Electroluminescence from pure resonant states in hBN-based vertical tunneling junctions.

Defect centers in wide-band-gap crystals have garnered interest for their potential in applications among optoelectronic and sensor technologies. However, defects embedded in highly insulating crystals, like diamond, silicon carbide, or aluminum oxide, have been notoriously difficult to excite electrically due to their large internal resistance. To address this challenge, we realized a new paradigm of exciting defects in vertical tunneling junctions based on carbon centers in hexagonal boron nitride (hBN). The rational design of the devices via van der Waals technology enabled us to raise and control optical processes related to defect-to-band and intradefect electroluminescence. The fundamental understanding of the tunneling events was based on the transfer of the electronic wave function amplitude between resonant defect states in hBN to the metallic state in graphene, which leads to dramatic changes in the characteristics of electrons due to different band structures of constituent materials. In our devices, the decay of electrons via tunneling pathways competed with radiative recombination, resulting in an unprecedented degree of tuneability of carrier dynamics due to the significant sensitivity of the characteristic tunneling times on the thickness and structure of the barrier. This enabled us to achieve a high-efficiency electrical excitation of intradefect transitions, exceeding by several orders of magnitude the efficiency of optical excitation in the sub-band-gap regime. This work represents a significant advancement towards a universal and scalable platform for electrically driven devices utilizing defect centers in wide-band-gap crystals with properties modulated via activation of different tunneling mechanisms at a level of device engineering.

2D Electrolytes: Theory, Modeling, Synthesis, and Characterization.

A class of compounds sharing the properties of 2D materials and electrolytes, namely 2D electrolytes is described theoretically and demonstrated experimentally. 2D electrolytes dissociate in different solvents, such as water, and become electrically charged. The chemical and physical properties of these compounds can be controlled by external factors, such as pH, temperature, electric permittivity of the medium, and ionic concentration. 2D electrolytes, in analogy with polyelectrolytes, present reversible morphological transitions from 2D to 1D, as a function of pH, due to the interplay of the elastic and Coulomb energies. Since these materials show stimuli-responsive behavior to the environmental conditions, 2D electrolytes can be considered as a novel class of smart materials that expand the functionalities of 2D materials and are promising for applications that require stimuli-responsive demeanor, such as drug delivery, artificial muscles, and energy storage.

Mechanical Properties of Atomically Thin Tungsten Dichalcogenides: WS2, WSe2, and WTe2.

Two-dimensional (2D) tungsten disulfide (WS2), tungsten diselenide (WSe2), and tungsten ditelluride (WTe2) draw increasing attention due to their attractive properties deriving from the heavy tungsten and chalcogenide atoms, but their mechanical properties are still mostly unknown. Here, we determine the intrinsic and air-aged mechanical properties of mono-, bi-, and trilayer (1-3L) WS2, WSe2, and WTe2 using a complementary suite of experiments and theoretical calculations. High-quality 1L WS2 has the highest Young's modulus (302.4 ± 24.1 GPa) and strength (47.0 ± 8.6 GPa) of the entire family, overpassing those of 1L WSe2 (258.6 ± 38.3 and 38.0 ± 6.0 GPa, respectively) and WTe2 (149.1 ± 9.4 and 6.4 ± 3.3 GPa, respectively). However, the elasticity and strength of WS2 decrease most dramatically with increased thickness among the three materials. We interpret the phenomenon by the different tendencies for interlayer sliding in an equilibrium state and under in-plane strain and out-of-plane compression conditions in the indentation process, revealed by the finite element method and density functional theory calculations including van der Waals interactions. We also demonstrate that the mechanical properties of the high-quality 1-3L WS2 and WSe2 are largely stable in air for up to 20 weeks. Intriguingly, the 1-3L WSe2 shows increased modulus and strength values with aging in the air. This is ascribed to oxygen doping, which reinforces the structure. The present study will facilitate the design and use of 2D tungsten dichalcogenides in applications such as strain engineering and flexible field-effect transistors.

In situ manipulation of van der Waals heterostructures for twistronics.

In van der Waals heterostructures, electronic bands of two-dimensional (2D) materials, their nontrivial topology, and electron-electron interactions can be markedly changed by a moiré pattern induced by twist angles between different layers. This process is referred to as twistronics, where the tuning of twist angle can be realized through mechanical manipulation of 2D materials. Here, we demonstrate an experimental technique that can achieve in situ dynamical rotation and manipulation of 2D materials in van der Waals heterostructures. Using this technique, we fabricated heterostructures where graphene is perfectly aligned with both top and bottom encapsulating layers of hexagonal boron nitride. Our technique enables twisted 2D material systems in one single stack with dynamically tunable optical, mechanical, and electronic properties.

Piezoelectricity in Monolayer Hexagonal Boron Nitride.

