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Controlling the Co–S coordination environment in Co-doped WS 2 nanosheets for electrochemical oxygen reduction
The impact of Co–S coordination environment in pH 7 ORR catalysis is evaluated using dilute Co atoms adsorbed on WS 2 nanosheets. Optimal reactivity is achieved when Co is coordinated to both sulfur atoms on WS 2 and labile solvent ligands.
In Situ Imaging Reveals Efficient Charge Separation in Monolayer MoS 2 –WS 2 Type-II Heterojunctions
Covalently bonded in-plane two-dimensional (2D) transition metal dichalcogenide (TMD) heterojunctions with atomically sharp interfaces hold great promise for photocatalytic applications in solar energy conversion and environmental remediation; however, their spatially resolved charge distribution and transport, particularly under operando conditions, remain poorly understood. Here, we employ photoscanning electrochemical microscopy (photo-SECM) to directly visualize photoinduced charge separation in monolayer MoS 2 –WS 2 in-plane heterojunctions. Spatial separation of photogenerated carriers is observed, with electrons accumulating in MoS 2 and holes in WS 2 , leading to strongly asymmetric interfacial kinetics: Fc + reduction proceeds rapidly on MoS 2 (0.6 cm s –1 ), whereas Fc oxidation on WS 2 is significantly slower (0.008 cm s –1 ). High-resolution surface photovoltage microscopy (SPVM) enables a quantitative comparison of charge-separation capacity across architectures. The in-plane MoS 2 –WS 2 heterojunction shows the largest photovoltage contrast (−35 mV in MoS 2 , 20 mV in WS 2 ), exceeding the vertical heterojunction (−18 mV in MoS 2 , 11 mV in WS 2 ) and the individual monolayers (−12 mV for MoS 2 , – 1 mV for WS 2 ), establishing the following trend: in-plane > vertical > monolayers. Ultraviolet photoelectron spectroscopy (UPS) indicates that this directional charge separation is driven by intrinsic type-II band alignment, while photoluminescence (PL) imaging shows that the interface acts as a recombination center that limits efficient carrier extraction. These results provide direct experimental evidence of type-II-driven charge separation in in-plane heterojunctions and offer critical insights for interface design in high-efficiency photocatalytic and optoelectronic systems.
A type-I van der Waals heterostructure formed by monolayer WS 2 and trilayer PdSe 2
Two-dimensional (2D) heterostructures, formed by stacking 2D semiconductors through the van der Waals force, have been extensively studied recently. However, the majority of the heterostructures discovered so far possess type-II interfaces that facilitate interlayer charge separation. Type-I interfaces, on the other hand, confine both electrons and holes in one layer, which is beneficial for optical applications that utilize electron–hole radiative recombination. So far, only a few type-I 2D heterostructures have been achieved, which has limited the construction of multilayer heterostructures with sophisticated band landscapes. Here, we report experimental evidence of a type-I interface between monolayer WS 2 and trilayer PdSe 2 . Two-dimensional PdSe 2 has emerged as a promising material for infrared optoelectronic and other applications. We fabricated the heterostructure by stacking an exfoliated monolayer WS 2 flake on top of a trilayer PdSe 2 film, synthesized by chemical vapor deposition. Photoluminescence spectroscopy measurements revealed that the WS 2 exciton peak is significantly quenched in the heterostructure, confirming efficient excitation transfer from WS 2 to PdSe 2 . Femtosecond transient absorption measurements with various pump/probe configurations showed that both electrons and holes photoexcited in the WS 2 layer of the heterostructure can efficiently transfer to PdSe 2 , while neither type of carriers excited in PdSe 2 can transfer to WS 2 . These experimental findings establish a type-I band alignment between monolayer WS 2 and trilayer PdSe 2 . Furthermore, our results further highlight PdSe 2 as an important 2D material for constructing van der Waals heterostructures with emergent electronic and optoelectronic properties.
