Direct observation of twisted stacking domains in the van der Waals magnet CrI3.

Van der Waals (vdW) stacking is a powerful technique to achieve desired properties in condensed matter systems through layer-by-layer crystal engineering. A remarkable example is the control over the twist angle between artificially-stacked vdW crystals, enabling the realization of unconventional phenomena in moiré structures ranging from superconductivity to strongly correlated magnetism. Here, we report the appearance of unusual 120° twisted faults in vdW magnet CrI3 crystals. In exfoliated samples, we observe vertical twisted domains with a thickness below 10 nm. The size and distribution of twisted domains strongly depend on the sample preparation methods, with as-synthesized unexfoliated samples showing tenfold thicker domains than exfoliated samples. Cooling induces changes in the relative populations among different twisting domains, rather than the previously assumed structural phase transition to the rhombohedral stacking. The stacking disorder induced by sample fabrication processes may explain the unresolved thickness-dependent magnetic coupling observed in CrI3.

Enhanced Long-Term Stability of Crystalline Nickel-Boride (Ni23B6) Electrocatalyst by Encapsulation with Hexagonal Boron Nitride.

Nickel boride catalysts show great potential as low-cost and efficient alternatives to noble-metal catalysts in acidic media; however, synthesizing and isolating a specific phase and composition of nickel boride is nontrivial, and issues persist in their long-term stability as electrocatalysts. Here, a single-crystal nickel boride, Ni23B6, is reported which exhibits high electrocatalytic activity for the hydrogen evolution reaction (HER) in an acidic solution, and that its poor long-term stability can be overcome via encapsulation by single-crystal trilayer hexagonal boron nitride (hBN) film. Interestingly, hBN-covered Ni23B6 on a Ni substrate shows an identical overpotential of 52 mV at a current density of 10 mA cm-2 to that of bare Ni23B6. This phenomenon indicates that the single-crystalline hBN layer is catalytically transparent and does not obstruct HER activation. The hBN/Ni23B6/Ni has remarkable long-term stability with negligible changes to its polarization curves for 2000 cycles, whereas the Ni23B6/Ni shows significant degradation after 650 cycles. Furthermore, chronoamperometric measurements indicate that stability is preserved for >20 h. Long-term stability tests also reveal that the surface morphology and chemical structure of the hBN/Ni23B6/Ni electrode remain preserved. This work provides a model for the practical design of robust and durable electrochemical catalysts through the use of hBN encapsulation.

Dimensionality Engineering of Magnetic Anisotropy from the Anomalous Hall Effect in Synthetic SrRuO3 Crystals.

Magnetic anisotropy in atomically thin correlated heterostructures is essential for exploring quantum magnetic phases for next-generation spintronics. Whereas previous studies have mostly focused on van der Waals systems, here we investigate the impact of dimensionality of epitaxially grown correlated oxides down to the monolayer limit on structural, magnetic, and orbital anisotropies. By designing oxide superlattices with a correlated ferromagnetic SrRuO3 and nonmagnetic SrTiO3 layers, we observed modulated ferromagnetic behavior with the change of the SrRuO3 thickness. Especially, for three-unit-cell-thick layers, we observe a significant 1500% improvement of the coercive field in the anomalous Hall effect, which cannot be solely attributed to the dimensional crossover in ferromagnetism. The atomic-scale heterostructures further reveal the systematic modulation of anisotropy for the lattice structure and orbital hybridization, explaining the enhanced magnetic anisotropy. Our findings provide valuable insights into engineering the anisotropic hybridization of synthetic magnetic crystals, offering a tunable spin order for various applications.

Ion transport induced room-temperature insulator-metal transition in single-crystalline Cu2Se.

