Monolayer WS2 Research Articles

Synaptic Plasticity and Visual Memory in a Neuromorphic 2D Memitter Based on WS2 Monolayers

AbstractNeuromorphic computing aims to leverage physical phenomena of adaptive materials for emulating information processing capabilities and effectiveness of biological neuronal circuits. In this framework, memristors (resistors with memory) based on 2D materials are demonstrated for the hardware implementation of highly integrated artificial neural networks. All the works reported thus far exploited electrical properties of 2D materials to emulate neuromorphic functionalities. Here, a 2D memitter (emitter with memory) is reported on that exploits the stimuli‐responsive photoluminescence of a monolayer WS2 for neuromorphic‐type of data processing. A combined experimental and modeling approach reveals that photoluminescent dynamics triggered by optical stimulation emulates Short‐Term synaptic Plasticity and Visual Short‐Term Memory typical of biological systems. While spatio‐temporal processing capabilities of input signals can be used for information processing in the context of reservoir computing, the capability of the 2D memitter of sensing, processing, and memorizing‐forgetting optical inputs in the same physical substrate can be utilized for in‐sensor computing.

Temperature-Dependent Excitonic Light Manipulation with Atomically Thin Optical Elements.

Monolayer 2D semiconductors, such as WS2, exhibit uniquely strong light-matter interactions due to exciton resonances that enable atomically thin optical elements. Similar to geometry-dependent plasmon and Mie resonances, these intrinsic material resonances offer coherent and tunable light scattering. Thus far, the impact of the excitons' temporal dynamics on the performance of such excitonic metasurfaces remains unexplored. Here, we show how the excitonic decay rates dictate the focusing efficiency of an atomically thin lens carved directly out of exfoliated monolayer WS2. By isolating the coherent exciton radiation from the incoherent background in the focus of the lens, we obtain a direct measure of the role of exciton radiation in wavefront shaping. Furthermore, we investigate the influence of exciton-phonon scattering by characterizing the focusing efficiency as a function of temperature, demonstrating an increased optical efficiency at cryogenic temperatures. Our results provide valuable insights into the role of excitonic light scattering in 2D nanophotonic devices.

Ferroelectric Polarization‐Mediated Modulation of Optical Properties in 2D van der Waals Architectures

AbstractThe integration of 2D ferroelectric materials with 2D photoelectric materials presents a promising avenue for addressing issues related to controlled doping and device integration in layered semiconductors. The reversible and non‐volatile residual polarization inherent to ferroelectrics can provide stable n‐ or p‐type doping for 2D semiconductors. Despite advances in doping strategies for 2D materials, existing techniques, and post‐doping characterization methodologies exhibit limitations, including the challenge of achieving high‐resolution graphical depictions of doped structures. Here, a WS2/CuInP2S6 heterostructure is demonstarted whereby the residual polarization of ferroelectric CuInP2S6 regions with anti‐parallel directions supplies screening charges of opposite signs to WS2 monolayers. This notably alters the ratio of neutral excitons and negatively charged trions within the recombination luminescence of the direct‐gap semiconductor, thereby offering a viable approach for controllable, non‐volatile modulation in 2D systems. Beyond proposing a feasible strategy for patterned doping and effective regulation in 2D semiconductors through interface engineering, this work enhances the understanding of the interplay between ferroelectrics and semiconductors.

Continuous-Wave Pumped Monolayer WS2 Lasing for Photonic Barcoding.

Micro/nano photonic barcoding has emerged as a promising technology for information security and anti-counterfeiting applications owing to its high security and robust tamper resistance. However, the practical application of conventional micro/nano photonic barcodes is constrained by limitations in encoding capacity and identification verification (e.g., broad emission bandwidth and the expense of pulsed lasers). Herein, we propose high-capacity photonic barcode labels by leveraging continuous-wave (CW) pumped monolayer tungsten disulfide (WS2) lasing. Large-area, high-quality monolayer WS2 films were grown via a vapor deposition method and coupled with external cavities to construct optically pumped microlasers, thus achieving an excellent CW-pumped lasing with a narrow linewidth (~0.39 nm) and a low threshold (~400 W cm-2) at room temperature. Each pixel within the photonic barcode labels consists of closely packed WS2 microlasers of varying sizes, demonstrating high-density and nonuniform multiple-mode lasing signals that facilitate barcode encoding. Notably, CW operation and narrow-linewidth lasing emission could significantly simplify detection. As proof of concept, a 20-pixel label exhibits a high encoding capacity (2.35 × 10108). This work may promote the advancement of two-dimensional materials micro/nanolasers and offer a promising platform for information encoding and security applications.

