Offcut Substrate-Induced Defect Trapping at Step Edges.

We report step edge-induced localized defects suppressing subsequent antiphase boundary formation in the bulk structure of a trilayer oxide heterostructure. The heterostructure encompasses a layer of La0.66Sr0.34MnO3 sandwiched between a superconducting La1.84Sr0.16CuO4 bottom layer and an insulating La2CuO4 top layer. The combination of a minor a-axis mismatch (0.11 Å) and a pronounced c-axis mismatch (2.73 Å) at the step edges leads to the emergence of localized defects exclusively forming at the step edge. Employing atomically resolved electron energy-loss spectroscopy maps, we discern the electronic state of those structures in the second La0.66Sr0.34MnO3 unit cell near the step edge. In particular, a reduction in the pre-edge region of the O-K edge indicates the formation of oxygen vacancies induced by the strained step edge. This study underscores our capability to control defects at the nanoscale.

Optical conductivity and superconductivity in highly overdoped La2-x Ca x CuO4 thin films.

We have used atomic layer-by-layer oxide molecular beam epitaxy to grow epitaxial thin films of [Formula: see text] with x up to 0.5, greatly exceeding the solubility limit of Ca in bulk systems ([Formula: see text]). A comparison of the optical conductivity measured by spectroscopic ellipsometry to prior predictions from dynamical mean-field theory demonstrates that the hole concentration p is approximately equal to x. We find superconductivity with [Formula: see text] of 15 to 20 K up to the highest doping levels and attribute the unusual stability of superconductivity in [Formula: see text] to the nearly identical radii of La and Ca ions, which minimizes the impact of structural disorder. We conclude that careful disorder management can greatly extend the "superconducting dome" in the phase diagram of the cuprates.

Direct observation of strong surface reconstruction in partially reduced nickelate films.

The polarity of a surface can affect the electronic and structural properties of oxide thin films through electrostatic effects. Understanding the mechanism behind these effects requires knowledge of the atomic structure and electrostatic characteristics at the surface. In this study, we use annular bright-field imaging to investigate the surface structure of a Pr0.8Sr0.2NiO2+x (0 < x < 1) film. We observe a polar distortion coupled with octahedral rotations in a fully oxidized Pr0.8Sr0.2NiO3 sample, and a stronger polar distortion in a partially reduced sample. Its spatial depth extent is about three unit cells from the surface. Additionally, we use four-dimensional scanning transmission electron microscopy (4D-STEM) to directly image the local atomic electric field surrounding Ni atoms near the surface and discover distinct valence variations of Ni atoms, which are confirmed by atomic-resolution electron energy-loss spectroscopy (EELS). Our results suggest that the strong surface reconstruction in the reduced sample is closely related to the formation of oxygen vacancies from topochemical reduction. These findings provide insights into the understanding and evolution of surface polarity at the atomic level.

Tracing the dynamics of superconducting order via transient terahertz third-harmonic generation.

Ultrafast optical control of quantum systems is an emerging field of physics. In particular, the possibility of light-driven superconductivity has attracted much of attention. To identify nonequilibrium superconductivity, it is necessary to measure fingerprints of superconductivity on ultrafast timescales. Recently, nonlinear THz third-harmonic generation (THG) was shown to directly probe the collective degrees of freedoms of the superconducting condensate, including the Higgs mode. Here, we extend this idea to light-driven nonequilibrium states in superconducting La2-xSrxCuO4, establishing an optical pump-THz-THG drive protocol to access the transient superconducting order-parameter quench and recovering on few-picosecond timescales. We show in particular the ability of two-dimensional TH spectroscopy to disentangle the effects of optically excited quasiparticles from the pure order-parameter dynamics, which are unavoidably mixed in the pump-driven linear THz response. Benchmarking the gap dynamics to existing experiments shows the ability of driven THG spectroscopy to overcome these limitations in ordinary pump-probe protocols.

