Microscopic View on a Chemical Vapor Deposition Route to Boron-Doped Graphene Nanostructures

Single layer boron-doped graphene layers have been grown on polycrystalline copper foils by chemical vapor deposition using methane and diborane as carbon and boron sources, respectively. Any attempt to deposit doped layers in one-step has been fruitless, the reason being the formation of very reactive boron species as a consequence of diborane decomposition on the Cu surface, which leads to disordered nonstoichiometric carbides. However, a two-step procedure has been optimized: as a first step, the surface is seeded with pure graphene islands, while the boron source is activated only in a second stage. In this case, the nonstochiometric boron carbides formed on the bare copper areas between preseeded graphene patches can be exploited to easily release boron, which diffuses from the peripheral areas inward of graphene islands. The effective substitutional doping (of the order of about 1%) has been demonstrated by Raman and photoemission experiments. The electronic properties of doped layers have been characterized by spatially resolved photoemission band mapping carried out on single domain graphene flakes using a photon beam with a spot size of 1 μm. The whole set of experiments allow us to clarify that boron is effective at promoting the anchoring carbon species on the surface. Taking the cue from this basic understanding, it is possible to envisage new strategies for the design of complex 2D graphene nanostructures with a spatially modulated doping. © 2013 American Chemical Society.