Syntropic spin alignment at the interface between ferromagnetic and superconducting nitrides.

The magnetic correlations at the superconductor/ferromagnet (S/F) interfaces play a crucial role in realizing dissipation-less spin-based logic and memory technologies, such as triplet-supercurrent spin-valves and 'π' Josephson junctions. Here we report the observation of an induced large magnetic moment at high-quality nitride S/F interfaces. Using polarized neutron reflectometry and DC SQUID measurements, we quantitatively determined the magnetization profile of the S/F bilayer and confirmed that the induced magnetic moment in the adjacent superconductor only exists below T C. Interestingly, the direction of the induced moment in the superconductors was unexpectedly parallel to that in the ferromagnet, which contrasts with earlier findings in S/F heterostructures based on metals or oxides. First-principles calculations verified that the unusual interfacial spin texture observed in our study was caused by the Heisenberg direct exchange coupling with constant J∼4.28 meV through d-orbital overlapping and severe charge transfer across the interfaces. Our work establishes an incisive experimental probe for understanding the magnetic proximity behavior at S/F interfaces and provides a prototype epitaxial 'building block' for superconducting spintronics.

Superfine Nanodomain Engineering Unleashing Ferroelectricity in Incipient Ferroelectrics.

Incipient ferroelectrics have emerged as an attractive class of functional materials owing to their potential to be engineered for exotic ferroelectric behavior, holding great promise for expanding the ferroelectric family. However, thus far, their artificially engineered ferroelectricity has fallen far short of rivaling classic ferroelectrics. In this study, we address this challenge by developing a superfine nanodomain engineering strategy. By applying this approach to representative incipient ferroelectric of SrTiO3-based films, we achieve unprecedentedly strong ferroelectricity, not only surpassing previous records for incipient ferroelectrics but also being comparable to classic ferroelectrics. The remanent polarization of the thin film reaches up to 17.0 µC cm-2 with an ultrahigh Curie temperature of 973 K. Atomic-scale investigations elucidate the origin of this robust ferroelectricity in the emergent high-density superfine nanodomains spanning merely 3-10 unit cells. Combining experimental results with theoretical assessments, we unveil the underlying mechanism, where the intentionally introduced diluted foreign Fe element creates a deeper Landau energy well and promotes a short-range ordering of polarization. Our developed strategy significantly streamlines the design of unconventional ferroelectrics, providing a versatile pathway for exploring new and superior ferroelectric materials.

High-performance terahertz modulators induced by substrate field in Te-based all-2D heterojunctions.

High-performance active terahertz modulators as the indispensable core components are of great importance for the next generation communication technology. However, they currently suffer from the tradeoff between modulation depth and speed. Here, we introduce two-dimensional (2D) tellurium (Te) nanofilms with the unique structure as a new class of optically controlled terahertz modulators and demonstrate their integrated heterojunctions can successfully improve the device performances to the optimal and applicable levels among the existing all-2D broadband modulators. Further photoresponse measurements confirm the significant impact of the stacking order. We first clarify the direction of the substrate-induced electric field through first-principles calculations and uncover the unusual interaction mechanism in the photoexcited carrier dynamics associated with the charge transfer and interlayer exciton recombination. This advances the fundamental and applicative research of Te nanomaterials in high-performance terahertz optoelectronics.

Photoinduced Phase Transition in Infinite-Layer Nickelates.

The quantum phase transition caused by regulating the electronic correlation in strongly correlated quantum materials has been a research hotspot in condensed matter science. Herein, a photon-induced quantum phase transition from the Kondo-Mott insulating state to the low temperature metallic one accompanying with the magnetoresistance changing from negative to positive in the infinite-layer NdNiO2 films is reported, where the antiferromagnetic coupling among the Ni1+ localized spins and the Kondo effect are effectively suppressed by manipulating the correlation of Ni-3d and Nd-5d electrons under the photoirradiation. Moreover, the critical temperature Tc of the superconducting-like transition exhibits a dome-shaped evolution with the maximum up to ≈42 K, and the electrons dominate the transport process proved by the Hall effect measurements. These findings not only make the photoinduction a promising way to control the quantum phase transition by manipulating the electronic correlation in Mott-like insulators, but also shed some light on the possibility of the superconducting in electron-doped nickelates.