2D hexagonal boron nitride (hBN) is a wide-bandgap van der Waals crystal with a unique combination of properties, including exceptional strength, large oxidation resistance at high temperatures, and optical functionalities. Furthermore, in recent years hBN crystals have become the material of choice for encapsulating other 2D crystals in a variety of technological applications, from optoelectronic and tunneling devices to composites. Monolayer hBN, which has no center of symmetry, is predicted to exhibit piezoelectric properties, yet experimental evidence is lacking. Here, by using electrostatic force microscopy, this effect is observed as a strain-induced change in the local electric field around bubbles and creases, in agreement with theoretical calculations. No piezoelectricity is found in bilayer and bulk hBN, where the center of symmetry is restored. These results add piezoelectricity to the known properties of monolayer hBN, which makes it a desirable candidate for novel electromechanical and stretchable optoelectronic devices, and pave a way to control the local electric field and carrier concentration in van der Waals heterostructures via strain. The experimental approach used here also shows a way to investigate the piezoelectric properties of other materials on the nanoscale by using electrostatic scanning probe techniques.

A Force-Engineered Lint Roller for Superclean Graphene.

Contamination is a major concern in surface and interface technologies. Given that graphene is a 2D monolayer material with an extremely large surface area, surface contamination may seriously degrade its intrinsic properties and strongly hinder its applicability in surface and interfacial regions. However, large-scale and facile treatment methods for producing clean graphene films that preserve its excellent properties have not yet been achieved. Herein, an efficient postgrowth treatment method for selectively removing surface contamination to achieve a large-area superclean graphene surface is reported. The as-obtained superclean graphene, with surface cleanness exceeding 99%, can be transferred to dielectric substrates with significantly reduced polymer residues, yielding ultrahigh carrier mobility of 500 000 cm2 V-1 s-1 and low contact resistance of 118 Ω µm. The successful removal of contamination is enabled by the strong adhesive force of the activated-carbon-based lint roller on graphene contaminants.

The Worldwide Graphene Flake Production.

There are hundreds of companies worldwide claiming to produce "graphene," showing a large variation in its properties. A systematic and reliable protocol is developed to test graphene quality using electron microscopy, atomic force microscopy, Raman spectroscopy, elemental analysis, X-ray photoelectron spectrometry, and scanning and transmission electron microscopy, which is used to study graphene from 60 producers. The statistical nature of the liquid-phase exfoliation of graphite is established. It is shown that the current classification of graphene flakes used in the market is erroneous. A new classification is proposed in terms of distribution functions for number of layers and flake size. It is shown unequivocally that the quality of the graphene produced in the world today is rather poor, not optimal for most applications, and most companies are producing graphite microplatelets. This is possibly the main reason for the slow development of graphene applications, which usually require a customized solution in terms of graphene properties. It is argued that the creation of stringent standards for graphene characterization and production, taking into account both the physical properties, as well as the requirements from the particular application, is the only way forward to create a healthy and reliable worldwide graphene market.

High electron mobility, quantum Hall effect and anomalous optical response in atomically thin InSe.

A decade of intense research on two-dimensional (2D) atomic crystals has revealed that their properties can differ greatly from those of the parent compound. These differences are governed by changes in the band structure due to quantum confinement and are most profound if the underlying lattice symmetry changes. Here we report a high-quality 2D electron gas in few-layer InSe encapsulated in hexagonal boron nitride under an inert atmosphere. Carrier mobilities are found to exceed 103 cm2 V-1 s-1 and 104 cm2 V-1 s-1 at room and liquid-helium temperatures, respectively, allowing the observation of the fully developed quantum Hall effect. The conduction electrons occupy a single 2D subband and have a small effective mass. Photoluminescence spectroscopy reveals that the bandgap increases by more than 0.5 eV with decreasing the thickness from bulk to bilayer InSe. The band-edge optical response vanishes in monolayer InSe, which is attributed to the monolayer's mirror-plane symmetry. Encapsulated 2D InSe expands the family of graphene-like semiconductors and, in terms of quality, is competitive with atomically thin dichalcogenides and black phosphorus.

Ultrasensitive gas detection of large-area boron-doped graphene.

Heteroatom doping is an efficient way to modify the chemical and electronic properties of graphene. In particular, boron doping is expected to induce a p-type (boron)-conducting behavior to pristine (nondoped) graphene, which could lead to diverse applications. However, the experimental progress on atomic scale visualization and sensing properties of large-area boron-doped graphene (BG) sheets is still very scarce. This work describes the controlled growth of centimeter size, high-crystallinity BG sheets. Scanning tunneling microscopy and spectroscopy are used to visualize the atomic structure and the local density of states around boron dopants. It is confirmed that BG behaves as a p-type conductor and a unique croissant-like feature is frequently observed within the BG lattice, which is caused by the presence of boron-carbon trimers embedded within the hexagonal lattice. More interestingly, it is demonstrated for the first time that BG exhibits unique sensing capabilities when detecting toxic gases, such as NO2 and NH3, being able to detect extremely low concentrations (e.g., parts per trillion, parts per billion). This work envisions that other attractive applications could now be explored based on as-synthesized BG.

