Unveiling Spatiotemporal Diffusion of Hot Carriers Influenced by Spatial Nonuniform Hot Phonon Bottleneck Effect in Monolayer MoS2.

The exceptional semiconducting properties of two-dimensional (2D) transition metal dichalcogenides (TMDs) have made them highly promising for the development of future electronic and optoelectronic devices. Extensive studies of TMDs are partly associated with their ability to generate 2D-confined hot carriers above the conduction band edges, enabling potential applications that rely on such transient excited states. In this work, room-temperature spatiotemporal hot carrier dynamics in monolayer MoS2 is studied by transient absorption microscopy (TAM), featuring an initial ultrafast expansion followed by a rapid negative diffusion, and ultimately a slow long-term expansion of the band edge C-excitons. We provide direct experimental evidence to identify the abnormal negative diffusion process as a spatial contraction of the hot carriers resulting from spatial variation in the hot phonon bottleneck effect due to the Gaussian intensity distribution of the pump laser beam.

Adsorption and dissociation of hydrogen molecules over S-vacancies in a Nb-doped MoS2monolayer.

Motivated by the recent interest in the hydrogen energy, we have carried out a complete study of the catalytic activity of a defective molybdenum disulfide monolayer (MoS2) by means of density functional theory (DFT) calculations. The MoS2monolayer is characterized by a nonreactive basal plane. In principle, its catalytic activity is concentrated at the edges, but an alternative way to increase such activity is obtained by creating active sites where the molecules can dissociate. These defects can be easily produced experimentally by different techniques. In our study, we have performed an atomic, energetic and electronic analysis of a hydrogen molecule adsorbed on a MoS2monolayer. In a first step, we have found that the H2molecule remains physisorbed over both doped-free and Nb-doped MoS2monolayers, showing that the Nb atom does not increase the poor reactivity of the clean MoS2layer. Interestingly, our energetic results suggest that the vacancies will prefer to be formed close to the Nb atoms in the doped monolayer, but the small energy difference would allow the formation in non-doped like sites. Theoretically, we found out the conditions for the molecular dissociation on a S vacancy. In both cases, with and without Nb, the molecule should rotate from the original perpendicular position to an almost parallel orientation jumping an energetic barrier. After that, the atoms are separated binding to the Mo atoms around the missing S atom. Ourab initiomolecular dynamics simulations show that for low pressure conditions (using one single molecule in the system) the H2prefers to desorb from the vacancy, while for larger pressures (when additional H2molecules are added to the system) the molecule is finally dissociated on the vacancy. Our long simulations confirm the great stability of the structure with the two H atoms binding to the Mo atoms close to the vacancy. Finally, the inclusion of a third (or a fourth) H atom in the vacancy leads to the formation and desorption of a H2molecule, leaving one (or two) atoms in the vacancy.

Exciton Lifetime and Optical Line Width Profile via Exciton-Phonon Interactions: Theory and First-Principles Calculations for Monolayer MoS2.

Exciton dynamics dictates the evolution of photoexcited carriers in photovoltaic and optoelectronic devices. However, interpreting their experimental signatures is a challenging theoretical problem due to the presence of both electron-phonon and many-electron interactions. We develop and apply here a first-principles approach to exciton dynamics resulting from exciton-phonon coupling in monolayer MoS2 and reveal the highly selective nature of exciton-phonon coupling due to the internal spin structure of excitons, which leads to a surprisingly long lifetime of the lowest-energy bright A exciton. Moreover, we show that optical absorption processes rigorously require a second-order perturbation theory approach, with photon and phonon treated on an equal footing, as proposed by Toyozawa and Hopfield. Such a treatment, thus far neglected in first-principles studies, gives rise to off-diagonal exciton-phonon self-energy, which is critical for the description of dephasing mechanisms and yields exciton line widths in excellent agreement with experiment.

Piezo-Activated Atomic-Thin Molybdenum Disulfide/MXene Nanoenzyme for Integrated and Efficient Tumor Therapy via Ultrasound-Triggered Schottky Electric Field.