Cu2Se is a superionic conductor above 414 K, with ionic conductivities reaching that of molten salts. The superionic behavior results from hopping Cu ions between different crystallographic sites within the Se scaffold. However, the properties of Cu2Se below 414 K are far less known due to experimental limitations imposed by the bulk or polycrystalline samples that have been available so far. Here, we report the synthesis of ultra-thin, large-area single crystalline Cu2Se samples using a chemical vapor deposition method. The as-synthesized Cu2Se crystals exhibit optically and electrically detectable and controllable robust phases at room temperature and above. We demonstrate that Cu ion vacancies can be manipulated to induce an insulator-metal transition, which exhibits 6 orders of magnitude change in the electrical resistance of two terminal devices, accompanied by an optical change in the phase configuration. Our experiments show that the high mobility of the liquid-like Cu ion vacancies in Cu2Se causes macroscopic ordering in the Cu vacancies. Consequently, phase distribution over the crystals is not dictated by the diffusive motion of the ions but by the local energy minima formed due to the phase transition. As a result, long-range vacancy ordering of the crystal below 414 K becomes optically observable at a micrometer scale. This work demonstrates that Cu2Se could be a prototypical system where long-range ordering properties can be studied via electrical and optical methods.

Symmetry Engineering of Epitaxial Hf0.5Zr0.5O2 Ultrathin Films.

Robust ferroelectricity in HfO2-based ultrathin films has the potential to revolutionize nonvolatile memory applications in nanoscale electronic devices because of their compatibility with the existing Si technology. However, to fully exploit the potential of ferroelectric HfO2-based thin films, it is crucial to develop strategies for the controlled stabilization of various HfO2-based polymorphs in nanoscale heterostructures. This study demonstrates how substrate-orientation-induced anisotropic strain can engineer the crystal symmetry, structural domain morphology, and growth orientation of ultrathin Hf0.5Zr0.5O2 (HZO) films. Epitaxial ultrathin HZO films were grown on the heterostructures of (001)- and (110)-oriented La2/3Sr1/3MnO3/SrTiO3 (LSMO/STO) substrate. Various structural analyses revealed that the (110)-oriented substrate promotes a higher degree of structural order (crystallinity) with improved stability of the (111)-oriented orthorhombic phase (Pca21) of HZO. Conversely, the (001)-oriented substrate not only induces a distorted orthorhombic structure but also facilitates the partial stabilization of nonpolar phases. Electrical measurements revealed robust ferroelectric properties in epitaxial thin films without any wake-up effect, where the well-ordered crystal symmetry stabilized by STO(110) facilitated better ferroelectric characteristics. This study suggests that tuning the epitaxial growth of ferroelectric HZO through substrate orientation can improve the stability of the metastable ferroelectric orthorhombic phase and thereby offer a better understanding of device applications.

Wafer-Scale Synthesis of Highly Oriented 2D Topological Semimetal PtTe2 via Tellurization.

Platinum ditelluride (1T-PtTe2) is a two-dimensional (2D) topological semimetal with a distinctive band structure and flexibility of van der Waals integration as a promising candidate for future electronics and spintronics. Although the synthesis of large-scale, uniform, and highly crystalline films of 2D semimetals system is a prerequisite for device application, the synthetic methods meeting these criteria are still lacking. Here, we introduce an approach to synthesize highly oriented 2D topological semimetal PtTe2 using a thermally assisted conversion called tellurization, which is a cost-efficient method compared to the other epitaxial deposition methods. We demonstrate that achieving highly crystalline 1T-PtTe2 using tellurization is not dependent on epitaxy but rather relies on two critical factors: (i) the crystallinity of the predeposited platinum (Pt) film and (ii) the surface coverage ratio of the Pt film considering lateral lattice expansion during transformation. By optimizing the surface coverage ratio of the epitaxial Pt film, we successfully obtained 2 in. wafer-scale uniformity without in-plane misalignment between antiparallelly oriented domains. The electronic band structure of 2D topological PtTe2 is clearly resolved in momentum space, and we observed an interesting 6-fold gapped Dirac cone at the Fermi surface. Furthermore, ultrahigh electrical conductivity down to ∼3.8 nm, which is consistent with that of single crystal PtTe2, was observed, proving its ultralow defect density.

Boltzmann Switching MoS2 Metal-Semiconductor Field-Effect Transistors Enabled by Monolithic-Oxide-Gapped Metal Gates at the Schottky-Mott Limit.

