We report a comparative study on the self-assembly from solution and electrical characterization of n-type semiconducting fibres obtained from five different perylenebis(dicarboximide) (PDI) derivatives. In particular we investigated the role of the nature of the alkyl chain covalently linked to the N,N′ sites of the PDI in modulating the molecular solubility and aggregation capacity. We explored the morphologies of the self-assembled architectures physisorbed on dielectric surfaces and in particular how they can be modified by tuning the deposition and post-deposition procedures, i.e. by modulating the kinetics of the self-assembly process. To this end, alongside the conventional spin-coating, solvent vapour annealing (SVA) and solvent induced precipitation (SIP) have been employed. Both approaches led to fibres having widths of several hundred nanometres and lengths up to tens of micrometres. SVA formed isolated fibres which were tens of nanometres high, flat, and tapered at the ends. Conversely, SIP fibres exhibited nearly matching heights and widths, but organized into bundles. Despite these morphological differences, the same intermolecular packing is found by XRD in each type of structure, albeit with differing degrees of long-range order. The study of the electrical characteristics of the obtained low dimensional nano-assemblies has been accomplished by fabricating and characterizing organic field-effect transistors.
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