Enhanced Ferromagnetism and Tunable Magnetic Anisotropy in a van der Waals Ferromagnet.

2D van der Waals (vdW) magnets have recently emerged as a promising material system for spintronic device innovations due to their intriguing phenomena in the reduced dimension and simple integration of magnetic heterostructures without the restriction of lattice matching. However, it is still challenging to realize Curie temperature far above room temperature and controllable magnetic anisotropy for spintronics application in 2D vdW magnetic materials. In this work, the pressure-tuned dome-like ferromagnetic-paramagnetic phase diagram in an iron-based 2D layered ferromagnet Fe3GaTe2 is reported. Continuously tunable magnetic anisotropy from out-of-plane to in-plane direction is achieved via the application of pressure. Such behavior is attributed to the competition between intralayer and interlayer exchange interactions and enhanced DOS near the Fermi level. The study presents the prominent properties of pressure-engineered 2D ferromagnetic materials, which can be used in the next-generation spintronic devices.

Ultrasensitive CCL2 Detection in Urine for Diabetic Nephropathy Diagnosis Using a WS2-Based Plasmonic Biosensor.

The accurate diagnosis of diabetic nephropathy relies on achieving ultrasensitive biosensing for biomarker detection. However, existing biosensors face challenges such as poor sensitivity, complexity, time-consuming procedures, and high assay costs. To address these limitations, we report a WS2-based plasmonic biosensor for the ultrasensitive detection of biomarker candidates in clinical human urine samples associated with diabetic nephropathy. Leveraging plasmonic-based electrochemical impedance microscopy (P-EIM) imaging, we observed a remarkable charge sensitivity in monolayer WS2 single crystals. Our biosensor exhibits an exceptionally low detection limit (0.201 ag/mL) and remarkable selectivity in detecting CC chemokine ligand 2 (CCL2) protein biomarkers, outperforming conventional techniques such as ELISA. This work represents a breakthrough in traditional protein sensors, providing a direction and materials foundation for developing ultrasensitive sensors tailored to clinical applications for biomarker sensing.

High-Performance Broadband Image Sensing Photodetector Based on MnTe/WS2 van der Waals Epitaxial Heterostructures.

Two-dimensional transition metal dichalcogenide (TMDC) heterostructure is receiving considerable attention due to its novel electronic, optoelectronic, and spintronic devices with design-oriented and functional features. However, direct design and synthesis of high-quality TMDC/MnTe heterostructures remain difficult, which severely impede further investigations of semiconductor/magnetic semiconductor devices. Herein, the synthesis of high-quality vertically stacked WS2/MnTe heterostructures is realized via a two-step chemical vapor deposition method. Raman, photoluminescence, and scanning transmission electron microscopy characterizations reveal the high-quality and atomically sharp interfaces of the WS2/MnTe heterostructure. WS2/MnTe-based van der Waals field effect transistors demonstrate high rectification behavior with rectification ratio up to 106, as well as a typical p-n electrical transport characteristic. Notably, the fabricated WS2/MnTe photodetector exhibits sensitive and broadband photoresponse ranging from UV to NIR with a maximum responsivity of 1.2 × 103 A/W, a high external quantum efficiency of 2.7 × 105%, and fast photoresponse time of ∼50 ms. Moreover, WS2/MnTe heterostructure photodetectors possess a broadband image sensing capability at room temperature, suggesting potential applications in next-generation high-performance and broadband image sensing photodetectors.

Plasmonic Imaging of Single DNA with Charge Sensitive Monolayer WS2.

Imaging the surface charge of biomolecules such as proteins and DNA, is crucial for comprehending their structure and function. Unfortunately, current methods for label-free, sensitive, and rapid imaging of the surface charge of single DNA molecules are limited. Here, we propose a plasmonic microscopy strategy that utilizes charge-sensitive single-crystal monolayer WS2 materials to image the local charge density of a single λ-DNA molecule. Our study reveals that WS2 is a highly sensitive charge-sensitive material that can accurately measure the local charge density of λ-DNA with high spatial resolution and sensitivity. The consistency of the surface charge density values obtained from the single-crystal monolayer WS2 materials with theoretical simulations demonstrates the reliability of our approach. Our findings suggest that this class of materials has significant implications for the development of label-free, scanning-free, and rapid optical detection and charge imaging of biomolecules.

