Germanium is emerging as the substrate of choice for the growth of graphene in CMOS-compatible processes. For future application in next generation devices the accurate control over the properties of high-quality graphene synthesized on Ge surfaces, such as number of layers and domain size, is of paramount importance. Here we investigate the role of the process gas flows on the CVD growth of graphene on Ge(100). The quality and morphology of the deposited material is assessed by using μ-Raman spectroscopy, X-ray photoemission spectroscopy, scanning electron microscopy, and atomic force microscopy. We find that by simply varying the carbon precursor flow different growth regimes yielding to graphene nanoribbons, graphene monolayer, and graphene multilayer are established. We identify the growth conditions yielding to a layer-by-layer growth regime and report on the achievement of homogeneous monolayer graphene with an average intensity ratio of 2D and G bands in the Raman map larger than 3.

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 µ-Raman 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 sp 2 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.

By combining scanning probe microscopy with Raman and x-ray photoelectron spectroscopies, we investigate the evolution of CVD-grown graphene/Ge(001) as a function of the deposition temperature in close proximity to the Ge melting point, highlighting an abrupt change of the graphene's quality, morphology, electronic properties and growth mode at 930 °C. We attribute this discontinuity to the incomplete surface melting of the Ge substrate and show how incomplete melting explains a variety of diverse and long-debated peculiar features of the graphene/Ge(001), including the characteristic nanostructuring of the Ge substrate induced by graphene overgrowth. We find that the quasi-liquid Ge layer formed close to 930 °C is fundamental to obtain high-quality graphene, while a temperature decrease of 10 degrees already results in a wrinkled and defective graphene film.

By tuning the growth parameters, we show that it is possible to drive the CVD synthesis of graphene on Ge(110) towards the formation of either ultrathin armchair nanoribbons or of continuous graphene films.The ribbons are aligned along specific high-symmetry directions of the Ge(110) surface and have a width of ~5 nm. Moreover, by merging spectroscopic and morphological information, we find that the quality of graphene films depends critically on the growth temperature improving significantly in a narrow range close to the Ge melting point. The abruptness of the temperature behavior observed indicates that achieving high-quality graphene is intimately connected to the quasi-liquid Ge layer formed close to 930 °C on the substrate. Being observed for diverse Ge orientations, this process, known as incomplete melting, is shown to be of general relevance for graphene synthesis on Ge, and explains why similar growth conditions present in literature lead to graphene of very diverse quality on these substrates.

We report on the investigation of the Schottky barrier (SB) formed at the junction between a metal-free graphene monolayer and Ge semiconductor substrate in the as-grown epitaxial graphene/Ge(100) system. In order to preserve the heterojunction properties, we defined submicron size graphene/Ge junctions using the scanning probe microscopy lithography in the local oxidation configuration, a low-invasive processing approach capable of inducing spatially controlled electrical separations among tiny graphene regions. Characteristic junction parameters were estimated from I–V curves obtained using conductive-atomic force microscopy. The current–voltage characteristics showed a p-type Schottky contact behavior, ascribed to the n-type to p-type conversion of the entire Ge substrate due to the formation of a large density of acceptor defects during the graphene growth process. We estimated, for the first time, the energy barrier height in the as-grown graphene/Ge Schottky junction (φB ≈ 0.45 eV) indicating an n-type doping of the graphene layer with a Fermi level ≈ 0.15 eV above the Dirac point. The SB devices showed ideality factor values around 1.5 pointing to the high quality of the heterojunctions.