Large-area nanoengineering of graphene corrugations for visible-frequency graphene plasmons.

Quantum confinement of the charge carriers of graphene is an effective way to engineer its properties. This is commonly realized through physical edges that are associated with the deterioration of mobility and strong suppression of plasmon resonances. Here, we demonstrate a simple, large-area, edge-free nanostructuring technique, based on amplifying random nanoscale structural corrugations to a level where they efficiently confine charge carriers, without inducing significant inter-valley scattering. This soft confinement allows the low-loss lateral ultra-confinement of graphene plasmons, scaling up their resonance frequency from the native terahertz to the commercially relevant visible range. Visible graphene plasmons localized into nanocorrugations mediate much stronger light-matter interactions (Raman enhancement) than previously achieved with graphene, enabling the detection of specific molecules from femtomolar solutions or ambient air. Moreover, nanocorrugated graphene sheets also support propagating visible plasmon modes, as revealed by scanning near-field optical microscopy observation of their interference patterns.

Transition Metal Chalcogenide Single Layers as an Active Platform for Single-Atom Catalysis.

Among the main appeals of single-atom catalysts are the ultimate efficiency of material utilization and the well-defined nature of the active sites, holding the promise of rational catalyst design. A major challenge is the stable decoration of various substrates with a high density of individually dispersed and uniformly active monatomic sites. Transition metal chalcogenides (TMCs) are broadly investigated catalysts, limited by the relative inertness of their pristine basal plane. We propose that TMC single layers modified by substitutional heteroatoms can harvest the synergistic benefits of stably anchored single-atom catalysts and activated TMC basal planes. These solid-solution TMC catalysts offer advantages such as simple and versatile synthesis, unmatched active site density, and a stable and well-defined single-atom active site chemical environment. The unique features of heteroatom-doped two-dimensional TMC crystals at the origin of their catalytic activity are discussed through the examples of various TMC single layers doped with individual oxygen heteroatoms.

Spontaneous doping of the basal plane of MoS2 single layers through oxygen substitution under ambient conditions.

The chemical inertness of the defect-free basal plane confers environmental stability to MoS2 single layers, but it also limits their chemical versatility and catalytic activity. The stability of pristine MoS2 basal plane against oxidation under ambient conditions is a widely accepted assumption however, here we report single-atom-level structural investigations that reveal that oxygen atoms spontaneously incorporate into the basal plane of MoS2 single layers during ambient exposure. The use of scanning tunnelling microscopy reveals a slow oxygen-substitution reaction, during which individual sulfur atoms are replaced one by one by oxygen, giving rise to solid-solution-type 2D MoS2-xOx crystals. Oxygen substitution sites present all over the basal plane act as single-atom reaction centres, substantially increasing the catalytic activity of the entire MoS2 basal plane for the electrochemical H2 evolution reaction.

Highly wear-resistant and low-friction Si3N4 composites by addition of graphene nanoplatelets approaching the 2D limit.

Graphene nanoplatelets (GNPs) have emerged as one of the most promising filler materials for improving the tribological performance of ceramic composites due to their outstanding solid lubricant properties as well as mechanical and thermal stability. Yet, the addition of GNPs has so far enabled only a very limited improvement in the tribological properties of ceramics, particularly concerning the reduction of their friction coefficient. This is most likely due to the challenges of achieving a continuous lubricating and protecting tribo-film through a high GNP coverage of the exposed surfaces. Here we demonstrate that this can be achieved by efficiently increasing the exfoliation degree of GNPs down to the few-layer (FL) range. By employing FL-GNPs as filler material, the wear resistance of Si3N4 composites can be increased by more than twenty times, the friction coefficient reduced to nearly its half, while the other mechanical properties are also preserved or improved. Confocal Raman spectroscopy measurements revealed that at the origin of the spectacular improvement of the tribological properties is the formation of a continuous FL- GNP tribo-film, already at 5 wt% FL-GNP content.

Exfoliation of large-area transition metal chalcogenide single layers.

Isolating large-areas of atomically thin transition metal chalcogenide crystals is an important but challenging task. The mechanical exfoliation technique can provide single layers of the highest structural quality, enabling to study their pristine properties and ultimate device performance. However, a major drawback of the technique is the low yield and small (typically < 10 µm) lateral size of the produced single layers. Here, we report a novel mechanical exfoliation technique, based on chemically enhanced adhesion, yielding MoS2 single layers with typical lateral sizes of several hundreds of microns. The idea is to exploit the chemical affinity of the sulfur atoms that can bind more strongly to a gold surface than the neighboring layers of the bulk MoS2 crystal. Moreover, we found that our exfoliation process is not specific to MoS2, but can be generally applied for various layered chalcogenides including selenites and tellurides, providing an easy access to large-area 2D crystals for the whole class of layered transition metal chalcogenides.

Tailoring the atomic structure of graphene nanoribbons by scanning tunnelling microscope lithography.

The practical realization of nanoscale electronics faces two major challenges: the precise engineering of the building blocks and their assembly into functional circuits. In spite of the exceptional electronic properties of carbon nanotubes, only basic demonstration devices have been realized that require time-consuming processes. This is mainly due to a lack of selective growth and reliable assembly processes for nanotubes. However, graphene offers an attractive alternative. Here we report the patterning of graphene nanoribbons and bent junctions with nanometre-precision, well-defined widths and predetermined crystallographic orientations, allowing us to fully engineer their electronic structure using scanning tunnelling microscope lithography. The atomic structure and electronic properties of the ribbons have been investigated by scanning tunnelling microscopy and tunnelling spectroscopy measurements. Opening of confinement gaps up to 0.5 eV, enabling room-temperature operation of graphene nanoribbon-based devices, is reported. This method avoids the difficulties of assembling nanoscale components and may prove useful in the realization of complete integrated circuits, operating as room-temperature ballistic electronic devices.