Large Electromechanical Response in a Polycrystalline Alkali-Deficient (K,Na)NbO3 Thin Film on Silicon.

The demand for large electromechanical performance in lead-free polycrystalline piezoelectric thin films is driven by the need for compact, high-performance microelectromechanical systems (MEMS) based devices operating at low voltages. Here we significantly enhance the electromechanical response in a polycrystalline lead-free oxide thin film by utilizing lattice-defect-induced structural inhomogeneities. Unlike prior observations in mismatched epitaxial films with limited low-frequency enhancements, we achieve large electromechanical strain in a polycrystalline (K,Na)NbO3 film integrated on silicon. This is achieved by inducing self-assembled Nb-rich planar faults with a nonstoichiometric composition. The film exhibits an effective piezoelectric coefficient of 565 pm V-1 at 1 kHz, surpassing those of lead-based counterparts. Notably, lattice defect growth is substrate-independent, and the large electromechanical response is extended to even higher frequencies in a polycrystalline film. Improved properties arise from unique lattice defect morphology and frequency-dependent relaxation behavior, offering a new route to remarkable electromechanical response in polycrystalline thin films.

Diverse Defects in Alkali Niobate Thin Films: Understanding at Atomic Scales and Their Implications on Properties.

Defects in ferroelectric materials have many implications on the material properties which, in most cases, are detrimental. However, engineering these defects can also create opportunities for property enhancement as well as for tailoring novel functionalities. To purposely manipulate these defects, a thorough knowledge of their spatial atomic arrangement, as well as elastic and electrostatic interactions with the surrounding lattice, is highly crucial. In this work, analytical scanning transmission electron microscopy (STEM) is used to reveal a diverse range of multidimensional crystalline defects (point, line, planar, and secondary phase) in (K,Na)NbO3 (KNN) ferroelectric thin films. The atomic-scale analyses of the defect-lattice interactions suggest strong elastic and electrostatic couplings which vary among the individual defects and correspondingly affect the electric polarization. In particular, the observed polarization orientations are correlated with lattice relaxations as well as strain gradients and can strongly impact the properties of the ferroelectric films. The knowledge and understanding obtained in this study open a new avenue for the improvement of properties as well as the discovery of defect-based functionalities in alkali niobate thin films.

Exciton-Enabled Meta-Optics in Two-Dimensional Transition Metal Dichalcogenides.

Optical wavefront engineering has been rapidly developing in fundamentals from phase accumulation in the optical path to the electromagnetic resonances of confined nanomodes in optical metasurfaces. However, the amplitude modulation of light has limited approaches that usually originate from the ohmic loss and absorptive dissipation of materials. Here, an atomically thin photon-sieve platform made of MoS2 multilayers is demonstrated for high-quality optical nanodevices, assisted fundamentally by strong excitonic resonances at the band-nesting region of MoS2. The atomic thin MoS2 significantly facilitates high transmission of the sieved photons and high-fidelity nanofabrication. A proof-of-concept two-dimensional (2D) nanosieve hologram exhibits 10-fold enhanced efficiency compared with its non-2D counterparts. Furthermore, a supercritical 2D lens with its focal spot breaking diffraction limit is developed to exhibit experimentally far-field label-free aberrationless imaging with a resolution of ∼0.44λ at λ = 450 nm in air. This transition-metal-dichalcogenide (TMDC) photonic platform opens new opportunities toward future 2D meta-optics and nanophotonics.

A Robust Hybrid Zn-Battery with Ultralong Cycle Life.