Synergistic effects of Fe and P doping in WS2 monolayers for enhanced bifunctional electrocatalysis in water splitting

The quest for efficient dual-purpose electrocatalysts to facilitate water splitting is an ongoing challenge in materials science. In this study, we introduce a novel approach involving the incorporation of Fe and P atoms into WS2 monolayers (MLs) through rigorous first-principle calculations. The introduction of Fe and P atoms brings about remarkable enhancements in the electronic properties of the WS2 MLs, significantly boosting the catalytic performance of the 1T’ phase. The doping-induced changes in energy levels lead to the formation of a spin-polarized density of states, which exhibits superior conductivity in the vicinity of the d-band center and Fermi level. These electronic alterations are intricately governed by the valence and conduction bands. In addition to this, the introduced dopants elevate the charge transfer rate while simultaneously reducing interfacial resistance. Furthermore, the strong bonding of the dopants plays a pivotal role in reducing the energy barrier during adsorption. This, in turn, leads to a substantial decrease in the Gibbs free energy (0.101 eV) for the hydrogen evolution reaction and a lowered overpotential (0.36 V) for the oxygen evolution reaction. These findings collectively offer a promising avenue for the development of advanced bifunctional catalysts in the context of water splitting, suggesting that substitutional heteroatom doping of 1T′-WS2 MLs holds substantial potential in this field.

Addressing the effects of gas adsorption on monolayers beyond charge population analysis: the case of WS2

The optoelectronic properties of two-dimensional (2D) materials can be significantly influenced by charge transfer resulting from surface molecular adsorption. One noteworthy example is observed in WS2 monolayers, where the behavior undergoes an anomalous change when exposed to air, primarily due to the adsorption of oxygen molecules. While the acceptor nature of O2 is widely acknowledged as the underlying cause, the precise electron transfer mechanism remains in need of a comprehensive explanation at the atomistic level. Going beyond conventional charge population analysis, we develop an approach describing the process of molecular adsorption and surface charge transfer that relies on the formalism commonly adopted for charged defects in semiconductors. This method clearly identifies two key factors contributing to electron transfer upon O2 physisorption: the presence of sulphur vacancies and the intrinsic n-type nature of WS2. This approach provides an effective and general scheme to characterize the surface charge transfer in 2D materials exposed to a gas atmosphere.

Enhancing dielectric passivation on monolayer WS2 via a sacrificial graphene oxide seeding layer

The full utilization of two-dimensional transition metal dichalcogenides (2D TMDCs) faces several challenges, among which is realizing uniform material deposition on the 2D surface. Typical strategies to enable material growth lead to a poor interface quality, degrading the 2D TMDC’s properties. In this work, a sacrificial, graphene oxide-based seeding layer is used (1) as passivation layer, protecting the underlying 2D TMDC and (2) as nucleation layer, enabling uniform material growth. Graphene is transferred on monolayer WS2, establishing a high-quality van der Waals interface. After transfer, the polymeric residues on graphene are cleaned via a combination of wet- and dry treatments and functionalized via dry UV/O3 oxidation. The rate of graphene oxidation is shown to be substrate dependent, which is explained by UV light-induced ultrafast charge transfer between the graphene and WS2 monolayer. The carbon-oxygen functionalities serve as nucleation sites in a subsequent HfO2 ALD process, achieving more uniform dielectric growth and faster layer closure compared to direct deposition. The graphene-based nucleation- / passivation approach offers adaptability, allowing for tailored surface chemistry to enable any alternative material growth, while maintaining a prefect van der Waals interface.

Lateral heterostructures of WS2 and MoS2 monolayers for photo-synaptic transistor

Von Neumann architecture-based computing, while widely successful in personal computers and embedded systems, faces inherent challenges including the von Neumann bottleneck, particularly amidst the ongoing surge of data-intensive tasks. Neuromorphic computing, designed to integrate arithmetic, logic, and memory operations, has emerged as a promising solution for improving energy efficiency and performance. This approach requires the construction of an artificial synaptic device that can simultaneously perform signal processing, learning, and memory operations. We present a photo-synaptic device with 32 analog multi-states by exploiting field-effect transistors based on the lateral heterostructures of two-dimensional (2D) WS2 and MoS2 monolayers, formed through a two-step metal–organic chemical vapor deposition process. These lateral heterostructures offer high photoresponsivity and enhanced efficiency of charge trapping at the interface between the heterostructures and SiO2 due to the presence of the WS2 monolayer with large trap densities. As a result, it enables the photo-synaptic transistor to implement synaptic behaviors of long-term plasticity and high recognition accuracy. To confirm the feasibility of the photo-synapse, we investigated its synaptic characteristics under optical and electrical stimuli, including the retention of excitatory post-synaptic currents, potentiation, habituation, nonlinearity factor, and paired-pulse facilitation. Our findings suggest the potential of versatile 2D material-synapse with a high density of device integration.

