Spin-valley Rashba monolayer laser.

Direct-bandgap transition metal dichalcogenide monolayers are appealing candidates to construct atomic-scale spin-optical light sources owing to their valley-contrasting optical selection rules. Here we report on a spin-optical monolayer laser by incorporating a WS2 monolayer into a heterostructure microcavity supporting high-Q photonic spin-valley resonances. Inspired by the creation of valley pseudo-spins in monolayers, the spin-valley modes are generated from a photonic Rashba-type spin splitting of a bound state in the continuum, which gives rise to opposite spin-polarized ±K valleys due to emergent photonic spin-orbit interaction under inversion symmetry breaking. The Rashba monolayer laser shows intrinsic spin polarizations, high spatial and temporal coherence, and inherent symmetry-enabled robustness features, enabling valley coherence in the WS2 monolayer upon arbitrary pump polarizations at room temperature. Our monolayer-integrated spin-valley microcavities open avenues for further classical and non-classical coherent spin-optical light sources exploring both electron and photon spins.

Mesoscale imperfections in MoS2 atomic layers grown by a vapor transport technique.

The success of isolating small flakes of atomically thin layers through mechanical exfoliation has triggered enormous research interest in graphene and other two-dimensional materials. For device applications, however, controlled large-area synthesis of highly crystalline monolayers with a low density of electronically active defects is imperative. Here, we demonstrate the electrical imaging of dendritic ad-layers and grain boundaries in monolayer molybdenum disulfide (MoS2) grown by a vapor transport technique using microwave impedance microscopy. The micrometer-sized precipitates in our films, which appear as a second layer of MoS2 in conventional height and optical measurements, show ∼ 2 orders of magnitude higher conductivity than that of the single layer. The zigzag grain boundaries, on the other hand, are shown to be more resistive than the crystalline grains, consistent with previous studies. Our ability to map the local electrical properties in a rapid and nondestructive manner is highly desirable for optimizing the growth process of large-scale MoS2 atomic layers.

Engineering the Performance and Stability of Molybdenum Disulfide for Heavy Metal Removal.

Molybdenum disulfide (MoS2) has recently emerged as one of the most promising water nano-based adsorbent materials for heavy metal removal with the potential to provide an alternative to conventional water decontamination technologies. In this study, we demonstrate the trade-off between mercuric removal capacity and overall MoS2 adsorbent stability, both driven by MoS2 synthesis parameters. A bottom-up hydrothermal synthesis setup at various growth temperatures was employed to grow flower-like MoS2 films onto planar alumina supports. A thorough material characterization suggests that an increase in growth temperature from 150 to 210 °C results in higher MoS2 crystallinity. Interestingly, elevated growth temperatures resulted in poor mercuric removal (525 mg g-1, K = 2.2 × 10-3 h-1), yet showed enhanced chemical stability (i.e., minimal molybdenum leaching during exposure to mercury). On the other hand, low growth temperatures produce amorphous supported MoS2, exhibiting superb mercuric removal capabilities (5158 mg g-1, K = 36.1 × 10-3 h-1) but displaying poor stability, resulting in substantial byproduct molybdate leaching. Mercuric removal by crystalline MoS2 was accomplished by adsorption and electrostatic attraction-based removal mechanisms, whereas redox reactions and HgS crystallization-based removal mechanisms were more dominant when using amorphous MoS2 for mercury removal. Overall, our study provides essential insights into the delicate balance between MoS2 mercuric removal capabilities and MoS2 degradation, both related to material synthesis growth conditions. Employment of nano-enabled water treatments in general, and MoS2 for heavy metal removal in particular, requires us to better understand these important fundamental trade-off behaviors to achieve sustainable, effective, and responsible implementation of nanotechnologies in large scale systems.

Edge-Based Two-Dimensional α-In2Se3-MoS2 Ferroelectric Field Effect Device.

