Optically Triggered Emergent Mesostructures in Monolayer WS2.

The ultrahigh surface area of two-dimensional materials can drive multimodal coupling between optical, electrical, and mechanical properties that leads to emergent dynamical responses not possible in three-dimensional systems. We observed that optical excitation of the WS2 monolayer above the exciton energy creates symmetrically patterned mechanical protrusions which can be controlled by laser intensity and wavelength. This observed photostrictive behavior is attributed to lattice expansion due to the formation of polarons, which are charge carriers dressed by lattice vibrations. Scanning Kelvin probe force microscopy measurements and density functional theory calculations reveal unconventional charge transport properties such as the spatially and optical intensity-dependent conversion in the WS2 monolayer from apparent n- to p-type and the subsequent formation of effective p-n junctions at the boundaries between regions with different defect densities. The strong opto-electrical-mechanical coupling in the WS2 monolayer reveals previously unexplored properties, which can lead to new applications in optically driven ultrathin microactuators.

Manipulations of Electronic and Spin States in Co-Quantum Dot/WS2 Heterostructure on a Metal-Dielectric Composite Substrate by Controlling Interfacial Carriers.

Charge and spin are two intrinsic attributes of carriers governing almost all of the physical processes and operation principles in materials. Here, we demonstrate the manipulation of electronic and spin states in designed Co-quantum dot/WS2 (Co-QDs/WS2) heterostructures by employing a metal-dielectric composite substrate and via scanning tunneling microscope. By repeatedly scanning under a unipolar bias, switching the bias polarity, or applying a pulse through nonmagnetic or magnetic tips, the Co-QDs morphologies exhibit a regular and reproducible transformation between bright and dark dots. First-principles calculations reveal that these tunable characters are attributed to the variation of density of states and the transition of magnetic anisotropy energy induced by carrier accumulation. It also suggests that the metal-dielectric composite substrate is successful in creating the interfacial potential for carrier accumulation and realizes the electrically controllable modulations. These results will promote the exploration of electron-matter interactions in quantum systems and provide an innovative way to facilitate the development of spintronics.

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.

Fine-Tuning of the Excitonic Response in Monolayer WS2 Domes via Coupled Pressure and Strain Variation.

We present a spectroscopic investigation of the vibrational and optoelectronic properties of WS2 domes in the 0-0.65 GPa range. The pressure evolution of the system morphology, deduced by the combined analysis of Raman and photoluminescence spectra, revealed a significant variation in the dome's aspect ratio. The modification of the dome shape caused major changes in the mechanical properties of the system resulting in a sizable increase of the out-of-plane compressive strain while keeping the in-plane tensile strain unchanged. The variation of the strain gradients drives a nonlinear behavior in both the exciton energy and radiative recombination intensity, interpreted as the consequence of a hybridization mechanism between the electronic states of two distinct minima in the conduction band. Our results indicate that pressure and strain can be efficiently combined in low dimensional systems with unconventional morphology to obtain modulations of the electronic band structure not achievable in planar crystals.

Synthesis of Arrayed Tungsten Disulfide Nanotubes.

Tungsten disulfide nanotubes (WS2-NTs), with their cylindrical structure composed of rolled WS2 sheets, have attracted much interest because of their unique physical properties reflecting quasi-one-dimensional chiral structures. They exhibit a semiconducting electronic structure regardless of their chirality, and various semiconducting and optoelectronic device applications have been demonstrated. The development of techniques to fabricate arrayed WS2-NTs is crucial to realizing the highest device performance. Since the discovery of WS2-NTs, various synthesis techniques have been reported; however, horizontally arrayed WS2-NTs have never been successfully synthesized. Here, we demonstrate a simple technique to synthesize arrayed WS2-NTs. Through precise temperature and gas control, W18O49 nanowires are grown along the [1̅101] direction on an r-plane sapphire substrate, and the nanowires are converted into nanotubes via sulfurization under optimized conditions. The demonstrated synthesis technique for arrayed WS2-NTs will play a central role in the fabrication of devices using transition-metal dichalcogenide nanotubes.

Exciton-Phonon Coupling Induces a New Pathway for Ultrafast Intralayer-to-Interlayer Exciton Transition and Interlayer Charge Transfer in WS2-MoS2 Heterostructure: A First-Principles Study.

