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.

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.

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.

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.

Pressure effect on the magnetism and crystal structure of magnetoelectric metal-organic framework [CH3NH3][Co(HCOO)3].

[CH3NH3][Co(HCOO)3] is the first perovskite-like metal-organic framework exhibiting spin-driven magnetoelectric effects. However, the high-pressure tuning effects on the magnetic properties and crystal structure of [CH3NH3][Co(HCOO)3] have not been studied. In this work, alongside ac magnetic susceptibility measurements, we investigate the magnetic transition temperature evolution under high pressure. Upon increasing the pressure from atmospheric pressure to 0.5 GPa, TN (15.2 K) remains almost unchanged. Continuing to compress the sample results in TN gradually decreasing to 14.8 K at 1.5 GPa. This may be due to pressure induced changes in the bond distance and bond angle of the O-C-O superexchange pathway. In addition, by using high pressure powder X-ray diffraction and Raman spectroscopy, we conducted in-depth research on the pressure dependence of the lattice parameters and Raman modes of [CH3NH3][Co(HCOO)3]. The increase in pressure gives rise to a phase transition from the orthorhombic Pnma to a monoclinic phase at approximately 6.13 GPa. Our study indicates that high pressure can profoundly alter the crystal structure and magnetic properties of perovskite type MOF materials, which could inspire new endeavors in exploring novel phenomena in compressed metal-organic frameworks.

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.

Magnetic field reversal of electric polarization and pressure-temperature-magnetic field magnetoelectric phase diagram of the hexaferrite Ba0.4Sr1.6Mg2Fe12O22.

Pressure, as an independent thermodynamic parameter, is an effective tool to obtain novel material system and exotic physical phenomena not accessible at ambient conditions, because it profoundly modifies the charge, orbital and spin state by reducing the interatomic distance in crystal structure. However, the studies of magnetoelectricity and multiferroicity are rarely extended to high pressure dimension due to properties measured inside the high pressure vessel being a challenge. Here we reported the temperature-magnetic field-pressure magnetoelectric (ME) phase diagram of Y type hexaferrite Ba0.4Sr1.6Mg2Fe12O22derived from static pyroelectric current measurement and dynamic magnetodielectric in diamond anvil cell and piston cylinder cell. We found that a new spin-driven ferroelectric phase emerged atP= 0.7 GPa and sequentially ME effect disappeared aroundP= 4.3 GPa. The external pressure may enhance easy plane anisotropy to destabilize the longitudinal conical magnetic structure with the suppression of ME coefficient. These results offer essential clues for the correlation between ME effect and magnetic structure evolution under high pressure.

Pressure Control of the Structure and Multiferroicity in a Hydrogen-Bonded Metal-Organic Framework.

Multiferroic materials with the cross-coupling of magnetic and ferroelectric orders provide a new platform for physics study and designing novel electronic devices. However, the weak coupling strength of ferroelectricity and magnetism is the main obstacle for potential applications. The recent research focuses on enhancing the coupling effect via synthesizing novel materials in a chemical route or tuning the multiferroicity in the physical way. Among them, pressure is an effective method to modify multiferroic materials, especially when the chemical doping has reached its tuning limit. In this work, we systemically studied the multiferroic properties in a hydrogen-bonded metal-organic framework (MOF) [(CH3)2NH2]Ni(HCOO)3 under high pressure. X-ray diffraction and Raman scattering reveal that a structural phase transition occurs in a pressure region of 6-9 GPa, and the crystal structure is greatly modified by pressure. With the ac magnetic susceptibility, pyroelectric current, and dielectric constant measurements, we obtain the multiferroic property evolution under high pressure and create a temperature-pressure phase diagram. Our study demonstrates that the pressure can modify the magnetic superexchange interaction and hydrogen bonding simultaneously in these perovskite-like MOFs. The multiferroic phase region has been expanded to higher temperature due to the pressure-enhanced spin-phonon coupling effect.

In Situ Grown Ultrafine RuO2 Nanoparticles on GeP5 Nanosheets as the Electrode Material for Flexible Planar Micro-Supercapacitors with High Specific Capacitance and Cyclability.