Seeding Atomic Silver into Internal Lattice Sites of Transition Metal Oxide for Advanced Electrocatalysis.

Transition metal oxides (TMOs) are widely studied for loading of various catalysts due to their low cost and high structure flexibility. However, the prevailing close-packed nature of most TMOs crystals has restricted the available loading sites to surface only, while their internal bulk lattice remains unactuated due to the inaccessible narrow space that blocks out most key reactants and/or particulate catalysts. Herein, using tunnel-structured MnO2, this study demonstrates how TMO's internal lattice space can be activated as extra loading sites for atomic Ag in addition to the conventional surface-only loading, via which a dual-form Ag catalyst within MnO2 skeleton is established. In this design, not only faceted Ag nanoparticles are confined onto MnO2 surface by coherent lattice-sharing, Ag atomic strings are also seeded deep into the sub-nanoscale MnO2 tunnel lattice, enriching the catalytically active sites. Tested for electrochemical CO2 reduction reaction (eCO2RR), such dual-form catalyst exhibits a high Faradaic efficiency (94%), yield (67.3 mol g-1 h-1) and durability (≈48 h) for CO production, exceeding commercial Ag nanoparticles and most Ag-based electrocatalysts. Theoretical calculations further reveal the concurrent effect of such dual-form catalyst featuring facet-dependent eCO2RR for Ag nanoparticles and lattice-confined eCO2RR for Ag atomic strings, inspiring the future design of catalyst-substrate configuration.

Ferroelectric Bi2O2Te-Based Plasmonic Biosensor for Ultrasensitive Biomolecular Detection.

Ultrasensitive detection of biomarkers, particularly proteins, and microRNA, is critical for disease early diagnosis. Although surface plasmon resonance biosensors offer label-free, real-time detection, it is challenging to detect biomolecules at low concentrations that only induce a minor mass or refractive index change on the analyte molecules. Here an ultrasensitive plasmonic biosensor strategy is reported by utilizing the ferroelectric properties of Bi2O2Te as a sensitive-layer material. The polarization alteration of ferroelectric Bi2O2Te produces a significant plasmonic biosensing response, enabling the detection of charged biomolecules even at ultralow concentrations. An extraordinary ultralow detection limit of 1 fm is achieved for protein molecules and an unprecedented 0.1 fm for miRNA molecules, demonstrating exceptional specificity. The finding opens a promising avenue for the integration of 2D ferroelectric materials into plasmonic biosensors, with potential applications spanning a wide range.

Mechanical quenching phenomenon in diamond.

The structure of dislocation cores, the fundamental knowledge on crystal plasticity, remains largely unexplored in covalent crystals. Here, we conducted atomically resolved characterizations of dislocation core structures in a plastically deformed diamond anvil cell tip that was unloaded from an exceptionally high pressure of 360 GPa. Our observations unveiled a series of nonequilibrium dislocation cores that deviate from the commonly accepted "five-seven-membered ring" dislocation core model found in FCC-structured covalent crystals. The nonequilibrium dislocation cores were generated through a process known as "mechanical quenching," analogous to the quenching process where a high-energy state is rapidly frozen. The density functional theory-based molecular dynamic simulations reveal that the phenomenon of mechanical quenching in diamond arises from the challenging relaxation of the nonequilibrium configuration, necessitating a large critical strain of 25% that is difficult to maintain. Further electronic-scale analysis suggested that such large critical strain is spent on the excitation of valance electrons for bond breaking and rebonding during relaxation. These findings establish a foundation for the plasticity theory of covalent materials and provide insights into the design of electrical and luminescent properties in diamond, which are intimately linked to the dislocation core structure.

Twisted-layer boron nitride ceramic with high deformability and strength.

Moiré superlattices formed by twisted stacking in van der Waals materials have emerged as a new platform for exploring the physics of strongly correlated materials and other emergent phenomena1-5. However, there remains a lack of research on the mechanical properties of twisted-layer van der Waals materials, owing to a lack of suitable strategies for making three-dimensional bulk materials. Here we report the successful synthesis of a polycrystalline boron nitride bulk ceramic with high room-temperature deformability and strength. This ceramic, synthesized from an onion-like boron nitride nanoprecursor with conventional spark plasma sintering and hot-pressing sintering, consists of interlocked laminated nanoplates in which parallel laminae are stacked with varying twist angles. The compressive strain of this bulk ceramic can reach 14% before fracture, about one order of magnitude higher compared with traditional ceramics (less than 1% in general), whereas the compressive strength is about six times that of ordinary hexagonal boron nitride layered ceramics. The exceptional mechanical properties are due to a combination of the elevated intrinsic deformability of the twisted layering in the nanoplates and the three-dimensional interlocked architecture that restricts deformation from propagating across individual nanoplates. The advent of this twisted-layer boron nitride bulk ceramic opens a gate to the fabrication of highly deformable bulk ceramics.