Despite the weak, van der Waals interlayer coupling, photoinduced charge transfer vertically across atomically thin interfaces can occur within surprisingly fast, sub-50 fs time scales. An early theoretical understanding of charge transfer is based on a noninteracting picture, neglecting excitonic effects that dominate optical properties of such materials. We employ an ab initio many-body perturbation theory approach, which explicitly accounts for the excitons and phonons in the heterostructure. Our large-scale first-principles calculations directly probe the role of exciton-phonon coupling in the charge dynamics of the WS2/MoS2 heterobilayer. We find that the exciton-phonon interaction induced relaxation time of photoexcited excitons at the K valley of MoS2 and WS2 is 67 and 15 fs at 300 K, respectively, which sets a lower bound to the intralayer-to-interlayer exciton transfer time and is consistent with experiment reports. We further show that electron-hole correlations facilitate novel transfer pathways that are otherwise inaccessible to noninteracting electrons and holes.

Phase-Selective Synthesis of Rhombohedral WS2 Multilayers by Confined-Space Hybrid Metal-Organic Chemical Vapor Deposition.

Rhombohedral polytype transition metal dichalcogenide (TMDC) multilayers exhibit non-centrosymmetric interlayer stacking, which yields intriguing properties such as ferroelectricity, a large second-order susceptibility coefficient χ(2), giant valley coherence, and a bulk photovoltaic effect. These properties have spurred significant interest in developing phase-selective growth methods for multilayer rhombohedral TMDC films. Here, we report a confined-space, hybrid metal-organic chemical vapor deposition method that preferentially grows 3R-WS2 multilayer films with thickness up to 130 nm. We confirm the 3R stacking structure via polarization-resolved second-harmonic generation characterization and the 3-fold symmetry revealed by anisotropic H2O2 etching. The multilayer 3R WS2 shows a dendritic morphology, which is indicative of diffusion-limited growth. Multilayer regions with large, stepped terraces enable layer-resolved evaluation of the optical properties of 3R-WS2 via Raman, photoluminescence, and differential reflectance spectroscopy. These measurements confirm the interfacial quality and suggest ferroelectric modification of the exciton energies.

Oriented Epitaxial Growth of Mixed-Dimensional van der Waals Heterostructures with One-Dimensional (1D) Bi2S3 Nanowires and Two-Dimensional (2D) WS2 Monolayers for Performance-Enhanced Photodetectors.

The synthesis of mixed-dimensional van der Waals heterostructures with controlled alignment by chemical vapor deposition (CVD) technique remains a big challenge due to the complex epitaxial growth mechanism. Herein, we report the epitaxial growth of mixed-dimensional Bi2S3/WS2 heterostructures by a two-step CVD method. Bi2S3 crystals grown on 2D WS2 monolayers exhibit 1D feature with the preferred orientation, indicating a strong epitaxial growth behavior at the 1D/2D interface. Furthermore, the heterostructure was carefully characterized by transmission electron microscopy, which reveals the preferential growth of Bi2S3 nanowires along the zigzag edge of WS2 monolayers. The experimental results are also consistent with the theoretical calculations by DFT, where the preferred orientation possesses minimal surface energy. The strong interaction between Bi2S3 and WS2 enables efficient charge transfer of photogenerated carriers at the heterointerface, which leads to a largely improved light harvesting capability with the highest responsivity of ∼48.1 AW-1 and detectivity of ∼5.9 × 1012 Jones.

Coexistence of Ferroelectricity and Ferromagnetism in Atomically Thin Two-Dimensional Cr2S3/WS2 Vertical Heterostructures.

Two-dimensional (2D) heterostructures with ferromagnetism and ferroelectricity provide a promising avenue to miniaturize the device size, increase computational power, and reduce energy consumption. However, the direct synthesis of such eye-catching heterostructures has yet to be realized up to now. Here, we design a two-step chemical vapor deposition strategy to growth of Cr2S3/WS2 vertical heterostructures with atomically sharp and clean interfaces on sapphire. The interlayer charge transfer and periodic moiré superlattice result in the emergence of room-temperature ferroelectricity in atomically thin Cr2S3/WS2 vertical heterostructures. In parallel, long-range ferromagnetic order is discovered in 2D Cr2S3 via the magneto-optical Kerr effect technique with the Curie temperature approaching 170 K. The charge distribution variation induced by the moiré superlattice changes the ferromagnetic coupling strength and enhances the Curie temperature. The coexistence of ferroelectricity and ferromagnetism in 2D Cr2S3/WS2 vertical heterostructures provides a cornerstone for the further design of logic-in-memory devices to build new computing architectures.

Interfacial and Electronic Modulation of W Bridging Heterostructure Between WS2 and Cobalt-Based Compounds for Efficient Overall Water Splitting.