GeP5, as the most representative phosphorus-based material in two-dimensional layered phosphorous compounds, has shown a fairly bright application prospect in the field of energy storage because of its ultrahigh electrical conductivity. However, high-yield exfoliation methods and effective structure construction strategies for GeP5 nanosheets are still missing, which completely restricts the further application of GeP5-based nanocomposites. Here, we not only improved the yield of GeP5 nanosheets by a liquid nitrogen-assisted liquid-phase exfoliation technique but also constructed the GeP5@RuO2 nanocomposites with the 0D/2D heterostructure by in situ introduction of ultrafine RuO2 nanoparticles on highly conductive GeP5 nanosheets using a simple hydrothermal synthesis method, and then applying it to micro-supercapacitors (MSCs) as electrode materials through a mask-assisted vacuum filtration technique. It is precisely because of the synergy of the electrical double-layer material, GeP5 nanosheets and the pseudocapacitance material RuO2 nanoparticles that endows the GeP5@RuO2 electrode with outstanding electrochemical performance in micro-supercapacitors with a large specific capacitance of 129.5 mF cm-2/107.9 F cm-3, high energy density of 17.98 µWh cm-2, remarkable long-term cycling stability with 98.4% capacitance retention after 10 000 cycles, the exceptional mechanical stability, outstanding environmental stability, and excellent integration features. This work opens up a new avenue to construct GeP5-based nanocomposites as a most promising novel electrode material for practical application in flexible portable/wearable micro-nanoelectronic devices.

High-sensitivity and versatile plasmonic biosensor based on grain boundaries in polycrystalline 1L WS2 films.

Structural defects play an important role in exploitation of two-dimensional layered materials (2DLMs) for advanced biosensors with the increasingly high sensitivity and low detection limit. Grain boundaries (GBs), as an important type of structural defect in polycrystalline 2DLM films, potentially provide sufficient active defect sites for the immobilization of bioreceptor units via chemical functionalization. In this work, we report the selective functionalization of high-density GBs with complementary DNA receptors, via gold nanoparticle (AuNP) linkers, in wafer-scale polycrystalline monolayer (1L) W(Mo)S2 films as versatile plasmonic biosensing platforms. The large surface area and GB-rich nature of the polycrystalline 1L WS2 film enabled the immobilization of bioreceptors in high surface density with spatial uniformity, while the AuNPs perform not only as bioreceptor linkers, but also promote detection sensitivity through surface plasmon resonance enhancement effect. Therefore, the presented biosensor demonstrated highly sensitive and selective sub-femto-molar detection of representative RNA sequences from the novel coronavirus (RdRp, ORF1ad and E). This work demonstrates the immense potential of AuNP-decorated GB-rich 2DLMs in the design of ultra-sensitive biosensing platforms for the detection of biological targets beyond RNA, bringing new opportunities for novel healthcare technologies.

Grain-boundary-rich polycrystalline monolayer WS2 film for attomolar-level Hg2+ sensors.

Emerging two-dimensional (2D) layered materials have been attracting great attention as sensing materials for next-generation high-performance biological and chemical sensors. The sensor performance of 2D materials is strongly dependent on the structural defects as indispensable active sites for analyte adsorption. However, controllable defect engineering in 2D materials is still challenging. In the present work, we propose exploitation of controllably grown polycrystalline films of 2D layered materials with high-density grain boundaries (GBs) for design of ultra-sensitive ion sensors, where abundant structural defects on GBs act as favorable active sites for ion adsorption. As a proof-of-concept, our fabricated surface plasmon resonance sensors with GB-rich polycrystalline monolayer WS2 films have exhibited high selectivity and superior attomolar-level sensitivity in Hg2+ detection owing to high-density GBs. This work provides a promising avenue for design of ultra-sensitive sensors based on GB-rich 2D layered materials.

Pressure Effect on Order-Disorder Ferroelectric Transition in a Hydrogen-Bonded Metal-Organic Framework.

