  In this work we shed light on the early stage of the chemical vapor
deposition of graphene on Ge(001) surfaces. By a combined use of microRaman and
x-ray photoelectron spectroscopies, and scanning tunneling microscopy and
spectroscopy, we were able to individuate a carbon precursor phase to graphene
nucleation which coexists with small graphene domains. This precursor phase is
made of C aggregates with different size, shape and local ordering which are
not fully sp2 hybridized. In some atomic size regions these aggregates show a
linear arrangement of atoms as well as the first signature of the hexagonal
structure of graphene. The carbon precursor phase evolves in graphene domains
through an ordering process, associated to a re-arrangement of the Ge surface
morphology. This surface structuring represents the embryo stage of the
hills-and-valleys faceting featured by the Ge(001) surface for longer
deposition times, when the graphene domains coalesce to form a single layer
graphene film.
