Interfacially Enhanced Superconductivity in Fe(Te,Se)/Bi4Te3 Heterostructures.

Realizing topological superconductivity by integrating high-transition-temperature (TC) superconductors with topological insulators can open new paths for quantum computing applications. Here, a new approach is reported for increasing the superconducting transition temperature ( T C onset ) $( {T_{\mathrm{C}}^{{\mathrm{onset}}}} )$ by interfacing the unconventional superconductor Fe(Te,Se) with the topological insulator Bi-Te system in the low-Se doping regime, near where superconductivity vanishes in the bulk. The critical finding is that the T C onset $T_{\mathrm{C}}^{{\mathrm{onset}}}$ of Fe(Te,Se) increases from nominally non-superconducting to as high as 12.5 K when Bi2Te3 is replaced with the topological phase Bi4Te3. Interfacing Fe(Te,Se) with Bi4Te3 is also found to be critical for stabilizing superconductivity in monolayer films where T C onset $T_{\mathrm{C}}^{{\mathrm{onset}}}$ can be as high as 6 K. Measurements of the electronic and crystalline structure of the Bi4Te3 layer reveal that a large electron transfer, epitaxial strain, and novel chemical reduction processes are critical factors for the enhancement of superconductivity. This novel route for enhancing TC in an important epitaxial system provides new insight on the nature of interfacial superconductivity and a platform to identify and utilize new electronic phases.

Reconfigurable Resistive Switching in VO2/La0.7Sr0.3MnO3/Al2O3 (0001) Memristive Devices for Neuromorphic Computing.

The coexistence of nonvolatile and volatile switching modes in a single memristive device provides flexibility to emulate both neuronal and synaptic functions in the brain. Furthermore, such a device structure may eliminate the need for additional circuit elements such as transistor-based selectors, enabling low-power consumption and high-density device integration in fully memristive spiking neural networks. In this work, we report dual resistive switching (RS) modes in VO2/La0.7Sr0.3MnO3 (LSMO) bilayer memristive devices. Specifically, the nonvolatile RS is driven by the movement of oxygen vacancies (Vo) at the VO2/LSMO interface and requires a higher biasing voltage, whereas the volatile RS is controlled by the metal-insulator transition (MIT) of VO2 under a lower biasing voltage. The simple device structure is electrically driven between the two RS modes and thus can operate as a one selector-one resistor (1S1R) cell, which is a desirable feature in memristive crossbar arrays to avoid the sneak-path current issue. The RS modes are found to be stable and repeatable and can be reconfigured by exploiting the interfacial and phase transition properties, and thus, they hold great promise for applications in memristive neural networks and neuromorphic computing.

Manipulating topological Hall-like signatures by interface engineering in epitaxial ruthenate/manganite heterostructures.

Topologically protected non-trivial spin textures (e.g. skyrmions) give rise to a novel phenomenon called the topological Hall effect (THE) and have promising implications in future energy-efficient nanoelectronic and spintronic devices. Here, we have studied the Hall effect in SrRuO3/La0.42Ca0.58MnO3 (SRO/LCMO) bilayers. Our investigation suggests that pure SRO has hard and soft magnetic characteristics but the anomalous Hall effect (AHE) in SRO is governed by the high coercivity phase. We have shown that the proximity effect of a soft magnetic LCMO on SRO plays a critical role in interfacial magnetic coupling and transport properties in SRO. Upon reducing the SRO thickness in the bilayer, the proximity effect becomes the dominant feature, enhancing the magnitude and temperature range of THE-like signatures. The THE-like features in bilayers can be explained by a diffusive Berry phase transition model in the presence of an emergent magnetic state due to interface coupling. This work provides an alternative understanding of THE-like signatures and their manipulation in SRO-based heterostructures, bilayers and superlattices.

Anisotropic Properties of Epitaxial Ferroelectric Lead-Free 0.5[Ba(Ti0.8Zr0.2)O3]-0.5(Ba0.7Ca0.3)TiO3 Films.

As the energy demand is expected to double over the next 30 years, there has been a major initiative towards advancing the technology of both energy harvesting and storage for renewable energy. In this work, we explore a subset class of dielectrics for energy storage since ferroelectrics offer a unique combination of characteristics needed for energy storage devices. We investigate ferroelectric lead-free 0.5[Ba(Ti0.8Zr0.2)O3]-0.5(Ba0.7Ca0.3)TiO3 epitaxial thin films with different crystallographic orientations grown by pulsed laser deposition. We focus our attention on the influence of the crystallographic orientation on the microstructure, ferroelectric, and dielectric properties. Our results indicate an enhancement of the polarization and strong anisotropy in the dielectric response for the (001)-oriented film. The enhanced ferroelectric, energy storage, and dielectric properties of the (001)-oriented film is explained by the coexistence of orthorhombic-tetragonal phase, where the disordered local structure is in its free energy minimum.

Emergent Magnetism with Continuous Control in the Ultrahigh-Conductivity Layered Oxide PdCoO2.