A gate stack that facilitates a high-quality interface and tight electrostatic control is crucial for realizing high-performance and low-power field-effect transistors (FETs). However, when constructing conventional metal-oxide-semiconductor structures with two-dimensional (2D) transition metal dichalcogenide channels, achieving these requirements becomes challenging due to inherent difficulties in obtaining high-quality gate dielectrics through native oxidation or film deposition. Here, a gate-dielectric-less device architecture of van der Waals Schottky gated metal-semiconductor FETs (vdW-SG MESFETs) using a molybdenum disulfide (MoS2) channel and surface-oxidized metal gates such as nickel and copper is reported. Benefiting from the strong SG coupling, these MESFETs operate at remarkably low gate voltages, <0.5 V. Notably, they also exhibit Boltzmann-limited switching behavior featured by a subthreshold swing of ≈60 mV dec-1 and negligible hysteresis. These ideal FET characteristics are attributed to the formation of a Fermi-level (EF) pinning-free gate stack at the Schottky-Mott limit. Furthermore, authors experimentally and theoretically confirm that EF depinning can be achieved by suppressing both metal-induced and disorder-induced gap states at the interface between the monolithic-oxide-gapped metal gate and the MoS2 channel. This work paves a new route for designing high-performance and energy-efficient 2D electronics.

Area-selective atomic layer deposition on 2D monolayer lateral superlattices.

The advanced patterning process is the basis of integration technology to realize the development of next-generation high-speed, low-power consumption devices. Recently, area-selective atomic layer deposition (AS-ALD), which allows the direct deposition of target materials on the desired area using a deposition barrier, has emerged as an alternative patterning process. However, the AS-ALD process remains challenging to use for the improvement of patterning resolution and selectivity. In this study, we report a superlattice-based AS-ALD (SAS-ALD) process using a two-dimensional (2D) MoS2-MoSe2 lateral superlattice as a pre-defining template. We achieved a minimum half pitch size of a sub-10 nm scale for the resulting AS-ALD on the 2D superlattice template by controlling the duration time of chemical vapor deposition (CVD) precursors. SAS-ALD introduces a mechanism that enables selectivity through the adsorption and diffusion processes of ALD precursors, distinctly different from conventional AS-ALD method. This technique facilitates selective deposition even on small pattern sizes and is compatible with the use of highly reactive precursors like trimethyl aluminum. Moreover, it allows for the selective deposition of a variety of materials, including Al2O3, HfO2, Ru, Te, and Sb2Se3.

Universal Platform for Robust Dual-Atom Doped 2D Catalysts with Superior Hydrogen Evolution in Wide pH Media.

Layered 2D transition metal dichalcogenides (TMDs) have been suggested as efficient substitutes for Pt-group metal electrocatalysts in the hydrogen evolution reaction (HER). However, poor catalytic activities in neutral and alkaline electrolytes considerably hinder their practical applications. Furthermore, the weak adhesion between TMDs and electrodes often impedes long-term durability and thus requires a binder. Here, a universal platform is reported for robust dual-atom doped 2D electrocatalysts with superior HER performance over a wide pH range media. V:Co-ReS2 on a wafer scale is directly grown on oxidized Ti foil by a liquid-phase precursor-assisted approach and subsequently used as highly efficient electrocatalysts. The catalytic performance surpasses that of Pt group metals in a high current regime (≥ 100 mA cm-2) at pH ≥ 7, with a high durability of more than 70 h in all media at 200 mA cm-2. First-principles calculations reveal that V:Co dual doping in ReS2 significantly reduces the water dissociation barrier and simultaneously enables the material to achieve the thermoneutral Gibbs free energy for hydrogen adsorption.

Layer-Controlled Growth of Single-Crystalline 2D Bi2O2Se Film Driven by Interfacial Reconstruction.

