According to theoretical studies, narrow graphene nanoribbons with atomically precise armchair edges and widths of o2 nm have a bandgap comparable to that in silicon (1.1 eV), which makes them potentially promising for logic applications. Different top-down fabrication approaches typically yield ribbons with width 410 nm and have limited control over their edge structure. Here we demonstrate a novel bottom-up approach that yields gram quantities of high-aspect-ratio graphene nanoribbons, which are only B1 nm wide and have atomically smooth armchair edges. These ribbons are shown to have a large electronic bandgap of B1.3 eV, which is significantly higher than any value reported so far in experimental studies of graphene nanoribbons prepared by top-down approaches. These synthetic ribbons could have lengths of 4100 nm and self-assemble in highly ordered few-micrometer-long 'nanobelts' that can be visualized by conventional microscopy techniques, and potentially used for the fabrication of electronic devices.

Large quantities of narrow graphene nanoribbons with edge-incorporated nitrogen atoms can be synthesized via Yamamoto coupling of molecular precursors containing nitrogen atoms followed by cyclodehydrogenation using Scholl reaction.

Narrow graphene nanoribbons (GNRs) constructed by atomically precise bottom-up synthesis from molecular precursors have attracted significant interest as promising materials for nanoelectronics. But there has been little awareness of the potential of GNRs to serve as nanoscale building blocks of novel materials. Here we show that the substitutional doping with nitrogen atoms can trigger the hierarchical self-assembly of GNRs into ordered metamaterials. We use GNRs doped with eight N atoms per unit cell and their undoped analogues, synthesized using both surface-assisted and solution approaches, to study this self-assembly on a support and in an unrestricted three-dimensional (3D) solution environment. On a surface, N-doping mediates the formation of hydrogen-bonded GNR sheets. In solution, sheets of side-by-side coordinated GNRs can in turn assemble via van der Waals and π-stacking interactions into 3D stacks, a process that ultimately produces macroscopic crystalline structures. The optoelectronic properties of these semiconducting GNR crystals are determined entirely by those of the individual nanoscale constituents, which are tunable by varying their width, edge orientation, termination, and so forth. The atomically precise bottom-up synthesis of bulk quantities of basic nanoribbon units and their subsequent self-assembly into crystalline structures suggests that the rapidly developing toolset of organic and polymer chemistry can be harnessed to realize families of novel carbon-based materials with engineered properties.

Engineering the electronic structure of organics through interface manipulation, particularly the interface dipole and the barriers to charge carrier injection, is of essential importance to improve organic devices. This requires the meticulous fabrication of desired organic structures by precisely controlling the interactions between molecules. The well-known principles of organic coordination chemistry cannot be applied without proper consideration of extra molecular hybridization, charge transfer and dipole formation at the interfaces. Here we identify the interplay between energy level alignment, charge transfer, surface dipole and charge pillow effect and show how these effects collectively determine the net force between adsorbed porphyrin 2H-TPP on Cu(111). We show that the forces between supported porphyrins can be altered by controlling the amount of charge transferred across the interface accurately through the relative alignment of molecular electronic levels with respect to the Shockley surface state of the metal substrate, and hence govern the self-assembly of the molecules.

Axel, "Proton transfer in surface-stabilized chiral motifs of croconic acid" (2013). Stephen Ducharme Publications. 89.