Heterostructures based on two-dimensional materials offer the possibility to achieve synergistic functionalities, which otherwise remain secluded by their individual counterparts. Herein, ferroelectric polarization switching in α-In2Se3 has been utilized to engineer multilevel nonvolatile conduction states in a partially overlapping α-In2Se3-MoS2-based ferroelectric semiconducting field effect device. In particular, we demonstrate how the intercoupled ferroelectric nature of α-In2Se3 allows to nonvolatilely switch between n-i and n-i-n type junction configurations based on a novel edge state actuation mechanism, paving the way for subnanometric scale nonvolatile device miniaturization. Furthermore, the induced asymmetric polarization enables enhanced photogenerated carriers' separation, resulting in an extremely high photoresponse of ∼1275 A/W in the visible range and strong nonvolatile modulation of the bright A- and B- excitonic emission channels in the overlaying MoS2 monolayer. Our results show significant potential to harness the switchable polarization in partially overlapping α-In2Se3-MoS2 based FeFETs to engineer multimodal, nonvolatile nanoscale electronic and optoelectronic devices.

Tungsten Oxide Mediated Quasi-van der Waals Epitaxy of WS2 on Sapphire.

Conventional epitaxy plays a crucial role in current state-of-the art semiconductor technology, as it provides a path for accurate control at the atomic scale of thin films and nanostructures, to be used as the building blocks in nanoelectronics, optoelectronics, sensors, etc. Four decades ago, the terms "van der Waals" (vdW) and "quasi-vdW (Q-vdW) epitaxy" were coined to explain the oriented growth of vdW layers on 2D and 3D substrates, respectively. The major difference with conventional epitaxy is the weaker interaction between the epi-layer and the epi-substrates. Indeed, research on Q-vdW epitaxial growth of transition metal dichalcogenides (TMDCs) has been intense, with oriented growth of atomically thin semiconductors on sapphire being one of the most studied systems. Nonetheless, there are some striking and not yet understood differences in the literature regarding the orientation registry between the epi-layers and epi-substrate and the interface chemistry. Here we study the growth of WS2 via a sequential exposure of the metal and the chalcogen precursors in a metal-organic chemical vapor deposition (MOCVD) system, introducing a metal-seeding step prior to the growth. The ability to control the delivery of the precursor made it possible to study the formation of a continuous and apparently ordered WO3 mono- or few-layer at the surface of a c-plane sapphire. Such an interfacial layer is shown to strongly influence the subsequent quasi-vdW epitaxial growth of the atomically thin semiconductor layers on sapphire. Hence, here we elucidate an epitaxial growth mechanism and demonstrate the robustness of the metal-seeding approach for the oriented formation of other TMDC layers. This work may enable the rational design of vdW and quasi-vdW epitaxial growth on different material systems.

Hyperspectral nanoscale imaging on dielectric substrates with coaxial optical antenna scan probes.

We have demonstrated hyperspectral tip-enhanced Raman imaging on dielectric substrates using linearly polarized light and nanofabricated coaxial antenna tips. A full Raman spectrum was acquired at each pixel of a 256 by 256 pixel contact-mode atomic force microscope image of carbon nanotubes grown on a fused silica microscope coverslip, allowing D and G mode intensity and D-mode peak shifts to be measured with ∼20 nm spatial resolution. Tip enhancement was sufficient to acquire useful Raman spectra in 50-100 ms. Coaxial scan probes combine the efficiency and enhanced, ultralocalized optical fields of plasmonically coupled antennae with the superior topographical imaging properties of sharp metal tips. The yield of the coaxial tip fabrication process is close to 100%, and the tips are sufficiently durable to support hours of contact-mode force microscope imaging. Our coaxial probes avoid the limitations associated with the "gap-mode" imaging geometry used in most tip-enhanced Raman studies to date, where a sharp metal tip is held ∼1 nm above a metallic substrate with the sample located in the gap.

Bright excitonic multiplexing mediated by dark exciton transition in two-dimensional TMDCs at room temperature.

2D-semiconductors with strong light-matter interaction are attractive materials for integrated and tunable optical devices. Here, we demonstrate room-temperature wavelength multiplexing of the two-primary bright excitonic channels (Ab-, Bb-) in monolayer transition metal dichalcogenides (TMDs) arising from a dark exciton mediated transition. We present how tuning dark excitons via an out-of-plane electric field cedes the system equilibrium from one excitonic channel to the other, encoding the field polarization into wavelength information. In addition, we demonstrate how such exciton multiplexing is dictated by thermal-scattering by performing temperature dependent photoluminescence measurements. Finally, we demonstrate experimentally and theoretically how excitonic mixing can explain preferable decay through dark states in MoX2 in comparison with WX2 monolayers. Such field polarization-based manipulation of excitonic transitions can pave the way for novel photonic device architectures.