As semiconductor scaling continues to reach sub-nanometer levels, two-dimensional (2D) semiconductors are emerging as a promising candidate for the post-silicon material. Among these alternatives, Bi2O2Se has risen as an exceptionally promising 2D semiconductor thanks to its excellent electrical properties, attributed to its appropriate bandgap and small effective mass. However, unlike other 2D materials, growth of large-scale Bi2O2Se films with precise layer control is still challenging due to its large surface energy caused by relatively strong interlayer electrostatic interactions. Here, we present the successful growth of a wafer-scale (∼3 cm) Bi2O2Se film with precise thickness control down to the monolayer level on TiO2-terminated SrTiO3 using metal-organic chemical vapor deposition (MOCVD). Scanning transmission electron microscopy (STEM) analysis confirmed the formation of a [BiTiO4]1- interfacial structure, and density functional theory (DFT) calculations revealed that the formation of [BiTiO4]1- significantly reduced the interfacial energy between Bi2O2Se and SrTiO3, thereby promoting 2D growth. Additionally, spectral responsivity measurements of two-terminal devices confirmed a bandgap increase of up to 1.9 eV in monolayer Bi2O2Se, which is consistent with our DFT calculations. Finally, we demonstrated high-performance Bi2O2Se field-effect transistor (FET) arrays, exhibiting an excellent average electron mobility of 56.29 cm2/(V·s). This process is anticipated to enable wafer-scale applications of 2D Bi2O2Se and facilitate exploration of intriguing physical phenomena in confined 2D systems.

3D microprinting of inorganic porous materials by chemical linking-induced solidification of nanocrystals.

Three-dimensional (3D) microprinting is considered a next-generation manufacturing process for the production of microscale components; however, the narrow range of suitable materials, which include mainly polymers, is a critical issue that limits the application of this process to functional inorganic materials. Herein, we develop a generalised microscale 3D printing method for the production of purely inorganic nanocrystal-based porous materials. Our process is designed to solidify all-inorganic nanocrystals via immediate dispersibility control and surface linking-induced interconnection in the nonsolvent linker bath and thereby creates multibranched gel networks. The process works with various inorganic materials, including metals, semiconductors, magnets, oxides, and multi-materials, not requiring organic binders or stereolithographic equipment. Filaments with a diameter of sub-10 µm are printed into designed complex 3D microarchitectures, which exhibit full nanocrystal functionality and high specific surface areas as well as hierarchical porous structures. This approach provides the platform technology for designing functional inorganics-based porous materials.

Jackfruit Anaphylaxis Due to Cross Reactivity with Latex.

Growing evidence has demonstrated that many common plant foods such as mangos, kiwis and jackfruit lead to cross reactivity with the latex antigen in latex allergic patients. Here, we discuss the case of a 68 year old female of Bangladeshi descent who developed shortness of breath in the setting of anaphylaxis following the ingestion of jackfruit (Artocarpus heterophyllus). The patient had a history of latex allergy described as mild rash along with seasonal allergies causing mild rhinorrhea, congestion and sneezing. Given the strong cultural significance of jackfruit consumption in Asian countries and growing popularity in the use of jackfruit as a superfood meat alternative in Western nations, along with growing Asian population, there is a need for extensive education on the cross reactivity between plant foods and latex to prevent deadly cross-reactivity induced anaphylaxis. With this case report, we hope to raise awareness of this rare, yet morbid association.

Accelerated Engineering of Optimized Functional Composite Hydrogels via High-Throughput Experimentation.

The Materials Genome Initiative (MGI) seeks to accelerate the discovery and engineering of advanced materials via high-throughput experimentation (HTE), which is a challenging task, given the common trade-off between design for optimal processability vs performance. Here, we report a HTE method based on automated formulation, synthesis, and multiproperty characterization of bulk soft materials in well plate formats that enables accelerated engineering of functional composite hydrogels with optimized properties for processability and performance. The method facilitates rapid high-throughput screening of hydrogel composition-property relations for multiple properties in well plate formats. The feasibility and utility of the method were demonstrated by application to several functional composite hydrogel systems, including alginate/poly(N-isopropylacrylamide) (PNIPAM) and poly(ethylene glycol) dimethacrylate (PEGDMA)/poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) hydrogels. The HTE method was leveraged to identify formulations of conductive PEGDMA/PEDOT:PSS composite hydrogels for optimized performance and processability in three-dimensional (3D) printing. This work provides an advance in experimental methods based on automated dispensing, mixing, and sensing for the accelerated engineering of soft functional materials.