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.

Enhanced upconversion luminescence of NaYF4:Er nanocrystals based on the synergy between whispering gallery mode excitation and förster resonant energy transfer

The upconversion luminescence at the visible band was excited by the high power density whispering gallery mode (WGM) on the surface of the microsphere. Under the WGM excitation, Er3+ of NaYF4:Er3+ directly absorbed three photons at 1525 nm, followed by the generation of upconversion luminescence. We used WS2 quantum dots (QDs) as donors and NaYF4:Er3+ upconversion nanoparticles (UCNPs) as acceptors to enhance upconversion luminescence by Förster resonant energy transfer (FRET). The physical mixture composed of monolayer WS2 and NaYF4:Er3+ nanoparticles was coated on SiO2 microsphere by immersion method. Excited by high power density WGM, three photons were absorbed by WS2-QDs based on the quantum size effect to generate excited electrons as donors and UCNPs as acceptors based on FRET, subsequently, the energy of the electrons were transferred to the luminescence center Er3+ to improve the upconversion luminescence efficiency. The mechanism model of upconversion luminescence enhancement based on FRET of WS2–NaYF4:Er3+ was proposed, and the enhancement effect was experimentally studied and demonstrated. To study the distance dependence of energy transfer between QD and UCNP pairs, we covered the surface of the silica microsphere with a controlled concentration of WS2 mixed with NaYF4:Er3+ nano-particles. When the mixed concentration of WS2-QDs was 0.15%, the upconversion luminescence reached the highest efficiency. The results showed that a twofold upconversion luminescence enhancement can be experimentally achieved. The proposed approach for enhancing the upconversion luminescence could benefit the improvement of imaging signal-to-noise ratio (SNR) using UCNPs for fluorescent labels in life sciences.

Defects in monolayer WS2 grown via sulfurization of WSe2

The conversion of chalcogen atoms into other types of chalcogen atoms in transition metal dichalcogenides exhibits significant advantages in tuning the bandgaps and constructing lateral heterojunctions. However, despite atomic defects at the atomic scale were inevitably formed during conversion process, the construction of dislocations remains difficult. Here, we conducted in-situ sulfurization to achieve structural transformation from monolayer WSe2 to WS2 successfully. We probe these transformations at atomic scale using high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and study structural defects of sulfurized-WS2 by strain and displacement fields. We discovered that high-quality WSe2 flakes were completely sulfurized while dislocations were successfully constructed, manifesting atomic surface roughness and structural disorders. Our work provides insights into designing and optimizing customized Transition metal dichalcogenides (TMDs) materials in controlled synthesis and defect engineering.

Atomic vs. sub-atomic layer deposition: impact of growth rate on the optical and structural properties of MoS2 and WS2

MoS2 and WS2 mono- and multilayers were grown on SiO2/Si substrates. Growth by atomic layer deposition (ALD) at fast growth rates is compared to sub-ALD, which is a slow growth rate process with only partial precursor surface coverage per cycle. A Raman spectroscopic analysis of the intensity and frequency difference of the modes reveals different stages of growth from partial to full surface layer coverage followed by layer-by-layer formation. The initial layer thickness and structural quality strongly depend on the growth rate and monolayers only form using sub-ALD. Optical activity is demonstrated by photoluminescence (PL) characterization which shows typical excitonic emission from MoS2 and WS2 monolayers. A chemical analysis confirming the stoichiometry of MoS2 is performed by x-ray photoelectron spectroscopy. The surface morphology of layers grown with different growth rates is studied by atomic force microscopy. Plan-view transmission electron microscopy analysis of MoS2 directly grown on freestanding graphene reveals the local crystalline quality of the layers, in agreement with Raman and PL results.

Tailoring the Photoluminescence of Monolayer WS2 under Weak and Strong Coupling Regimes

Tailoring the Photoluminescence of Monolayer WS₂ under Weak and Strong Coupling Regimes

Defect Passivation of 2D Semiconductors by Fixating Chemisorbed Oxygen Molecules via h-BN Encapsulations.

