Twist angle-dependent valley polarization switching in heterostructures.

The twist engineering of moiré superlattice in van der Waals heterostructures of transition metal dichalcogenides can manipulate valley physics of interlayer excitons (IXs), paving the way for next-generation valleytronic devices. However, the twist angle-dependent control of excitonic potential on valley polarization is not investigated so far in electrically controlled heterostructures and the physical mechanism underneath needs to be explored. Here, we demonstrate the dependence of both polarization switching and degree of valley polarization on the moiré period. We also find the mechanisms to reveal the modulation of twist angle on the exciton potential and the electron-hole exchange interaction, which elucidate the experimentally observed twist angle-dependent valley polarization of IXs. Furthermore, we realize the valley-addressable devices based on polarization switch. Our work demonstrates the manipulation of the valley polarization of IXs by tunning twist angle in electrically controlled heterostructures, which opens an avenue for electrically controlling the valley degrees of freedom in twistronic devices.

Reconfigurable optoelectronic transistors for multimodal recognition.

Biological nervous system outperforms in both dynamic and static information perception due to their capability to integrate the sensing, memory and processing functions. Reconfigurable neuromorphic transistors, which can be used to emulate different types of biological analogues in a single device, are important for creating compact and efficient neuromorphic computing networks, but their design remains challenging due to the need for opposing physical mechanisms to achieve different functions. Here we report a neuromorphic electrolyte-gated transistor that can be reconfigured to perform physical reservoir and synaptic functions. The device exhibits dynamics with tunable time-scales under optical and electrical stimuli. The nonlinear volatile property is suitable for reservoir computing, which can be used for multimodal pre-processing. The nonvolatility and programmability of the device through ion insertion/extraction achieved via electrolyte gating, which are required to realize synaptic functions, are verified. The device's superior performance in mimicking human perception of dynamic and static multisensory information based on the reconfigurable neuromorphic functions is also demonstrated. The present study provides an exciting paradigm for the realization of multimodal reconfigurable devices and opens an avenue for mimicking biological multisensory fusion.

Ferroelastically protected reversible orthorhombic to monoclinic-like phase transition in ZrO2 nanocrystals.

Robust ferroelectricity in nanoscale fluorite oxide-based thin films enables promising applications in silicon-compatible non-volatile memories and logic devices. However, the polar orthorhombic (O) phase of fluorite oxides is a metastable phase that is prone to transforming into the ground-state non-polar monoclinic (M) phase, leading to macroscopic ferroelectric degradation. Here we investigate the reversibility of the O-M phase transition in ZrO2 nanocrystals via in situ visualization of the martensitic transformation at the atomic scale. We reveal that the reversible shear deformation pathway from the O phase to the monoclinic-like (M') state, a compressive-strained M phase, is protected by 90° ferroelectric-ferroelastic switching. Nevertheless, as the M' state gradually accumulates localized strain, a critical tensile strain can pin the ferroelastic domain, resulting in an irreversible M'-M strain relaxation and the loss of ferroelectricity. These findings demonstrate the key role of ferroelastic switching in the reversibility of phase transition and also provide a tensile-strain threshold for stabilizing the metastable ferroelectric phase in fluorite oxide thin films.

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.

Interface-type tunable oxygen ion dynamics for physical reservoir computing.

Reservoir computing can more efficiently be used to solve time-dependent tasks than conventional feedforward network owing to various advantages, such as easy training and low hardware overhead. Physical reservoirs that contain intrinsic nonlinear dynamic processes could serve as next-generation dynamic computing systems. High-efficiency reservoir systems require nonlinear and dynamic responses to distinguish time-series input data. Herein, an interface-type dynamic transistor gated by an Hf0.5Zr0.5O2 (HZO) film was introduced to perform reservoir computing. The channel conductance of Mott material La0.67Sr0.33MnO3 (LSMO) can effectively be modulated by taking advantage of the unique coupled property of the polarization process and oxygen migration in hafnium-based ferroelectrics. The large positive value of the oxygen vacancy formation energy and negative value of the oxygen affinity energy resulted in the spontaneous migration of accumulated oxygen ions in the HZO films to the channel, leading to the dynamic relaxation process. The modulation of the channel conductance was found to be closely related to the current state, identified as the origin of the nonlinear response. In the time series recognition and prediction tasks, the proposed reservoir system showed an extremely low decision-making error. This work provides a promising pathway for exploiting dynamic ion systems for high-performance neural network devices.