Formation of bandgap and subbands in graphene nanomeshes with sub-10 nm ribbon width fabricated via nanoimprint lithography.

We fabricated hexagonal graphene nanomeshes (GNMs) with sub-10 nm ribbon width. The fabrication combines nanoimprint lithography, block-copolymer self-assembly for high-resolution nanoimprint template patterning, and electrostatic printing of graphene. Graphene field-effect transistors (GFETs) made from GNMs exhibit very different electronic characteristics in comparison with unpatterned GFETs even at room temperature. We observed multiplateaus in the drain current-gate voltage dependence as well as an enhancement of ON/OFF current ratio with reduction of the average ribbon width of GNMs. These effects are attributed to the formation of electronic subbands and a bandgap in GNMs. Such mesoscopic graphene structures and the nanofabrication methods could be employed to construct future electronic devices based on graphene superlattices.

Direct chemical vapor deposition of graphene on dielectric surfaces.

Direct deposition of graphene on various dielectric substrates is demonstrated using a single-step chemical vapor deposition process. Single-layer graphene is formed through surface catalytic decomposition of hydrocarbon precursors on thin copper films predeposited on dielectric substrates. The copper films dewet and evaporate during or immediately after graphene growth, resulting in graphene deposition directly on the bare dielectric substrates. Scanning Raman mapping and spectroscopy, scanning electron microscopy, and atomic force microscopy confirm the presence of continuous graphene layers on tens of micrometer square metal-free areas. The revealed growth mechanism opens new opportunities for deposition of higher quality graphene films on dielectric materials.

Modulating the electronic properties along carbon nanotubes via tube-substrate interaction.

We study single wall carbon nanotubes (SWNTs) deposited on quartz. Their Raman spectrum depends on the tube-substrate morphology, and in some cases, it shows that the same SWNT-on-quartz system exhibits a mixture of semiconductor and metal behavior, depending on the orientation between the tube and the substrate. We also address the problem using electric force microscopy and ab initio calculations, both showing that the electronic properties along a single SWNT are being modulated via tube-substrate interaction.

Maskless Device Fabrication and Laser-Induced Doping in MoS2 Field Effect Transistors Using a Thermally Activated Cyclic Polyphthalaldehyde Resist.

We present a novel maskless device fabrication technique for rapid prototyping of two-dimensional (2D)-based electronic materials. The technique is based on a thermally activated and self-developed cyclic polyphthalaldehyde (c-PPA) resist using a commercial Raman system and 532 nm laser illumination. Following the successful customization of electrodes to form field effect transistors based on MoS2 monolayers, the laser-induced electronic doping of areas beneath the metal contacts that were exposed during lithography was investigated using both surface potential mapping and device characterization. An effective change in the doping level was introduced depending on the laser intensity, i.e., low laser powers resulted in p-doping, while high laser powers resulted in n-doping. Fabricated devices present a low contact resistance down to 10 kΩ·µm at a back-gate voltage of VG = 80 V, which is attributed to the laser-induced n-type doping at the metal contact regions.

Modulating the Optoelectronic Properties of MoS2 by Highly Oriented Dipole-Generating Monolayers.

The noncovalent functionalization of two-dimensional materials (2DMs) with bespoke organic molecules is of central importance for future nanoscale electronic devices. Of particular interest is the incorporation of molecular functionalities that can modulate the physicochemical properties of the 2DMs via noninvasive external stimuli. In this study, we present the reversible modulation of the photoluminescence, spectroscopic properties (Raman), and charge transport characteristics of molybdenum disulfide (MoS2)-based devices via photoisomerization of a self-assembled monolayer of azobenzene-modified triazatriangulene molecules. The observed (opto)electronic modulations are explained by the n-type doping of the MoS2 lattice induced by the photoisomerization of the highly ordered azobenzene monolayer. This novel behavior could have profound effects on future composite 2DM-based (opto)electronics.

