Delocalized spin states at zigzag termini of armchair graphene nanoribbon.

Using scanning tunneling microscopy and spectroscopy we demonstrate a revival of magnetism in 7-armchair nanoribbon by unpassivated atoms at the termini. Namely, a pair of intense Kondo resonances emerges at the peripheries of zigzag terminus revealing the many-body screening effects of local magnetic moments. Although Kondo resonance originates from a missing local orbital, it extends to a distance of 2.5 nm along the edge of the ribbon. The results are complemented by density functional theory calculations which suggest a possible coupling between Kondo states despite screening effects of substrate electrons. These findings indicate a possibility to restore intrinsic magnetic ordering in graphene nanoribbon without major structural modifications.

Real-space imaging of several molecular layers of C60in the rotational glass phase.

C60is a model system to study molecule-surface interactions and phase transitions due to its high symmetry and strong covalentπbonding within the molecule versus weak van-der-Waals coupling between neighboring molecules. In the solid, at room temperature, the molecule rotates and behaves as a sphere. However, the pentagonal and hexagonal atomic arrangement imposes deviations from the spherical symmetry that become important at low temperatures. The orientation of the C60can be viewed to represent classic spins. For geometrical reasons the preferred orientation of neighboring C60cannot be satisfied for all of the neighboring molecules, making C60a model for disordered spin systems with frustration. We study several molecular layers of C60islands on highly oriented pyrolytic graphite using scanning tunneling microscopy at liquid nitrogen temperatures. By imaging several layers we obtain a limited access to the three-dimensional rotational structure of the molecules in an island. We find one rotationally disordered layer between two partially rotationally ordered layers with hexagonal patterns. This exotic pattern shows an example of the local distribution of order and disorder in geometrically frustrated systems. Scanning tunneling spectroscopy data confirms the weak interactions of neighboring molecules.

Molecular self-assembly of DBBA on Au(111) at room temperature.

We have investigated the self-assembly of the graphene nanoribbon molecular precursor 10,10'-dibromo-9,9'-bianthryl (DBBA) on Au(111) with frequency modulation scanning force microscopy (FM-SFM) at room temperature combined with ab initio calculations. For low molecular coverages, the molecules aggregate along the substrate herringbone reconstruction main directions while remaining mobile. At intermediate coverage, two phases coexist, zigzag stripes of monomer chains and decorated herringbones. For high coverage, the molecules assemble in a dimer-striped phase. The adsorption behaviour of DBBA molecules and their interactions are discussed and compared with the results from ab initio calculations.

Graphene as a Mechanically Active, Deformable Two-Dimensional Surfactant.

In crystal growth, surfactants are additive molecules used in dilute amount or as dense, permeable layers to control surface morphologies. We investigate the properties of a strikingly different surfactant: a 2D and covalent layer with close atomic packing, graphene. Using in situ, real-time electron microscopy, scanning tunneling microscopy, kinetic Monte Carlo simulations, and continuum mechanics calculations, we reveal why metallic atomic layers can grow in a 2D manner below an impermeable graphene membrane. Upon metal growth, graphene dynamically opens nanochannels called wrinkles, facilitating mass transport while at the same time storing and releasing elastic energy via lattice distortions. Graphene thus behaves as a mechanically active, deformable surfactant. The wrinkle-driven mass transport of the metallic layer intercalated between graphene and the substrate is observed for two graphene-based systems, characterized by different physicochemical interactions, between graphene and the substrate and between the intercalated material and graphene. The deformable surfactant character of graphene that we unveil should then apply to a broad variety of species, opening new avenues for using graphene as a 2D surfactant forcing the growth of flat films, nanostructures, and unconventional crystalline phases.

Ultra-narrow metallic armchair graphene nanoribbons.

Graphene nanoribbons (GNRs)-narrow stripes of graphene-have emerged as promising building blocks for nanoelectronic devices. Recent advances in bottom-up synthesis have allowed production of atomically well-defined armchair GNRs with different widths and doping. While all experimentally studied GNRs have exhibited wide bandgaps, theory predicts that every third armchair GNR (widths of N=3m+2, where m is an integer) should be nearly metallic with a very small bandgap. Here, we synthesize the narrowest possible GNR belonging to this family (five carbon atoms wide, N=5). We study the evolution of the electronic bandgap and orbital structure of GNR segments as a function of their length using low-temperature scanning tunnelling microscopy and density-functional theory calculations. Already GNRs with lengths of 5 nm reach almost metallic behaviour with ∼100 meV bandgap. Finally, we show that defects (kinks) in the GNRs do not strongly modify their electronic structure.

Strain Relaxation in CVD Graphene: Wrinkling with Shear Lag.

We measure uniaxial strain fields in the vicinity of edges and wrinkles in graphene prepared by chemical vapor deposition (CVD), by combining microscopy techniques and local vibrational characterization. These strain fields have magnitudes of several tenths of a percent and extend across micrometer distances. The nonlinear shear-lag model remarkably captures these strain fields in terms of the graphene-substrate interaction and provides a complete understanding of strain-relieving wrinkles in graphene for any level of graphene-substrate coherency.