Controlled thermodynamics for tunable electron doping of graphene on Ir(111)

Abstract

The electronic properties and surface structures of K-doped graphene supported on Ir(111) are characterized as a function of temperature and coverage by combining low-energy electron diffraction, angle-resolved photoemission spectroscopy, and density functional theory (DFT) calculations. Deposition of K on graphene at room temperature (RT) yields a stable $(\ensuremath{\surd}3\ifmmode\times\else\texttimes\fi{}\ensuremath{\surd}3)$ R30\ifmmode^\circ\else\textdegree\fi{} surface structure having an intrinsic electron doping that shifts the graphene Dirac point by ${E}_{D}=1.30\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$ below the Fermi level. Keeping the graphene substrate at 80 K during deposition generates instead a $(2\ifmmode\times\else\texttimes\fi{}2)$ phase, which is stable until full monolayer coverage. Further deposition of K followed by RT annealing develops a double-layer K-doped graphene that effectively doubles the K coverage and the related charge transfer, as well as maximizing the doping level $({E}_{D}=1.61\phantom{\rule{0.16em}{0ex}}\mathrm{eV})$. The measured electron doping and the surface reconstructions are rationalized by DFT calculations. These indicate a large thermodynamic driving force for K intercalation below the graphene layer. The electron doping and Dirac point shifts calculated for the different structures are in agreement with the experimental measurements. In particular, the ${\mathrm{K}}_{4s}$ bands are shown to be sensitive to both the K intercalation and periodicity and are therefore suggested as a fingerprint for the location and ordering of the K dopants.