The current challenge to realizing continuously tunable magnetism lies in our inability to systematically change properties, such as valence, spin, and orbital degrees of freedom, as well as crystallographic geometry. Here, we demonstrate that ferromagnetism can be externally turned on with the application of low-energy helium implantation and can be subsequently erased and returned to the pristine state via annealing. This high level of continuous control is made possible by targeting magnetic metastability in the ultrahigh-conductivity, nonmagnetic layered oxide PdCoO2 where local lattice distortions generated by helium implantation induce the emergence of a net moment on the surrounding transition metal octahedral sites. These highly localized moments communicate through the itinerant metal states, which trigger the onset of percolated long-range ferromagnetism. The ability to continuously tune competing interactions enables tailoring precise magnetic and magnetotransport responses in an ultrahigh-conductivity film and will be critical to applications across spintronics.

Machine Learning-Enabled Superior Energy Storage in Ferroelectric Films with a Slush-Like Polar State.

Heterogeneities in structure and polarization have been employed to enhance the energy storage properties of ferroelectric films. The presence of nonpolar phases, however, weakens the net polarization. Here, we achieve a slush-like polar state with fine domains of different ferroelectric polar phases by narrowing the large combinatorial space of likely candidates using machine learning methods. The formation of the slush-like polar state at the nanoscale in cation-doped BaTiO3 films is simulated by phase field simulation and confirmed by aberration-corrected scanning transmission electron microscopy. The large polarization and the delayed polarization saturation lead to greatly enhanced energy density of 80 J/cm3 and transfer efficiency of 85% over a wide temperature range. Such a data-driven design recipe for a slush-like polar state is generally applicable to quickly optimize functionalities of ferroelectric materials.

Superconducting Fourfold Fe(Te,Se) Film on Sixfold Magnetic MnTe via Hybrid Symmetry Epitaxy.

Epitaxial Fe(Te,Se) thin films have been grown on various substrates but never been grown on magnetic layers. Here we report the epitaxial growth of fourfold Fe(Te,Se) film on a sixfold antiferromagnetic insulator, MnTe. The Fe(Te,Se)/MnTe heterostructure shows a clear superconducting transition at around 11 K, and the critical magnetic field measurement suggests the origin of the superconductivity to be bulk-like. Structural characterizations suggest that the uniaxial lattice match between Fe(Te,Se) and MnTe allows a hybrid symmetry epitaxy mode, which was recently discovered between Fe(Te,Se) and Bi2Te3. Furthermore, the Te/Fe flux ratio during deposition of the Fe(Te,Se) layer is found to be critical for its superconductivity. Now that superconducting Fe(Te,Se) can be grown on two related hexagonal platforms, Bi2Te3 and MnTe, this result opens a new possibility of combining topological superconductivity of Fe(Te,Se) with the rich physics in the intrinsic magnetic topological materials (MnTe)n(Bi2Te3)m family.

High Entropy Oxide Relaxor Ferroelectrics.

Relaxor ferroelectrics are important in technological applications due to strong electromechanical response, energy storage capacity, electrocaloric effect, and pyroelectric energy conversion properties. Current efforts to discover and design materials in this class generally rely on substitutional doping as slight changes to local compositional order can significantly affect the Curie temperature, morphotropic phase boundary, and electromechanical responses. In this work, we demonstrate that moving to the strong limit of compositional complexity in an ABO3 perovskite allows stabilization of relaxor responses that do not rely on a single narrow phase transition region. Entropy-assisted synthesis approaches are utilized to synthesize single-crystal Ba(Ti0.2Sn0.2Zr0.2Hf0.2Nb0.2)O3 [Ba(5B)O] films. The high levels of configurational disorder present in this system are found to influence dielectric relaxation, phase transitions, nanopolar domain formation, and Curie temperature. Temperature-dependent dielectric, Raman spectroscopy, and second-harmonic generation measurements reveal multiple phase transitions, a high Curie temperature of 570 K, and the relaxor ferroelectric nature of Ba(5B)O films. The first-principles theory calculations are used to predict possible combinations of cations to design relaxor ferroelectrics and quantify the relative feasibility of synthesizing these highly disordered single-phase perovskite systems. The ability to stabilize single-phase perovskites with various cations on the B-sites offers possibilities for designing high-performance relaxor ferroelectric materials for piezoelectric, pyroelectric, and electrocaloric applications.

Designing Magnetism in High Entropy Oxides.

In magnetic systems, spin and exchange disorder can provide access to quantum criticality, frustration, and spin dynamics, but broad tunability of these responses and a deeper understanding of strong limit disorder are lacking. Here, it is demonstrated that high entropy oxides present a previously unexplored route to designing materials in which the presence of strong local compositional disorder may be exploited to generate tunable magnetic behaviors-from macroscopically ordered states to frustration-driven dynamic spin interactions. Single-crystal La(Cr0.2 Mn0.2 Fe0.2 Co0.2 Ni0.2 )O3 films are used as a model system hosting a magnetic sublattice with a high degree of microstate disorder in the form of site-to-site spin and exchange type inhomogeneity. A classical Heisenberg model simplified to represent the highest probability microstates well describes how compositionally disordered systems can paradoxically host magnetic uniformity and demonstrates a path toward continuous control over ordering types and critical temperatures. Model-predicted materials are synthesized and found to possess an incipient quantum critical point when magnetic ordering types are designed to be in direct competition, this leads to highly controllable exchange bias behaviors previously accessible only in intentionally designed bilayer heterojunctions.