Anomalous expansion of the copper-apical-oxygen distance in superconducting cuprate bilayers.

We have introduced an improved x-ray phase-retrieval method with unprecedented speed of convergence and precision, and used it to determine with sub-Angstrom resolution the complete atomic structure of epitaxial La(2-x)Sr(x)CuO(4) ultrathin films. We focus on superconducting heterostructures built from constituent materials that are not superconducting in bulk samples. Single-phase metallic or superconducting films are also studied for comparison. The results show that this phase-retrieval diffraction method enables accurate measurement of structural modifications in near-surface layers, which may be critically important for elucidation of surface-sensitive experiments. Specifically we find that, while the copper-apical-oxygen distance remains approximately constant in single-phase films, it shows a dramatic increase from the metallic-insulating interface of the bilayer towards the surface by as much as 0.45 A. The apical-oxygen displacement is known to have a profound effect on the superconducting transition temperature.

Generation of Terahertz Radiation via the Transverse Thermoelectric Effect.

Terahertz (THz) radiation is a powerful tool with widespread applications ranging from imaging, sensing, and broadband communications to spectroscopy and nonlinear control of materials. Future progress in THz technology depends on the development of efficient, structurally simple THz emitters that can be implemented in advanced miniaturized devices. Here, it is shown how the natural electronic anisotropy of layered conducting transition metal oxides enables the generation of intense terahertz radiation via the transverse thermoelectric effect. In thin films grown on off-cut substrates, femtosecond laser pulses generate ultrafast out-of-plane temperature gradients, which in turn launch in-plane thermoelectric currents, thus allowing efficient emission of the resulting THz field out of the film structure. This scheme is demonstrated in experiments on thin films of the layered metals PdCoO2 and La1.84 Sr0.16 CuO4 , and model calculations that elucidate the influence of the material parameters on the intensity and spectral characteristics of the emitted THz field are presented. Due to its simplicity, the method opens up a promising avenue for the development of highly versatile THz sources and integrable emitter elements.

Superconductivity at Interfaces in Cuprate-Manganite Superlattices.

One of the unsolved problems for using high-Tc superconducting cuprates for spintronic applications are the short coherence lengths of Cooper pairs in oxides (a few Å), which requires atomically sharp and defect-free interfaces. This research demonstrates the presence of high-Tc superconducting La1.84 Sr0.16 CuO4 in direct proximity to SrLaMnO4 and provides evidence for the sharpness of interfaces between the cuprate and the manganite layers at the atomic scale. These findings shed light on the impact of the chemical potential at the interface of distinct materials on highly sensitive physical properties, such as superconductivity. Additionally, this results show the high stability of ultrathin layers from the same K2 NiF4 -type family, specifically one unit cell of Sr2- x Lax MnO4 and three unit cells of La1.84 Sr0.16 CuO4 . This work advances both the fundamental understanding of the proximity region between superconducting cuprates and manganite phases and the potential use of oxide-based materials in quantum computing.

Design and Differentiation of Quantum States at Subnanometer Scale in La2CuO4-Sr2CuO4-δ Superlattices.

We present a study on the properties of superlattices made of ultrathin Sr2CuO4-δ layers sandwiched between La2CuO4 layers beyond the antiferromagnetic insulating nature of the individual layers of choice. Using molecular beam epitaxy, we synthesized these superlattices and observed superconductivity and metallicity at the interfaces. We probed the hole distribution to determine the discernible quantum states and found that the high-quality epitaxy, combined with mapping the electronic fine structure by electron energy-loss spectroscopy, allowed for the differentiation of insulating, metallic, and superconducting layers at the atomic-column scale. Our results demonstrate the possibility of exploring specific electronic properties at the subnanometer scale and highlight the potential of utilizing metastable Sr2CuO4-δ slabs.

Fano interference between collective modes in cuprate high-Tc superconductors.