Advanced batteries with long cycle life and capable of harnessing more energies from multiple electrochemical reactions are both fundamentally interesting and practically attractive. Herein, we report a robust hybrid zinc-battery that makes use of transition-metal-based redox reaction (M-O-OH → M-O, M = Ni and Co) and oxygen reduction reaction (ORR) to deliver more electrochemical energies of comparably higher voltage with much longer cycle life. The hybrid battery was constructed using an integrated electrode of NiCo2O4 nanowire arrays grown on carbon-coated nickel foam, coupled with a zinc plate anode in alkaline electrolyte. Benefitted from the M-O/M-O-OH redox reactions and rich ORR active sites in NiCo2O4, the battery has concurrently exhibited high working voltage (by M-O-OH → M-O) and high energy density (by ORR). The good oxygen evolution reaction (OER) activity of the electrode and the reversible M-O ↔ M-O-OH reactions also enabled smooth recharging of the batteries, leading to excellent cycling stabilities. Impressively, the hybrid batteries maintained highly stable charge-discharge voltage profile under various testing conditions, for example, almost no change was observed over 5000 cycles at a current density of 5 mA cm-2 after some initial stabilization. With merits of higher working voltage, high energy density, and ultralong cycle life, such hybrid batteries promise high potential for practical applications.

Visible-Near-Infrared-Light-Driven Oxygen Evolution Reaction with Noble-Metal-Free WO2-WO3 Hybrid Nanorods.

Understanding and manipulating the one half-reaction of photoinduced hole-oxidation to oxygen are of fundamental importance to design and develop an efficient water-splitting process. To date, extensive studies on oxygen evolution from water splitting have focused on visible-light harvesting. However, capturing low-energy photons for oxygen evolution, such as near-infrared (NIR) light, is challenging and not well-understood. This report presents new insights into photocatalytic water oxidation using visible and NIR light. WO2-WO3 hybrid nanorods were in situ fabricated using a wet-chemistry route. The presence of metallic WO2 strengthens light absorption and promotes the charge-carrier separation of WO3. The efficiency of the oxygen evolution reaction over noble-metal-free WO2-WO3 hybrids was found to be significantly promoted. More importantly, NIR light (≥700 nm) can be effectively trapped to cause the photocatalytic water oxidation reaction. The oxygen evolution rates are even up to around 220 (λ = 700 nm) and 200 (λ = 800 nm) mmol g-1 h-1. These results demonstrate that the WO2-WO3 material is highly active for water oxidation with low-energy photons and opens new opportunities for multichannel solar energy conversion.

Defect assisted coupling of a MoS2/TiO2 interface and tuning of its electronic structure.

Although MoS2 based heterostructures have drawn increased attention, the van der Waals forces within MoS2 layers make it difficult for the layers to form strong chemical coupled interfaces with other materials. In this paper, we demonstrate the successful strong chemical attachment of MoS2 on TiO2 nanobelts after appropriate surface modifications. The etch-created dangling bonds on TiO2 surfaces facilitate the formation of a steady chemically bonded MoS2/TiO2 interface. With the aid of high resolution transmission electron microscope measurements, the in-plane structure registry of MoS2/TiO2 is unveiled at the atomic scale, which shows that MoS2[1-10] grows along the direction of TiO2[001] and MoS2[110] parallel to TiO2[100] with every six units of MoS2 superimposed on five units of TiO2. Electronically, type II band alignments are realized for all surface treatments. Moreover, the band offsets are delicately correlated to the surface states, which plays a significant role in their photocatalytic performance.

Electrochemically "writing" graphene from graphene oxide.

A novel approach of patterning graphene on conductive surfaces based on local electrochemical reduction of graphene oxide is reported. Graphene is "written" from typical graphene oxide dispersion by applying negative potential on conductive surfaces vs. a micrometer-sized counter electrode "pen" with scanning electrochemical microscopy (SECM). Micrometer scaled patterns are successfully generated on gold and stainless steel surfaces.

Near-infrared active metamaterials and their applications in tunable surface-enhanced Raman scattering.