Reversible Hydrogen-Induced Phase Transformations in La0.7Sr0.3MnO3 Thin Films Characterized by In Situ Neutron Reflectometry.

We report on the mechanism for hydrogen-induced topotactic phase transitions in perovskite (PV) oxides using La0.7Sr0.3MnO3 as a prototypical example. Hydrogenation starts with lattice expansion confirmed by X-ray diffraction (XRD). The strain- and oxygen-vacancy-mediated electron-phonon coupling in turn produces electronic structure changes that manifest through the appearance of a metal insulator transition accompanied by a sharp increase in resistivity. The ordering of initially randomly distributed oxygen vacancies produces a PV to brownmillerite phase (La0.7Sr0.3MnO2.5) transition. This phase transformation proceeds by the intercalation of oxygen vacancy planes confirmed by in situ XRD and neutron reflectometry (NR) measurements. Despite the prevailing picture that hydrogenation occurs by reaction with lattice oxygen, NR results are not consistent with deuterium (hydrogen) presence in the La0.7Sr0.3MnO3 lattice at steady state. The film can reach a highly oxygen-deficient La0.7Sr0.3MnO2.1 metastable state that is reversible to the as-grown composition simply by annealing in air. Theoretical calculations confirm that hydrogenation-induced oxygen vacancy formation is energetically favorable in La0.7Sr0.3MnO3. The hydrogenation-driven changes of the oxygen sublattice periodicity and the electrical and magnetic properties similar to interface effects induced by oxygen-deficient cap layers persist despite hydrogen not being present in the lattice.

Hybrid Symmetry Epitaxy of the Superconducting Fe(Te,Se) Film on a Topological Insulator.

It is challenging to grow an epitaxial 4-fold compound superconductor (SC) on a 6-fold topological insulator (TI) platform due to the stringent lattice-matching requirement. Here, we demonstrate that Fe(Te,Se) can grow epitaxially on a TI (Bi2Te3) layer due to accidental, uniaxial lattice match, which is dubbed as "hybrid symmetry epitaxy". This new growth mode is critical to stabilizing robust superconductivity with TC as high as 13 K. Furthermore, the superconductivity in this FeTe1-xSex/Bi2Te3 system survives in the Te-rich phase with Se content as low as x = 0.03 but vanishes at Se content above x = 0.56, exhibiting a phase diagram that is quite different from that of the conventional Fe(Te,Se) systems. This unique heterostructure platform that can be formed in both TI-on-SC and SC-on-TI sequences opens a route to unprecedented topological heterostructures.

Magnetic Texture in Insulating Single Crystal High Entropy Oxide Spinel Films.

Magnetic insulators are important materials for a range of next-generation memory and spintronic applications. Structural constraints in this class of devices generally require a clean heterointerface that allows effective magnetic coupling between the insulating layer and the conducting layer. However, there are relatively few examples of magnetic insulators that can be synthesized with surface qualities that would allow these smooth interfaces and precisely tuned interfacial magnetic exchange coupling, which might be applicable at room temperature. In this work, we demonstrate an example of how the configurational complexity in the magnetic insulator layer can be used to realize these properties. The entropy-assisted synthesis is used to create single-crystal (Mg0.2Ni0.2Fe0.2Co0.2Cu0.2)Fe2O4 films on substrates spanning a range of strain states. These films show smooth surfaces, high resistivity, and strong magnetic responses at room temperature. Local and global magnetic measurements further demonstrate how strain can be used to manipulate the magnetic texture and anisotropy. These findings provide insight into how precise magnetic responses can be designed using compositionally complex materials that may find application in next-generation magnetic devices.

Applying Configurational Complexity to the 2D Ruddlesden-Popper Crystal Structure.

The layered Ruddlesden-Popper crystal structure can host a broad range of functionally important behaviors. Here we establish extraordinary configurational disorder in a layered Ruddlesden-Popper (RP) structure using entropy stabilization assisted synthesis. A protype A2CuO4 RP cuprate oxide with five cations on the A-site sublattice is designed and fabricated into epitaxial single crystal films using pulsed laser deposition. When grown on a near lattice matched substrate, the (La0.2Pr0.2Nd0.2Sm0.2Eu0.2)2CuO4 film features a T'-type RP structure with uniform A-site cation mixing and square-planar CuO4 units. These observations are made with a range of combined characterizations using X-ray diffraction, atomic-resolution scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray absorption spectroscopy measurements. It is further found that heteroepitaxial strain plays an important role in crystal phase formation during synthesis. Compressive strain over ∼1.5% results in the formation of a non-RP cubic phase consistent with a CuX2O4 spinel structure. The ability to manipulate configurational complexity and move between 2D layered RP and 3D cubic crystal structures in cuprate and related materials promises to enable flexible design strategies for a range of functionalities, such as magnetoresistance, unconventional superconductivity, ferroelectricity, catalysis, and ion transport.