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.

The intrinsic defect structure of exfoliated MoS2 single layers revealed by Scanning Tunneling Microscopy.

MoS2 single layers have recently emerged as strong competitors of graphene in electronic and optoelectronic device applications due to their intrinsic direct bandgap. However, transport measurements reveal the crucial role of defect-induced electronic states, pointing out the fundamental importance of characterizing their intrinsic defect structure. Transmission Electron Microscopy (TEM) is able to image atomic scale defects in MoS2 single layers, but the imaged defect structure is far from the one probed in the electronic devices, as the defect density and distribution are substantially altered during the TEM imaging. Here, we report that under special imaging conditions, STM measurements can fully resolve the native atomic scale defect structure of MoS2 single layers. Our STM investigations clearly resolve a high intrinsic concentration of individual sulfur atom vacancies, and experimentally identify the nature of the defect induced electronic mid-gap states, by combining topographic STM images with ab intio calculations. Experimental data on the intrinsic defect structure and the associated defect-bound electronic states that can be directly used for the interpretation of transport measurements are essential to fully understand the operation, reliability and performance limitations of realistic electronic devices based on MoS2 single layers.

Nanomesh-Type Graphene Superlattice on Au(111) Substrate.

The adherence of graphene to various crystalline substrates often leads to a periodic out-of-plane modulation of its atomic structure due to the lattice mismatch. While, in principle, convex (protrusion) and concave (depression) superlattice geometries are nearly equivalent, convex superlattices have predominantly been observed for graphene on various metal surfaces. Here we report the STM observation of a graphene superlattice with concave (nanomesh) morphology on Au(111). DFT and molecular dynamics simulations confirm the nanomesh nature of the graphene superlattice on Au(111) and also reveal its potential origin as a surface reconstruction, consisting of the imprinting of the nanomesh morphology into the Au(111) surface. This unusual surface reconstruction can be attributed to the particularly large mobility of the Au atoms on Au(111) surfaces and most probably plays an important role in stabilizing the concave graphene superlattice. We report the simultaneous observation of both convex and concave graphene superlattices on herringbone reconstructed Au(111) excluding the contrast inversion as the origin of the observed concave morphology. The observed graphene nanomesh superlattice can provide an intriguing nanoscale template for self-assembled structures and nanoparticles that cannot be stabilized on other surfaces.

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.

Room-temperature magnetic order on zigzag edges of narrow graphene nanoribbons.

The possibility that non-magnetic materials such as carbon could exhibit a novel type of s-p electron magnetism has attracted much attention over the years, not least because such magnetic order is predicted to be stable at high temperatures. It has been demonstrated that atomic-scale structural defects of graphene can host unpaired spins, but it remains unclear under what conditions long-range magnetic order can emerge from such defect-bound magnetic moments. Here we propose that, in contrast to random defect distributions, atomic-scale engineering of graphene edges with specific crystallographic orientation--comprising edge atoms from only one sub-lattice of the bipartite graphene lattice--can give rise to a robust magnetic order. We use a nanofabrication technique based on scanning tunnelling microscopy to define graphene nanoribbons with nanometre precision and well-defined crystallographic edge orientations. Although so-called 'armchair' ribbons display quantum confinement gaps, ribbons with the 'zigzag' edge structure that are narrower than 7 nanometres exhibit an electronic bandgap of about 0.2-0.3 electronvolts, which can be identified as a signature of interaction-induced spin ordering along their edges. Moreover, upon increasing the ribbon width, a semiconductor-to-metal transition is revealed, indicating the switching of the magnetic coupling between opposite ribbon edges from the antiferromagnetic to the ferromagnetic configuration. We found that the magnetic order on graphene edges of controlled zigzag orientation can be stable even at room temperature, raising hopes of graphene-based spintronic devices operating under ambient conditions.