Monolayer molybdenum disulfide (MoS2 ) nanoenzymes exhibit a piezoelectric polarization, which generates reactive oxygen species to inactivate tumors under ultrasonic strain. However, its therapeutic efficiency is far away from satisfactory, due to stackable MoS2 , quenching of piezo-generated charges, and monotherapy. Herein, chitosan-exfoliated monolayer MoS2 (Ch-MS) is composited with atomic-thin MXene, Ti3 C2 (TC), to self-assemble a multimodal nanoplatform, Ti3 C2 -Chitosan-MoS2 (TC@Ch-MS), for tumor inactivation. TC@Ch-MS not only inherits piezoelectricity from monolayer MoS2 , but also maintains remarkable stability. Intrinsic metallic MXene combines with MoS2 to construct an interfacial Schottky heterojunction, facilitating the separation of electron-hole pairs and endowing TC@Ch-MS increase-sensitivity magnetic resonance imaging responding. Schottky interface also leads to peroxidase mimetics with excellent catalytic performance toward H2 O2 in the tumor microenvironment under mechanical vibration. TC@Ch-MS possesses the superior photothermal conversion efficiency than pristine TC under near-infrared ray illumination, attributed to its enhanced interlaminar conductivity. Meanwhile, TC@Ch-MS realizes optimized efficiency on tumor apoptosis with immunotherapy. Therefore, TC@Ch-MS achieves an integrated diagnosis and multimodal treatment nanoplatform, whereas the toxicity to normal tissue cells is negligible. This work may shed fresh light on optimizing the piezoelectric materials in biological applications, and also give prominence to the significance of intrinsic metallicity in MXene.

Resistive switching mechanism of MoS2based atomristor.

The non-volatile resistive switching process of a MoS2based atomristor with a vertical structure is investigated by first-principles calculations. It is found that the monolayer MoS2with a S vacancy defect (VS) could maintain an insulation characteristic and a high resistance state (HRS) is remained. As an electrode metal atom is adsorbed on the MoS2monolayer, the semi-conductive filament is formed with the assistance ofVS. Under this condition, the atomristor presents a low resistance state (LRS). The ON state current of this semi-filament is increased close to two orders of magnitude larger than that without the filament. The energy barrier for an Au-atom to penetrate the monolayer MoS2viaVSis as high as 6.991 eV. When it comes to a double S vacancy (VS2), the energy barrier is still amounted to 3.554 eV, which manifests the bridge-like full conductive filament cannot form in monolayer MoS2based atomristor. The investigation here promotes the atomic level understanding of the resistive switching properties about the monolayer MoS2based memristor. The physics behind should also work in atomristors based on other monolayer transition-metal dichalcogenides, like WSe2and MoTe2. The investigation will be a reference for atomristor-device design or optimization.

Electrical performance of monolayer MoS2transistor with MoS2nanobelt metallic edges as electrodes.

The contact electrodes have great influence on the performance of monolayer MoS2devices. In this paper, monolayer MoS2and MoS2nanobelts were synthesized on SiO2/Si substrates via the chemical vapor deposition method. By using wet and dry transfer process, MoS2nanobelt metallic edges were designed as the source/drain contact electrodes of monolayer MoS2field effect transistor. The 'nanobelt metallic edges' refers to the top surface of the nanobelt being metallic. Because the base planes of MoS2nanobelt vertically stand on the substrate, which makes the layer edges form the top surface of the nanobelt. The nonlinearIds-Vdscharacteristics of the device indicates that the contact between the monolayer MoS2and MoS2metallic edges displays a Schottky-like behavior. The back-gated transfer characteristics indicate that monolayer MoS2device with MoS2nanobelt metallic edges as electrodes shows an n-type behavior with a mobility of ∼0.44 cm2V-1·s-1, a carrier concentration of ∼7.31 × 1011cm-2, and an on/off ratio of ∼103. The results enrich the electrode materials of two-dimensional material devices and exhibit potential for future application of MoS2metallic edges in electronic devices.

A modified CVD method for the synthesis of monolayer MoS2and photoelectric improvement by HfO2passivation.

Molybdenum disulfide (MoS2) is an emerging class of new materials with a wide range of potential practical applications. However, the uncontrollability of monolayer MoS2synthesized by traditional chemical vapor deposition method and the low responsivity of MoS2photodetectors limit its further development in the field of photoelectric detection. To achieve controlled growth of monolayer MoS2and construct MoS2photodetectors with a high responsivity, we propose a novel single crystal growth strategy of high-quality MoS2by controlling the Mo to S vapor ratio near the substrate, and deposit a layer of hafnium oxide (HfO2) on the surface of MoS2to enhance the performance of the pristine metal-semiconductor-metal structure photodetector. At a reverse bias of 8 V, the HfO2passivated MoS2photodetector features an extremely high responsivity of1201AW-1,a response time of around 0.5 s, and a detectivity of7.7×1011Jones.Meanwhile, we deeply investigate the effect of the HfO2layer on the performance of the fabricated MoS2photodetector and propose a physical mechanism to interpret the obtained experiment results. These results might facilitate a better understanding on the performance modulation of the MoS2photodetectors and accelerate the development of MoS2-based optoelectronic devices.

