Reconfigurable MoS2 Memtransistors for Continuous Learning in Spiking Neural Networks.

Artificial intelligence and machine learning are growing computing paradigms, but current algorithms incur undesirable energy costs on conventional hardware platforms, thus motivating the exploration of more efficient neuromorphic architectures. Toward this end, we introduce here a memtransistor with gate-tunable dynamic learning behavior. By fabricating memtransistors from monolayer MoS2 grown on sapphire, the relative importance of the vertical field effect from the gate is enhanced, thereby heightening reconfigurability of the device response. Inspired by biological systems, gate pulses are used to modulate potentiation and depression, resulting in diverse learning curves and simplified spike-timing-dependent plasticity that facilitate unsupervised learning in simulated spiking neural networks. This capability also enables continuous learning, which is a previously underexplored cognitive concept in neuromorphic computing. Overall, this work demonstrates that the reconfigurability of memtransistors provides unique hardware accelerator opportunities for energy efficient artificial intelligence and machine learning.

Lateral Monolayer MoSe2 -WSe2 p-n Heterojunctions with Giant Built-In Potentials.

2D transition metal dichalcogenides (TMDs) have exhibited strong application potentials in new emerging electronics because of their atomic thin structure and excellent flexibility, which is out of field of tradition silicon technology. Similar to 3D p-n junctions, 2D p-n heterojunctions by laterally connecting TMDs with different majority charge carriers (electrons and holes), provide ideal platform for current rectifiers, light-emitting diodes, diode lasers and photovoltaic devices. Here, growth and electrical studies of atomic thin high-quality p-n heterojunctions between molybdenum diselenide (MoSe2 ) and tungsten diselenide (WSe2 ) by one-step chemical vapor deposition method are reported. These p-n heterojunctions exhibit high built-in potential (≈0.7 eV), resulting in large current rectification ratio without any gate control for diodes, and fast response time (≈6 ms) for self-powered photodetectors. The simple one-step growth and electrical studies of monolayer lateral heterojunctions open up the possibility to use TMD heterojunctions for functional devices.

Quantum plasmonic control of trions in a picocavity with monolayer WS2.

Monitoring and controlling the neutral and charged excitons (trions) in two-dimensional (2D) materials are essential for the development of high-performance devices. However, nanoscale control is challenging because of diffraction-limited spatial resolution of conventional far-field techniques. Here, we extend the classical tip-enhanced photoluminescence based on tip-substrate nanocavity to quantum regime and demonstrate controlled nano-optical imaging, namely, tip-enhanced quantum plasmonics. In addition to improving the spatial resolution, we use the scanning probe to control the optoelectronic response of monolayer WS2 by varying the neutral/charged exciton ratio via charge tunneling in Au-Ag picocavity. We observe trion "hot spots" generated by varying the picometer-scale probe-sample distance and show the effects of weak and strong coupling, which depend on the spatial location. Our experimental results are in agreement with simulations and open an unprecedented view of a new range of quantum plasmonic phenomena with 2D materials that will help to design new quantum optoelectronic devices.

Room-Temperature Magnetic Order in Air-Stable Ultrathin Iron Oxide.

Manual assembly of atomically thin materials into heterostructures with desirable electronic properties is an approach that holds great promise. Despite the rapid expansion of the family of ultrathin materials, stackable and stable ferro/ferri magnets that are functional at room temperature are still out of reach. We report the growth of air-stable, transferable ultrathin iron oxide crystals that exhibit magnetic order at room temperature. These crystals require no passivation and can be prepared by scalable and cost-effective chemical vapor deposition. We demonstrate that the bonding between iron oxide and its growth substrate is van der Waals-like, enabling us to remove the crystals from their growth substrate and prepare iron oxide/graphene heterostructures.

Monolayer MoS2 Nanoribbon Transistors Fabricated by Scanning Probe Lithography.

Monolayer MoS2 is a promising material for nanoelectronics; however, the lack of nanofabrication tools and processes has made it very challenging to realize nanometer-scale electronic devices from monolayer MoS2. Here, we demonstrate the fabrication of monolayer MoS2 nanoribbon field-effect transistors as narrow as 30 nm using scanning probe lithography (SPL). The SPL process uses a heated nanometer-scale tip to deposit narrow nanoribbon polymer structures onto monolayer MoS2. The polymer serves as an etch mask during a XeF2 vapor etch, which defines the channel of a field-effect transistor (FET). We fabricated seven devices with a channel width ranging from 30 to 370 nm, and the fabrication process was carefully studied by electronic measurements made at each process step. The nanoribbon devices have a current on/off ratio > 104 and an extrinsic field-effect mobility up to 8.53 cm2/(V s). By comparing a 30 nm wide device with a 60 nm wide device that was fabricated on the same MoS2 flake, we found the narrower device had a smaller mobility, a lower on/off ratio, and a larger subthreshold swing. To our knowledge, this is the first published work that describes a working transistor device from monolayer MoS2 with a channel width smaller than 100 nm.