Emergent Magnetic States and Tunable Exchange Bias at 3d Nitride Heterointerfaces.

Interfacial magnetism stimulates the discovery of giant magnetoresistance (MR) and spin-orbital coupling across the heterointerfaces, facilitating the intimate correlation between spin transport and complex magnetic structures. Over decades, functional heterointerfaces composed of nitrides have seldom been explored due to the difficulty in synthesizing high-quality nitride films with correct compositions. Here, the fabrication of single-crystalline ferromagnetic Fe3 N thin films with precisely controlled thicknesses is reported. As film thickness decreases, the magnetization dramatically deteriorates, and the electronic state changes from metallic to insulating. Strikingly, the high-temperature ferromagnetism is maintained in a Fe3 N layer with a thickness down to 2 u.c. (≈8 Å). The MR exhibits a strong in-plane anisotropy; meanwhile, the anomalous Hall resistivity reverses its sign when the Fe3 N layer thickness exceeds 5 u.c. Furthermore, a sizable exchange bias is observed at the interfaces between a ferromagnetic Fe3 N and an antiferromagnetic CrN. The exchange bias field and saturation moment strongly depend on the controllable bending curvature using the cylinder diameter engineering technique, implying the tunable magnetic states under lattice deformation. This work provides a guideline for exploring functional nitride films and applying their interfacial phenomena for innovative perspectives toward practical applications.

Braiding Lateral Morphotropic Grain Boundaries in Homogenetic Oxides.

Interfaces formed by correlated oxides offer a critical avenue for discovering emergent phenomena and quantum states. However, the fabrication of oxide interfaces with variable crystallographic orientations and strain states integrated along a film plane is extremely challenging by conventional layer-by-layer stacking or self-assembling. Here, the creation of morphotropic grain boundaries (GBs) in laterally interconnected cobaltite homostructures is reported. Single-crystalline substrates and suspended ultrathin freestanding membranes provide independent templates for coherent epitaxy and constraint on the growth orientation, resulting in seamless and atomically sharp GBs. Electronic states and magnetic behavior in hybrid structures are laterally modulated and isolated by GBs, enabling artificially engineered functionalities in the planar matrix. This work offers a simple and scalable method for fabricating unprecedented innovative interfaces through controlled synthesis routes as well as providing a platform for exploring potential applications in neuromorphics, solid-state batteries, and catalysis.

Atomically engineered cobaltite layers for robust ferromagnetism.

Emergent phenomena at heterointerfaces are directly associated with the bonding geometry of adjacent layers. Effective control of accessible parameters, such as the bond length and bonding angles, offers an elegant method to tailor competing energies of the electronic and magnetic ground states. In this study, we construct unit-thick syntactic layers of cobaltites within a strongly tilted octahedral matrix via atomically precise synthesis. The octahedral tilt patterns of adjacent layers propagate into cobaltites, leading to a continuation of octahedral tilting while maintaining substantial misfit tensile strain. These effects induce severe rumpling within an atomic plane of neighboring layers, further triggering the electronic reconstruction between the splitting orbitals. First-principles calculations reveal that the cobalt ions transit to a higher spin state level upon octahedral tilting, resulting in robust ferromagnetism in ultrathin cobaltites. This work demonstrates a design methodology for fine-tuning the lattice and spin degrees of freedom in correlated quantum heterostructures by exploiting epitaxial geometric engineering.

Ferroelectric Single-Molecule Magnet with Toroidal Magnetic Moments.

Materials that coexist magnetic and electric properties on the molecular scale in single-molecule magnets (SMMs) with peculiar quantum behaviors have promise in molecular electronics and spintronics. Nevertheless, such molecular materials are limited in potentials because their magnetic signal cannot be transformed into an electrical signal through magnetoresistance or Hall effects for their high insulativity. The discovery of an entirely new material, ferroelectric SMMs (FE SMMs) is reported. This FE SMM also shows single-molecule magnetic behaviors, toroidal magnetic moments, and room-temperature ferroelectricity. The toroidal moment is formed by a vortex distribution of magnetic dipoles in triangular Dy3 clusters. The analysis of ac magnetic susceptibility reveals the coexistence of three distinct magnetic relaxation processes at low temperatures. The ferroelectricity is introduced by incorporating polar alcohol molecules in the structure, which is confirmed by the X-ray diffraction and optical second harmonic generation (SHG) measurements. Moreover, the dielectric measurements reveal a ferroelectric-to-ferroelectric phase transition around 150 K due to the symmetry change from Pc to Pna21 . The coexistence of toroidal moment and ferroelectricity along with quantum magnetism in the rare-earth single-molecule magnets yields a unique class of multiferroics.

