Mingmei Yang

Janus graphene from asymmetric two-dimensional chemistry

Janus materials have distinct surfaces on their opposite faces. Graphene, a two-dimensional giant molecule, provides an excellent candidate to fabricate the thinnest Janus discs and study the asymmetric chemistry of atomic-thick nanomembranes using covalent chemical functionalisation. Here we present the first experimental realisation of nonsymmetrically modified single-layer graphene--Janus graphene--which is fabricated by a two-step surface covalent functionalisation assisted by a poly(methyl methacrylate)-mediated transfer approach. Four types of Janus graphene are produced by co-grafting of halogen and aryl/oxygen-functional groups on each side. Chemical decorations on one side are found to be capable of affecting both chemical reactivity and physical wettability of the opposite side, indicative of communication between the two grafted groups. This novel asymmetric structure provides a platform for theoretical and experimental studies of two-dimensional chemistry and graphene devices with multiple functions.

Inverse relationship between carrier mobility and bandgap in graphene

A frequently stated advantage of gapless graphene is its high carrier mobility. However, when a nonzero bandgap is opened, the mobility drops dramatically. The hardness to achieve high mobility and large on∕off ratio simultaneously limits the development of graphene electronics. To explore the underlying mechanism, we investigated the intrinsic mobility of armchair graphene nanoribbons (AGNRs) under phonon scattering by combining first-principles calculations and a tight-binding analysis. A linear dependence of the effective mass on bandgap was demonstrated to be responsible for the inverse mobility-gap relationship. The deformation-potential constant was found to be determined by the strain dependence of the Fermi energy and the bandgap, resulting in two mobility branches, and is essential for the high mobility of AGNRs. In addition, we showed that the transport polarity of AGNRs can be switched by applying a uniaxial strain.

Free Radical Reactions in Two Dimensions: A Case Study on Photochlorination of Graphene

Graphene, a two-dimensional giant-molecule of sp(2) -bonded carbon atoms, provides a perfect platform for studying free radical reaction chemistry in two-dimensions, which holds promise to control the chemical functionality of graphene. Free-radical photochlorination of graphene is used as an example to investigate the thickness, stacking order, and single- and double-side dependent reactivity in graphene. Anomalously low reactivity is observed in the photochlorination of AB-stacked bilayer graphene in comparison with that of few-layer graphene. Double-sided chlorination of graphene shows higher reactivity and chlorine coverage than single-sided reaction. It is also experimentally and theoretically demonstrated that chlorine free radicals at low coverage prefer to form a stable charge-transfer complex with graphene, which highly enhances graphenes conductivity and simultaneously generates a pseudo-bandgap through noninvasive doping. Moreover, the initial accumulation of chlorine radicals is considered as the rate-determining step of photochlorination of graphene.

Bandgap opening in Janus-type mosaic graphene

We demonstrate a novel Janus-type mosaic graphene (J-MOG) for achieving a ubiquitous bandgap opening by asymmetrical modification with covalently bonded H, F, Cl, and Br on opposing sides of graphene sheet. The theoretical capacity of J-MOG is shown to break the pattern restrictions, giving a robust non-zero gap. Our approach provides an effective pathway for the bandgap engineering of graphene for various electronic applications.

Trifluoromethylation of graphene

We demonstrate trifluoromethylation of graphene by copper-catalyzed free radical reaction. The covalent addition of CF3 to graphene, which changes the carbon atom hybridization from sp2 to sp3, and modifies graphene in a homogeneous and nondestructive manner, was verified with Raman spectroscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. X-ray photoelectron spectroscopy reveals that CF3 groups are grafted to the basal plane of graphene, with about 4 at. % CF3 coverage. After trifluoromethylation, the average resistance increases by nearly one order of magnitude, and an energy gap of about 98 meV appears. The noninvasive and mild reaction to synthesize trifluoromethylated graphene paves the way for graphenes applications in electronics and biomedical areas.