Phenyl Functionalization of Atomically Precise Graphene Nanoribbons for Engineering Inter-ribbon Interactions and Graphene Nanopores
Graphene nanoribbons (GNRs) attract a great attention from researchers due to their tunable physical properties and potential for becoming nanoscale building blocks of electronic devices. GNRs can be synthesized with atomic precision by on-surface approaches from specially designed molecular precursors. While a considerable number of ribbons with very diverse structures and properties have been demonstrated in recent years, there have been only limited examples of on-surface synthesized GNRs modified with functional groups. In this study, we designed a nanoribbon, in which the chevron GNR backbone is decorated with phenyl functionalities, and demonstrate the on-surface synthesis of these GNRs on Au(111). We show that the phenyl modification affects the assembly of the GNR polymer precursors through π-π interactions. Scanning tunneling spectroscopy of the modified GNRs on Au(111) revealed that they have a band gap of 2.50±0.02 eV, which is comparable to that of the parent chevron GNR. The phenyl functionalization leads to a shift of the band edges to lower energies, suggesting that it could be a useful tool for the GNR band structure engineering. We also investigated lateral fusion of the phenyl-modified GNRs and demonstrate that it could be used to engineer different kinds of atomically precise graphene nanopores. A similar functionalization approach could be potentially applied to other GNRs to affect their on-surface assembly, modify their electronic properties, and realize graphene nanopores with a variety of structures.