By utilizing the phase change properties of vanadium dioxide (VO2), we have demonstrated the tuning of the electric and magnetic modes of split ring resonators (SRRs) simultaneously within the near IR range. The electric resonance wavelength is blue-shift about 73 nm while the magnetic resonance mode is red-shifted about 126 nm during the phase transition from insulating to metallic phases. Due to the hysteresis phenomenon of VO2 phase transition, both the electric and magnetic modes shifts are hysteretic. In addition to the frequency shift, the magnetic mode has a trend to vanish due to the fact that the metallic phase VO2 has the tendency to short the gap of SRR. We have also demonstrated the application of this active metamaterials in tunable surface-enhanced Raman scattering (SERS), for a fixed excitation laser wavelength, the Raman intensity can be altered significantly by tuning the electric mode frequency of SRR, which is accomplished by controlling the phase of VO2 with an accurate temperature control.

Preparation of MoS2-MoO3 hybrid nanomaterials for light-emitting diodes.

A facile strategy to prepare MoS2 -MoO3 hybrid nanomaterials is developed, based on the heat-assisted partial oxidation of lithium-exfoliated MoS2  nanosheets in air followed by thermal-annealing-driven crystallization. The obtained MoS2 -MoO3 hybrid nanomaterial exhibits p-type conductivity. As a proof-of-concept application, an n-type SiC/p-type MoS2 -MoO3 heterojunction is used as the active layer for light-emitting diodes. The origins of the electroluminescence from the device are theoretically investigated. This facile synthesis and application of hybrid nanomaterials opens up avenues to develop new advanced materials for various functional applications, such as in electrics, optoelectronics, clean energy, and information storage.

Strain-Induced Ferromagnetism in Monolayer T″-Phase VTe2: Unveiling Magnetic States and Anisotropy for Spintronics Advancement.

Two-dimensional (2D) ferromagnets have attracted significant interest for their potential in spintronic device miniaturization, especially since the discovery of ferromagnetic ordering in monolayer materials such as CrI3 and Fe3GeTe2 in 2017. This study presents a detailed investigation into the effects of the Hubbard U parameter, biaxial strain, and structural distortions on the magnetic characteristics of T″-phase VTe2. We demonstrate that setting the Hubbard U to 0 eV provides an accurate representation of the observed structural, magnetic, and electronic features for both bulk and monolayer T″-phase VTe2. The application of strain reveals two distinct ferromagnetic states in the monolayer T″-phase VTe2, each characterized by minor structural differences, but notably different magnetic moments. The T″-1 state, with reduced magnetic moments, emerges under compressive strain, while the T″-2 state, featuring increased magnetic moments, develops under tensile strain. Our analysis also compares the magnetic anisotropy between the T and T″ phases of VTe2, highlighting that the periodic lattice distortion in the T″-phase induces an in-plane anisotropy, which makes it a material with an easy-axis of magnetization. Monte Carlo simulations corroborate our findings, indicating a high Curie temperature of approximately 191 K for the T″-phase VTe2. Our research not only sheds light on the critical aspects of the VTe2 system but also suggests new pathways for enhancing low-dimensional magnetism, contributing to the advancement of spintronics and straintronics.

Electrical Control Grain Dimensionality with Multilevel Magnetic Anisotropy.

In alignment with the increasing demand for larger storage capacity and longer data retention, the electrical control of magnetic anisotropy has been a research focus in the realm of spintronics. Typically, magnetic anisotropy is determined by grain dimensionality, which is set during the fabrication of magnetic thin films. Despite the intrinsic correlation between magnetic anisotropy and grain dimensionality, there is a lack of experimental evidence for electrically controlling grain dimensionality, thereby impairing the efficiency of magnetic anisotropy modulation. Here, we demonstrate an electric field control of grain dimensionality and prove it as the active mechanism for tuning interfacial magnetism. The reduction in grain dimensionality is associated with a transition from ferromagnetic to superparamagnetic behavior. We achieve a nonvolatile and reversible modulation of the coercivity in both the ferromagnetic and superparamagnetic regimes. Subsequent electrical and elemental analysis confirms the variation in grain dimensionality upon the application of gate voltages, revealing a transition from a multidomain to a single-domain state, accompanied by a reduction in grain dimensionality. Furthermore, we exploit the influence of grain dimensionality on domain wall motion, extending its applicability to multilevel magnetic memory and synaptic devices. Our results provide a strategy for tuning interfacial magnetism through grain size engineering for advancements in high-performance spintronics.

