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

TL;DR

This study uses ARPES to compare two in-plane orientations of monolayer graphene on Ir(111), revealing differences in electronic structure, stability, and Raman spectra linked to their interaction modes with the substrate.

Contribution

It provides new insights into how in-plane orientation affects the electronic properties, stability, and Raman features of graphene on Ir(111), highlighting the transition from chemisorption to physisorption.

Findings

R0 variant is nearly charge-neutral with hybridized bands near Fermi level.

R30 variant is p-doped with no band gap or replica bands.

Interaction mode changes from chemisorption in R0 to physisorption in R30.

Abstract

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 moir\'e interference pattern between graphene and Ir lattices) is shown to be non-uniform along the mini- zone 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{\deg} 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.