Room-Temperature Ferromagnetism at an Oxide-Nitride Interface.

Heterointerfaces have led to the discovery of novel electronic and magnetic states because of their strongly entangled electronic degrees of freedom. Single-phase chromium compounds always exhibit antiferromagnetism following the prediction of the Goodenough-Kanamori rules. So far, exchange coupling between chromium ions via heteroanions has not been explored and the associated quantum states are unknown. Here, we report the successful epitaxial synthesis and characterization of chromium oxide (Cr_{2}O_{3})-chromium nitride (CrN) superlattices. Room-temperature ferromagnetic spin ordering is achieved at the interfaces between these two antiferromagnets, and the magnitude of the effect decays with increasing layer thickness. First-principles calculations indicate that robust ferromagnetic spin interaction between Cr^{3+} ions via anion-hybridization across the interface yields the lowest total energy. This work opens the door to fundamental understanding of the unexpected and exceptional properties of oxide-nitride interfaces and provides access to hidden phases at low-dimensional quantum heterostructures.

Ferroelectric Proximity Effect and Topological Hall Effect in SrRuO3/BiFeO3 Multilayers.

Interfaces between complex oxides provide a unique opportunity to discover novel interfacial physics and functionalities. Here, we fabricate the multilayers of itinerant ferromagnet SrRuO3 (SRO) and multiferroic BiFeO3 (BFO) with atomically sharp interfaces. Atomically resolved transmission electron microscopy reveals that a large ionic displacement in BFO can penetrate into SRO layers near the BFO/SRO interfaces to a depth of 2-3 unit cells, indicating the ferroelectric proximity effect. A topological Hall effect is indicated by hump-like anomalies in the Hall measurements of the multilayer with a moderate thickness of the SRO layer. With magnetic measurements, it can be further confirmed that each SRO layer in the multilayers can be divided into interfacial and middle regions, which possess different magnetic ground states. Our work highlights the key role of functional heterointerfaces in exotic properties and provides an important guideline to design spintronic devices based on magnetic skyrmions.

Ultrahigh energy storage in superparaelectric relaxor ferroelectrics.

Electrostatic energy storage technology based on dielectrics is fundamental to advanced electronics and high-power electrical systems. Recently, relaxor ferroelectrics characterized by nanodomains have shown great promise as dielectrics with high energy density and high efficiency. We demonstrate substantial enhancements of energy storage properties in relaxor ferroelectric films with a superparaelectric design. The nanodomains are scaled down to polar clusters of several unit cells so that polarization switching hysteresis is nearly eliminated while relatively high polarization is maintained. We achieve an ultrahigh energy density of 152 joules per cubic centimeter with markedly improved efficiency (>90% at an electric field of 3.5 megavolts per centimeter) in superparaelectric samarium-doped bismuth ferrite­barium titanate films. This superparaelectric strategy is generally applicable to optimize dielectric and other related functionalities of relaxor ferroelectrics.

Near-room temperature ferromagnetic insulating state in highly distorted LaCoO2.5 with CoO5 square pyramids.

Dedicated control of oxygen vacancies is an important route to functionalizing complex oxide films. It is well-known that tensile strain significantly lowers the oxygen vacancy formation energy, whereas compressive strain plays a minor role. Thus, atomic reconstruction by extracting oxygen from a compressive-strained film is challenging. Here we report an unexpected LaCoO2.5 phase with a zigzag-like oxygen vacancy ordering through annealing a compressive-strained LaCoO3 in vacuum. The synergetic tilt and distortion of CoO5 square pyramids with large La and Co shifts are quantified using scanning transmission electron microscopy. The large in-plane expansion of CoO5 square pyramids weaken the crystal field splitting and facilitated the ordered high-spin state of Co2+, which produces an insulating ferromagnetic state with a Curie temperature of ~284 K and a saturation magnetization of ~0.25 µB/Co. These results demonstrate that extracting targeted oxygen from a compressive-strained oxide provides an opportunity for creating unexpected crystal structures and novel functionalities.