Cuprate high-Tc superconductors are known for their intertwined interactions and the coexistence of competing orders. Uncovering experimental signatures of these interactions is often the first step in understanding their complex relations. A typical spectroscopic signature of the interaction between a discrete mode and a continuum of excitations is the Fano resonance/interference, characterized by the asymmetric light-scattering amplitude of the discrete mode as a function of the electromagnetic driving frequency. In this study, we report a new type of Fano resonance manifested by the nonlinear terahertz response of cuprate high-Tc superconductors, where we resolve both the amplitude and phase signatures of the Fano resonance. Our extensive hole-doping and magnetic field dependent investigation suggests that the Fano resonance may arise from an interplay between the superconducting fluctuations and the charge density wave fluctuations, prompting future studies to look more closely into their dynamical interactions.

Emergent Magnetic Fan Structures in Manganite Homojunction Arrays.

Devices with tunable magnetic noncollinearity are important components of superconducting electronics and spintronics, but they typically require epitaxial integration of several complex materials. The spin-polarized neutron reflectometry measurements on La1-x Srx MnO3 homojunction arrays with modulated Sr concentration reported herein have led to the discovery of magnetic fan structures with highly noncollinear alignment of Mn spins and an emergent periodicity twice as large as the array's unit cell. The neutron data show that these magnetic superstructures can be fully long-range ordered, despite the gradual modulation of the doping level created by charge transfer and chemical intermixing. The degree of noncollinearity can be effectively adjusted by low magnetic fields. Notwithstanding their chemical and structural simplicity, oxide homojunctions thus show considerable promise as a platform for tunable complex magnetism and as a powerful design element of spintronic devices.

Imaging mesoscopic antiferromagnetic spin textures in the dilute limit from single-geometry resonant coherent x-ray diffraction.

The detection and manipulation of antiferromagnetic domains and topological antiferromagnetic textures are of central interest to solid-state physics. A fundamental step is identifying tools to probe the mesoscopic texture of an antiferromagnetic order parameter. In this work, we demonstrate that Bragg coherent diffractive imaging can be extended to study the mesoscopic texture of an antiferromagnetic order parameter using resonant magnetic x-ray scattering. We study the onset of the antiferromagnet transition in PrNiO3, focusing on a temperature regime in which the antiferromagnetic domains are dilute in the beam spot and the coherent diffraction pattern modulating the antiferromagnetic peak is greatly simplified. We demonstrate that it is possible to extract the arrangements and sizes of these domains from single diffraction patterns and show that the approach could be extended to a time-structured light source to study the motion of dilute domains or the motion of topological defects in an antiferromagnetic spin texture.

Visualizing the unusual spectral weight transfer in DyBa2Cu3O7-δ thin film.

We report a Spectroscopic Imaging Scanning Tunneling Microscopy (SI-STM) study of a DyBa2Cu3O7-δ (DBCO) thin film (Tc ~ 79 K) synthesized by the molecular beam epitaxy (MBE). We observed an unusual transfer of spectral weight in the local density of states (LDOS) spectra occurring only within the superconducting gap. By a systematic control of the tip-sample distance and the junction resistance, we demonstrate that the spectral weight transfer can be switched at a nano-meter length scale. These results suggest that an interaction between the STM tip and the sample alters the electronic configurations in the film. This probably originates from a combination of an intrinsic band bending at the interface between the surface and the bulk, and a tip-induced band bending. These results may open a new avenue for band engineering and applications of thin films of high-Tc cuprates.

Formation mechanism of Ruddlesden-Popper faults in compressive-strained ABO3 perovskite superlattices.

Ruddlesden-Popper (RP) faults have emerged as a promising candidate for defect engineering in epitaxial ABO3 perovskites. Functionalities could be fine-tuned by incorporating RP faults into ABO3 thin films and superlattices. However, due to the lattice expansion at AO-AO interfaces, it is generally believed that RP faults are only energetically favorable under tensile strain. Contrary to this common cognition, here we present that compressive strain must be regarded as an alternative driving force for creating RP faults. Unlike the conventional perovskite-to-rock-salt transition, the RP faults originated from Shockley partial dislocations bounded by stacking faults on the basal plane. The edge-type partials gave rise to strain relaxation, facilitating the formation of RP faults under compressive strain. We envisage that our results will give new insights into the rational design and defect engineering in epitaxial-strained ABO3 perovskites.