Self-Oxidation Resistance of the Curved Surface of Achromatic Copper.

Copper surfaces that exhibit a wide range of achromatic colors while still metallic have not been studied, despite advancements in antireflection coatings. A series of achromatic copper films grown with [111] preferred orientation by depositing 3D porous nanostructures is introduced via coherent/incoherent atomic sputtering epitaxy. The porous copper nanostructures self-regulate the giant oxidation resistance by constructing a curved surface that generates a series of monoatomic steps, followed by shrinkage of the lattice spacing of one or two surface layers. First-principles calculations confirm that these structural components cooperatively increase the energy barrier against oxygen penetration. The achromaticity of the single-crystalline porous copper films is systematically tuned by geometrical parameters such as pore size distribution and 3D linkage. The optimized achromatic copper films with high oxidation resistance show an unusual switching effect between superhydrophilicity and superhydrophobicity. The tailored 3D porous nanostructures can be a candidate material for numerous applications, such as antireflection coatings, microfluidic devices, droplet tweezers, and reversible wettability switches.

Atomic Layer Deposition Route to Scalable, Electronic-Grade van der Waals Te Thin Films.

Scalable production and integration techniques for van der Waals (vdW) layered materials are vital for their implementation in next-generation nanoelectronics. Among available approaches, perhaps the most well-received is atomic layer deposition (ALD) due to its self-limiting layer-by-layer growth mode. However, ALD-grown vdW materials generally require high processing temperatures and/or additional postdeposition annealing steps for crystallization. Also, the collection of ALD-producible vdW materials is rather limited by the lack of a material-specific tailored process design. Here, we report the annealing-free wafer-scale growth of monoelemental vdW tellurium (Te) thin films using a rationally designed ALD process at temperatures as low as 50 °C. They exhibit exceptional homogeneity/crystallinity, precise layer controllability, and 100% step coverage, all of which are enabled by introducing a dual-function co-reactant and adopting a so-called repeating dosing technique. Electronically, vdW-coupled and mixed-dimensional vertical p-n heterojunctions with MoS2 and n-Si, respectively, are demonstrated with well-defined current rectification as well as spatial uniformity. Additionally, we showcase an ALD-Te-based threshold switching selector with fast switching time (∼40 ns), selectivity (∼104), and low Vth (∼1.3 V). This synthetic strategy allows the low-thermal-budget production of vdW semiconducting materials in a scalable fashion, thereby providing a promising approach for monolithic integration into arbitrary 3D device architectures.

Freestanding Oxide Membranes for Epitaxial Ferroelectric Heterojunctions.

Since facile routes to fabricate freestanding oxide membranes were previously established, tremendous efforts have been made to further improve their crystallinity, and fascinating physical properties have been also reported in heterointegrated freestanding membranes. Here, we demonstrate our synthetic recipe to manufacture highly crystalline perovskite SrRuO3 freestanding membranes using new infinite-layer perovskite SrCuO2 sacrificial layers. To accomplish this, SrRuO3/SrCuO2 bilayer thin films are epitaxially grown on SrTiO3 (001) substrates, and the topmost SrRuO3 layer is chemically exfoliated by etching the SrCuO2 template layer. The as-exfoliated SrRuO3 membranes are mechanically transferred to various nonoxide substrates for the subsequent BaTiO3 film growth. Finally, freestanding heteroepitaxial junctions of ferroelectric BaTiO3 and metallic SrRuO3 are realized, exhibiting robust ferroelectricity. Intriguingly, the enhancement of piezoelectric responses is identified in freestanding BaTiO3/SrRuO3 heterojunctions with mixed ferroelectric domain states. Our approaches will offer more opportunities to develop heteroepitaxial freestanding oxide membranes with high crystallinity and enhanced functionality.