Growth-Etch Metal-Organic Chemical Vapor Deposition Approach of WS2 Atomic Layers.

Metal-organic chemical vapor deposition (MOCVD) is one of the main methodologies used for thin-film fabrication in the semiconductor industry today and is considered one of the most promising routes to achieve large-scale and high-quality 2D transition metal dichalcogenides (TMDCs). However, if special measures are not taken, MOCVD suffers from some serious drawbacks, such as small domain size and carbon contamination, resulting in poor optical and crystal quality, which may inhibit its implementation for the large-scale fabrication of atomic-thin semiconductors. Here we present a growth-etch MOCVD (GE-MOCVD) methodology, in which a small amount of water vapor is introduced during the growth, while the precursors are delivered in pulses. The evolution of the growth as a function of the amount of water vapor, the number and type of cycles, and the gas composition is described. We show a significant domain size increase is achieved relative to our conventional process. The improved crystal quality of WS2 (and WSe2) domains wasis demonstrated by means of Raman spectroscopy, photoluminescence (PL) spectroscopy, and HRTEM studies. Moreover, time-resolved PL studies show very long exciton lifetimes, comparable to those observed in mechanically exfoliated flakes. Thus, the GE-MOCVD approach presented here may facilitate their integration into a wide range of applications.

Scalable Integration of Coplanar Heterojunction Monolithic Devices on Two-Dimensional In2Se3.

The formation of lateral heterojunction arrays within two-dimensional (2D) crystals is an essential step to realize high-density, ultrathin electro-optical integrated circuits, although the assembling of such structures remains elusive. Here we demonstrated a rapid, scalable, and site-specific integration of lateral 2D heterojunction arrays using few-layer indium selenide (In2Se3). We use a scanning laser probe to locally convert In2Se3 into In2O3, which shows a significant increase in carrier mobility and transforms the metal-semiconductor junctions from Schottky to ohmic type. In addition, a lateral p-n heterojunction diode within a single nanosheet is demonstrated and utilized for photosensing applications. The presented method enables high-yield, site-specific formation of lateral 2D In2Se3-In2O3-based hybrid heterojunctions for realizing nanoscale devices with multiple advanced functionalities.

Light and complex 3D MoS2/graphene heterostructures as efficient catalysts for the hydrogen evolution reaction.

Multi-component 3D porous structures are highly promising hierarchical materials for numerous applications. Herein we show that atomic-layer deposition (ALD) of MoS2 on graphene foams with variable pore size is a promising methodology to prepare complex 3D heterostructures to be used as electrocatalysts for the hydrogen evolution reaction (HER). The effect of MoS2 crystallinity is studied and a trade-off between the high density of defects naturally presented in amorphous MoS2 coatings and the highly crystalline phase obtained after annealing at 800 °C is established. Specifically, an optimal annealing at 500 °C is shown to yield improved catalytic performance with an overpotential of 180 mV, a low Tafel slope of 47 mV dec-1, and a high exchange current of 17 µA cm-2. The ALD deposition is highly conformal, and thus advantageous when coating 3D porous structures with small pore sizes, as required for real-world applications. This approach is enabled by conformal thin film deposition on porous structures with controlled crystallinity by tuning the annealing temperature. The results presented here therefore serve as an effective and general platform for the design of chemically and structurally tunable, binder-free, complex, lightweight, and highly efficient 3D porous heterostructures to be used for catalysis, energy storage, composite materials, sensors, water treatment, and more.

Seeded-growth of WS2 atomic layers: the effect on chemical and optical properties.