Atomic-Scale Tuning of the Charge Distribution by Strain Engineering in Oxide Heterostructures.

Strain engineering of complex oxide heterostructures has provided routes to explore the influence of the local perturbations to the physical properties of the material. Due to the challenge of disentangling intrinsic and extrinsic effects at oxide interfaces, the combined effects of epitaxial strain and charge transfer mechanisms have been rarely studied. Here, we reveal the local charge distribution in manganite slabs by means of high-resolution electron microscopy and spectroscopy via investigating how the strain locally alters the electronic and magnetic properties of La0.5Sr0.5MnO3-La2CuO4 heterostructures. The charge rearrangement results in two different magnetic phases: an interfacial ferromagnetically reduced layer and an enhanced ferromagnetic metallic region away from the interfaces. Further, the magnitude of the charge redistribution can be controlled via epitaxial strain, which further influences the macroscopic physical properties in a way opposed to strain effects reported on single-phase films. Our work highlights the important role played by epitaxial strain in determining the spatial distribution of microscopic charge and spin interactions in manganites and provides a different perspective for engineering interface properties.

Phase-resolved Higgs response in superconducting cuprates.

In high-energy physics, the Higgs field couples to gauge bosons and fermions and gives mass to their elementary excitations. Experimentally, such couplings can be inferred from the decay product of the Higgs boson, i.e., the scalar (amplitude) excitation of the Higgs field. In superconductors, Cooper pairs bear a close analogy to the Higgs field. Interaction between the Cooper pairs and other degrees of freedom provides dissipation channels for the amplitude mode, which may reveal important information about the microscopic pairing mechanism. To this end, we investigate the Higgs (amplitude) mode of several cuprate thin films using phase-resolved terahertz third harmonic generation (THG). In addition to the heavily damped Higgs mode itself, we observe a universal jump in the phase of the driven Higgs oscillation as well as a non-vanishing THG above Tc. These findings indicate coupling of the Higgs mode to other collective modes and potentially a nonzero pairing amplitude above Tc.

High-Temperature Thermoelectricity in LaNiO3-La2CuO4 Heterostructures.

Transition metal oxides exhibit a high potential for application in the field of electronic devices, energy storage, and energy conversion. The ability of building these types of materials by atomic layer-by-layer techniques provides a possibility to design novel systems with favored functionalities. In this study, by means of the atomic layer-by-layer oxide molecular beam epitaxy technique, we designed oxide heterostructures consisting of tetragonal K2NiF4-type insulating La2CuO4 (LCO) and perovskite-type conductive metallic LaNiO3 (LNO) layers with different thicknesses to assess the heterostructure-thermoelectric property-relationship at high temperatures. We observed that the transport properties depend on the constituent layer thickness, interface intermixing, and oxygen-exchange dynamics in the LCO layers, which occurs at high temperatures. As the thickness of the individual layers was reduced, the electrical conductivity decreased and the sign of the Seebeck coefficient changed, revealing the contribution of the individual layers where possible interfacial contributions cannot be ruled out. High-resolution scanning transmission electron microscopy investigations showed that a substitutional solid solution of La2(CuNi)O4 was formed when the thickness of the constituent layers was decreased.

Transparent EuTiO3 films: a possible two-dimensional magneto-optical device.