Enhancement of Out-of-Plane Spin-Orbit Torque by Interfacial Modification.

Spin-orbit torque (SOT)-induced switching of perpendicular magnetization in the absence of magnetic field is crucial for the application of SOT-based spintronic devices. Recent works have demonstrated that the low-symmetry crystal structure in CuPt/CoPt can give rise to an out-of-plane (OOP) spin torque and lead to deterministic magnetization switching without an external field. However, it is essential to improve OOP effective field for the efficient switching. In this work, the impact of interface oxidation on the generation of OOP effective field in a CuPt/ferromagnet heterostructure is systematically studied. By introducing an oxidized CuPt surface, it is found that the field-free switching performance shows remarkable improvement. OOP effective field measurement indicates that the oxidation treatment can enhance the OOP effective field by more than two times. It is also demonstrated that this oxidation-induced OOP SOT efficiency enhancement is independent of the device shapes, magnetic materials, or magnetization easy axis. This work contributes to improve the performance of SOT devices and provides an effective fabrication guidance for future spintronic devices that utilize OOP SOT.

Sublimation-based wafer-scale monolayer WS2 formation via self-limited thinning of few-layer WS2.

Atomically-thin monolayer WS2 is a promising channel material for next-generation Moore's nanoelectronics owing to its high theoretical room temperature electron mobility and immunity to short channel effect. The high photoluminescence (PL) quantum yield of the monolayer WS2 also makes it highly promising for future high-performance optoelectronics. However, the difficulty in strictly growing monolayer WS2, due to its non-self-limiting growth mechanism, may hinder its industrial development because of the uncontrollable growth kinetics in attaining the high uniformity in thickness and property on the wafer-scale. In this study, we report a scalable process to achieve a 4 inch wafer-scale fully-covered strictly monolayer WS2 by applying the in situ self-limited thinning of multilayer WS2 formed by sulfurization of WOx films. Through a pulsed supply of sulfur precursor vapor under a continuous H2 flow, the self-limited thinning process can effectively trim down the overgrown multilayer WS2 to the monolayer limit without damaging the remaining bottom WS2 monolayer. Density functional theory (DFT) calculations reveal that the self-limited thinning arises from the thermodynamic instability of the WS2 top layers as opposed to a stable bottom monolayer WS2 on sapphire above a vacuum sublimation temperature of WS2. The self-limited thinning approach overcomes the intrinsic limitation of conventional vapor-based growth methods in preventing the 2nd layer WS2 domain nucleation/growth. It also offers additional advantages, such as scalability, simplicity, and possibility for batch processing, thus opening up a new avenue to develop a manufacturing-viable growth technology for the preparation of a strictly-monolayer WS2 on the wafer-scale.

Liquid-Metal-Printed Ultrathin Oxides for Atomically Smooth 2D Material Heterostructures.

Two-dimensional (2D) semiconductors are promising channel materials for continued downscaling of complementary metal-oxide-semiconductor (CMOS) logic circuits. However, their full potential continues to be limited by a lack of scalable high-k dielectrics that can achieve atomically smooth interfaces, small equivalent oxide thicknesses (EOTs), excellent gate control, and low leakage currents. Here, large-area liquid-metal-printed ultrathin Ga2O3 dielectrics for 2D electronics and optoelectronics are reported. The atomically smooth Ga2O3/WS2 interfaces enabled by the conformal nature of liquid metal printing are directly visualized. Atomic layer deposition compatibility with high-k Ga2O3/HfO2 top-gate dielectric stacks on a chemical-vapor-deposition-grown monolayer WS2 is demonstrated, achieving EOTs of ∼1 nm and subthreshold swings down to 84.9 mV/dec. Gate leakage currents are well within requirements for ultrascaled low-power logic circuits. These results show that liquid-metal-printed oxides can bridge a crucial gap in dielectric integration of 2D materials for next-generation nanoelectronics.