The development of high performance electrocatalysts for effective hydrogen production is urgently needed. Herein, three hybrid catalysts formed by WS2 and Co-based metal-organic frameworks (MOFs) derivatives are constructed, in which the small amount of W in the MOFs derivatives acts as a bridge to provide the charge transfer channel and enhance the stability. In addition, the effects of the surface charge distribution on the catalytic performance are fully investigated. Due to the optimal interfacial electron coupling and rearrangement as well as its unique porous morphology, WS2 @W-CoPx exhibits superior bifunctional performance in alkaline media with low overpotentials in hydrogen evolution reaction (HER) (62 mV at 10 mA cm-2 ) and oxygen evolution reaction (OER) (278 mV at 100 mA cm-2 ). For overall water splitting (OWS), WS2 @W-CoPx only requires a cell voltage of 1.78 V at 50 mA cm-2 and maintains good stability within 72 h. Density functional theory calculations verify that the combination of W-CoPx with WS2 can effectively enhance the activity of OER and HER with weakened OH (or O) adsorption and enhanced H atom adsorption. This work provides a feasible idea for the design and practical application of WS2 or phosphide-based catalysts in OWS.

Nanotubes from Transition Metal Dichalcogenides: Recent Progress in the Synthesis, Characterization and Electrooptical Properties.

Inorganic layered compounds (2D-materials), particularly transition metal dichalcogenide (TMDC), are the focus of intensive research in recent years. Shortly after the discovery of carbon nanotubes (CNTs) in 1991, it was hypothesized that nanostructures of 2D-materials can also fold and seam forming, thereby nanotubes (NTs). Indeed, nanotubes (and fullerene-like nanoparticles) of WS2 and subsequently from MoS2 were reported shortly after CNT. However, TMDC nanotubes received much less attention than CNT until recently, likely because they cannot be easily produced as single wall nanotubes with well-defined chiral angles. Nonetheless, NTs from inorganic layered compounds have become a fertile field of research in recent years. Much progress has been achieved in the high-temperature synthesis of TMDC nanotubes of different kinds, as well as their characterization and the study of their properties and potential applications. Their multiwall structure is found to be a blessing rather than a curse, leading to intriguing observations. This concise minireview is dedicated to the recent progress in the research of TMDC nanotubes. After reviewing the progress in their synthesis and structural characterization, their contributions to the research fields of energy conversion and storage, polymer nanocomposites, andunique optoelectronic devices are being reviewed. These studies suggest numerous potential applications for TMDC nanotubes in various technologies, which are briefly discussed.

Encapsulation of Uranium Oxide in Multiwall WS2 Nanotubes.

Uranium is a high-value energy element, yet also poses an appreciable environmental burden. The demand for a straightforward, low energy, and environmentally friendly method for encapsulating uranium species can be beneficial for long-term storage of spent uranium fuel and a host of other applications. Leveraging on the low melting point (60 °C) of uranyl nitrate hexahydrate and nanocapillary effect, a uranium compound is entrapped in the hollow core of WS2 nanotubes. Followingly, the product is reduced at elevated temperatures in a hydrogen atmosphere. Nanocrystalline UO2 nanoparticles anchor within the WS2 nanotube lumen are obtained through this procedure. Such methodology can find utilization in the processing of spent nuclear fuel or other highly active radionuclides as well as a fuel for deep space missions. Moreover, the low melting temperatures of different heavy metal-nitrate hydrates, pave the way for their encapsulation within the hollow core of the WS2 nanotubes, as demonstrated herein.

Photo-Driven Ion Directional Transport across Artificial Ion Channels: Band Engineering of WS2 via Peptide Modification.

Biological photo-responsive ion channels play important roles in the important metabolic processes of living beings. To mimic the unique functions of biological prototypes, the transition metal dichalcogenides, owing to their excellent mechanical, electrical, and optical properties, are already used for artificial intelligent channel constructions. However, there remain challenges to building artificial bio-semiconductor nanochannels with finely tuned band gaps for accurately simulating or regulating ion transport. Here, two well-designed peptides are employed for the WS2 nanosheets functionalization with the sequences of PFPFPFPFC and DFDFDFDFC (PFC and DFC; P: proline, D: aspartate, and F: phenylalanine) through cysteine (Cys, C) linker, and an asymmetric peptide-WS2 membrane (AP-WS2M) could be obtained via self-assembly of peptide-WS2 nanosheets. The AP-WS2M could realize the photo-driven anti-gradient ion transport and vis-light enhanced osmotic energy conversion by well-designed working patterns. The photo-driven ion transport mechanism stems from a built-in photovoltaic motive force with the help of formed type II band alignment between the PFC-WS2 and DFC-WS2. As a result, the ions would be driven across the channels of the membrane for different applications. The proposed system provides an effective solution for building photo-driven biomimetic 2D bio-semiconductor ion channels, which could be extensively applied in the fields of drug delivery, desalination, and energy conversion.