The magneto-optical activity of high quality transparent thin films of insulating EuTiO3 (ETO) deposited on a thin SrTiO3 (STO) substrate, both being non-magnetic materials, are demonstrated to be a versatile tool for light modulation. The operating temperature is close to room temperature and allows for multiple device engineering. By using small magnetic fields birefringence of the samples can be switched off and on. Similarly, rotation of the sample in the field can modify its birefringence Δn. In addition, Δn can be increased by a factor of 4 in very modest fields with simultaneously enhancing the operating temperature by almost 100 K.

Dopant size effects on novel functionalities: High-temperature interfacial superconductivity.

Among the range of complex interactions, especially at the interfaces of epitaxial oxide systems, contributing to the occurrence of intriguing effects, a predominant role is played by the local structural parameters. In this study, oxide molecular beam epitaxy grown lanthanum cuprate-based bilayers (consisting of a metallic (M) and an insulating phase (I)), in which high-temperature superconductivity arises as a consequence of interface effects, are considered. With the aim of assessing the role of the dopant size on local crystal structure and chemistry, and on the interface functionalities, different dopants (Ca2+, Sr2+ and, Ba2+) are employed in the M-phase, and the M-I bilayers are investigated by complementary techniques, including spherical-aberration-corrected scanning transmission electron microscopy. A series of exciting outcomes are found: (i) the average out-of-plane lattice parameter of the bilayers is linearly dependent on the dopant ion size, (ii) each dopant redistributes at the interface with a characteristic diffusion length, and (iii) the superconductivity properties are highly dependent on the dopant of choice. Hence, this study highlights the profound impact of the dopant size and related interface chemistry on the functionalities of superconducting oxide systems.

Atomic-Scale Quantitative Analysis of Lattice Distortions at Interfaces of Two-Dimensionally Sr-Doped La2CuO4 Superlattices.

Using spherical aberration corrected high-resolution and analytical scanning transmission electron microscopy, we have quantitatively studied the lattice distortion and the redistribution of charges in two-dimensionally strontium (Sr)-doped La2CuO4 superlattices, in which single LaO planes are periodically replaced by SrO planes. As shown previously, such structures show Tc up to 35 K as a consequence of local charge accumulation on both sides of the nominal SrO planes position. This is caused by two distinct mechanisms of doping: heterogeneous doping at the downward side of the interface (space-charge effect) and "classical" homogeneous doping at the upward side. The comparative chemical and atomic-structural analyses reveal an interrelation between local CuO6 octahedron distortions, hole spatial distribution, and chemical composition. In particular we observe an anomalous expansion of the apical oxygen-oxygen distance in the heterogeneously doped (space-charge) region, and a substantial shrinkage of the apical oxygen-oxygen distance in the homogeneously doped region. Such findings are interpreted in terms of different Jahn-Teller effects occurring at the two interface sides (downward and upward).

Cationic Redistribution at Epitaxial Interfaces in Superconducting Two-Dimensionally Doped Lanthanum Cuprate Films.

The exploration of interface effects in complex oxide heterostructures has led to the discovery of novel intriguing phenomena in recent years and has opened the path toward the precise tuning of material properties at the nanoscale. One recent example is space-charge superconductivity. Among the complex range of effects which may arise from phase interaction, a crucial role is played by cationic intermixing, which defines the final chemical composition of the interface. In this work, we performed a systematic study on the local cationic redistribution of two-dimensionally doped lanthanum cuprate films grown by oxide molecular beam epitaxy, in which single LaO layers in the epitaxial crystal structure were substituted by layers of differently sized and charged dopants (Ca, Sr, Ba, and Dy). In such a model system, in which the dopant undergoes an asymmetric redistribution across the interface, the evolution of the cationic concentration profile can be effectively tracked by means of atomically resolved imaging and spectroscopic methods. This allowed for the investigation of the impact of the dopant chemistry (ionic size and charge) and of the growth conditions (temperature) on the final superconducting and structural properties. A qualitative model for interface cationic intermixing, based on thermodynamic considerations, is proposed. This work highlights the key role which cationic redistribution may have in the definition of the final interface properties and represents a further step forward the realization of heterostructures with improved quality.