Effects of regional transport from different potential pollution areas on volatile organic compounds (VOCs) in Northern Beijing during non-heating and heating periods.

Despite the adoption of air quality control measures, the influence of regional transport on volatile organic compounds (VOCs) pollution has gradually increased in Beijing. In this study, the whole observation period (September 24 to December 12, 2020) was divided into heating period and non-heating period to explore the impact of changing VOCs sources in different observation periods, and also classified into "Type-N" and "Type-S" periods both in non-heating period and heating period to explore the impact of regional transport from the northern and southern regions of sampling site, respectively. The average VOCs concentrations in northern Beijing during observation period were 22.6 ± 12.6 ppbv, which showed a decrease trend in recent years compared with other studies. And higher VOCs concentrations were observed in Type-S than in Type-N period. The positive matrix factorization results showed that vehicular exhaust dominated VOCs (26.1%-33.7%), but coal combustion could not be ignored in heating period, when it was twice that in non-heating period. In particular, coal combustion dominated VOCs in southern trajectories (30.9%) in heating period. The analysis of concentration weighted trajectory showed that coal combustion was affected by regional transport from the southeast regions of Beijing, while vehicular exhaust was affected by urban and the southeast regions of Beijing. Regarding human health risks, the carcinogenic risks of benzene and ethylbenzene exceeded the acceptable cancer risk value (1 × 10-6), and were higher in Type-S than in Type-N period. The results indicated that regional transport from urban areas and the areas south of Beijing had a significant impact on VOCs in northern Beijing. Thus, targeted control measures for different potential pollution regions are important for controlling VOCs pollution in Beijing.

Rashba-Edelstein Effect in the h-BN Van Der Waals Interface for Magnetization Switching.

Van der Waals materials are attracting great attention in the field of spintronics due to their novel physical properties. For example, they are utilized as spin-current generating materials in spin-orbit torque (SOT) devices, which offers an electrical way to control the magnetic state and is promising for future low-power electronics. However, SOTs have mostly been demonstrated in vdW materials with strong spin-orbit coupling (SOC). Here, the observation of a current-induced SOT in the h-BN/SrRuO3 bilayer structure is reported, where the vdW material (h-BN) is an insulator with negligible SOC. Importantly, this SOT is strong enough to induce the switching of the perpendicular magnetization in SrRuO3 . First-principles calculations suggest a giant Rashba effect at the interface between vdW material and SrRuO3 (110)pc thin film, which leads to the observed SOT based on a simplified tight-binding model. Furthermore, it is demonstrated that the current-induced magnetization switching can be modulated by the electric field. This study paves the way for exploring the current-induced SOT and magnetization switching by integrating vdW materials with ferromagnets.

MoS2 /Polymer Heterostructures Enabling Stable Resistive Switching and Multistate Randomness.

Resistive random-access memories (ReRAMs) based on transition metal dichalcogenide layers are promising physical sources for random number generation (RNG). However, most ReRAM devices undergo performance degradation from cycle to cycle, which makes preserving a normal probability distribution during operation a challenging task. Here, ReRAM devices with excellent stability are reported by using a MoS2 /polymer heterostructure as active layer. The stability enhancement manifests in outstanding cumulative probabilities for both high- and low-resistivity states of the memory cells. Moreover, the intrinsic values of the high-resistivity state are found to be an excellent source of randomness as suggested by a Chi-square test. It is demonstrated that one of these cells alone can generate ten distinct random states, in contrast to the four conventional binary cells that would be required for an equivalent number of states. This work unravels a scalable interface engineering process for the production of high-performance ReRAM devices, and sheds light on their promising application as reliable RNGs for enhanced cybersecurity in the big data era.

Revealing the Grain Boundary Formation Mechanism and Kinetics during Polycrystalline MoS2 Growth.

