X‐Ray Spectroscopic Investigation of Chlorinated Graphene: Surface Structure and Electronic Effects

Chemical doping of graphene represents a powerful means of tailoring its electronic properties. Synchrotron‐based X‐ray spectroscopy offers an effective route to investigate the surface electronic and chemical states of functionalizing dopants. In this work, a suite of X‐ray techniques is used, including near edge X‐ray absorption fine structure spectroscopy, X‐ray photoemission spectroscopy, and photoemission threshold measurements, to systematically study plasma‐based chlorinated graphene on different substrates, with special focus on its dopant concentration, surface binding energy, bonding configuration, and work function shift. Detailed spectroscopic evidence of C–Cl bond formation at the surface of single layer graphene and correlation of the magnitude of p‐type doping with the surface coverage of adsorbed chlorine is demonstrated for the first time. It is shown that the chlorination process is a highly nonintrusive doping technology, which can effectively produce strongly p‐doped graphene with the 2D nature and long‐range periodicity of the electronic structure of graphene intact. The measurements also reveal that the interaction between graphene and chlorine atoms shows strong substrate effects in terms of both surface coverage and work function shift.     

Connecting dopant bond type with electronic structure in N-doped graphene

Robust methods to tune the unique electronic properties of graphene by chemical modification are in great demand due to the potential of the two dimensional material to impact a range of device applications. Here we show that carbon and nitrogen core-level resonant X-ray spectroscopy is a sensitive probe of chemical bonding and electronic structure of chemical dopants introduced in single-sheet graphene films. In conjunction with density functional theory based calculations, we are able to obtain a detailed picture of bond types and electronic structure in graphene doped with nitrogen at the sub-percent level. We show that different N-bond types, including graphitic, pyridinic, and nitrilic, can exist in a single, dilutely N-doped graphene sheet. We show that these various bond types have profoundly different effects on the carrier concentration, indicating that control over the dopant bond type is a crucial requirement in advancing graphene electronics.     

Reticulated Organic Photovoltaics

This paper shows how the self‐assembled interlocking of two nanostructured materials can lead to increased photovoltaic performance. A detailed picture of the reticulated 6‐DBTTC/C₆₀ organic photovoltaic (OPV) heterojunction, which produces devices approaching the theoretical maximum for these materials, is presented from near edge X‐ray absorption spectroscopy (NEXAFS), X‐ray photoelectron spectroscopy (XPS), Grazing Incidence X‐ray diffraction (GIXD) and transmission electron microscopy (TEM). The complementary suite of techniques shows how self‐assembly can be exploited to engineer the interface and morphology between the cables of donor (6‐DBTTC) material and a polycrystalline acceptor (C₆₀) to create an interpenetrating network of pure phases expected to be optimal for OPV device design. Moreover, we find that there is also a structural and electronic interaction between the two materials at the molecular interface. The data show how molecular self‐assembly can facilitate 3‐D nanostructured photovoltaic cells that are made with the simplicity and control of bilayer device fabrication. The significant improvement in photovoltaic performance of the reticulated heterojunction over the flat analog highlights the potential of these strategies to improve the efficiency of organic solar cells.     

Molecular beam growth of graphene nanocrystals on dielectric substrates

We demonstrate the growth of graphene nanocrystals by molecular beam methods that employ a solid carbon source, and that can be used on a diverse class of large area dielectric substrates. Characterization by Raman and near edge X-ray absorption fine structure spectroscopies reveal a sp² hybridized hexagonal carbon lattice in the nanocrystals. Lower growth rates (below 0.5 Å/min) favor the formation of layered, larger size multi-layer graphene crystallites (up to 22 nm) on all investigated substrates. The surface morphology is determined by the roughness of the underlying substrate (RMS ～8 Å) and graphitic monolayer steps are observed by ambient scanning tunneling microscopy.