Application of NiS modified WS2/TiO2heterostructure in photocathodic protection.

Stainless steel, as a popular corrosion resistant material, is still vulnerable to pitting corrosion in the marine environment. Therefore, in order to ensure the safety of stainless steel in the marine environment, it is necessary to implement corresponding protective measures. Titanium dioxide (TiO2), as an N-type semiconductor with excellent photoelectric properties, is widely used in the field of cathodic protection. However, as a photogenerated cathodic corrosion protection material, TiO2has the disadvantages of low conductivity and high carrier recombination rate. Therefore, WS2and NIS were introduced in this paper to modify it. TiO2/WS2/NiS (TWN) composites with Type-Ⅱ heterojunction structure were prepared by hydrothermal method and titration method. The results reveal TWN5 showed the best photoelectrochemical (PEC) performance, and the photocurrent density was 69% higher than that of a pure TiO2photoanode, and the photochemical and photocathodic protection performance was significantly better than that of pure TiO2. Under simulated ocean conditions, the self-corrosion potential of 304ss combined with TW5 and TWN5 photoanodes is reduced to -0.64 V and -0.7 V, respectively. The main reason is that the contact surfaces of WS2and TiO2formed a Type II heterostructure, which accelerates the separation and diffusion processes of photoinduced carriers. In addition, the plasmon resonance effect of NiS improves the ability to absorb visible light, and the metallic-like feature of NiS also promotes charge separation.

High-performance flexible piezoelectric nanogenerator assisted by a three-phase PVDF/WS2/rGO nanocomposite.

The emergence of piezoelectric nanogenerators (PENGs) presents a promising alternative to supply energy demands within the realms of portable and miniaturized devices. In this article, the role of 2D transition metal dichalcogenide tungsten sulfide (WS2) and conductive rGO sheets as filler materials inside the polyvinylidene fluoride (PVDF) matrix on piezoelectric performances has been investigated extensively. The strong electrostatic interaction between C-F and C-H monomer bonds of PVDF interacted with the large surface area of the WS2nanosheets, increasing the electroactive polar phases and resulting in enhanced ferroelectricity in the PVDF/WS2nanocomposite. Further, the inclusion of rGO sheets in the PVDF/WS2composite allows mobile charge carriers to move freely through the conductive network provided by the rGO basal planes, which improves the internal polarization of the PVDF/WS2/rGO nanocomposites and increases the electrical performance of the PENGs. The PVDF/WS2/0.3rGO nanocomposite-based PENG exhibits maximum piezoresponses with ∼8.1 times enhancements in the output power density than the bare PVDF-based PENG. The mechanism behind the enhanced piezoresponses in the PVDF/WS2/rGO nanocomposites has been discussed.

PVDF-HFP encapsulated WS2nanosheets in droplet-based triboelectric nanogenerators for possible detection of human Na+/K+ion concentration.

Here we report the liquid-solid interaction in droplet-based triboelectric nanogenerators (TENG) for estimation of human Na+/K+levels. The exploitation of PVDF-HFP encapsulated WS2as active layer in the droplet-based TENG (DTENG) leads to the generation of electrical signal during the impact of water droplet. Comparison over the control devices indicates that surface quality and dielectric nature of the PVDF-HFP/WS2composite largely dictates the performance of the DTENG. The demonstration of excellent sensitivity of the DTENG towards water quality indicates its promising application towards water testing. In addition, the alteration in output signal with slightest variation in ionic concentration (Na+or K+) in water has been witnessed and is interpreted with charge transfer and ion transfer processes during liquid-solid interaction. The study reveals that the ion mobility largely affects the ion adsorption process on the active layer of PVDF-HFP/WS2and thus generates distinct output profiles for diverse ions like Na+and K+. Following that, the DTENG characteristics have been exploited to artificial urine where the varying output signals have been recorded for variation in urinary Na+ion concentration. Therefore, the deployment of PVDF-HFP/WS2in DTENG holds promising application towards the analyse of ionic characteristics of body fluids.

Enhancement of photovoltaic parameters of thermally stable graphene/LaVO3semitransparent solar cell by employing interfacial graphene quantum dots.