Hydrogenation of Graphene by Reaction at High Pressure and High Temperature.

The chemical reaction between hydrogen and purely sp(2)-bonded graphene to form graphene's purely sp(3)-bonded analogue, graphane, potentially allows the synthesis of a much wider variety of novel two-dimensional materials by opening a pathway to the application of conventional chemistry methods in graphene. Graphene is currently hydrogenated by exposure to atomic hydrogen in a vacuum, but these methods have not yielded a complete conversion of graphene to graphane, even with graphene exposed to hydrogen on both sides of the lattice. By heating graphene in molecular hydrogen under compression to modest high pressure in a diamond anvil cell (2.6-5.0 GPa), we are able to react graphene with hydrogen and propose a method whereby fully hydrogenated graphane may be synthesized for the first time.

A Facile Route for Patterned Growth of Metal-Insulator Carbon Lateral Junction through One-Pot Synthesis.

Precise graphene patterning is of critical importance for tailor-made and sophisticated two-dimensional nanoelectronic and optical devices. However, graphene-based heterostructures have been grown by delicate multistep chemical vapor deposition methods, limiting preparation of versatile heterostructures. Here, we report one-pot synthesis of graphene/amorphous carbon (a-C) heterostructures from a solid source of polystyrene via selective photo-cross-linking process. Graphene is successfully grown from neat polystyrene regions, while patterned cross-linked polystyrene regions turn into a-C because of a large difference in their thermal stability. Since the electrical resistance of a-C is at least 2 orders of magnitude higher than that for graphene, the charge transport in graphene/a-C heterostructure occurs through the graphene region. Measurement of the quantum Hall effect in graphene/a-C lateral heterostructures clearly confirms the reliable quality of graphene and well-defined graphene/a-C interface. The direct synthesis of patterned graphene from polymer pattern could be further exploited to prepare versatile heterostructures.

Electron transfer kinetics on natural crystals of MoS2 and graphite.

Here, we evaluate the electrochemical performance of sparsely studied natural crystals of molybdenite and graphite, which have increasingly been used for fabrication of next generation monolayer molybdenum disulphide and graphene energy storage devices. Heterogeneous electron transfer kinetics of several redox mediators, including Fe(CN)6(3-/4-), Ru(NH3)6(3+/2+) and IrCl6(2-/3-) are determined using voltammetry in a micro-droplet cell. The kinetics on both materials are studied as a function of surface defectiveness, surface ageing, applied potential and illumination. We find that the basal planes of both natural MoS2 and graphite show significant electroactivity, but a large decrease in electron transfer kinetics is observed on atmosphere-aged surfaces in comparison to in situ freshly cleaved surfaces of both materials. This is attributed to surface oxidation and adsorption of airborne contaminants at the surface exposed to an ambient environment. In contrast to semimetallic graphite, the electrode kinetics on semiconducting MoS2 are strongly dependent on the surface illumination and applied potential. Furthermore, while visibly present defects/cracks do not significantly affect the response of graphite, the kinetics on MoS2 systematically accelerate with small increase in disorder. These findings have direct implications for use of MoS2 and graphene/graphite as electrode materials in electrochemistry-related applications.

Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems.

We present the science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems, targeting an evolution in technology, that might lead to impacts and benefits reaching into most areas of society. This roadmap was developed within the framework of the European Graphene Flagship and outlines the main targets and research areas as best understood at the start of this ambitious project. We provide an overview of the key aspects of graphene and related materials (GRMs), ranging from fundamental research challenges to a variety of applications in a large number of sectors, highlighting the steps necessary to take GRMs from a state of raw potential to a point where they might revolutionize multiple industries. We also define an extensive list of acronyms in an effort to standardize the nomenclature in this emerging field.

Growth dynamics and gas transport mechanism of nanobubbles in graphene liquid cells.

Formation, evolution and vanishing of bubbles are common phenomena in nature, which can be easily observed in boiling or falling water, carbonated drinks, gas-forming electrochemical reactions and so on. However, the morphology and the growth dynamics of the bubbles at nanoscale have not been fully investigated owing to the lack of proper imaging tools that can visualize nanoscale objects in the liquid phase. Here, we demonstrate for the first time that the nanobubbles in water encapsulated by graphene membrane can be visualized by in-situ ultra-high vacuum transmission electron microscopy. Our microscopic results indicate two distinct growth mechanisms of merging nanobubbles and the existence of a critical radius of nanobubbles that determines the unusually long stability of nanobubbles. Interestingly, the gas transport through ultrathin water membranes at nanobubble interface is free from dissolution, which is clearly different from conventional gas transport that includes condensation, transmission and evaporation.

