Fabián Calleja

Periodically Rippled Graphene: Growth and Spatially Resolved Electronic Structure

We grow epitaxial graphene monolayers on Ru(0001) that cover uniformly the substrate over lateral distances larger than several microns. The weakly coupled graphene monolayer is periodically rippled and it shows charge inhomogeneities in the charge distribution. Real space measurements by scanning tunneling spectroscopy reveal the existence of electron pockets at the higher parts of the ripples, as predicted by a simple theoretical model. We also visualize the geometric and electronic structure of edges of graphene nanoislands.

Reactivity of periodically rippled graphene grown on Ru(0001)

We report here the reactivity of epitaxial graphene islands and complete monolayers on Ru(0001) towards molecular oxygen and air. The graphene is prepared by thermal decomposition of ethylene molecules pre-adsorbed on an Ru(0001) surface in an ultra-high vacuum chamber. The graphene layer presents a periodically rippled structure that is dictated by the misfit between graphene and Ru(0001) lattice parameters. The periodic ripples produce spatial charge redistribution in the graphene and modifies its electronic structure around the Fermi level. In order to investigate the reactivity of graphene we expose graphene islands to a partial pressure of oxygen and following the evolution of the surface by STM during the exposure. For the exposure to air we removed the sample from the UHV chamber and we re-introduce it after several hours, taking STM images before and after. The surface areas not covered by the graphene islands present a dramatic change but the graphene structure, even the borders of the islands, remain intact. In the case of a complete graphene monolayer the exposure to oxygen or to air does not affect or destroy the rippled structure of the graphene monolayer.

Probing the site-dependent Kondo response of nanostructured graphene with organic molecules.

TCNQ molecules are used as a sensitive probe for the Kondo response of the electron gas of a nanostructured graphene grown on Ru(0001) presenting a moiré pattern. All adsorbed molecules acquired an extra electron by charge transfer from the substrate, but only those adsorbed in the FCC-Top areas of the moiré show magnetic moment and Kondo resonance in the STS spectra. DFT calculations trace back this behavior to the existence of a surface resonance in the low areas of the graphene moiré, whose density distribution strongly depends on the stacking sequence of the moiré area and effectively quenches the magnetic moment for HCP-Top sites.

Organic Covalent Patterning of Nanostructured Graphene with Selectivity at the Atomic Level.

Organic covalent functionalization of graphene with long-range periodicity is highly desirable-it is anticipated to provide control over its electronic, optical, or magnetic properties-and remarkably challenging. In this work we describe a method for the covalent modification of graphene with strict spatial periodicity at the nanometer scale. The periodic landscape is provided by a single monolayer of graphene grown on Ru(0001) that presents a moiré pattern due to the mismatch between the carbon and ruthenium hexagonal lattices. The moiré contains periodically arranged areas where the graphene-ruthenium interaction is enhanced and shows higher chemical reactivity. This phenomenon is demonstrated by the attachment of cyanomethyl radicals (CH2CN(•)) produced by homolytic breaking of acetonitrile (CH3CN), which is shown to present a nearly complete selectivity (>98%) binding covalently to graphene on specific atomic sites. This method can be extended to other organic nitriles, paving the way for the attachment of functional molecules.

Observation of Localized Vibrational Modes of Graphene Nanodomes by Inelastic Atom Scattering.

Inelastic helium atom scattering (HAS) is suitable to determine low-energy (few meV) vibrations spatially localized on structures in the nanometer range. This is illustrated for the nanodomes that appear often on graphene (Gr) epitaxially grown on single crystal metal surfaces. The nature of the inelastic losses observed in Gr/Ru(0001) and Gr/Cu/Ru(0001) has been clarified by intercalation of Cu below the Gr monolayer, which decouples the Gr layer from the Ru substrate and changes substantially the out-of-plane, flexural phonon dispersion of epitaxial Gr, while maintaining the nanodomes and their localized vibrations. He diffraction proves that the Cu-intercalated Gr layer is well ordered structurally, while scanning tunneling microscopy reveals the persistence of the (slightly modified) periodic array of Gr nanodomes. A simple model explains the order of magnitude of the energy losses associated with the Gr nanodomes and their size dependence. The dispersionless, low-energy phonon branches may radically alter the transport of heat in intercalated Gr.

Electronic Structure of Organic Films on Graphene

Graphene is a suitable substrate to study organic films due to the chemical stability of graphene derived from its structure and the low density of states around the Fermi level (Dirac point for neutral graphene). These two characteristics result in a reduced perturbation on the adsorbed molecules. There are few examples showing the unperturbed frontier molecular orbitals for individual molecules adsorbed on graphene or the formation of unperturbed intermolecular bands in self-assembled molecular overlayers. Simultaneously noncovalent functionalization using molecules has been suggested as a means of tailoring graphene’s band structure without compromising its overall excellent electron properties.

Electronic Properties of Sulfur Covered Ru(0001) Surfaces

The structural properties of sulfur superstructures adsorbed on Ru(0001) have been widely studied in the past. However, much less effort has been devoted to determine their electronic properties. To understand the connection between structural and electronic properties, we have carried out density functional theory periodic boundary calculations mimicking the four long-range ordered sulfur superstructures identified experimentally by means of scanning tunneling microscopy (STM) techniques. Our simulations allow us to characterize the nature of the sulfur-Ru bond, the charge transfer between the Ru substrate and the sulfur adlayers, the interface states, and a parabolic state recently identified in STM experiments. A simple analysis, based on a one-dimensional model, reveals that this parabolic state is related to a potential well state, formed in the surface when the concentration of sulfur atoms is large enough to generate a new minimum in the surface potential.