Unraveling the Mechanism of Interfacial Charge Transfer and Photoresponsivity of WS 2 Quantum Dots/MoS 2 (0D–2D) Heterostructure-Based Transistors
To assess the efficacy of a mixed-dimensional van der Waals (vdW) heterostructure in modulating the optoelectronic responses of nanodevices, the charge transport properties of the transition-metal dichalcogenide (TMD)-based heterostructure comprising zero-dimensional (0D) WS 2 quantum dots (QDs) and two-dimensional (2D) MoS 2 flakes are critically analyzed. Herein, a facile strategy was materialized in developing an atomically thin phototransistor assembled from mechanically exfoliated MoS 2 and WS 2 QDs synthesized using a one-pot hydrothermal route. The amalgamated photodetectors exhibited a high responsivity of ∼8000 A/W at an incident power of 0.05 nW of white light, surpassing that of the pristine MoS 2 devices. Furthermore, the detectivity of pristine MoS 2 , which was on the order of 10 10 , increased to 10 12 Jones for the WS 2 QDs/MoS 2 heterostructure photodetector, outperforming other WS 2 -based materials. The quasiparticle band gap and density of states (DOS) are further analyzed to elucidate the photophysics of the WS 2 QD/MoS 2 hybrid assembly. The difference in the work function between MoS 2 and WS 2 QDs gives rise to an electric field across the 0D–2D interface, facilitating effective charge separation and migration and contributing to the enhancement of photoresponsivity. The analysis of optical responses using density functional theory (DFT) revealed stronger absorption and less reflection over a broader spectrum of wavelengths for the heterostructure compared to the pristine materials. The estimated optical conductivity aligns well with the experimentally predicted maximum photoresponsivity under visible light, which is attributed to the high absorbance of 2D MoS 2 . In conclusion, combining diverse spectroscopic and imaging techniques with quantum simulation provides insights that clarify the pertinence of 0D–2D TMDs in designing phototransistors.
Two-Dimensional 2M-WS 2 Nanolayers for Superconductivity
Recently, a newly discovered VIB group transition metal dichalcogenide (TMD) material, 2M-WS 2 , has attracted extensive attention due to its interesting physical properties such as topological superconductivity, nodeless superconductivity, and anisotropic Majorana bound states. However, the techniques to grow high-quality 2M-WS 2 bulk crystals and the study of their physical properties at the nanometer scale are still limited. In this work, we report a new route to grow high-quality 2M-WS 2 single crystals and the observation of superconductivity in its thin layers. The crystal structure of the as-grown 2M-WS 2 crystals was determined by X-ray diffraction (XRD) and scanning tunneling microscopy (STM). The chemical composition of the 2M-WS 2 crystals was determined by energy dispersive X-ray spectroscopy (EDS) analysis. At 77 K, we observed the spatial variation of the local tunneling conductance (dI/dV) of the 2M-WS2 thin flakes by scanning tunneling spectroscopy (STS). Our low temperature transport measurements demonstrate clear signatures of superconductivity of a 25 nm-thick 2M-WS 2 flake with a critical temperature (T C ) of ~8.5 K and an upper critical field of ~2.5 T at T = 1.5 K. Our work may pave new opportunities in studying the topological superconductivity at the atomic scale in simple 2D TMD materials.
Insight the process of hydrazine gas adsorption on layered WS 2 : a first principle study
The process of hydrazine gas adsorption on layered WS 2 has been systematically studied from first principle calculations. Our results demonstrate that this adsorption process is exothermic, and hydrazine molecules are physically adsorbed. The layer-dependent adsorption energy and interlayer separation induced by van der Waals interaction exerted by hydrazine molecules lead to the difficulty in desorbing hydrazine molecules from layered WS 2 as the number of layers increases. The most interesting finding is the emergence of localized impurity states below the Fermi level upon the hydrazine adsorption, irrespective of the number of WS 2 layers, resulting in a significant effect on the band structures and subsequently changing its electrical conductivity. Furthermore, a layer-dependent small charge transfer occurs between hydrazine and layered WS 2 , leading to a charge redistribution and considerable polarization in the adsorbed systems. The existence of defects and the humidity, on the other hand, influences the sensitivity of layered WS 2 to the hydrazine adsorption. Here, obtained results show that a perfectly layered WS 2 might be a promising candidate as an efficient nanosensor to detect such toxic gas in dry environment.
