Electron beam controlled covalent attachment of small organic molecules to graphene.

The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and C=C bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The "standing up" molecules, covalently anchored to graphene, exhibit two types of oscillatory motion--bending and twisting--caused by the presence of acoustic phonons in graphene and dispersion attraction to the substrate. The theoretically derived mechanisms are confirmed by near atomic resolution imaging of individual perchlorocoronene (C24Cl12) molecules on graphene. Our results facilitate the understanding of controlled functionalization of graphene employing electron irradiation as well as mechanisms of attachment of impurities via the processing of graphene nanoelectronic devices by electron beam lithography.

Atomic scale microstructure and properties of Se-deficient two-dimensional MoSe2.

We study the atomic scale microstructure of nonstoichiometric two-dimensional (2D) transition metal dichalcogenide MoSe2-x by employing aberration-corrected high-resolution transmission electron microscopy. We show that a Se-deficit in single layers of MoSe2 grown by molecular beam epitaxy gives rise to a dense network of mirror-twin-boundaries (MTBs) decorating the 2D-grains. With the use of density functional theory calculations, we further demonstrate that MTBs are thermodynamically stable structures in Se-deficient sheets. These line defects host spatially localized states with energies close to the valence band minimum, thus giving rise to enhanced conductance along straight MTBs. However, electronic transport calculations show that the transmission of hole charge carriers across MTBs is strongly suppressed due to band bending effects. We further observe formation of MTBs during in situ removal of Se atoms by the electron beam of the microscope, thus confirming that MTBs appear due to Se-deficit, and not coalescence of individual grains during growth. At a very high local Se-deficit, the 2D sheet becomes unstable and transforms to a nanowire. Our results on Se-deficient MoSe2 suggest routes toward engineering the properties of 2D transition metal dichalcogenides by deviations from the stoichiometric composition.

Numerical correction of anti-symmetric aberrations in single HRTEM images of weakly scattering 2D-objects.

Here, we present a numerical post-processing method for removing the effect of anti-symmetric residual aberrations in high-resolution transmission electron microscopy (HRTEM) images of weakly scattering 2D-objects. The method is based on applying the same aberrations with the opposite phase to the Fourier transform of the recorded image intensity and subsequently inverting the Fourier transform. We present the theoretical justification of the method, and its verification based on simulated images in the case of low-order anti-symmetric aberrations. Ultimately the method is applied to experimental hardware aberration-corrected HRTEM images of single-layer graphene and MoSe2 resulting in images with strongly reduced residual low-order aberrations, and consequently improved interpretability. Alternatively, this method can be used to estimate by trial and error the residual anti-symmetric aberrations in HRTEM images of weakly scattering objects.

Implantation and atomic-scale investigation of self-interstitials in graphene.

Crystallographic defects play a key role in determining the properties of crystalline materials. The new class of two-dimensional materials, foremost graphene, have enabled atomically resolved studies of defects, such as vacancies,1-4 grain boundaries,(5-7) dislocations,(8,9) and foreign atom substitutions.(10-14) However, atomic resolution imaging of implanted self-interstitials has so far been reported neither in any three-dimensional nor in any two-dimensional material. Here, we deposit extra carbon into single-layer graphene at soft landing energies of ∼ 1 eV using a standard carbon coater. We identify all the self-interstitial dimer structures theoretically predicted earlier,(15-17) employing 80 kV aberration-corrected high-resolution transmission electron microscopy. We demonstrate accumulation of the interstitials into larger aggregates and dislocation dipoles, which we predict to have strong local curvature by atomistic modeling, and to be energetically favorable configurations as compared to isolated interstitial dimers. Our results contribute to the basic knowledge on crystallographic defects and lay out a pathway into engineering the properties of graphene by pushing the crystal into a state of metastable supersaturation.

Experimental observation of boron nitride chains.

We report the formation and characterization of boron nitride atomic chains. The chains were made from hexagonal boron nitride sheets using the electron beam inside a transmission electron microscope. We find that the stability and lifetime of the chains are significantly improved when they are supported by another boron nitride layer. With the help of first-principles calculations, we prove the heteroatomic structure of the chains and determine their mechanical and electronic properties. Our study completes the analogy between various boron nitride and carbon polymorphs, in accordance with earlier theoretical predictions.

