrier thickness limits and enhance the overall CB-FTJ performances beyond those of SB-FTJ. Our results reveal a new paradigm to manipulate the FTJs through designing multilayer tunneling barriers with hybrid functionalities.

Evidence for Anionic Excess Electrons in a Quasi-Two-Dimensional Ca2N Electride by Angle-Resolved Photoemission Spectroscopy.

Angle-resolved photoemission spectroscopy (ARPES) study of a layered electride Ca2N was carried out to reveal its quasi-two-dimensional electronic structure. The band dispersions and the Fermi-surface map are consistent with the density functional theory results except for a chemical potential shift that may originate from the high reactivity of surface excess electrons. Thus, the existence of anionic excess electrons in the interlayer region of Ca2N is strongly supported by ARPES.

Humidity effect on nanoscale electrochemistry in solid silver ion conductors and the dual nature of its locality.

Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically nonlocal cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor. We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and nonlocal) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.

Suppression of Three-Dimensional Charge Density Wave Ordering via Thickness Control.

Barium bismuth oxide (BaBiO_{3}) is the end member of two families of high-T_{c} superconductors, i.e., BaPb_{1-x}Bi_{x}O_{3} and Ba_{1-x}K_{x}BiO_{3}. The undoped parent compound is an insulator, exhibiting a charge density wave that is strongly linked to a static breathing distortion in the oxygen sublattice of the perovskite structure. We report a comprehensive spectroscopic and x-ray diffraction study of BaBiO_{3} thin films, showing that the minimum film thickness required to stabilize the breathing distortion and charge density wave is ≈11 unit cells, and that both phenomena are suppressed in thinner films. Our results constitute the first experimental observation of charge density wave suppression in bismuthate compounds without intentionally introducing dopants.

Role of preferential weak hybridization between the surface-state of a metal and the oxygen atom in the chemical adsorption mechanism.

We report on the chemical adsorption mechanism of atomic oxygen on the Pt(111) surface using angle-resolved-photoemission spectroscopy (ARPES) and density functional calculations. The detailed band structure of Pt(111) from ARPES reveals that most of the bands near the Fermi level are surface-states. By comparing band maps of Pt and O/Pt, we identify that dxz (dyz) and dz(2) orbitals are strongly correlated in the surface-states around the symmetry point M and K, respectively. Additionally, we demonstrate that the s- or p-orbital of oxygen atoms hybridizes preferentially with the dxz (dyz) orbital near the M symmetry point. This weak hybridization occurs with minimal charge transfer.

Flexoelectric rectification of charge transport in strain-graded dielectrics.

Flexoelectricity is emerging as a fascinating means for exploring the physical properties of nanoscale materials. Here, we demonstrated the unusual coupling between electronic transport and the mechanical strain gradient in a dielectric epitaxial thin film. Utilizing the nanoscale strain gradient, we showed the unique functionality of flexoelectricity to generate a rectifying diode effect. Furthermore, using conductive atomic force microscopy, we found that the flexoelectric effect can govern the local transport characteristics, including spatial conduction inhomogeneities, in thin-film epitaxy systems. Consideration of the flexoelectric effect will improve understanding of the charge conduction mechanism at the nanoscale and may facilitate the advancement of novel nanoelectronic device design.