The growth of high quality materials from well-defined seeds is a well-established and beneficial procedure, as it enables the control of the crystal orientation, domain size, phase and chemical composition of nanocrystals, thin films and 3D crystals. The seeded-growth approach for 2D transition metal dichalcogenides (TMDs) is investigated, envisaging that seeds have a great impact on the chemical composition of the grown layers and thus, on their chemical and optical properties. The controlled nucleation and narrow domain size distribution of single crystalline WS2 atomic layers are demonstrated by employing the seeded-growth approach. The growth of single layer WS2 domains from well-defined Au seeds leads to nanoparticle (NP) decoration over the domain in a very peculiar way that might be related to the growth mechanism of such atomic-layers. The segmentation in Raman enhancement and photoluminescence maps of exciton and trion emissions well correlate with the presence of Au NPs observed in electron microscopy and chemical maps obtained by time-of-flight secondary ion mass spectroscopic imaging. This work emphasizes the importance of the seed material and its effect on the grown 2D material and may lead to novel methodologies for controlled growth, doping and the formation of hybrid materials to be used in catalysis, sensors and optoelectronics.

Flatlands in the Holy Land: The Evolution of Layered Materials Research in Israel.

The experimental identification of fullerenes in 1985, carbon nanotubes in 1991, inorganic nanotubes in 1992, and graphene in 2004 are cornerstone events that have marked the beginning of the layered nanostructures era of materials science. Nowadays, the synthesis of such low-dimensional systems is a routine practice allowing the controlled fabrication of 0-, 1-, and 2D layered structures of diverse chemical compositions. These systems possess unique physical properties that stem from their structural anisotropy characterized by strong intralayer covalent bonding and weaker interlayer dispersive interactions. This, in turn, results in promising functionality that attracts the attention of scientists from many disciplines including chemists, physicists, material scientists, engineers, as well as life scientists that are interested in both their basic and applied science aspects. Here, a short review of the contribution of the Israeli scientific community to this effort over the past 3 decades, is provided.

Revealing the planar chemistry of two-dimensional heterostructures at the atomic level.

Two-dimensional (2D) atomic crystals and their heterostructures are an intense area of study owing to their unique properties that result from structural planar confinement. Intrinsically, the performance of a planar vertical device is linked to the quality of its 2D components and their interfaces, therefore requiring characterization tools that can reveal both its planar chemistry and morphology. Here, we propose a characterization methodology combining (micro-) Raman spectroscopy, atomic force microscopy and time-of-flight secondary ion mass spectrometry to provide structural information, morphology and planar chemical composition at virtually the atomic level, aimed specifically at studying 2D vertical heterostructures. As an example system, a graphene-on-h-BN heterostructure is analysed to reveal, with an unprecedented level of detail, the subtle chemistry and interactions within its layer structure that can be assigned to specific fabrication steps. Such detailed chemical information is of crucial importance for the complete integration of 2D heterostructures into functional devices.

Graphene synthesis via magnetic inductive heating of copper substrates.

Scaling graphene growth using an oven to heat large substrates becomes less energy efficient as system size is increased. We report a route to graphene synthesis in which radio frequency (RF) magnetic fields inductively heat metal foils, yielding graphene of quality comparable to or higher than that of current chemical vapor deposition techniques. RF induction heating allows for rapid temperature ramp up/down, with great potential for large scale and rapid manufacturing of graphene with much better energy efficiency. Back-gated field effect transistors on a SiO2/Si substrate showed carrier mobility up to ∼14 000 cm(2) V(-1) s(-1) measured under ambient conditions. Many advantages of RF heating are outlined, and some fundamental aspects of this approach are discussed.

Progress, challenges, and opportunities in two-dimensional materials beyond graphene.

Graphene's success has shown that it is possible to create stable, single and few-atom-thick layers of van der Waals materials, and also that these materials can exhibit fascinating and technologically useful properties. Here we review the state-of-the-art of 2D materials beyond graphene. Initially, we will outline the different chemical classes of 2D materials and discuss the various strategies to prepare single-layer, few-layer, and multilayer assembly materials in solution, on substrates, and on the wafer scale. Additionally, we present an experimental guide for identifying and characterizing single-layer-thick materials, as well as outlining emerging techniques that yield both local and global information. We describe the differences that occur in the electronic structure between the bulk and the single layer and discuss various methods of tuning their electronic properties by manipulating the surface. Finally, we highlight the properties and advantages of single-, few-, and many-layer 2D materials in field-effect transistors, spin- and valley-tronics, thermoelectrics, and topological insulators, among many other applications.