Large-Scale Ultrafast Strain Engineering of CVD-Grown Two-Dimensional Materials on Strain Self-Limited Deformable Nanostructures toward Enhanced Field-Effect Transistors.

Strain engineering of 2D materials is capable of tuning the electrical and optical properties of the materials without introducing additional atoms. Here, a method for large-scale ultrafast strain engineering of CVD-grown 2D materials is proposed. Locally nonuniform strains are introduced through the cooperative deformation of materials and metal@metal oxide nanoparticles through cold laser shock. The tensile strain of MoS2 changes and the band gap decreases after laser shock. The mechanism of the ultrafast straining is investigated by MD simulations. MoS2 FETs were fabricated, and the field-effect mobility of devices could be increased from 1.9 to 44.5 cm2 V-1 s-1 by adjusting the strain level of MoS2. This is currently the maximum value of MoS2 FETs grown by CVD with SiO2 as the dielectric. As a large-scale and ultrafast manufacturing method, laser shock provides a universal strategy for large-scale adjustment of 2D material strain, which will help to promote the manufacturing of 2D nanoelectronic devices.

Affinities and Kinetics Detection of Protein-Small Molecule Interactions with a Monolayer MoS2 -Based Optical Imaging Platform.

Quantifying the binding kinetics and affinities of protein-small molecule interactions is critical for biomarker validation, drug discovery, and deep understanding of various biological processes at the molecular-scale. Novel approaches are demanded as most common label-free techniques are mass-sensitive, which are not suitable for the detection of small molecule interactions. Here, an optical imaging platform is developed to measure the binding kinetics of both protein-small molecules and protein-ions based on monolayer MoS2 , an ultra-thin 2D material whose optical absorption is extremely sensitive to charge. A model is established to calibrate the optical response due to the charged analyte binding and it is applied to quantify the interactions between abl1 kinase and different small-molecule inhibitors. Such a presented method is capable of distinguishing different inhibitors binding to a wild or mutated kinase, which provides guidance for drug evaluation and drug mechanism exploration. The binding kinetics of calcium ions to calmodulin is also measured, further broadening the application field of the method. In addition, the imaging capability allows mapping the local binding kinetics of the molecular interactions with a high resolution, which reveals visible spatial variability and offers a promising tool for studying heterogeneous local interfacial interactions.

In Situ Atomic-Scale Observation of Monolayer MoS2 Devices under High-Voltage Biasing via Transmission Electron Microscopy.

2D materials have great potential for not only device scaling but also various applications. To prompt the development of 2D electronics and optoelectronics, a better understanding of the limitation of materials is essential. Material failure caused by bias can lead to variations in device behavior and even electrical breakdown. In this study, the structural evolution of monolayer MoS2 with high bias is revealed via in situ transmission electron microscopy at the atomic scale. The biasing process is recorded and studied with the aid of aberration-corrected scanning transmission electron microscopy. The effects of electron beam irradiation and biasing are also discussed through the combination of experiments and theory. It is found that the Mo nanoclusters result from disintegration of MoS2 and sulfur depletion, which are induced by Joule heating. The thermal stress can also damage the MoS2 layer and form long cracks in both in situ and ex situ biasing cases. Investigation of the results obtained with different applied voltages helps to further verify the mechanism of evolution and provide a comprehensive study of the function of biasing.

Improving the photoresponse performance of monolayer MoS2photodetector via local flexoelectric effect.

Strain engineering is an effective means of modulating the optical and electrical properties of two-dimensional materials. The flexoelectric effect caused by inhomogeneous strain exists in most dielectric materials, which breaks the limit of the materials' non-centrosymmetric structure for piezoelectric effect. However, there is a lack of understanding of the impact on optoelectronic behaviour of monolayer MoS2photodetector via local flexoelectric effect triggered by biaxial strain. In this paper, we develop a probe tip (Pt)-MoS2-Au asymmetric Schottky barrier photodetector based on conductive atomic force microscopy to investigate the impact of flexoelectric effect on the photoresponse performance. Consequently, when the probe force increases from 24 nN to 720 nN, the photocurrent, responsivity and detectivity increase 28.5 times, 29.6 times and 5.3 times at forward bias under 365 nm light illumination, respectively. These results indicate that local flexoelectric effect plays a critical role to improve the photoresponse performance of photodetector. Our approach suggests a new route to improve the performance of photodetectors by introducing local flexoelectric polarization field, offering the potential for the application of strain modulated photoelectric devices.