Perovskite-like ABX3 metal-organic frameworks (MOFs) have gathered great interest due to their intriguing chemical and physical properties, including their magnetism, ferroelectricity, and multiferroicity. Pressure is an effective thermal parameter in tuning related properties in MOFs due to the adjustable organic framework. Though spectrum experiments have been made on the structural evolution during decompression, there is a lack of electrical studies on the order-disorder ferroelectric transition in the metal-organic frameworks under pressure. In this work, we use a static pyroelectric current measurement, a dynamic dielectric method combined with a Raman scattering technique with applying in situ pressure, to explore the order-disorder ferroelectric transition in [(CH3)2NH2]Co(HCOO)3. The ferroelectric transition vanishes around the external pressure of 1.6 GPa, emerging with a new paraelectric phase. Another phase transition was observed at 6.32 GPa, mainly associated with the distortive transition of DMA+ cations. A phenomenological theory of ferroelectricity vanishing at 1.6 GPa for [(CH3)2NH2]Co(HCOO)3 is also discussed. Our study gives a comprehensive understanding in the pressure tuning of ferroelectric properties in hybrid inorganic-organic materials.

Direct one-step synthesis of CoFex@Co@C hybrids derived from a metal organic framework for a lightweight and high-performance microwave absorber.

It involves invariably strong expectations and a tough challenge to explore lightweight microwave absorption materials with high efficiency and agile tenability. Here, we successfully synthesized CoFex@Co nanoparticles embedded into a carbon matrix that was directly derived from the metal organic frameworks (MOFs) via a facile method. Benefiting from the unique multi-dimensional construction and synergistic effects of carbon material with magnetic nanoparticles in both the electromagnetic energy loss and impedance matching, CoFe0.26@Co@C composite exhibited excellent microwave absorption performance, which showed a minimum reflection loss of -62.5 dB at the thickness of 1.5 mm and a broad absorption bandwidth of 14.7 GHz exceeding -10 dB at the thickness range of 1.4 to 5 mm. This study not only provides a reference for future preparation of MOF-based lightweight microwave absorption materials, but also offers the possible application owing to its simple procedure and outstanding absorption properties.

Atomic-Scale Observation of Reversible Thermally Driven Phase Transformation in 2D In2Se3.

Phase transformation in emerging two-dimensional (2D) materials is crucial for understanding and controlling the interplay between structure and electronic properties. In this work, we investigate 2D In2Se3 synthesized via chemical vapor deposition, a recently discovered 2D ferroelectric material. We observed that In2Se3 layers with thickness ranging from a single layer to ∼20 layers stabilized at the ß phase with a superstructure at room temperature. At around 180 K, the ß phase converted to a more stable ß' phase that was distinct from previously reported phases in 2D In2Se3. The kinetics of the reversible thermally driven ß-to-ß' phase transformation was investigated by temperature-dependent transmission electron microscopy and Raman spectroscopy, corroborated with the expected minimum-energy pathways obtained from our first-principles calculations. Furthermore, density functional theory calculations reveal in-plane ferroelectricity in the ß' phase. Scanning tunneling spectroscopy measurements show that the indirect bandgap of monolayer ß' In2Se3 is 2.50 eV, which is larger than that of the multilayer form with a measured value of 2.05 eV. Our results on the reversible thermally driven phase transformation in 2D In2Se3 with thickness down to the monolayer limit and the associated electronic properties will provide insights to tune the functionalities of 2D In2Se3 and other emerging 2D ferroelectric materials and shed light on their numerous potential applications (e.g., nonvolatile memory devices).

One-Step Growth of Spatially Graded Mo1- xW xS2 Monolayers with a Wide Span in Composition (from x = 0 to 1) at a Large Scale.