Doping Nanoscale Graphene Domains Improves Magnetism in Hexagonal Boron Nitride.

Carbon doping can induce unique and interesting physical properties in hexagonal boron nitride (h-BN). Typically, isolated carbon atoms are doped into h-BN. Herein, however, the insertion of nanometer-scale graphene quantum dots (GQDs) is demonstrated as whole units into h-BN sheets to form h-CBN. The h-CBN is prepared by using GQDs as seed nucleations for the epitaxial growth of h-BN along the edges of GQDs without the assistance of metal catalysts. The resulting h-CBN sheets possess a uniform distrubution of GQDs in plane and a high porosity macroscopically. The h-CBN tends to form in small triangular sheets which suggests an enhanced crystallinity compared to the h-BN synthesized under the same conditions without GQDs. An enhanced ferromagnetism in the h-CBN emerges due to the spin polarization and charge asymmetry resulting from the high density of CN and CB bonds at the boundary between the GQDs and the h-BN domains. The saturation magnetic moment of h-CBN reaches 0.033 emu g-1 at 300 K, which is three times that of as-prepared single carbon-doped h-BN.

Surface enhanced resonant Raman scattering in hybrid MoSe2@Au nanostructures.

We report on the surface enhanced resonant Raman scattering (SERRS) in hybrid MoSe2@Au plasmonic-excitonic nanostructures, focusing on the situation where the localized surface plasmon resonance of Au nanodisks is finely tuned to the exciton absorption of monolayer MoSe2. Using a resonant excitation, we investigate the SERRS in MoSe2@Au and the resonant Raman scattering (RRS) in a MoSe2@SiO2 reference. Both optical responses are compared to the non-resonant Raman scattering signal, thus providing an estimate of the relative contributions from the localized surface plasmons and the confined excitons to the Raman scattering enhancement. We determine a SERRS/RRS enhancement factor exceeding one order of magnitude. Furthermore, using numerical simulations, we explore the optical near-field properties of the hybrid MoSe2@Au nanostructure and investigate the SERRS efficiency dependence on the nanodisk surface morphology and on the excitation wavelength. We demonstrate that a photothermal effect, due to the resonant plasmonic pumping of electron-hole pairs into the MoSe2 layer, and the surface roughness of the metallic nanostructures are the main limiting factors of the SERRS efficiency.

Author Correction: Ultrafast probes of electron-hole transitions between two atomic layers.

The original version of this Article omitted an affiliation of Xiewen Wen: 'College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing 100871, China'. This has been corrected in both the PDF and HTML versions of the Article.

Ultrafast probes of electron-hole transitions between two atomic layers.

Phase transitions of electron-hole pairs on semiconductor/conductor interfaces determine fundamental properties of optoelectronics. To investigate interfacial dynamical transitions of charged quasiparticles, however, remains a grand challenge. By employing ultrafast mid-infrared microspectroscopic probes to detect excitonic internal quantum transitions and two-dimensional atomic device fabrications, we are able to directly monitor the interplay between free carriers and insulating interlayer excitons between two atomic layers. Our observations reveal unexpected ultrafast formation of tightly bound interlayer excitons between conducting graphene and semiconducting MoSe2. The result suggests carriers in the doped graphene are no longer massless, and an effective mass as small as one percent of free electron mass is sufficient to confine carriers within a 2D hetero space with energy 10 times larger than the room-temperature thermal energy. The interlayer excitons arise within 1 ps. Their formation effectively blocks charge recombination and improves charge separation efficiency for more than one order of magnitude.

Direct Assessment of the Toxicity of Molybdenum Disulfide Atomically Thin Film and Microparticles via Cytotoxicity and Patch Testing.

