Arkady V. Krasheninnikov

Structural Defects in Graphene

Graphene is one of the most promising materials in nanotechnology. The electronic and mechanical properties of graphene samples with high perfection of the atomic lattice are outstanding, but structural defects, which may appear during growth or processing, deteriorate the performance of graphene-based devices. However, deviations from perfection can be useful in some applications, as they make it possible to tailor the local properties of graphene and to achieve new functionalities. In this article, the present knowledge about point and line defects in graphene are reviewed. Particular emphasis is put on the unique ability of graphene to reconstruct its lattice around intrinsic defects, leading to interesting effects and potential applications. Extrinsic defects such as foreign atoms which are of equally high importance for designing graphene-based devices with dedicated properties are also discussed.

Ion and electron irradiation-induced effects in nanostructured materials

A common misconception is that the irradiation of solids with energetic electrons and ions has exclusively detrimental effects on the properties of target materials. In addition to the well-known cases of doping of bulk semiconductors and ion beam nitriding of steels, recent experiments show that irradiation can also have beneficial effects on nanostructured systems. Electron or ion beams may serve as tools to synthesize nanoclusters and nanowires, change their morphology in a controllable manner, and tailor their mechanical, electronic, and even magnetic properties. Harnessing irradiation as a tool for modifying material properties at the nanoscale requires having the full microscopic picture of defect production and annealing in nanotargets. In this article, we review recent progress in the understanding of effects of irradiation on various zero-dimensional and one-dimensional nanoscale systems, such as semiconductor and metal nanoclusters and nanowires, nanotubes, and fullerenes. We also consider the t...

Two-Dimensional Transition Metal Dichalcogenides under Electron Irradiation: Defect Production and Doping

Using first-principles atomistic simulations, we study the response of atomically thin layers of transition metal dichalcogenides (TMDs)--a new class of two-dimensional inorganic materials with unique electronic properties--to electron irradiation. We calculate displacement threshold energies for atoms in 21 different compounds and estimate the corresponding electron energies required to produce defects. For a representative structure of MoS2, we carry out high-resolution transmission electron microscopy experiments and validate our theoretical predictions via observations of vacancy formation under exposure to an 80 keV electron beam. We further show that TMDs can be doped by filling the vacancies created by the electron beam with impurity atoms. Thereby, our results not only shed light on the radiation response of a system with reduced dimensionality, but also suggest new ways for engineering the electronic structure of TMDs.

From point defects in graphene to two-dimensional amorphous carbon.

While crystalline two-dimensional materials have become an experimental reality during the past few years, an amorphous 2D material has not been reported before. Here, using electron irradiation we create an sp2-hybridized one-atom-thick flat carbon membrane with a random arrangement of polygons, including four-membered carbon rings. We show how the transformation occurs step by step by nucleation and growth of low-energy multivacancy structures constructed of rotated hexagons and other polygons. Our observations, along with first-principles calculations, provide new insights to the bonding behavior of carbon and dynamics of defects in graphene. The created domains possess a band gap, which may open new possibilities for engineering graphene-based electronic devices.