Regulating d-Orbital Hybridization of Subgroup-IVB Single Atoms for Efficient Oxygen Reduction Reaction.

Highly active single-atom electrocatalysts for the oxygen reduction reaction are crucial for improving the energy conversion efficiency, but they suffer from a limited choice of metal centers and unsatisfactory stabilities. Here, this work reports that optimization of the binding energies for reaction intermediates by tuning the d-orbital hybridization with axial groups converts inactive subgroup-IVB (Ti, Zr, Hf) moieties (MN4) into active motifs (MN4O), as confirmed with theoretical calculations. The competition between metal-ligand covalency and metal-intermediate covalency affects the d-p orbital hybridization between the metal site and the intermediates, converting the metal centers into active sites. Subsequently, dispersed single-atom M sites coordinated by nitrogen/oxygen groups have been prepared on graphene (s-M-N/O-C) catalysts on a large-scale with high-energy milling and pyrolysis. Impressively, the s-Hf-N/O-C catalyst with 5.08 wt% Hf exhibits a half-wave potential of 0.920 V and encouraging performance in a zinc-air battery with an extraordinary cycling life of over 1600 h and a large peak power-density of 256.9 mW cm-2. This work provides promising single-atom electrocatalysts and principles for preparing other catalysts for the oxygen reduction reaction.

Atomic-scale manipulation of polar domain boundaries in monolayer ferroelectric In2Se3.

Domain boundaries have been intensively investigated in bulk ferroelectric materials and two-dimensional materials. Many methods such as electrical, mechanical and optical approaches have been utilized to probe and manipulate domain boundaries. So far most research focuses on the initial and final states of domain boundaries before and after manipulation, while the microscopic understanding of the evolution of domain boundaries remains elusive. In this paper, we report controllable manipulation of the domain boundaries in two-dimensional ferroelectric In2Se3 with atomic precision using scanning tunneling microscopy. We show that the movements of the domain boundaries can be driven by the electric field from a scanning tunneling microscope tip and proceed by the collective shifting of atoms at the domain boundaries. Our density functional theory calculations reveal the energy path and evolution of the domain boundary movement. The results provide deep insight into domain boundaries in two-dimensional ferroelectric materials and will inspire inventive applications of these materials.

Structural transition and migration of incoherent twin boundary in diamond.

Grain boundaries (GBs), with their diversity in both structure and structural transitions, play an essential role in tailoring the properties of polycrystalline materials1-5. As a unique GB subset, {112} incoherent twin boundaries (ITBs) are ubiquitous in nanotwinned, face-centred cubic materials6-9. Although multiple ITB configurations and transitions have been reported7,10, their transition mechanisms and impacts on mechanical properties remain largely unexplored, especially in regard to covalent materials. Here we report atomic observations of six ITB configurations and structural transitions in diamond at room temperature, showing a dislocation-mediated mechanism different from metallic systems11,12. The dominant ITBs are asymmetric and less mobile, contributing strongly to continuous hardening in nanotwinned diamond13. The potential driving forces of ITB activities are discussed. Our findings shed new light on GB behaviour in diamond and covalent materials, pointing to a new strategy for development of high-performance, nanotwinned materials.

Self-healing of fractured diamond.

Materials that possess the ability to self-heal cracks at room temperature, akin to living organisms, are highly sought after. However, achieving crack self-healing in inorganic materials, particularly with covalent bonds, presents a great challenge and often necessitates high temperatures and considerable atomic diffusion. Here we conducted a quantitative evaluation of the room-temperature self-healing behaviour of a fractured nanotwinned diamond composite, revealing that the self-healing properties of the composite stem from both the formation of nanoscale diamond osteoblasts comprising sp2- and sp3-hybridized carbon atoms at the fractured surfaces, and the atomic interaction transition from repulsion to attraction when the two fractured surfaces come into close proximity. The self-healing process resulted in a remarkable recovery of approximately 34% in tensile strength for the nanotwinned diamond composite. This discovery sheds light on the self-healing capability of nanostructured diamond, offering valuable insights for future research endeavours aimed at enhancing the toughness and durability of brittle ceramic materials.