Tunable electronic structure and magnetic anisotropy in bilayer ferromagnetic semiconductor Cr2Ge2Te6.

The emergence of ferromagnetism in two-dimensional van der Waals materials has aroused broad interest. However, the ferromagnetic instability has been a problem remained. In this work, by using the first-principles calculations, we identified the critical ranges of strain and doping for the bilayer Cr2Ge2Te6 within which the ferromagnetic stability can be enhanced. Beyond the critical range, the tensile strain can induce the phase transition from the ferromagnetic to the antiferromagnetic, and the direction of magnetic easy axis can be converted from out-of-plane to in-plane due to the increase of compressive strain, or electrostatic doping. We also predicted an electron doping range, within which the ferromagnetism can be enhanced, while the ferromagnetic stability was maintained. Moreover, we found that the compressive strain can reverse the spin polarization of electrons at the conduction band minimum, so that two categories of half-metal can be induced by controlling electrostatic doping in the bilayer Cr2Ge2Te6. These results should shed a light on achieving ferromagnetic stability for low-dimensional materials.

Strong Ferromagnetism Achieved via Breathing Lattices in Atomically Thin Cobaltites.

Low-dimensional quantum materials that remain strongly ferromagnetic down to monolayer thickness are highly desired for spintronic applications. Although oxide materials are important candidates for the next generation of spintronics, ferromagnetism decays severely when the thickness is scaled to the nanometer regime, leading to deterioration of device performance. Here, a methodology is reported for maintaining strong ferromagnetism in insulating LaCoO3 (LCO) layers down to the thickness of a single unit cell. It is found that the magnetic and electronic states of LCO are linked intimately to the structural parameters of adjacent "breathing lattice" SrCuO2 (SCO). As the dimensionality of SCO is reduced, the lattice constant elongates over 10% along the growth direction, leading to a significant distortion of the CoO6 octahedra, and promoting a higher spin state and long-range spin ordering. For atomically thin LCO layers, surprisingly large magnetic moment (0.5 µB /Co) and Curie temperature (75 K), values larger than previously reported for any monolayer oxides are observed. The results demonstrate a strategy for creating ultrathin ferromagnetic oxides by exploiting atomic heterointerface engineering, confinement-driven structural transformation, and spin-lattice entanglement in strongly correlated materials.

Strain-Mediated High Conductivity in Ultrathin Antiferromagnetic Metallic Nitrides.

Strain engineering provides the ability to control the ground states and associated phase transition in epitaxial films. However, the systematic study of the intrinsic character and strain dependency in transition-metal nitrides remains challenging due to the difficulty in fabricating stoichiometric and high-quality films. Here the observation of an electronic state transition in highly crystalline antiferromagnetic CrN films with strain and reduced dimensionality is reported. By shrinking the film thickness to a critical value of ≈30 unit cells, a profound conductivity reduction accompanied by unexpected volume expansion is observed in CrN films. The electrical conductivity is observed surprisingly when the CrN layer is as thin as a single unit cell thick, which is far below the critical thickness of most metallic films. It is found that the metallicity of an ultrathin CrN film recovers from insulating behavior upon the removal of the as-grown strain by the fabrication of freestanding nitride films. Both first-principles calculations and linear dichroism measurements reveal that the strain-mediated orbital splitting effectively customizes the relatively small bandgap at the Fermi level, leading to an exotic phase transition in CrN. The ability to achieve highly conductive nitride ultrathin films by harnessing strain-control over competing phases can be used for utilizing their exceptional characteristics.

Influence of micro-structure on modulation properties in VO2 composite terahertz memory metamaterials.

We have grown VO2 films and combined with terahertz metamaterials to manipulate the memory effect during the insulator-to-metal transition. The temperature-dependent resonant frequency of hybrid structure shows a thermal hysteresis accompanied with frequency shift and bandwidth variation due to the presence of a VO2 dielectric layer. This frequency memory effect significantly depends on the metallic micro-structure. Further theoretical calculation demonstrates this phenomenon mainly originates from the different coupling strength between VO2 and metallic structures. Our findings could facilitate the application of VO2 films in the smart window and dynamical terahertz modulators.