Spin-half paramagnetism in graphene induced by point defects

T he possibility to induce a magnetic response in graphene by the introduction of defects has been generating much interest, as this would expand the already impressive list of its special properties and allow novel devices where charge and spin manipulation could be combined. So far there have been many theoretical studies (for reviews, see refs 1‐3) predicting that point defects in graphene should carry magnetic moments B and these can in principle couple (anti)ferromagnetically 1‐12 . However, experimental evidence for such magnetism remains both scarce and controversial 13‐16 . Here we show that point defects in graphene—(1) fluorine adatoms in concentrations x gradually increasing to stoichiometric fluorographene CFxD1:0 (ref. 17) and (2) irradiation defects (vacancies)—carry magnetic moments with spin 1=2. Both types of defect lead to notable paramagnetism but no magnetic ordering could be detected down to liquid helium temperatures. The induced paramagnetism dominates graphene’s low-temperature magnetic properties, despite the fact that the maximum response we could achieve was limited to one moment per approximately 1,000 carbon atoms. This limitation is explained by clustering of adatoms and, for the case of vacancies, by the loss of graphene’s structural stability. Our work clarifies the controversial issue of graphene’s magnetism and sets limits for other graphitic compounds. The emerging consensus that magnetism in carbon-based systems can exist is based mostly on a large body of work on magnetic measurements of highly-oriented pyrolytic graphite (HOPG) and carbon films, with many reports of weak ferromagnetic signals at room temperature (T) observed in both pristine HOPG and after itsionirradiation(see,forexample,refs18,19).However,thewhole subject remains controversial, especially concerning (1) the role of possible contamination and (2) the mechanism responsible for the strong interaction required to lead to ferromagnetic ordering at room temperature. Some observations of ferromagnetism are probably artefacts, doing little justice to the subject (one frequent artefact is identified and described in the Supplementary Information, where we show that commonly used HOPG crystals contain micrometre-sized magnetic particles). Adatom magnetism in graphite is also contentious and, for example, different studies of fluorinatedgraphitehavereportedinconsistentresults 20,21 .

Van der Waals bonding in layered compounds from advanced density-functional first-principles calculations

Although the precise microscopic knowledge of van der Waals interactions is crucial for understanding bonding in weakly bonded layered compounds, very little quantitative information on the strength of interlayer interaction in these materials is available, either from experiments or simulations. Here, using many-body perturbation and advanced density-functional theory techniques, we calculate the interlayer binding and exfoliation energies for a large number of layered compounds and show that, independent of the electronic structure of the material, the energies for most systems are around 20  meV/Å2. This universality explains the successful exfoliation of a wide class of layered materials to produce two-dimensional systems, and furthers our understanding the properties of layered compounds in general.

A novel hybrid carbon material

Both fullerenes and single-walled carbon nanotubes (SWNTs) exhibit many advantageous properties. Despite the similarities between these two forms of carbon, there have been very few attempts to physically merge them. We have discovered a novel hybrid material that combines fullerenes and SWNTs into a single structure in which the fullerenes are covalently bonded to the outer surface of the SWNTs. These fullerene-functionalized SWNTs, which we have termed NanoBuds, were selectively synthesized in two different one-step continuous methods, during which fullerenes were formed on iron-catalyst particles together with SWNTs during CO disproportionation. The field-emission characteristics of NanoBuds suggest that they may possess advantageous properties compared with single-walled nanotubes or fullerenes alone, or in their non-bonded configurations.

Carbon Nanotubes as High-Pressure Cylinders and Nanoextruders

Closed-shell carbon nanostructures, such as carbon onions, have been shown to act as self-contracting high-pressure cells under electron irradiation. We report that controlled irradiation of multiwalled carbon nanotubes can cause large pressure buildup within the nanotube cores that can plastically deform, extrude, and break solid materials that are encapsulated inside the core. We further showed by atomistic simulations that the internal pressure inside nanotubes can reach values higher than 40 gigapascals. Nanotubes can thus be used as robust nanoscale jigs for extruding and deforming hard nanomaterials and for modifying their properties, as well as templates for the study of individual nanometer-sized crystals under high pressure.

Triazine‐Based Graphitic Carbon Nitride: a Two‐Dimensional Semiconductor

Graphitic carbon nitride has been predicted to be structurally analogous to carbon-only graphite, yet with an inherent bandgap. We have grown, for the first time, macroscopically large crystalline thin films of triazine-based, graphitic carbon nitride (TGCN) using an ionothermal, interfacial reaction starting with the abundant monomer dicyandiamide. The films consist of stacked, two-dimensional (2D) crystals between a few and several hundreds of atomic layers in thickness. Scanning force and transmission electron microscopy show long-range, in-plane order, while optical spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations corroborate a direct bandgap between 1.6 and 2.0 eV. Thus TGCN is of interest for electronic devices, such as field-effect transistors and light-emitting diodes.

Electronic structures and optical properties of realistic transition metal dichalcogenide heterostructures from first principles

We calculate from first principles the electronic structure and optical properties of a number of transition metal dichalcogenide (TMD) bilayer heterostructures consisting of MoS