Electron transfer kinetics on mono- and multilayer graphene.

Understanding of the electrochemical properties of graphene, especially the electron transfer kinetics of a redox reaction between the graphene surface and a molecule, in comparison to graphite or other carbon-based materials, is essential for its potential in energy conversion and storage to be realized. Here we use voltammetric determination of the electron transfer rate for three redox mediators, ferricyanide, hexaammineruthenium, and hexachloroiridate (Fe(CN)(6)(3-), Ru(NH3)(6)(3+), and IrCl(6)(2-), respectively), to measure the reactivity of graphene samples prepared by mechanical exfoliation of natural graphite. Electron transfer rates are measured for varied number of graphene layers (1 to ca. 1000 layers) using microscopic droplets. The basal planes of mono- and multilayer graphene, supported on an insulating Si/SiO(2) substrate, exhibit significant electron transfer activity and changes in kinetics are observed for all three mediators. No significant trend in kinetics with flake thickness is discernible for each mediator; however, a large variation in kinetics is observed across the basal plane of the same flakes, indicating that local surface conditions affect the electrochemical performance. This is confirmed by in situ graphite exfoliation, which reveals significant deterioration of initially, near-reversible kinetics for Ru(NH3)(6)(3+) when comparing the atmosphere-aged and freshly exfoliated graphite surfaces.

Electromechanical sensing of substrate charge hidden under atomic 2D crystals.

The functionality of graphene and other two-dimensional materials in electronic devices is highly influenced by the film-substrate charge transfer affecting local carrier density. We demonstrate that charges buried under the few layer graphene on/in the insulating substrate can be detected using electromechanical actuation of the conductive atomically thin layers, allowing measurements of areal density of film-substrate transferred charges under few layer graphene and MoS2 suspended films.

Thermal properties of graphene-copper-graphene heterogeneous films.

We demonstrated experimentally that graphene-Cu-graphene heterogeneous films reveal strongly enhanced thermal conductivity as compared to the reference Cu and annealed Cu films. Chemical vapor deposition of a single atomic plane of graphene on both sides of 9 µm thick Cu films increases their thermal conductivity by up to 24% near room temperature. Interestingly, the observed improvement of thermal properties of graphene-Cu-graphene heterofilms results primarily from the changes in Cu morphology during graphene deposition rather than from graphene's action as an additional heat conducting channel. Enhancement of thermal properties of graphene-capped Cu films is important for thermal management of advanced electronic chips and proposed applications of graphene in the hybrid graphene-Cu interconnect hierarchies.

Control of radiation damage in MoS(2) by graphene encapsulation.

Recent dramatic progress in studying various two-dimensional (2D) atomic crystals and their heterostructures calls for better and more detailed understanding of their crystallography, reconstruction, stacking order, etc. For this, direct imaging and identification of each and every atom is essential. Transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) are ideal and perhaps the only tools for such studies. However, the electron beam can in some cases induce dramatic structure changes, and radiation damage becomes an obstacle in obtaining the desired information in imaging and chemical analysis in the (S)TEM. This is the case of 2D materials such as molybdenum disulfide MoS2, but also of many biological specimens, molecules, and proteins. Thus, minimizing damage to the specimen is essential for optimum microscopic analysis. In this article we demonstrate, on the example of MoS2, that encapsulation of such crystals between two layers of graphene allows for a dramatic improvement in stability of the studied 2D crystal and permits careful control over the defect nature and formation in it. We present STEM data collected from single-layer MoS2 samples prepared for observation in the microscope through three distinct procedures. The fabricated single-layer MoS2 samples were either left bare (pristine), placed atop a single-layer of graphene, or finally encapsulated between single graphene layers. Their behavior under the electron beam is carefully compared, and we show that the MoS2 sample "sandwiched" between the graphene layers has the highest durability and lowest defect formation rate compared to the other two samples, for very similar experimental conditions.

Graphene reknits its holes.

Nanoholes, etched under an electron beam at room temperature in single-layer graphene sheets as a result of their interaction with metal impurities, are shown to heal spontaneously by filling up with either nonhexagon, graphene-like, or perfect hexagon 2D structures. Scanning transmission electron microscopy was employed to capture the healing process and study atom-by-atom the regrown structure. A combination of these nanoscale etching and reknitting processes could lead to new graphene tailoring approaches.

Scanning tunnelling microscopy of suspended graphene.

Suspended graphene has been studied by STM for the first time. Atomic resolution on mono- and bi-layer graphene samples has been obtained after ridding the graphene surface of contamination via high-temperature annealing. Static local corrugations (ripples) have been observed on both types of structures.