Hexagonal boron nitride (h-BN) is a key ingredient for various 2D van der Waals heterostructure devices, but the exact role of h-BN encapsulation in relation to the internal defects of 2D semiconductors remains unclear. Here, it is reported that h-BN encapsulation greatly removes the defect-related gap states by stabilizing the chemisorbed oxygen molecules onto the defects of monolayer WS2 crystals. Electron energy loss spectroscopy (EELS) combined with theoretical analysis clearly confirms that the oxygen molecules are chemisorbed onto the defects of WS2 crystals and are fixated by h-BN encapsulation, with excluding a possibility of oxygen molecules trapped in bubbles or wrinkles formed at the interface between WS2 and h-BN. Optical spectroscopic studies show that h-BN encapsulation prevents the desorption of oxygen molecules over various excitation and ambient conditions, resulting in a greatly lowered and stabilized free electron density in monolayer WS2 crystals. This suppresses the exciton annihilation processes by two orders of magnitude compared to that of bare WS2. Furthermore, the valley polarization becomes robust against the various excitation and ambient conditions in the h-BN encapsulated WS2 crystals.

Realization of exciton-polariton optical chirality based on strong coupling between intrinsic chiral quasibound states in the continuum and monolayer WS2.

Hybrid quasiparticles produced by the strong interaction between nanostructures and excitons will exhibit optical chirality when one of the coupled components is chiral. Due to the tunability of hybrid states, the coupled system has potential applications in chiral devices and chiral sensing. However, reported chiral materials including chiral molecules and three-dimensional chiral structures in the coupled system limit the application due to the weak chiroptical responses and difficult fabrication, respectively. In this paper, we design chiral quasibound states in the continuum (q-BIC) metasurface by introducing planar symmetry-breaking and z-axis perturbation into an array structure whose unit cell is a C4 rotational symmetric disk. By tuning the polarization state of the eigenmode, a significant chiroptical response is obtained in our q-BIC metasurface. Furthermore, mode splitting is observed not only in the reflection spectrum but also in the circular dichroism (CD) spectrum in the chiral q-BIC and monolayer WS2 strong coupling system, which indicates the realization of the exciton-polariton optical chirality. More importantly, one order of magnitude difference in the reflection to left and right circularly polarized light is achieved resulting in significant CD signals. Our work provides a new strategy to realize the exciton polaritons with significant chiroptical responses, which exhibits promising applications in on-chip chiral devices.

Support-Based Transfer and Contacting of Individual Nanomaterials for In Situ Nanoscale Investigations.

Although in situ transmission electron microscopy (TEM) of nanomaterials has been gaining importance in recent years, difficulties in sample preparation have limited the number of studies on electrical properties. Here, a support-based preparation method of individual 1D and 2D materials is presented, which yields a reproducible sample transfer for electrical investigation by in situ TEM. A mechanically rigid support grid facilitates the transfer and contacting to in situ chips by focused ion beam with minimum damage and contamination. The transfer quality is assessed by exemplary specimens of different nanomaterials, including a monolayer of WS2 . Possible studies concern the interplay between structural properties and electrical characteristics on the individual nanomaterial level as well as failure analysis under electrical current or studies of electromigration, Joule heating, and related effects. The TEM measurements can be enriched by additional correlative microscopy and spectroscopy carried out on the identical object with techniques that allow a characterization with a spatial resolution in the range of a few microns. Although developed for in situ TEM, the present transfer method is also applicable to transferring nanomaterials to similar chips for performing further studies or even for using them in potential electrical/optoelectronic/sensingdevices.

Mechanical properties of bilayer WS2 and Graphene-WS2 Hybrid composites by molecular dynamics simulations

In the present work, by using molecular dynamics (MD) simulations, we investigate the mechanical properties of different nanostructures that may be core elements in next generation flexible/wearable photovoltaic devices, namely double layer WS2 nanosheets (DLNS), graphene/WS2 (layer) composites and graphene/WS2 nanotube (NT) composites. Our results reveal that the mechanical properties of DLNS deteriorate when compared to those of monolayer WS2. Owing to graphene’s reinforcement action, the mechanical properties of graphene/WS2 (layer) composite with both layers deformed are superior than those of WS2, even though inferior than those of bare graphene. If stress is applied only to the graphene layer, the graphene/WS2 composite retains the most of the strength and toughness of monolayer graphene, decreasing the fracture strength and Young’s modulus by only 9.7% and 16.3%, respectively. Similarly, in the case of the graphene/WS2 NT composite the mechanical strength and toughness experience a reduction compared to monolayer graphene, specifically by 15% and 53% for fracture strength and Young’s modulus, respectively. Considering the market’s keen interest in nanomaterials, particularly van der Waals (vdW) ones, for flexible and wearable photovoltaic devices, the findings presented here will significantly enhance the effective utilization of vdW composites.

