In-plane orientation effects on the electronic structure, stability, and Raman scattering of monolayer graphene on Ir(111)

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 moire interference pattern between graphene and Ir lattices) is shown to be nonuniform along the minizone boundary owing to hybridization with Ir bands. An electronically mediated interaction is proposed to account for the stability of the R0 variant. The variant rotated 30 degrees 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 and 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.