Semitransparent solar cells are attracting attention not only for their visual effects but also for their ability to effectively utilize solar energy. Here, we demonstrate a translucent solar cell composed of bis(trifluoromethane sulfonyl)-amide (TFSA)-doped graphene (Gr), graphene quantum dots (GQDs), and LaVO3. By introducing a GQDs intermediate layer at the TFSA-Gr/LaVO3interface, we can improve efficiency by preventing carrier recombination and promoting charge collection/separation in the device. As a result, the efficiency of the GQDs-based solar cell was 4.35%, which was higher than the 3.52% of the device without GQDs. Furthermore, the average visible transmittance of the device is 28%, making it suitable for translucent solar cells. The Al reflective mirror-based system improved the power conversion efficiency by approximately 7% compared to a device without a mirror. Additionally, the thermal stability of the device remains at 90% even after 2000 h under an environment with a temperature of 60 °C and 40% relative humidity. These results suggest that TFSA-Gr/GQDs/LaVO3-based cells have a high potential for practical use as a next-generation translucent solar energy power source.

Modification of WS2thin film properties using high dose gamma irradiation.

The tunability of the transition metal dichalcogenide properties has gained attention from numerous researchers due to their wide application in various fields including quantum technology. In the present work, WS2has been deposited on fluorine doped tin oxide substrate and its properties have been studied systematically. These samples were irradiated using gamma radiation for various doses, and the effect on structural, morphological, optical and electrical properties has been reported. The crystallinity of the material is observed to be decreased, and the results are well supported by x-ray diffraction, Raman spectroscopy techniques. The increase in grain boundaries has been supported by the agglomeration observed in the scanning electron microscopy micrographs. The XPS results of WS2after gamma irradiation show evolution of oxygen, carbon, C=O, W-O and SO4-2peaks, confirming the addition of impurities and formation of point defect. The gamma irradiation creates point defects, and their density increases considerably with increasing gamma dosage. These defects crucially altered the structural, optical and electrical properties of the material. The reduction in the optical band gap with increased gamma irradiation is evident from the absorption spectra and respective Tauc plots. TheI-Vgraphs show a 1000-fold increase in the saturation current after 100 kGy gamma irradiation dose. This work has explored the gamma irradiation effect on the WS2and suggests substantial modification in the material and enhancement in electrical properties.

Wafer scale WS2based ultrafast photosensing and memory computing devices for neuromorphic computing.

Integration of optical sensors with memristors can establish the bridge between photosensing and memory devices for Internet of Things (IoT) based applications. This paper presents the realization of integrated sensing and computing memory (ISCM) devices using tungsten disulfide (WS2) and their application for neuromorphic computing. The ISCM device fabrication process is scalable as microfabrication steps followed on 2″ wafer, ISCM device testing and image classification for neuromorphic computing. The photosensing/memory tests were conducted using electrical and optical stimulations (broadband spectrum). The fabricated photosensing device offers a higher responsivity (8 A W-1), higher detectivity (2.85 × 1011Jones) and fast response speed (80.2/78.3µs) at 950 nm. The memory device has shown a set/reset time of 51.6/73.5µs respectively. Further, the repeatability, stability and reproducibility tests were conducted by stimulating the device with different modulating frequencies. The frequency modulation tests confirm that the ISCM devices are stable and perfect candidate for real-time IoT applications. Moreover, the device's potentiation and depression results were used for image classification with the accuracy of 98.27%. These demonstrated device's test results provide possibilities to fabricate the smart sensors with integrated functionalities.

TEM-processed defect densities in single-layer TMDCs and their substrate-dependent signature in PL and Raman spectroscopy.

The optical properties of the direct-bandgap transition metal dichalcogenides (TMDCs) MoS2and WS2are heavily influenced by their atomic defect structure and substrate interaction. In this work we use low-voltage chromatic and spherical aberration (CC/CS)-corrected high-resolution transmission electron microscopy to simultaneously create and image chalcogen vacancies in TMDCs. However, correlating the defect structure, produced and analyzed using transmission electron microscopy (TEM), with optical spectroscopy often presents challenges because of very different fields of view and sample platforms involved. Here we employ a reverse transfer technique to transfer electron-irradiated single-layer MoS2and WS2from the TEM grid to various substrates for subsequent optical examination. The dynamics of defect creation are studied in atomic resolution on a separate sample, which allows to apply the derived statistics to larger irradiated areas on the other samples. The intensity of both the defect-bound exciton peak in photoluminescence (PL) and the defect-inducedLA(M) mode in Raman spectra increase with defect density. The best substrates for defect-density determination by optical spectroscopy are polystyrene for PL and SiC and Si/SiO2for Raman spectroscopy. These investigations represent an important step towards the quantification of defects using solely optical spectroscopy, paving the way for fast, reliable, and automatable optical quality control of optoelectronic devices.