Scalable integration of hybrid high-κ dielectric materials on two-dimensional semiconductors.

Two-dimensional (2D) semiconductors are promising channel materials for next-generation field-effect transistors (FETs). However, it remains challenging to integrate ultrathin and uniform high-κ dielectrics on 2D semiconductors to fabricate FETs with large gate capacitance. We report a versatile two-step approach to integrating high-quality dielectric film with sub-1 nm equivalent oxide thickness (EOT) on 2D semiconductors. Inorganic molecular crystal Sb2O3 is homogeneously deposited on 2D semiconductors as a buffer layer, which forms a high-quality oxide-to-semiconductor interface and offers a highly hydrophilic surface, enabling the integration of high-κ dielectrics via atomic layer deposition. Using this approach, we can fabricate monolayer molybdenum disulfide-based FETs with the thinnest EOT (0.67 nm). The transistors exhibit an on/off ratio of over 106 using an ultra-low operating voltage of 0.4 V, achieving unprecedently high gating efficiency. Our results may pave the way for the application of 2D materials in low-power ultrascaling electronics.

An Ultrasensitive SPR biosensor for RNA detection based on robust GeP5 nanosheets.

Ultrasensitive and rapid detection of biomarkers is among the upmost priorities in promoting healthcare advancements. Improved sensitivity of photonic sensors based on two-dimensional (2D) materials have brought exciting prospects for achieving real-time and label-free biosensing at dilute target concentrations. Here, we report a high-sensitivity surface plasmon resonance (SPR) RNA sensor using metallic 2D GeP5 nanosheets as the sensing material. Theoretical evaluations revealed that the presence of GeP5 nanosheets can greatly enhance the plasmonic electric field of the Au film thereby boosting sensing sensitivity, and that optimal sensitivity (146° RIU-1) can be achieved with 3-nm-thick GeP5. By functionalizing GeP5 nanosheets with specific cDNA probes, detection of SARS-CoV-2 RNA sequences were achieved using the GeP5-based SPR sensor, with high sensitivity down to a detection limit of 10 aM and excellent selectivity. This work demonstrates the immense potential of GeP5-based SPR sensors for advanced biosensing applications and paves the way for utilizing GeP5 nanosheets in novel sensor devices.

An Ultrasensitive Plasmonic Sensor Based on 2D Ferroelectric Bi2 O2 Se.

Plasmonic biosensing is a label-free detection method that is commonly used to measure various biomolecular interactions. However, one of the main challenges in this approach is the ability to detect biomolecules at low concentrations with sufficient sensitivity and detection limits. Here, 2D ferroelectric materials are employed to address the issues with sensitivity in biosensor design. A plasmonic sensor based on Bi2 O2 Se nanosheets, a ferroelectric 2D material, is presented for the ultrasensitive detection of the protein molecule. Through imaging the surface charge density of Bi2 O2 Se, a detection limit of 1 fM is achieved for bovine serum albumin (BSA). These findings underscore the potential of ferroelectric 2D materials as critical building blocks for future biosensor and biomaterial architectures.

Broadband Polarization-Sensitive Photodetection of Magnetic Semiconducting MnTe Nanoribbons.

2D materials with low symmetry are explored in recent years because of their anisotropic advantage in polarization-sensitive photodetection. Herein the controllably grown hexagonal magnetic semiconducting α-MnTe nanoribbons are reported with a highly anisotropic (100) surface and their high sensitivity to polarization in a broadband photodetection, whereas the hexagonal structure is highly symmetric. The outstanding photoresponse of α-MnTe nanoribbons occurs in a broadband range from ultraviolet (UV, 360 nm) to near infrared (NIR, 914 nm) with short response times of 46 ms (rise) and 37 ms (fall), excellent environmental stability, and repeatability. Furthermore, due to highly anisotropic (100) surface, the α-MnTe nanoribbons as photodetector exhibit attractive sensitivity to polarization and high dichroic ratios of up to 2.8 under light illumination of UV-to-NIR wavelengths. These results demonstrate that 2D magnetic semiconducting α-MnTe nanoribbons provide a promising platform to design the next-generation polarization-sensitive photodetectors in a broadband range.

