  Graphene is an excellent candidate for the next generation of electronic
materials due to the strict two-dimensionality of its electronic structure as
well as the extremely high carrier mobility. A prerequisite for the development
of graphene based electronics is the reliable control of the type and density
of the charge carriers by external (gate) and internal (doping) means. While
gating has been successfully demonstrated for graphene flakes and epitaxial
graphene on silicon carbide, the development of reliable chemical doping
methods turns out to be a real challenge. In particular hole doping is an
unsolved issue. So far it has only been achieved with reactive molecular
adsorbates, which are largely incompatible with any device technology. Here we
show by angle-resolved photoemission spectroscopy that atomic doping of an
epitaxial graphene layer on a silicon carbide substrate with bismuth, antimony
or gold presents effective means of p-type doping. Not only is the atomic
doping the method of choice for the internal control of the carrier density. In
combination with the intrinsic n-type character of epitaxial graphene on SiC,
the charge carriers can be tuned from electrons to holes, without affecting the
conical band structure.