Magnetoresistance in Organic Spin Valves Based on Acid-Exfoliated 2D Covalent Organic Frameworks Thin Films.

Covalent organic frameworks (COFs), as a burgeoning class of crystalline porous materials, have made significant progress in their application to optoelectronic devices such as field-effect transistors, memristors, and photodetectors. However, the insoluble features of microcrystalline two-dimensional (2D) COF powders limit development of their thin film devices. Additionally, the exploration of spin transport properties in this category of π-conjugated skeleton materials remains vacant thus far. Herein, an imine-linked 2D Py-Np COF nanocrystalline powder was synthesized by Schiff base condensation of 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayl)tetraaniline and naphthalene-2,6-dicarbaldehyde. Then, we prepared a large-scale free-standing Py-Np COF film via a top-down strategy of chemically assisted acid exfoliation. Moreover, high-quality COF films acted as active layers were transferred onto ferromagnetic La0.67 Sr0.33 MnO3 (LSMO) electrodes for the first attempt to fabricate organic spin valves (OSVs) based on 2D COF materials. This COF-based OSV device with a configuration of LSMO/Py-Np COF/Co/Au demonstrated a remarkable magnetoresistance (MR) value up to -26.5 % at 30 K. Meanwhile, the MR behavior of the COF-based OSVs exhibited a highly temperature dependence and operational stability. This work highlights the enormous application prospects of 2D COFs in organic spintronics and provides a promising approach for developing electronic and spintronic devices based on acid-exfoliated COF thin films.

Tunable heterostructural prism for planar polaritonic switch.

The study of phonon polaritons in van der Waals materials at the nanoscale has gained significant attention in recent years due to its potential applications in nanophotonics. The unique properties of these materials, such as their ability to support sub-diffraction imaging, sensing, and hyperlenses, have made them a promising avenue for the development of new techniques in the field. Despite these advancements, there still exists a challenge in achieving dynamically reversible manipulation of phonon polaritons in these materials due to their insulating properties. In this study, we present experimental results on the reversible manipulation of anisotropic phonon polaritons in α-MoO3 on top of a VO2 film, a phase-change material known for its dramatic changes in dielectric properties between its insulating and metallic states. Our findings demonstrate that the engineered VO2 film enables a switch in the propagation of polaritons in the mid-infrared region by modifying the dielectric properties of the film through temperature changes. Our results represent a promising approach to effectively control the flow of light energy at the nanoscale and offer the potential for the design and fabrication of integrated, flat sub-diffraction polaritonic devices. This study adds to the growing body of work in the field of nanophotonics and highlights the importance of considering phase-change materials for the development of new techniques in this field.

Revealing broken valley symmetry of quantum emitters in WSe2 with chiral nanocavities.

Single photon emission of quantum emitters (QEs) carrying internal degrees of freedom such as spin and angular momentum plays an important role in quantum optics. Recently, QEs in two-dimensional semiconductors have attracted great interest as promising quantum light sources. However, whether those QEs are characterized by the same valley physics as delocalized valley excitons is still under debate. Moreover, the potential applications of such QEs still need to be explored. Here we show experimental evidence of valley symmetry breaking for neutral QEs in WSe2 monolayer by interacting with chiral plasmonic nanocavities. The anomalous magneto-optical behaviour of the coupled QEs suggests that the polarization state of emitted photon is modulated by the chiral nanocavity instead of the valley-dependent optical selection rules. Calculations of cavity quantum electrodynamics further show the absence of intrinsic valley polarization. The cavity-dependent circularly polarized single-photon output also offers a strategy for future applications in chiral quantum optics.

Anion-induced robust ferroelectricity in sulfurized pseudo-rhombohedral epitaxial BiFeO3 thin films via polarization rotation.