Extreme Thermal Insulation and Tradeoff of Thermal Transport Mechanisms between Graphene and WS2 Monolayers.

Controlling and understanding the heat flow at a nanometer scale are challenging, but important for fundamental science and applications. Two-dimensional (2D) layered materials provide perhaps the ultimate solution for meeting these challenges. While there have been reports of low thermal conductivities (several mW m-1 K-1) across the 2D heterostructures, phonon-dominant thermal transport remains strong due to the nearly-ideal contact between the layers. Here, this work experimentally explores the heat transport mechanisms by increasing the interlayer distance from perfect contact to a few nanometers and demonstrates that the phonon-dominated thermal conductivity across the WS2/graphene interface decreases further with the increasing interlayer distance until the air-dominated thermal conductivity increases again. This work finds that the resulting tradeoff of the two heat conduction mechanisms leads to the existence of a minimum thermal conductivity at 2.11nm of 1.41×10-5W m-1 K-1, which is two thousandths of the smallest value reported previously. This work provides an effective methodology for engineering thermal insulation structures and understanding heat transport at the ultimate small scales.

CO and HCHO Sensing by Single Au Atom-Decorated WS2 Monolayer for Diagnosis of Thermal Aging Faults in the Dry-Type Reactor: A First-Principles Study.

CO and HCHO are the main pyrolysis gases in long-term running dry-type reactors, and thus the diagnosis of thermal insulation faults inside such devices can be realized by sensing these gases. In this paper, a single Au atom-decorated WS2 (Au-WS2) monolayer is proposed as an original sensing material for CO or HCHO detection to evaluate the operation status of dry-type reactors. It was found that the Au atom prefers to be adsorbed at the top of the S atom of the pristine WS2 monolayer, wherein the binding force is calculated as -3.12 eV. The Au-WS2 monolayer behaves by chemisorption upon the introduction of CO and HCHO molecules, with the adsorption energies of -0.82 and -1.01 eV, respectively. The charge density difference was used to analyze the charge-transfer and bonding behaviors in the gas adsorptions, and the analysis of density of state as well as band structure indicate gas-sensing mechanisms. As calculated, the sensing responses of the Au-WS2 monolayer upon CO and HCHO molecule introduction were 58.7% and -74.4%, with recovery times of 0.01 s and 11.86 s, respectively. These findings reveal the favorable potential of the Au-WS2 monolayer to be a reusable and room-temperature sensing candidate for CO and HCHO detections. Moreover, the work function of the Au-WS2 monolayer was decreased by 13.0% after the adsorption of CO molecules, while it increased by 1.2% after the adsorption of HCHO molecules, which implies its possibility to be a work-function-based gas sensor for CO detection. This theoretical report paves the way for further investigations into WS2-based gas sensors in some other fields, and it is our hope that our findings can stimulate more reports on novel gas-sensing materials for application in evaluating the operation conditions of dry-type reactors.

Global imaging for polarization resolved second harmonic generation of WS2 monolayers

Second-harmonic generation (SHG) is a nonlinear optical effect enhanced by broken crystallin symmetry and is very sensitive to electronic structures. SHG has recently been applied to two-dimensional transition metals dichalcogenides (2D-TMDs). 2D-TMDs have been the focus of much recent research due to their ultrathin scale, high quantum confinement, and energy gap toning ability that results in unique linear or nonlinear optical and electrical properties. WS2 monolayers are well-known 2D TMDs with strong SHG. They have attracted a great deal of interest due to their potential applications in fundamental material characterization and nanophotonic device development. In this study, we grew WS2 monolayers using the chemical vapor deposition (CVD) technique and characterized them with Raman and photoluminescence (PL) spectroscopy. The intense direct excitonic peak A at 630 nm was identified in the PL spectra, while the Raman spectra exhibited the two distinctive modes A1g (at 418 cm−1) and E2g (at 356 cm−1). The monolayers were pumped by an 830 nm circularly polarized and defused pulsed laser to produce the SHG image. global one-shot SH images for different growth shapes were obtained and crystalline domains were identified using polarization-resolved second-harmonic generation imaging (PRSHGI). The defect level was observed to clearly enhance the SHG signal following the increase in broken crystalline centrosymmetric and relaxing the optical selection roles at the valley degree of freedom.