Controllable synthesis of MoS2 with desired grain morphology via chemical vapor deposition (CVD) or physical vapor deposition (PVD) remains a challenge. Hence, it is important to understand polycrystalline growth of MoS2 and further provide guidelines for its CVD/PVD growth. Here, we formulate a kinetic Monte Carlo (kMC) model aiming at predicting the grain boundary (GB) formation in the CVD/PVD growth of polycrystalline MoS2. In the kMC model, the grain growth is via kink nucleation and propagation, whose energetic parameters and initial nucleus details are either from first-principles calculations or from experiments. Using the kMC model, we perform extensive simulations to predict the GB formation by using two, three, four, and five initial nuclei and compare the simulation results with previous experimental results. The obtained GB morphologies are in an excellent agreement with those experimental results. These agreements suggest that the proposed kMC model can correctly capture the mechanism and kinetics of GB formation. In particular, we reveal that the formation of smooth/rough GB is dictated by the two growth vectors for the kink propagation at the two associated grain edges, which is validated by our high-resolution scanning transmission electron microscopy images for PVD growth of MoS2 grains. Besides, we have made predictions beyond reproducing experimental observations, including the growth with artificially designed nuclei, the morphology transformation by tuning the Mo and S sources, and the formation of high-quality single-crystalline monolayer MoS2 by using single-crystalline substrates with vicinal steps. Our kMC model may serve as a powerful predictive tool for the CVD/PVD growth of monolayer MoS2 with desired GB configurations.

Employing a Bifunctional Molybdate Precursor To Grow the Highly Crystalline MoS2 for High-Performance Field-Effect Transistors.

Growth of the large-sized and high-quality MoS2 single crystals for high-performance low-power electronic applications is an important step to pursue. Despite the significant improvement made in minimizing extrinsic MoS2 contact resistance based on interfacial engineering of the devices, the electron mobility of field-effect transistors (FETs) made of a synthetic monolayer MoS2 is yet far below the expected theoretical values, implying that the MoS2 crystal quality needs to be further improved. Here, we demonstrate the high-performance two-terminal MoS2 FETs with room-temperature electron mobility up to ∼90 cm2 V-1 s-1 based on the sulfurization growth of the bifunctional precursor, sodium molybdate dihydrate. This unique transition-metal precursor, serving as both the crystalline Mo source and seed promotor (sodium), could facilitate the lateral growth of the highly crystalline monolayer MoS2 crystals (edge length up to ∼260 µm). Substrate surface treatment with oxygen plasma prior to the deposition of the Mo precursor is fundamental to increase the wettability between the Mo source and the substrate, promoting the thinning and coalescence of the source clusters during the growth of large-sized MoS2 single crystals. The control of growth temperature is also an essential step to grow a strictly monolayer MoS2 crystal. A proof-of-concept for thermoelectric device integration utilizing monolayer MoS2 sheds light on its potential in low-voltage and self-powered electronics.

Giant Enhancements of Perpendicular Magnetic Anisotropy and Spin-Orbit Torque by a MoS2 Layer.

2D transition metal dichalcogenides have attracted much attention in the field of spintronics due to their rich spin-dependent properties. The promise of highly compact and low-energy-consumption spin-orbit torque (SOT) devices motivates the search for structures and materials that can satisfy the requirements of giant perpendicular magnetic anisotropy (PMA) and large SOT simultaneously in SOT-based magnetic memory. Here, it is demonstrated that PMA and SOT in a heavy metal/transition metal ferromagnet structure, Pt/[Co/Ni]2 , can be greatly enhanced by introducing a molybdenum disulfide (MoS2 ) underlayer. According to first-principles calculation and X-ray absorption spectroscopy (XAS), the enhancement of the PMA is ascribed to the modification of the orbital hybridization at the interface of Pt/Co due to MoS2 . The enhancement of SOT by the role played by MoS2 is explained, which is strongly supported by the identical behavior of SOT and PMA as a function of Pt thickness. This work provides new possibilities to integrate 2D materials into promising spintronics devices.