Polarization rotation caused by various strains, such as substrate and/or chemical strain, is essential to control the electronic structure and properties of ferroelectric materials. This study proposes anion-induced polarization rotation with chemical strain, which effectively improves ferroelectricity. A method for the sulfurization of BiFeO3 thin films by introducing sulfur anions is presented. The sulfurized films exhibited substantial enhancement in room-temperature ferroelectric polarization through polarization rotation and distortion, with a 170% increase in the remnant polarization from 58 to 100.7 µC cm-2. According to first-principles calculations and the results of X-ray absorption spectroscopy and high-angle annular dark-field scanning transmission electron microscopy, this enhancement arose from the introduction of S atoms driving the re-distribution of the lone-pair electrons of Bi, resulting in the rotation of the polarization state from the [001] direction to the [110] or [111] one. The presented method of anion-driven polarization rotation might enable the improvement of the properties of oxide materials.

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.

Controllable spin-resolved photon emission enhanced by a slow-light mode in photonic crystal waveguides on a chip.

We report the slow-light enhanced spin-resolved in-plane emission from a single quantum dot (QD) in a photonic crystal waveguide (PCW). The slow light dispersions in PCWs are designed to match the emission wavelengths of single QDs. The resonance between two spin states emitted from a single QD and a slow light mode of a waveguide is investigated under a magnetic field with Faraday configuration. Two spin states of a single QD experience different degrees of enhancement as their emission wavelengths are shifted by combining diamagnetic and Zeeman effects with an optical excitation power control. A circular polarization degree up to 0.81 is achieved by changing the off-resonant excitation power. Strongly polarized photon emission enhanced by a slow light mode shows great potential to attain controllable spin-resolved photon sources for integrated optical quantum networks on chip.

Magnetoelectric coupling in multiferroics probed by optical second harmonic generation.

Magnetoelectric coupling, as a fundamental physical nature and with the potential to add functionality to devices while also reducing energy consumption, has been challenging to be probed in freestanding membranes or two-dimensional materials due to their instability and fragility. In this paper, we report a magnetoelectric coupling probed by optical second harmonic generation with external magnetic field, and show the manipulation of the ferroelectric and antiferromagnetic orders by the magnetic and thermal fields in BiFeO3 films epitaxially grown on the substrates and in the freestanding ones. Here we define an optical magnetoelectric-coupling constant, denoting the ability of controlling light-induced nonlinear polarization by the magnetic field, and found the magnetoelectric-coupling was suppressed by strain releasing but remain robust against thermal fluctuation for freestanding BiFeO3.

Polarization Switching and Correlated Phase Transitions in Fluorite-Structure ZrO2 Nanocrystals.

Unconventional ferroelectricity in fluorite-structure oxides enables tremendous opportunities in nanoelectronics owing to their superior scalability and silicon compatibility. However, their polarization order and switching process remain elusive due to the challenges of visualizing oxygen ions in nanocrystalline films. In this work, the oxygen shifting during polarization switching and correlated polar-nonpolar phase transitions are directly captured among multiple metastable phases in freestanding ZrO2 thin films by low-dose integrated differential phase-contrast scanning transmission electron microscopy (iDPC-STEM). Bidirectional transitions between antiferroelectric and ferroelectric orders and interfacial polarization relaxation are clarified at unit-cell scale. Meanwhile, polarization switching is strongly correlated with Zr-O displacement in reversible martensitic transformation between monoclinic and orthorhombic phases and two-step tetrahedral-to-orthorhombic phase transition. These findings provide atomic insights into the transition pathways between metastable polymorphs and unravel the evolution of polarization orders in (anti)ferroelectric fluorite oxides.

Reversible fatigue-rejuvenation procedure and its mechanism in Hf0.5Zr0.5O2epitaxial films.