Monolayer Iron Oxychloride with a Resonant Band Structure for Ultrasensitive Molecular Sensing.

Two-dimensional layered materials (2DLMs) are expected to be next-generation commercial sensors for surface-enhanced Raman scattering (SERS) sensing owing to their unique structural features and physicochemical properties. The low sensitivity and poor universality of 2DLMs are the dominant barriers toward their practical applications. Herein, we report that monolayer iron oxychloride (FeOCl) with a naturally suitable band structure is a promising candidate for ultrasensitive SERS sensing. The generally boosted Raman scattering cross section of different analyte-FeOCl systems benefits from the resonant photoinduced charge transfer processes and strong ground-state interactions. In addition, the strong adsorption ability of monolayer FeOCl is crucial for rapid detection in practical applications, which is proven to be much better than those of conventional SERS sensors. Consequently, monolayer FeOCl enables diverse SERS applications, including multicomponent analysis, chemical reaction monitoring, and indirect ion sensing.

Architecture Design and Catalytic Activity: Non-Noble Bimetallic CoFe/fe3 O4 Core-Shell Structures for CO2 Hydrogenation.

Non-noble metal catalysts now play a key role in promoting efficiently and economically catalytic reduction of CO2 into clean energy, which is an important strategy to ameliorate global warming and resource shortage issues. Here, a non-noble bimetallic catalyst of CoFe/Fe3 O4 nanoparticles is successfully designed with a core-shell structure that is well dispersed on the defect-rich carbon substrate for the hydrogenation of CO2 under mild conditions. The catalysts exhibit a high CO2 conversion activity with the rate of 30% and CO selectivity of 99%, and extremely robust stability without performance decay over 90 h in the reverse water gas shift reaction process. Notably, it is found that the reversible exsolution/dissolution of cobalt in the Fe3 O4 shell will lead to a dynamic and reversible deactivation/regeneration of the catalysts, accompanying by shell thickness breathing during the repeated cycles, via atomic structure study of the catalysts at different reaction stages. Combined with density functional theory calculations, the catalytic activity reversible regeneration mechanism is proposed. This work reveals the structure-property relationship for rational structure design of the advanced non-noble metallic catalyst materials with much improved performance.

In Situ Observation of Fracture along Twin Boundaries in Boron Carbide.

The observation of fracture behaviors in perfect and twinned B4 C crystals via in situ transmission electron microscopy (TEM) mechanical testing is reported. The crystal structure of the synthesized B4 C, composed of B11 C icosahedra connected by boron-deficient C-▫-C chains in a chemical formula of B11 C3 , is determined by state-of-the-art aberration-corrected scanning TEM. The in situ TEM observations reveal that cracking is preferentially initiated at the twin boundaries (TBs) in B4 C under both indentation and tension loading. The cracks then propagate along the TBs, thus resulting in the fracture of B4 C. These results are consistent with the theoretical calculations that show that TBs have a softening effect on B4 C with amorphous bands preferentially nucleated at the TBs. These findings elucidate the atomic arrangement and the role of planar defects in the failure of B4 C. Furthermore, they can guide the design of advanced superhard materials via planar defect control.

Atomic Mechanisms of Cation Adsorption/Exchange in Octahedral Molecular Sieves.

Octahedral molecular sieves (OMSs) based on MnO2 have been widely studied in the fields of deionization, geochemistry, and energy storage due to their microporous tunnel framework capable of adsorbing and exchanging various ions, particularly cations. The understanding of cation adsorption/exchange within OMS tunnels demands atomic-scale exploration, which has been scarcely reported. Here, we disclose how various cations (K+/Ag+/Na+) interplay within the OMS tunnel space on an atomic scale. Not only are the lattice sites for each adsorbed cation species pinpointed but the scenario of dual-cation adsorption within single tunnels is also demonstrated, together with the discovery of characteristic concentration-dependent cation ordering. Moreover, compared with the theoretical parent tunnel phase, the heterogeneous tunnels, though sparsely distributed, exhibit a distinct yet orderly cationic accommodation, highlighting the non-negligible role of tunnel heterogeneity in regulating OMS physiochemistry. Our findings clarify the long-existing ambiguities in nano- and atomic-scale science of the ion adsorption process in OMS materials and are expected to inspire their structural/compositional engineering toward functionality enhancement in various fields.