Alloying is an effective way to modulate material's properties. In particular, graded alloying within a single domain of two-dimensional transition-metal chalcogenide (2D-TMC) is of great technological importance, for example, for achieving band gap modulations. Here, we report a facile method to grow gradient alloying of Mo1- xW xS2 monolayers with large domain sizes and high crystal qualities via the chemical vapor deposition technique. The as-grown Mo1- xW xS2 monolayers have a gradient composition of W from x = ∼0 to ∼1 in a single domain with a lateral dimension up to 300 µm, and the span in band gap can be readily tuned. Owing to the grading in band offsets, the compositionally graded Mo1- xW xS2 alloy monolayer demonstrates an excellent rectifying effect with the ratio of forward to reverse current up to ∼104. Moreover, phototransistors based on the compositionally graded Mo1- xW xS2 monolayers exhibit a high responsivity up to 298.4 A/W in the visible light regime, and particularly a decent responsivity of 28.7 A/W in the near-infrared regime. The control of band gap offset gradient and span in alloyed 2D-TMC semiconductors provides an additional degree of freedom in designing fascinating applications in achieving multifunctional optoelectronic devices on individual substrates.

Effect of layer and stacking sequence in simultaneously grown 2H and 3R WS2 atomic layers.

In two-dimensional layered materials, layer number and stacking order have strong effects on the optical and electronic properties. Tungsten disulfide (WS2) crystal, as one important member among transition metal dichalcogenides, has been usually prepared in a layered 2H prototype structure with space group P63/mmc ([Formula: see text]) in spite of many other expected ones such as 3R. Here, we report simultaneous growth of 2H and 3R stacked multilayer (ML) WS2 crystals in large scale by chemical vapor deposition and effects of layer number and stacking order on optical and electronic properties. As revealed in Raman and photoluminescence (PL) measurements, with an increase in layer number, 2H and 3R stacked ML WS2 crystals show similar variation of PL and Raman peaks in position and intensity. Compared to 2H stacked ML WS2, however, 3R stacked one always exhibits the larger red (blue) shift of Raman [Formula: see text] (A1g) peak and the appearance of PL A, B and I peaks at lower energies. Thereby, PL and Raman features depend on not only layer number but also stacking order. In addition, circularly polarized luminescence from two prototype WS2 crystals under circularly polarized excitation has also been investigated, showing obvious spin or valley polarization of these CVD-grown multilayer WS2 crystals.

Liquid-exfoliation of S-doped black phosphorus nanosheets for enhanced oxygen evolution catalysis.

Black phosphorus (BP) has recently drawn great attention in the field of electrocatalysis due to its distinct electrocatalytic activity for the oxygen evolution reaction (OER). However, the slow OER kinetics and the poor environmental stability of BP seriously limits its overall OER performance and prevents its electrocatalysis application. Here, sulfur (S)-doped BP nanosheets, which are prepared using high-pressure synthesis followed by liquid exfoliation, have been demonstrated to have much better OER electrocatalytic activity and environmental stability compared to their undoped counterparts. The S-doped BP nanosheets display a Tafel slope of 75 mV dec-1, which is a favorable value refered to the kinetics of OER in electrochemical tests. Notably, there is no degradation of S-doped BP nanosheets after six days exposure to ambient, indicating an excellent environmental stability of the S-doped BP. The density functional theory calculations show that the OER activity of BP originate from its crystal defects and heteroatom S doping can effectively enhance its OER activity and stability. These results highlight the doping effect on electrocatalytic activities and stability of BP and provide a simple and effective method to design highly efficient OER catalysts based on the modification of BP.

Giant Valley Coherence at Room Temperature in 3R WS2 with Broken Inversion Symmetry.

Breaking the space-time symmetries in materials can markedly influence their electronic and optical properties. In 3R-stacked transition metal dichalcogenides, the explicitly broken inversion symmetry enables valley-contrasting Berry curvature and quantization of electronic angular momentum, providing an unprecedented platform for valleytronics. Here, we study the valley coherence of 3R WS2 large single-crystal with thicknesses ranging from monolayer to octalayer at room temperature. Our measurements demonstrate that both A and B excitons possess robust and thickness-independent valley coherence. The valley coherence of direct A (B) excitons can reach 0.742 (0.653) with excitation conditions on resonance with it. Such giant and thickness-independent valley coherence of large single-crystal 3R WS2 at room temperature would provide a firm foundation for quantum manipulation of the valley degree of freedom and practical application of valleytronics.