Narrow atomically precise graphene nanoribbons hold great promise for electronic and optoelectronic applications, but the previously demonstrated nanoribbon-based devices typically suffer from low currents and mobilities. In this study, we explored the idea of lateral extension of graphene nanoribbons for improving their electrical conductivity. We started with a conventional chevron graphene nanoribbon, and designed its laterally extended variant. We synthesized these new graphene nanoribbons in solution and found that the lateral extension results in decrease of their electronic bandgap and improvement in the electrical conductivity of nanoribbon-based thin films. These films were employed in gas sensors and an electronic nose system, which showed improved responsivities to low molecular weight alcohols compared to similar sensors based on benchmark graphitic materials, such as graphene and reduced graphene oxide, and a reliable analyte recognition. This study shows the methodology for designing new atomically precise graphene nanoribbons with improved properties, their bottom-up synthesis, characterization, processing and implementation in electronic devices.

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.

Atomically precise chevron graphene nanoribbons (GNRs) have been synthesized on Cu(111) substrates by the surface-assisted coupling of 6,11-dibromo-1,2,3,4-tetraphenyltriphenylene (CBrH) and thermal cyclodehydrogenation of the resulting polymer. The GNRs form on Cu(111) epitaxially along the 〈112〉 crystallographic directions, which was found to be in agreement with the computational results, and at lower temperatures than on Au(111). This work demonstrates that the substrate plays an important role in the on-surface synthesis of GNRs and can result in new assembly modes of GNR structures.

Because of their intriguing electronic and optical properties, atomically precise graphene nanoribbons (GNRs) are considered to be promising materials for electronics and photovoltaics. However, significant aggregation and low solubility of GNRs in conventional solvents result in their poor processability for materials characterization and device studies. In this paper, we demonstrate a new fabrication approach for large-scale uniform thin films of nonfunctionalized atomically precise chevron-type GNRs. The method is based on (1) the exceptional solubility of graphitic materials in chlorosulfonic acid and (2) the original interfacial self-assembly approach by which uniform films that are single-GNR (∼2 nm) thick can be routinely prepared. These films can be transferred to various substrates including Si/SiO and used for the streamlined fabrication of arrays of GNR-based devices. The described self-assembly approach should be applicable to other types of solution-synthesized atomically precise GNRs as well as large polyaromatic hydrocarbon (PAH) molecules and therefore should facilitate and streamline their device characterization.