Non-invasive transmission electron microscopy of vacancy defects in graphene produced by ion irradiation.

Irradiation with high-energy ions has been widely suggested as a tool to engineer properties of graphene. Experiments show that it indeed has a strong effect on graphene's transport, magnetic and mechanical characteristics. However, to use ion irradiation as an engineering tool requires understanding of the type and detailed characteristics of the produced defects which is still lacking, as the use of high-resolution transmission microscopy (HRTEM)--the only technique allowing direct imaging of atomic-scale defects--often modifies or even creates defects during imaging, thus making it impossible to determine the intrinsic atomic structure. Here we show that encapsulating the studied graphene sample between two other (protective) graphene sheets allows non-invasive HRTEM imaging and reliable identification of atomic-scale defects. Using this simple technique, we demonstrate that proton irradiation of graphene produces reconstructed monovacancies, which explains the profound effect that such defects have on graphene's magnetic and transport properties. This finding resolves the existing uncertainty with regard to the effect of ion irradiation on the electronic structure of graphene.

Defects in bilayer silica and graphene: common trends in diverse hexagonal two-dimensional systems.

By combining first-principles and classical force field calculations with aberration-corrected high-resolution transmission electron microscopy experiments, we study the morphology and energetics of point and extended defects in hexagonal bilayer silica and make comparison to graphene, another two-dimensional (2D) system with hexagonal symmetry. We show that the motifs of isolated point defects in these 2D structures with otherwise very different properties are similar, and include Stone-Wales-type defects formed by structural unit rotations, flower defects and reconstructed double vacancies. The morphology and energetics of extended defects, such as grain boundaries have much in common as well. As both sp(2)-hybridised carbon and bilayer silica can also form amorphous structures, our results indicate that the morphology of imperfect 2D honeycomb lattices is largely governed by the underlying symmetry of the lattice.

Ion impacts on graphene/Ir(111): interface channeling, vacancy funnels, and a nanomesh.

By combining ion beam experiments and atomistic simulations we study the production of defects in graphene on Ir(111) under grazing incidence of low energy Xe ions. We demonstrate that the ions are channeled in between graphene and the substrate, giving rise to chains of vacancy clusters with their edges bending down toward the substrate. These clusters self-organize to a graphene nanomesh via thermally activated diffusion as their formation energy varies within the graphene moiré supercell.

Ion-irradiation-induced defects in isotopically-labeled two layered graphene: enhanced in-situ annealing of the damage.

Contrary to theoretical estimates based on the conventional binary collision model, experimental results indicate that the number of defects in the lower layer of the bi-layer graphene sample is smaller than in the upper layer. This observation is explained by in situ self-annealing of the defects.

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.

Atom-by-atom observation of grain boundary migration in graphene.

Grain boundary (GB) migration in polycrystalline solids is a materials science manifestation of survival of the fittest, with adjacent grains competing to add atoms to their outer surfaces at each other's expense. This process is thermodynamically favored when it lowers the total GB area in the sample, thereby reducing the excess free energy contributed by the boundaries. In this picture, a curved boundary is expected to migrate toward its center of curvature with a velocity proportional to the local radius of boundary curvature (R). Investigating the underlying mechanism of boundary migration in a 3D material, however, has been reserved for computer simulation or analytical theory, as capturing the dynamics of individual atoms in the core region of a GB is well beyond the spatial and temporal resolution limits of current characterization techniques. Here, we similarly overcome the conventional experimental limits by investigating a 2D material, polycrystalline graphene, in an aberration-corrected transmission electron microscope, exploiting the energy of the imaging electrons to stimulate individual bond rotations in the GB core region. The resulting morphological changes are followed in situ, atom-by-atom, revealing configurational fluctuations that take on a time-averaged preferential direction only in the presence of significant boundary curvature, as confirmed by Monte Carlo simulations. Remarkably, in the extreme case of a small graphene grain enclosed within a larger one, we follow its shrinkage to the point of complete disappearance.