Periodic spatial variation of the electron-phonon interaction in epitaxial graphene on Ru(0001

We have performed low temperature scanning tunnelling spectroscopy (STS) measurements on graphene epitaxially grown on Ru(0001). An inelastic feature, related to the excitation of a vibrational breathing mode of the graphene lattice, was found at 360 meV. The change in the differential electrical conductance produced by this inelastic feature, which is associated with the electron-phonon interaction strength, varies spatially from one position to other of the graphene supercell. This inhomogeneity in the electronic properties of graphene on Ru(0001) results from local variations of the carbon-ruthenium interaction due to the lattice mismatch between the graphene and the Ru(0001) lattices.Comment: 6 Pages, 3 figure

Growth and characterization of 7,7,8,8-tetracyano-quinodimethane crystals on chemical vapor deposition graphene

Chemical functionalization of graphene could pave the way for favorably modifying its already remarkable properties. Organic molecules have been utilized to this end as a way to alter graphene’s structural, chemical, electrical, optical and even magnetic properties. One such promising organic molecule is 7,7,8,8-tetracyano-quinodimethane (TCNQ), a strong electron acceptor which has been shown to be an effective p-dopant of graphene. This study explores the thermal evaporation of TCNQ onto graphene transferred onto SiO2/Si substrates. Using two different home-made thermal evaporators, a wide range of TCNQ growth regimes are explored, from thin films to crystals . The resulting graphene/TCNQ structure is characterized via optical microscopy, Raman spectroscopy and atomic force microscopy (AFM). TCNQ films are found to be comprised of TCNQ and the oxidized product of TCNQ, α,α-dicyano-p-toluoylcyanide (DCTC), which confirms the electron charge transfer from graphene to the TCNQ films. AFM measurements of these films show that after forming a rather smooth layer covering the graphene surface, small clusters start to form. For higher TCNQ coverage, the clusters agglomerate, becoming quite large in size and forming ripples or wrinkles across the surface

Graphene grown on transition metal substrates: Versatile templates for organic molecules with new properties and structures

The interest in graphene (a carbon monolayer) adsorbed on metal surfaces goes back to the 60’s, long before isolated graphene was produced in the laboratory. Owing to the carbon-metal interaction and the lattice mismatch between the carbon monolayer and the metal surface, graphene usually adopts a rippled structure, known as moir´e, that confers it interesting electronic properties not present in isolated graphene. These moir´e structures can be used as versatile templates where to adsorb, isolate and assemble organic-molecule structures with some desired geometric and electronic properties. In this review, we first describe the main experimental techniques and the theoretical methods currently available to produce and characterize these complex systems. Then, we review the diversity of moir´e structures that have been reported in the literature and the consequences for the electronic properties of graphene, attending to the magnitude of the lattice mismatch and the type of interaction, chemical or physical, between graphene and the metal surface. Subsequently, we address the problem of the adsorption of single organic molecules and then of several ones, from dimers to complete monolayers, describing both the different arrangements that these molecules can adopt as well as their physical and chemical properties. We pay a special attention to graphene/Ru(0001) due to its exceptional electronic properties, which have been used to induce long-range magnetic order in tetracyanoquinodimethane (TCNQ) monolayers, to catalyze the (reversible) reaction between acetonitrile and TCNQ molecules and to efficiently photogenerate large acenes

Highly reproducible low temperature scanning tunnelling microscopy and spectroscopy with in situ prepared tips

An in situ tip preparation procedure compatible with ultra-low temperature and high magnetic field scanning tunneling microscopes is presented. This procedure does not require additional preparation techniques such as thermal annealing or ion milling. It relies on the local electric-field-induced deposition of material from the tip onto the studied surface. Subsequently, repeated indentations are performed onto the sputtered cluster to mechanically anneal the tip apex and thus to ensure the stability of the tip. The efficiency of this method is confirmed by comparing the topography and spectroscopy data acquired with either unprepared or in situ prepared tips on epitaxial graphene grown on Ru (0001). We demonstrate that the use of in situ prepared tips increases the stability of the scanning tunneling images and the reproducibility of the spectroscopic measurements.Comment: 9 Pages, 4 figures (including supp. material

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