Developing Dual Polarization Applications For 45th Weather Squadron's (45 WS) New Weather Radar: A Cooperative Project With The National Space Science and Technology Center (NSSTC)
A new weather radar is being acquired for use in support of America s space program at Cape Canaveral Air Force Station, NASA Kennedy Space Center, and Patrick AFB on the east coast of central Florida. This new radar includes dual polarization capability, which has not been available to 45 WS previously. The 45 WS has teamed with NSSTC with funding from NASA Marshall Spaceflight Flight Center to improve their use of this new dual polarization capability when it is implemented operationally. The project goals include developing a temperature profile adaptive scan strategy, developing training materials, and developing forecast techniques and tools using dual polarization products. The temperature profile adaptive scan strategy will provide the scan angles that provide the optimal compromise between volume scan rate, vertical resolution, phenomena detection, data quality, and reduced cone-of-silence for the 45 WS mission. The mission requirements include outstanding detection of low level boundaries for thunderstorm prediction, excellent vertical resolution in the atmosphere electrification layer between 0 C and -20 C for lightning forecasting and Lightning Launch Commit Criteria evaluation, good detection of anvil clouds for Lightning Launch Commit Criteria evaluation, reduced cone-of-silence, fast volume scans, and many samples per pulse for good data quality. The training materials will emphasize the appropriate applications most important to the 45 WS mission. These include forecasting the onset and cessation of lightning, forecasting convective winds, and hopefully the inference of electrical fields in clouds. The training materials will focus on annotated radar imagery based on products available to the 45 WS. Other examples will include time sequenced radar products without annotation to simulate radar operations. This will reinforce the forecast concepts and also allow testing of the forecasters. The new dual polarization techniques and tools will focus on the appropriate applications for the 45 WS mission. These include forecasting the onset of lightning, the cessation of lightning, convective winds, and hopefully the inference of electrical fields in clouds. This presentation will report on the results achieved so far in the project.
Anisotropic Raman Scattering and Lattice Orientation Identification of 2M-WS 2
Anisotropic materials with low symmetries hold significant promise for next-generation electronic and quantum devices. 2M-WS 2 , which is a candidate for topological superconductivity, has garnered considerable interest. However, a comprehensive understanding of how its anisotropic features contribute to unconventional superconductivity, along with a simple, reliable method to identify its crystal orientation, remains elusive. Here, we combine theoretical and experimental approaches to investigate angle- and polarization-dependent anisotropic Raman modes of 2M-WS 2 . Through first-principles calculations, we predict and analyze the phonon dispersion and lattice vibrations of all Raman modes in 2M-WS 2 . We establish a direct correlation between their anisotropic Raman spectra and high-resolution transmission electron microscopy images. Finally, we demonstrate that anisotropic Raman spectroscopy can accurately determine the crystal orientation and twist angle between two stacked 2M-WS 2 layers. Furthermore, our findings provide insights into the electron–phonon coupling and anisotropic properties of 2M-WS 2 , paving the way for the use of anisotropic materials in advanced electronic and quantum devices.
Controllable superconducting to semiconducting phase transition in topological superconductor 2M-WS 2
The investigation of exotic properties in two-dimensional (2D) topological superconductors has garnered increasing attention in condensed matter physics, particularly for applications in topological qubits. Despite this interest, a reliable way of fabricating topological Josephson junctions (JJs) utilizing topological superconductors has yet to be demonstrated. Controllable structural phase transition presents a unique approach to achieving topological JJs in atomically thin 2D topological superconductors. In this work, we report the pioneering demonstration of a structural phase transition from the superconducting to the semiconducting phase in the 2D topological superconductor 2M-WS 2 . We reveal that the metastable 2M phase of WS 2 remains stable in ambient conditions but transitions to the 2H phase when subjected to temperatures above 150°C. We further locally induced the 2H phase within 2M-WS 2 nanolayers using laser irradiation. Notably, the 2H phase region exhibits a hexagonal shape, and scanning tunneling microscopy (STM) uncovers an atomically sharp crystal structural transition between the 2H and 2M phase regions. Moreover, the 2M to 2H phase transition can be induced at the nanometer scale by a 200 keV electron beam. The electrical transport measurements further confirmed the superconductivity of the pristine 2M-WS 2 and the semiconducting behavior of the laser-irradiated 2M-WS 2 . Furthermore, our results establish a novel approach for controllable topological phase change in 2D topological superconductors, significantly impacting the development of atomically scaled planar topological JJs.