HfO2-based ferroelectrics, such as Hf0.5Zr0.5O2, arouse great attention in recent years because of their CMOS compatibility and robust nano-scale ferroelectricity. However, fatigue is one of the toughest problems for ferroelectric applications. The fatigue mechanism of HfO2-based ferroelectrics is different from conventional ferroelectric materials, and research on the fatigue mechanism in HfO2-based epitaxial films have been rarely reported. In this work, we fabricate 10 nm Hf0.5Zr0.5O2epitaxial films and investigate the fatigue mechanism. The experimental data show that the remanent ferroelectric polarization value decreased by 50% after 108cycles. It is worth noting that the fatigued Hf0.5Zr0.5O2epitaxial films can be recovered through applying electric stimulus. Combined with the temperature-dependent endurance analysis, we propose that fatigue of our Hf0.5Zr0.5O2films comes from both phase transition between ferroelectric Pca21and antiferroelectric Pbca as well as defects generation and dipole pinned. This result offers a fundamental understanding of HfO2-based film system, and could provide an important guideline for subsequent studies and future applications.

The Evolution of Band Topology in Two-Dimensional Weyl Half-Metals.

Two-dimensional ferromagnetic Weyl half-metals that are robust against spin-orbital coupling were theoretically proposed recently, in which the nodal points and the nodal loops are protected by specific symmetries. As the symmetry of a ferromagnetic material is highly dependent on the magnetization orientation, here we predict a family of two-dimensional ferromagnetic Weyl half-metals, Mn2X3 (X = S, Se, Te) monolayers, to investigate the band topology under different magnetization orientations in the presence of spin-orbital coupling. The Curie temperatures (∼1000 K) were estimated to be much higher than room temperature due to the strong double exchange interaction and the suppression of spin fluctuation for the two-sublayer structure. Taking a Mn2Te3 monolayer as an example, we demonstrated the evolution of the nodal points and the nodal loops in the presence of spin-orbital coupling via manipulating magnetization orientation. Our work provides a family of high temperature two-dimensional ferromagnetic Weyl half-metals for investigating the nontrivial band topology.

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.

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.

Space-Charge Control of Magnetism in Ferromagnetic Metals: Coupling Giant Magnitude and Robust Endurance.

Ferromagnetic metals show great prospects in ultralow-power-consumption spintronic devices, due to their high Curie temperature and robust magnetization. However, there is still a lack of reliable solutions for giant and reversible voltage control of magnetism in ferromagnetic metal films. Here, a novel space-charge approach is proposed which allows for achieving a modulation of 30.3 emu/g under 1.3 V in Co/TiO2 multilayer granular films. The robust endurance with more than 5000 cycles is demonstrated. Similar phenomena exist in Ni/TiO2 and Fe/TiO2 multilayer granular films, which shows its universality. The magnetic change of 107% in Ni/TiO2 underlines its potential in a voltage-driven ON-OFF magnetism. Such giant and reversible voltage control of magnetism can be ascribed to space-charge effect at the ferromagnetic metals/TiO2 interfaces, in which spin-polarized electrons are injected into the ferromagnetic metal layer with the adsorption of lithium-ions on the TiO2 surface. These results open the door for a promising method to modulate the magnetization in ferromagnetic metals, paving the way toward the development of ionic-magnetic-electric coupled applications.

Phase Competition in High-Quality Epitaxial Antiferroelectric PbZrO3 Thin Films.

Antiferroelectric PbZrO3 has attracted renewed interest in recent years because of its unique properties and wide range of potential applications. However, the nature of antiferroelectricity and its evolution with the electric field and temperature remain controversial, mostly due to the difficulty of obtaining high-quality single-crystal samples. The lack of consensus regarding the phase transition in PbZrO3 is not only important on a fundamental side but also greatly hinders further applications. Herein, high-quality PbZrO3 epitaxial thin films are successfully fabricated by pulsed laser deposition. The structural and physical properties of the films are systematically studied via a combination of electric property measurements, X-ray diffraction, scanning transmission electron microscopy imaging, and second-harmonic generation studies. Our studies unveil the noncentrosymmetric nature of PbZrO3 films at room temperature. Moreover, the Curie temperature increased to 270°, ∼40° higher than that in the bulk, and no intermediate ferroelectric phase was observed. Besides, an incipient ferroelectric with relaxor-like behavior above the Curie temperature due to the existence of a local polar cluster in the high-temperature paraelectric phase is experimentally observed for the first time. Our studies provide a better understanding of PbZrO3 thin films and pave the way for practical applications of antiferroelectric material in modern electronic devices.

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.