Additive manufacturing of patterned 2D semiconductor through recyclable masked growth.

The 2D van der Waals crystals have shown great promise as potential future electronic materials due to their atomically thin and smooth nature, highly tailorable electronic structure, and mass production compatibility through chemical synthesis. Electronic devices, such as field effect transistors (FETs), from these materials require patterning and fabrication into desired structures. Specifically, the scale up and future development of "2D"-based electronics will inevitably require large numbers of fabrication steps in the patterning of 2D semiconductors, such as transition metal dichalcogenides (TMDs). This is currently carried out via multiple steps of lithography, etching, and transfer. As 2D devices become more complex (e.g., numerous 2D materials, more layers, specific shapes, etc.), the patterning steps can become economically costly and time consuming. Here, we developed a method to directly synthesize a 2D semiconductor, monolayer molybdenum disulfide (MoS2), in arbitrary patterns on insulating SiO2/Si via seed-promoted chemical vapor deposition (CVD) and substrate engineering. This method shows the potential of using the prepatterned substrates as a master template for the repeated growth of monolayer MoS2 patterns. Our technique currently produces arbitrary monolayer MoS2 patterns at a spatial resolution of 2 µm with excellent homogeneity and transistor performance (room temperature electron mobility of 30 cm2 V-1 s-1 and on-off current ratio of 107). Extending this patterning method to other 2D materials can provide a facile method for the repeatable direct synthesis of 2D materials for future electronics and optoelectronics.

High-responsivity photodetector based on scrolling monolayer MoS2hybridized with carbon quantum dots.

The monolayer MoS2based photodetectors have been widely investigated, which show limited photoelectric performances due to its low light absorption and uncontrollable adsorbates. In this paper, we present a MoS2-based hybrid nanoscrolls device, in which one-dimensional nanoscrollsof MoS2is hybridized with carbon quantum dots (CQDs). This device architecture effectively enhanced the photodetection performance. The photoresponsivity and detectivity values of MoS2/CQDs-NS photodetectors are respectively 1793 A W-1and 5.97 × 1012Jones, which are 830-fold and 268-fold higher than those of pristine MoS2under 300 nm illumination atVds = 5 V. This research indicates a significant progress in fabricating high-performance MoS2photodetectors.

Adsorption of atomic hydrogen on monolayer MoS2.

The adsorption of atomic hydrogen on monolayer MoS2has been intensively studied, but the ground-state adsorption configuration remains controversial. In this study, we investigate the adsorption properties of atomic hydrogen on monolayer MoS2systematically using first-principles density functional theory calculations. We considered all the previously proposed adsorption sites, S-top, bridge, and hollow sites. Among them, S-top is the most energetically preferred, with a tilted S-H bond. Its calculated adsorption energy is -0.72 eV. The next lowest-energy configuration is that the H atom is located at the hollow site; the adsorption energy is slightly higher than the former, by 0.22 eV. The tilting of the S-H bond contributes to the adsorption energy up to -0.29 eV, a factor unrecognized in previous first-principles studies. These results account for the discrepancy in theory. Besides, the effects of spin-polarization also change the relative energetics of possible adsorption configurations.

Many-particle induced band renormalization processes in few- and mono-layer MoS2.

Band renormalization effects play a significant role for two-dimensional (2D) materials in designing a device structure and customizing their optoelectronic performance. However, the intrinsic physical mechanism about the influence of these effects cannot be revealed by general steady-state studies. Here, band renormalization effects in organic superacid treated monolayer MoS2, untreated monolayer MoS2and few-layer MoS2are quantitatively analyzed by using broadband femtosecond transient absorption spectroscopy. In comparison with the untreated monolayer, organic superacid treated monolayer MoS2maintains a direct bandgap structure with two thirds of carriers populated at K valley, even when the initial exciton density is as high as 2.05 × 1014cm-2(under 400 nm excitations). While for untreated monolayer and few-layer MoS2, many-particle induced band renormalizations lead to a stronger imbalance for the carrier population between K and Q valleys inkspace, and the former experiences a direct-to-indirect bandgap transition when the initial exciton density exceeds 5.0 × 1013cm-2(under 400 nm excitations). Those many-particle induced band renormalization processes further suggest a band-structure-controlling method in practical 2D devices.

A Critical Review on Enhancement of Photocatalytic Hydrogen Production by Molybdenum Disulfide: From Growth to Interfacial Activities.