30 WS North Base Wind Study
The 30 Weather Squadron (30 WS) is concerned about strong winds observed at their northern towers without advance warning. They state that terrain influences along the extreme northern fringes of Vandenberg Air Force Base (VAFB) make it difficult for forecasters to issue timely and accurate high wind warnings for northeasterly wind events. These events tend to occur during the winter or early spring when they are under the influence of the Great Basin high pressure weather regime. The Launch Weather Officers (LWOs) have seen these rapid wind increases in the current northern Towers 60, 70 and 71 in excess of their 35 kt operational warning threshold. For this task, the 30 WS requested the Applied Meteorology Unit (AMU) analyze data from days when these towers reported winds in excess of 35 kt and determine if there were any precursors in the observations that would allow the LWOs to better forecast and warn their operational customers for these wind events. The 30 WS provided wind tower data for the cool season (October - March) from the period January 2004-March 20 IO. The AMU decoded and evaluated the wind tower data for 66 days identified by the 30 WS as having high-wind events. Out of the 66 event days, only 30 had wind speed observations of > or =35 kt from at least one of the three northern towers. The AMU analyzed surface and upper air charts to determine the synoptic conditions for each event day along with tower peak wind speed and direction time series and wind rose charts for all 30 event days. The analysis revealed a trend on all event days in which the tower winds shifted to the northeast for a period of time before the first recorded > or =35 kt wind speed. The time periods for the 30 event days ranged from 20 minutes to several hours, with a median value of 110 minutes. This trend, if monitored, could give the 30 WS forecasters a precursor to assist in issuing an operational warning before a high wind event occurs. The AMU recommends developing a high-wind alert capability for VAFB using a local mesoscale model to forecast these wind events. The model should incorporate all of the VAFB local data sets and have a forecast capability of between 2 to 24 hours. Such a model would allow the meteorologists at VAFB to alert the operational customers of high wind events in a timely manner so protective action could be taken.
Evolution of the Electronic Gap of Directly Synthesized Versus Mechanically Transferred WS 2 Monolayer to Multilayer Films
The electronic properties of 2D materials play a critical role in determining their potential for device applications. Despite rapid developments in 2D semiconductors, studies of fundamental electronic parameters, including the electronic gap and ionization energy, are limited, with significant discrepancies in reported values. The study focuses on tungsten disulfide (WS₂) and investigates the electronic structure of films comprising an increasing number of layers deposited with two different methods: direct synthesis via metal–organic chemical vapor deposition (MOCVD) and additive mechanical transfer of exfoliated single layers. The films are characterized via Raman, UV–vis, and photoluminescence spectroscopies, as well as ultraviolet photoelectron and inverse photoemission spectroscopies (UPS/IPES). The electronic gap of WS₂ is found to decrease from 2.43 eV for the monolayer to 1.97 eV for the trilayer, indicating a bulk transition at the trilayer thickness. This reduction in the electronic gap is primarily due to the downward shift of the conduction band minimum relative to the valence band maximum. A comparative analysis with MOCVD-grown WS₂ reveals a slightly larger electronic gap for MOCVD-grown samples, attributed to differences in defect densities. The electronic levels evaluated through UPS/IPES highlight the significant influence of preparation methods on the electronic properties of WS₂.