The low toxicity of molybdenum disulfide (MoS2 ) atomically thin film and microparticles is confirmed via cytotoxicity and patch testing in this report. The toxicity of MoS2 thin film and microparticles is extensively studied but is still inconclusive due to potential organic contamination in the preparations of samples. Such contamination is avoided here through preparing MoS2 atomically thin film via direct sulfurization of molybdenum thin film on quartz plate, which permits a direct assessment of its toxicity without any contamination. Six different types of cells, including normal, cancer, and immortal cells, are cultured in the media containing MoS2 thin film on quartz plates or dispersed MoS2 microparticles and their viability is evaluated with respect to the concentrations of samples. Detached thin films from the quartz plates are also investigated to estimate the toxicity of dispersed MoS2 in biological media. Allergy testing on skin of guinea pigs is also conducted to understand their effect on animal skins. By avoiding possible organic contamination, the low toxicity of MoS2 atomically thin film and microparticles to cells and animal skins paves the way for its applications in flexible biosensing/bioimaging devices and biocompatible coatings.

Unveiling Active Sites for the Hydrogen Evolution Reaction on Monolayer MoS2.

Here, the hydrogen evolution reaction (HER) activities at the edge and basal-plane sites of monolayer molybdenum disulfide (MoS2 ) synthesized by chemical vapor deposition (CVD) are studied using a local probe method enabled by selected-area lithography. Reaction windows are opened by e-beam lithography at sites of interest on poly(methyl methacrylate) (PMMA)-covered monolayer MoS2 triangles. The HER properties of MoS2 edge sites are obtained by subtraction of the activity of the basal-plane sites from results containing both basal-plane and edge sites. The catalytic performances in terms of turnover frequencies (TOFs) are calculated based on the estimated number of active sites on the selected areas. The TOFs follow a descending order of 3.8 ± 1.6, 1.6 ± 1.2, 0.008 ± 0.002, and 1.9 ± 0.8 × 10-4 s-1 , found for 1T'-, 2H-MoS2 edges, and 1T'-, 2H-MoS2 basal planes, respectively. Edge sites of both 2H- and 1T'-MoS2 are proved to have comparable activities to platinum (≈1-10 s-1 ). When fitted into the HER volcano plot, the MoS2 active sites follow a trend distinct from conventional metals, implying a possible difference in the reaction mechanism between transition-metal dichalcogenides (TMDs) and metal catalysts.

Ultrafast formation of interlayer hot excitons in atomically thin MoS2/WS2 heterostructures.

Van der Waals heterostructures composed of two-dimensional transition-metal dichalcogenides layers have recently emerged as a new family of materials, with great potential for atomically thin opto-electronic and photovoltaic applications. It is puzzling, however, that the photocurrent is yielded so efficiently in these structures, despite the apparent momentum mismatch between the intralayer/interlayer excitons during the charge transfer, as well as the tightly bound nature of the excitons in 2D geometry. Using the energy-state-resolved ultrafast visible/infrared microspectroscopy, we herein obtain unambiguous experimental evidence of the charge transfer intermediate state with excess energy, during the transition from an intralayer exciton to an interlayer exciton at the interface of a WS2/MoS2 heterostructure, and free carriers moving across the interface much faster than recombining into the intralayer excitons. The observations therefore explain how the remarkable charge transfer rate and photocurrent generation are achieved even with the aforementioned momentum mismatch and excitonic localization in 2D heterostructures and devices.

Thickness-Dependent and Magnetic-Field-Driven Suppression of Antiferromagnetic Order in Thin V5S8 Single Crystals.

With materials approaching the 2D limit yielding many exciting systems with intriguing physical properties and promising technological functionalities, understanding and engineering magnetic order in nanoscale, layered materials is generating keen interest. One such material is V5S8, a metal with an antiferromagnetic ground state below the Néel temperature TN ∼ 32 K and a prominent spin-flop signature in the magnetoresistance (MR) when H∥c ∼ 4.2 T. Here we study nanoscale-thickness single crystals of V5S8, focusing on temperatures close to TN and the evolution of material properties in response to systematic reduction in crystal thickness. Transport measurements just below TN reveal magnetic hysteresis that we ascribe to a metamagnetic transition, the first-order magnetic-field-driven breakdown of the ordered state. The reduction of crystal thickness to ∼10 nm coincides with systematic changes in the magnetic response: TN falls, implying that antiferromagnetism is suppressed; and while the spin-flop signature remains, the hysteresis disappears, implying that the metamagnetic transition becomes second order as the thickness approaches the 2D limit. This work demonstrates that single crystals of magnetic materials with nanometer thicknesses are promising systems for future studies of magnetism in reduced dimensionality and quantum phase transitions.

Metal diselenide nanoparticles as highly active and stable electrocatalysts for the hydrogen evolution reaction.