Synthesis and Characterization of Multi-Reducing-End Polysaccharides.

Site-specific modification is a great challenge for polysaccharide scientists. Chemo- and regioselective modification of polysaccharide chains can provide many useful natural-based materials and help us illuminate fundamental structure-property relationships of polysaccharide derivatives. The hemiacetal reducing end of a polysaccharide is in equilibrium with its ring-opened aldehyde form, making it the most uniquely reactive site on the polysaccharide molecule, ideal for regioselective decoration such as imine formation. However, all natural polysaccharides, whether they are branched or not, have only one reducing end per chain, which means that only one aldehyde-reactive substituent can be added. We introduce a new approach to selective functionalization of polysaccharides as an entrée to useful materials, appending multiple reducing ends to each polysaccharide molecule. Herein, we reduce the approach to practice using amide formation. Amine groups on monosaccharides such as glucosamine or galactosamine can react with carboxyl groups of polysaccharides, whether natural uronic acids like alginates, or derivatives with carboxyl-containing substituents such as carboxymethyl cellulose (CMC) or carboxymethyl dextran (CMD). Amide formation is assisted using the coupling agent 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM). By linking the C2 amines of monosaccharides to polysaccharides in this way, a new class of polysaccharide derivatives possessing many reducing ends can be obtained. We refer to this class of derivatives as multi-reducing-end polysaccharides (MREPs). This new family of derivatives creates the potential for designing polysaccharide-based materials with many potential applications, including in hydrogels, block copolymers, prodrugs, and as reactive intermediates for other derivatives.

A Highly Reliable Molybdenum Disulfide-Based Synaptic Memristor Using a Copper Migration-Controlled Structure.

Memristors are drawing attention as neuromorphic hardware components because of their non-volatility and analog programmability. In particular, electrochemical metallization (ECM) memristors are extensively researched because of their linear conductance controllability. Two-dimensional materials as switching medium of ECM memristors give advantages of fast speed, low power consumption, and high switching uniformity. However, the multistate retention in the switching conductance range for the long-term reliable neuromorphic system has not been achieved using two-dimensional materials-based ECM memristors. In this study, the copper migration-controlled ECM memristor showing excellent multistate retention characteristics in the switching conductance range using molybdenum disulfide (MoS2 ) and aluminum oxide (Al2 O3 ) is proposed. The fabricated device exhibits gradual resistive switching with low switching voltage (<0.5 V), uniform switching (σ/µ âˆ¼ 0.07), and a wide switching range (>12). Importantly, excellent reliabilities with robustness to cycling stress and retention over 104 s for more than 5-bit states in the switching conductance range are achieved. Moreover, the contribution of the Al2 O3 layer to the retention characteristic is investigated through filament morphology observation using transmission electron microscopy (TEM) and copper migration component analysis. This study provides a practical approach to developing highly reliable memristors with exceptional switching performance.

Heterosynaptic MoS2 Memtransistors Emulating Biological Neuromodulation for Energy-Efficient Neuromorphic Electronics.

Heterosynaptic neuromodulation is a key enabler for energy-efficient and high-level biological neural processing. However, such manifold synaptic modulation cannot be emulated using conventional memristors and synaptic transistors. Thus, reported herein is a three-terminal heterosynaptic memtransistor using an intentional-defect-generated molybdenum disulfide channel. Particularly, the defect-mediated space-charge-limited conduction in the ultrathin channel results in memristive switching characteristics between the source and drain terminals, which are further modulated using a gate terminal according to the gate-tuned filling of trap states. The device acts as an artificial synapse controlled by sub-femtojoule impulses from both the source and gate terminals, consuming lower energy than its biological counterpart. In particular, electrostatic gate modulation, corresponding to biological neuromodulation, additionally regulates the dynamic range and tuning rate of the synaptic weight, independent of the programming (source) impulses. Notably, this heterosynaptic modulation not only improves the learning accuracy and efficiency but also reduces energy consumption in the pattern recognition. Thus, the study presents a new route leading toward the realization of highly networked and energy-efficient neuromorphic electronics.