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Graphene-based nanostructures exhibit a vast range of exciting electronicproperties that are absent in extended graphene. For example, quantumconfinement in carbon nanotubes and armchair graphene nanoribbons (AGNRs) leadsto the opening of substantial electronic band gaps that are directly linked totheir structural boundary conditions. Even more intriguing are nanostructureswith zigzag edges, which are expected to host spin-polarized electronic edgestates and can thus serve as key elements for graphene-based spintronics. Themost prominent example is zigzag graphene nanoribbons (ZGNRs) for which theedge states are predicted to couple ferromagnetically along the edge andantiferromagnetically between them. So far, a direct observation of thespin-polarized edge states for specifically designed and controlled zigzag edgetopologies has not been achieved. This is mainly due to the limited precisionof current top-down approaches, which results in poorly defined edgestructures. Bottom-up fabrication approaches, on the other hand, were so faronly successfully applied to the growth of AGNRs and related structures. Here,we describe the successful bottom-up synthesis of ZGNRs, which are fabricatedby the surface-assisted colligation and cyclodehydrogenation of specificallydesigned precursor monomers including carbon groups that yield atomicallyprecise zigzag edges. Using scanning tunnelling spectroscopy we prove theexistence of edge-localized states with large energy splittings. We expect thatthe availability of ZGNRs will finally allow the characterization of theirpredicted spin-related properties such as spin confinement and filtering, andultimately add the spin degree of freedom to graphene-based circuitry.

On-surface synthesis of graphene nanoribbons with zigzag edge topology