In this communication, nickel diselenide (NiSe2) nanoparticles are synthesized by a facile and low-cost hydrothermal method. The synthesis method can be extended to other metal diselenides as well. The electrode made of NiSe2 exhibits superior electrocatalytic activity in the hydrogen evolution reaction (HER). A low Tafel slope of 31.1 mV per decade is achieved for NiSe2, which is comparable to that of platinum (∼30 mV per decade). Moreover, the catalytic activity of NiSe2 is very stable and no obvious degradation is found even after 1000 cyclic voltammetric sweeps.

Facile Synthesis of Single Crystal Vanadium Disulfide Nanosheets by Chemical Vapor Deposition for Efficient Hydrogen Evolution Reaction.

A facile chemical vapor deposition method to prepare single-crystalline VS2 nanosheets for the hydrogen evolution reaction is reported. The electrocatalytic hydrogen evolution reaction (HER) activities of VS2 show an extremely low overpotential of -68 mV at 10 mA cm(-2), small Tafel slopes of ≈34 mV decade(-1), as well as high stability, demonstrating its potential as a candidate non-noble-metal catalyst for the HER.

Photoluminescence quenching and charge transfer in artificial heterostacks of monolayer transition metal dichalcogenides and few-layer black phosphorus.

Transition metal dichalcogenides monolayers and black phosphorus thin crystals are emerging two-dimensional materials that demonstrated extraordinary optoelectronic properties. Exotic properties and physics may arise when atomic layers of different materials are stacked together to form van der Waals solids. Understanding the important interlayer couplings in such heterostructures could provide avenues for control and creation of characteristics in these artificial stacks. Here we systematically investigate the optical and optoelectronic properties of artificial stacks of molybdenum disulfide, tungsten disulfide, and black phosphorus atomic layers. An anomalous photoluminescence quenching was observed in tungsten disulfide-molybdenum disulfide stacks. This was attributed to a direct to indirect band gap transition of tungsten disulfide in such stacks while molybdenum disulfide maintains its monolayer properties by first-principles calculations. On the other hand, due to the strong build-in electric fields in tungsten disulfide-black phosphorus or molybdenum disulfide-black phosphorus stacks, the excitons can be efficiently splitted despite both the component layers having a direct band gap in these stacks. We further examine optoelectronic properties of tungsten disulfide-molybdenum disulfide artificial stacks and demonstrate their great potentials in future optoelectronic applications.

Synthesis and defect investigation of two-dimensional molybdenum disulfide atomic layers.

CONSPECTUS: The unique physical properties of two-dimensional (2D) molybdenum disulfide (MoS2) and its promising applications in future optoelectronics have motivated an extensive study of its physical properties. However, a major limiting factor in investigation of 2D MoS2 is its large area and high quality preparation. The existence of various types of defects in MoS2 also makes the characterization of defect types and the understanding of their roles in the physical properties of this material of critical importance. In this Account, we review the progress in the development of synthetic approaches for preparation of 2D MoS2 and the understanding of the role of defects in its electronic and optical properties. We first examine our research efforts in understanding exfoliation, direct sulfurization, and chemical vapor deposition (CVD) of MoS2 monolayers as main approaches for preparation of such atomic layers. Recognizing that a natural consequence of the synthetic approaches is the addition of sources of defects, we initially focus on identifying these imperfections with intrinsic and extrinsic origins in CVD MoS2. We reveal the predominant types of point and grain boundary defects in the crystal structure of polycrystalline MoS2 using transmission electron microscopy (TEM) and understand how they modify the electronic band structure of this material using first-principles-calculations. Our observations and calculations reveal the main types of vacancy defects, substitutional defects, and dislocation cores at the grain boundaries (GBs) of MoS2. Since the sources of defects in two-dimensional atomic layers can, in principle, be controlled and studied with more precision compared with their bulk counterparts, understanding their roles in the physical properties of this material may provide opportunities for changing their properties. Therefore, we next examine the general electronic properties of single-crystalline 2D MoS2 and study the role of GBs in the electrical transport and photoluminescence properties of its polycrystalline counterparts. These results reveal the important role played by point defects and GBs in affecting charge carrier mobility and excitonic properties of these atomic layers. In addition to the intrinsic defects, growth process induced substrate impurities and strain induced band structure perturbations are revealed as major sources of disorder in CVD grown 2D MoS2. We further explore substrate defects for modification and control of electronic and optical properties of 2D MoS2 through interface engineering. Self-assembled monolayer based interface modification, as a versatile technique adaptable to different conventional and flexible substrates, is used to promote significant tunability in the key MoS2 field-effect device parameters. This approach provides a powerful tool for modification of native substrate defect characteristics and allows for a wide range of property modulations. Our results signify the role of intrinsic and extrinsic defects in the physical properties of MoS2 and unveil strategies that can utilize these characteristics.