Sulfurization Engineering of One–Step Low–Temperature MoS 2 and WS 2 Thin Films for Memristor Device Applications
2D materials have been of considerable interest as new materials for device applications. Non-volatile resistive switching applications of MoS 2 and WS 2 have been previously demonstrated; however, these applications are dramatically limited by high temperatures and extended times needed for the large-area synthesis of 2D materials on crystalline substrates. The experimental results demonstrate a one-step sulfurization method to synthesize MoS 2 and WS 2 at 550 °C in 15 min on sapphire wafers. Furthermore, a large area transfer of the synthesized thin films to SiO 2 /Si substrates is achieved. Following this, MoS 2 and WS 2 memristors are fabricated that exhibit stable non-volatile switching and a satisfactory large on/off current ratio (10 3 –10 5 ) with good uniformity. Tuning the sulfurization parameters (temperature and metal precursor thickness) is found to be a straightforward and effective strategy to improve the performance of the memristors. Furthermore, the demonstration of large-scale MoS 2 and WS 2 memristors with a one-step low-temperature sulfurization method with simple strategy to tuning can lead to potential applications such as flexible memory and neuromorphic computing.
Photocarrier Dynamics in TlGaS 2 Nanoflakes and van der Waals Heterostructures with Hexagonal Boron Nitride and WS 2 Nanoflakes: Implications for Optoelectronic Applications
We present an experimental investigation on photocarrier dynamics in a TlGaS 2 bulk crystal and its heterostructures with hexagonal BN and WS 2 . The samples were obtained by mechanical exfoliation and dry transfer techniques. The photocarrier dynamics was monitored by a transient absorption technique. We observed a direct optical transition of about 555 nm in the TlGaS 2 crystal. By utilizing transient absorption of that transition, we obtained a hot-carrier energy relaxation time of less than 1 ps and a carrier lifetime of about 300 ps in TlGaS 2 at room temperature. In the hexagonal-BN-TlGaS 2 heterostructure, the photocarrier dynamics was similar to that in TlGaS 2 , indicating the type-I band alignment of this structure with both band extremes located in TlGaS 2 . In the monolayer WS 2 -TlGaS 2 heterostructure, we observed charge transfer from TlGaS 2 to WS 2 and an extended lifetime of the transferred carriers in WS 2 . Here, these results introduce TlGaS 2 as a promising layered material for developing two-dimensional van der Waals materials that can be combined with other two-dimensional materials for various optoelectronic devices.
Excitation Laser Energy Dependence of the Gap-Mode TERS Spectra of WS 2 and MoS 2 on Silver
In this work we present a systematic study of the dependence of the gap mode tip-enhanced Raman scattering (TERS) response of the mono- and bi-layer WS 2 and MoS 2 on silver as a function of the excitation laser energy in a broad spectral range from 473nm to 830 nm. For this purpose, we collected consecutive TERS maps of the same area in the sample containing mono-and bi-layer regions with the same TERS probe with 6 different excitation lasers. To decrease the number of collected TERS maps, we used for the first time to the best of our knowledge, concurrent excitation and collection with two lasers simultaneously. We found that the E 2g /A 1g peak intensity ratio for the bilayer WS 2 @Ag and the ratio of the A’/A 1g peak intensity of the out-of-plane mode for the mono- and the bilayer, change in a significantly non-monotonous way as the excitation laser energy is swept from 1.58 eV to 2.62 eV. The former ratio increases at energies corresponding to A and B excitons (~2.0 eV and 2.4 eV correspondingly) in bilayer WS 2 . The absolute intensity of the A’ peak in the monolayer, and correspondingly the A’/A 1g ratio, is surprisingly high at lower excitation energies, but dips dramatically at the energy corresponding to the A exciton, being restored partially in between A and B excitons, but still showing the descending trend as the excitation laser energy increases. A somewhat similar picture was observed in mono- and bi-layers of MoS 2 @Ag, though the existing set of excitation lasers did not match the excitonic profile of this material as nicely as for the case of WS 2 . We attribute the observed behavior to the presence of intermediate (Fano resonance) or strong (Rabi splitting) coupling between the excitons in transition metal dichalcogenides (TMDs) and the plasmons in the tip-substrate nanocavity. This is akin to the so-called Fano (Rabi) transparency experimentally observed in far field scattering from transition metal dichalcogenides between two plasmonic metals. The possibility of the formation of intermediate/strong coupling between the excitonic resonances in TMDs and the nanocavity re-evaluates the role of various resonances in the gap-mode TERS and should become an important factor to be considered by TERS practitioners during planning the experiments. Lastly, based on observed phenomena and its explanation, we propose the “ideal” substrate for efficient TERS and tip enhanced photoluminescence (TEPL) measurements.