Ultrathin 2D molybdenum disulfide (MoS2 ), which is the flagship of 2D transition-metal dichalcogenide nanomaterials, has drawn much attention in the last few years. 2D MoS2 has been banked as an alternative to platinum for highly active hydrogen evolution reaction because of its low cost, high surface-to-volume ratio, and abundant active sites. However, when MoS2 is used directly as a photocatalyst, contrary to public expectation, it still performs poorly due to lateral size, high recombination ratio of excitons, and low optical cross section. Besides, simply compositing MoS2 as a cocatalyst with other semiconductors cannot satisfy the practical application, which stimulates the pursual of a comprehensive insight into recent advances in synthesis, properties, and enhanced hydrogen production of MoS2 . Therefore, in this Review, emphasis is given to synthetic methods, phase transitions, tunable optical properties, and interfacial engineering of 2D MoS2 . Abundant ways of band edge tuning, structural modification, and phase transition are addressed, which can generate the neoteric photocatalytic systems. Finally, the main challenges and opportunities with respect to MoS2 being a cocatalyst and coherent light-matter interaction of MoS2 in photocatalytic systems are proposed.

Photonic Potentiation and Electric Habituation in Ultrathin Memristive Synapses Based on Monolayer MoS2.

Monolayer of 2D transition metal dichalcogenides, with a thickness of less than 1 nm, paves a feasible path to the development of ultrathin memristive synapses, to fulfill the requirements for constructing large-scale high density 3D stacking neuromorphic chips. Herein, memristive devices based on monolayer n-MoS2 on p-Si substrate with a large self-rectification ratio, exhibiting photonic potentiation and electric habituation, are successfully fabricated. Versatile synaptic neuromorphic functions, such as potentiation/habituation, short-term/long-term plasticity, and paired-pulse facilitation, are successfully mimicked based on the inherent persistent photoconductivity performance and the volatile resistive switching behavior. These findings demonstrate the potential applications of ultrathin transition metal dichalcogenides for memristive synapses. These memristive synapses with the combination of photonic and electric neuromorphic functions have prospective in the applications of synthetic retinas and optoelectronic interfaces for integrated photonic circuits based on mixed-mode electro-optical operation.

Low-Temperature Ohmic Contact to Monolayer MoS2 by van der Waals Bonded Co/h-BN Electrodes.

Monolayer MoS2, among many other transition metal dichalcogenides, holds great promise for future applications in nanoelectronics and optoelectronics due to its ultrathin nature, flexibility, sizable band gap, and unique spin-valley coupled physics. However, careful study of these properties at low temperature has been hindered by an inability to achieve low-temperature Ohmic contacts to monolayer MoS2, particularly at low carrier densities. In this work, we report a new contact scheme that utilizes cobalt (Co) with a monolayer of hexagonal boron nitride (h-BN) that has the following two functions: modifies the work function of Co and acts as a tunneling barrier. We measure a flat-band Schottky barrier of 16 meV, which makes thin tunnel barriers upon doping the channels, and thus achieve low-T contact resistance of 3 kΩ.µm at a carrier density of 5.3 × 1012/cm2. This further allows us to observe Shubnikov-de Haas oscillations in monolayer MoS2 at much lower carrier densities compared to previous work.

Precisely Aligned Monolayer MoS2 Epitaxially Grown on h-BN basal Plane.

Control of the precise lattice alignment of monolayer molybdenum disulfide (MoS2 ) on hexagonal boron nitride (h-BN) is important for both fundamental and applied studies of this heterostructure but remains elusive. The growth of precisely aligned MoS2 domains on the basal plane of h-BN by a low-pressure chemical vapor deposition technique is reported. Only relative rotation angles of 0° or 60° between MoS2 and h-BN basal plane are present. Domains with same orientation stitch and form single-crystal, domains with different orientations stitch and from mirror grain boundaries. In this way, the grain boundary is minimized and a continuous film stitched by these two types of domains with only mirror grain boundaries is obtained. This growth strategy is also applicable to other 2D materials growth.

Defects Engineered Monolayer MoS2 for Improved Hydrogen Evolution Reaction.

MoS2 is a promising and low-cost material for electrochemical hydrogen production due to its high activity and stability during the reaction. However, the efficiency of hydrogen production is limited by the amount of active sites, for example, edges, in MoS2. Here, we demonstrate that oxygen plasma exposure and hydrogen treatment on pristine monolayer MoS2 could introduce more active sites via the formation of defects within the monolayer, leading to a high density of exposed edges and a significant improvement of the hydrogen evolution activity. These as-fabricated defects are characterized at the scale from macroscopic continuum to discrete atoms. Our work represents a facile method to increase the hydrogen production in electrochemical reaction of MoS2 via defect engineering, and helps to understand the catalytic properties of MoS2.