Long and isolated graphene nanoribbons by on-surface polymerization on Au(111).

Low electronic gap graphene nanoribbons (GNRs) are used for the fabrication of nanomaterial-based devices and, when isolated, for mono-molecular electronics experiences, for which a well-controlled length is crucial. Here, an on-surface chemistry protocol is monitored for producing long and well-isolated GNR molecular wires on an Au(111) surface. The two-step Ullmann coupling reaction is sequenced in temperature from 100 °C to 350 °C by steps of 50 °C, returning at room temperature between each step and remaining in ultrahigh vacuum conditions. After the first annealing step at 100 °C, the monomers self-organize into 2-monolayered nano-islands. Next, the Ullmann coupling reaction takes place in both 1st and 2nd layers of those nano-islands. The nano-island lateral size and shape are controlling the final GNR lengths. Respecting the above on-surface chemistry protocol, an optimal initial monomer coverage of ~1.5 monolayer produces isolated GNRs with a final length distribution reaching up to 50 nm and a low surface coverage of ~0.4 monolayer suitable for single molecule experiments.