Direct intercalation of MoS 2 and WS 2 thin films by vacuum filtration
In the development of next-generation electronics and energy devices, intercalation compounds of transition metal dichalcogenides (TMDCs) are gaining attention for their unique properties that result from synergistic interactions between guest species and host materials. Nowadays, intercalation compounds of MoS 2 and WS 2 are commonly prepared by a two-step process: (1) exfoliation to form single-layer and/or few-layer nanosheets and (2) restacking the nanosheets with the guest species by vigorously mixing the exfoliated suspension with the solution of guest species. While a wide variety of intercalation compounds have been synthesized using this approach, the intercalation process is often timeconsuming, and the product slurry limits material quality and impedes characterization and applications. Herein, we report a versatile method for preparing intercalated TMDCs in a thin-film morphology. Using this approach, we successfully prepared a range of existing intercalation compounds of MoS 2 and WS 2 (e.g., ferrocene and amine intercalated MoS 2 and WS 2 ). Additionally, by leveraging the versatility of this intercalation method, we report we intercalated phenazine and benzoquinone into MoS 2 and WS 2 for the first time.
Proximity-enhanced valley Zeeman splitting at the WS 2 /graphene interface
The valley Zeeman physics of excitons in monolayer transition metal dichalcogenides provides valuable insight into the spin and orbital degrees of freedom inherent to these materials. Being atomically-thin materials, these degrees of freedom can be influenced by the presence of adjacent layers, due to proximity interactions that arise from wave function overlap across the 2D interface. Here, we report 60 T magnetoreflection spectroscopy of the A- and B- excitons in monolayer WS 2 , systematically encapsulated in monolayer graphene. While the observed variations of the valley Zeeman effect for the A- exciton are qualitatively in accord with expectations from the bandgap reduction and modification of the exciton binding energy due to the graphene-induced dielectric screening, the valley Zeeman effect for the B- exciton behaves markedly different. We investigate prototypical WS 2 /graphene stacks employing first-principles calculations and find that the lower conduction band of WS 2 at the <?CDATA $K/K^{^{\prime}}$?> K / K ′ valleys (the <:tex-math><?CDATA $\mathrm{CB}^-$?> C B − band) is strongly influenced by the graphene layer on the orbital level. Specifically, our detailed microscopic analysis reveals that the conduction band at the Q point of WS 2 mediates the coupling between <?CDATA $\mathrm{CB}^-$?> C B − and graphene due to resonant energy conditions and strong coupling to the Dirac cone. This leads to variations in the valley Zeeman physics of the B- exciton, consistent with the experimental observations. Our results therefore expand the consequences of proximity effects in multilayer semiconductor stacks, showing that wave function hybridization can be a multi-step energetically resonant process, with different bands mediating the interlayer interactions. Such effects can be further exploited to resonantly engineer the spin-valley degrees of freedom in van der Waals and moiré heterostructures.
Photocarrier dynamics at the interface between WS 2 and ozone-irradiated graphene
We investigate the photocarrier properties of heterostructures (HSs) formed by WS 2 and ozone-irradiated graphene (OI-graphene), with a focus on the impact of ozone irradiation. Photoluminescence and Raman spectroscopy reveal a pronounced doping effect induced by ozone irradiation on the graphene layer. Transient absorption measurements demonstrate a substantial suppression of charge transfer efficiency across the interface in the presence of ozone molecules. Spatially resolved pump-probe measurements further show a significant reduction in the diffusion coefficient of photocarriers in WS 2 on OI-graphene compared to that of individual WS 2 monolayers. The slower diffusion suggests enhanced spatial separation of electrons and holes in the WS 2 layer, induced by a built-in electric field at the interface. This effect arises from the combined influences of doping and dielectric property changes caused by ozone molecules. These findings highlight the critical influence of ozone irradiation on graphene and HS interfaces, offering valuable insights for the design of future graphene-based two-dimensional HSs.