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Selective Nucleation of Poly(3-hexyl thiophene) Nanofibers on Multilayer Graphene Substrates.

We demonstrate that graphene surfaces provide highly selective nucleation of poly(3-hexyl thiophene) (P3HT) nanofibers (NFs) from supersaturated solutions. Solvent conditions are identified that give rise to a wide hysteresis between crystallization and melting centered around room temperature, yielding metastable solutions that are stable against homogeneous nucleation for long periods of time but that allow for heterogeneous nucleation by graphene. Selective growth of P3HT crystals is found for multilayer graphene (MLG) supported on either Si or ITO substrates, with nucleation kinetics that are more rapid for MLG on Si but slower in both cases than for highly oriented pyrolytic graphite (HOPG). Although the NFs grow vertically from the substrate with face-on orientation of P3HT chains, we observe edge-on orientation in dried films, presumably due to capillary forces that cause collapse of the NFs onto the substrate during solvent evaporation.