We employ angle-resolved photoemission spectroscopy (ARPES) to investigate the electronic structures of two rotational variants of epitaxial, single-layer graphene on Ir(111). As grown, the more-abundant R0 variant is nearly charge-neutral, with strong hybridization between graphene and Ir bands near the Fermi level. The graphene Fermi surface and its replicas exactly coincide with Van Hove singularities in the Ir Fermi surface. Sublattice symmetry breaking introduces a small gap-inducing potential at the Dirac crossing, which is revealed by n-doping the graphene using K atoms. The energy gaps between main and replica bands (originating from the moiré interference pattern between graphene and Ir lattices) is shown to be non-uniform along the minizone boundary due to hybridization with Ir bands. An electronically mediated interaction is proposed to account for the stability of the R0 variant. The variant rotated 30° in-plane, R30, is p-doped as grown and K doping reveals no band gap at the Dirac crossing. No replica bands are found in ARPES measurements. Raman spectra from the R30 variant exhibit the characteristic phonon modes of graphene, while R0 spectra are featureless. These results show that the film/substrate interaction changes from chemisorption (R0) to physisorption (R30) with in-plane orientation. Finally, graphene-covered Ir has a work function lower than the clean substrate but higher than graphite.-2 -

Selected-area diffraction establishes that at least six different in-plane orientations of monolayer graphene on Pd(111) can form during graphene growth. From the intensities of low-energy electron microscopy images as a function of incident electron energy, we find that the work functions of the different rotational domains vary by up to 0.15 eV. Density functional theory calculations show that these significant variations result from orientation-dependent charge transfer from Pd to graphene. These findings suggest that graphene electronics will require precise control over the relative orientation of the graphene and metal contacts.

We elucidate how graphene bilayers form on Ir(111). Low-energy electron diffraction (LEED) reveals that the two graphene layers are not always rotationally aligned. Monitoring this misalignment during growth shows that second-layer islands nucleate between the existing layer and the substrate. This mechanism occurs both when C segregates from the Ir and when elemental C is deposited from above. Low-energy electron microscopy (LEEM) and angle-resolved photoemission spectroscopy (ARPES) show that second-layer nucleation occurs preferentially under the first-layer rotational variants that are more weakly bound to the substrate. New-layer nucleation tends to occur inhomogeneously at substrate defects. Thus new-layer nucleation should be rapid on substrates that weakly bind graphene, making growth unstable toward mound formation initiated at substrate defects. In contrast, stronger binding permits layer-by-layer growth, as for Ru(0001). ARPES shows that bilayer graphene has two slightly p-doped π-bands. The work function of bilayer graphene is dominated by the orientation of the bottom layer.

We use low-energy electron microscopy to investigate how graphene is removed from Ru (0001) and Ir(111) by reaction with oxygen. We find two mechanisms on Ru(0001). At short times, oxygen reacts with carbon monomers on the surrounding Ru surface, decreasing their concentration below the equilibrium value. This undersaturation causes a flux of carbon from graphene to the monomer gas. In this initial mechanism, graphene is etched at a rate that is given precisely by the same non-linear dependence on carbon monomer concentration that governs growth. Thus, during both growth and etching, carbon attaches and detaches to graphene as clusters of several carbon atoms. At later times, etching accelerates. We present evidence that this process involves intercalated oxygen, which destabilizes graphene. On Ir, this mechanism creates observable holes. It also occurs mostly quickly near wrinkles in the graphene islands, depends on the orientation of the graphene with respect to the Ir substrate, and, in contrast to the first mechanism, can increase the density of carbon monomers. We also observe that both layers of bilayer graphene islands on Ir etch together, not sequentially.

Pristine, single-crystalline graphene displays a unique collection of remarkable electronic properties that arise from its two-dimensional, honeycomb structure. Using in situ low-energy electron microscopy, we show that when deposited on the (111) surface of Au carbon forms such a structure. The resulting monolayer, epitaxial film is formed by the coalescence of dendritic graphene islands that nucleate at a high density. Over 95% of these islands can be identically aligned with respect to each other and to the Au substrate. Remarkably, the dominant island orientation is not the better lattice-matched 30 • rotated orientation but instead one in which the graphene [01] and Au [011] inplane directions are parallel. The epitaxial graphene film is only weakly coupled to the Au surface, which maintains its reconstruction under the slightly p-type doped graphene. The linear electronic dispersion characteristic of free-standing 6