Tuning Charge Carrier and Spin Transport Properties via Structural Modification of Polymer Semiconductors.

Targeted design of organic semiconductors in organic spintronics is relatively limited. Therefore, four conjugated polymers with analogous structures based on isoindigo (IID) units were designed and synthesized to investigate the structure-property relationships in spin and charge carrier transport. Structural design strategies include introduction of pyridinic nitrogen atoms into IID units to change electronic structures and alteration of different branching points of alkyl chains to adjust the aggregation structure. By fabricating polymer field-effect transistors (PFETs) and organic spin valves (OSVs), all of the polymers exhibited good ambipolar field-effect properties (all of the mobilities exceeding 0.3 cm2 V-1 s-1) and relatively high magnetoresistance (MR) values (maximum up to 25%). Most importantly, it is found that the introduction of pyridinic nitrogen into the IID units can improve MR values of OSVs and electron mobilities of PFETs, whereas the extension of alkyl chain branching points can reduce MR values of the conjugated polymers. This work is the first attempt to thoroughly study the structure-property relationship in the OSVs, combined with molecular design of the conjugated polymers, which provides a guideline for molecular engineering, especially for organic spintronics.

A Ferrite Synaptic Transistor with Topotactic Transformation.

Hardware implementation of artificial synaptic devices that emulate the functions of biological synapses is inspired by the biological neuromorphic system and has drawn considerable interest. Here, a three-terminal ferrite synaptic device based on a topotactic phase transition between crystalline phases is presented. The electrolyte-gating-controlled topotactic phase transformation between brownmillerite SrFeO2.5 and perovskite SrFeO3- δ is confirmed from the examination of the crystal and electronic structure. A synaptic transistor with electrolyte-gated ferrite films by harnessing gate-controllable multilevel conduction states, which originate from many distinct oxygen-deficient perovskite structures of SrFeOx induced by topotactic phase transformation, is successfully constructed. This three-terminal artificial synapse can mimic important synaptic functions, such as synaptic plasticity and spike-timing-dependent plasticity. Simulations of a neural network consisting of ferrite synaptic transistors indicate that the system offers high classification accuracy. These results provide insight into the potential application of advanced topotactic phase transformation materials for designing artificial synapses with high performance.

Artificial Synapses Emulated by an Electrolyte-Gated Tungsten-Oxide Transistor.

Considering that the human brain uses ≈1015 synapses to operate, the development of effective artificial synapses is essential to build brain-inspired computing systems. In biological synapses, the voltage-gated ion channels are very important for regulating the action-potential firing. Here, an electrolyte-gated transistor using WO3 with a unique tunnel structure, which can emulate the ionic modulation process of biological synapses, is proposed. The transistor successfully realizes synaptic functions of both short-term and long-term plasticity. Short-term plasticity is mimicked with the help of electrolyte ion dynamics under low electrical bias, whereas the long-term plasticity is realized using proton insertion in WO3 under high electrical bias. This is a new working approach to control the transition from short-term memory to long-term memory using different gate voltage amplitude for artificial synapses. Other essential synaptic behaviors, such as paired pulse facilitation, the depression and potentiation of synaptic weight, as well as spike-timing-dependent plasticity are also implemented in this artificial synapse. These results provide a new recipe for designing synaptic electrolyte-gated transistors through the electrostatic and electrochemical effects.

High-Responsivity Photodetection by a Self-Catalyzed Phase-Pure p-GaAs Nanowire.

Defects are detrimental for optoelectronics devices, such as stacking faults can form carrier-transportation barriers, and foreign impurities (Au) with deep-energy levels can form carrier traps and nonradiative recombination centers. Here, self-catalyzed p-type GaAs nanowires (NWs) with a pure zinc blende (ZB) structure are first developed, and then a photodetector made from these NWs is fabricated. Due to the absence of stacking faults and suppression of large amount of defects with deep energy levels, the photodetector exhibits room-temperature high photoresponsivity of 1.45 × 105 A W-1 and excellent specific detectivity (D*) up to 1.48 × 1014 Jones for a low-intensity light signal of wavelength 632.8 nm, which outperforms previously reported NW-based photodetectors. These results demonstrate these self-catalyzed pure-ZB GaAs NWs to be promising candidates for optoelectronics applications.