The preparation of large area coverage of films with uniaxially aligned poly(3-hexylthiophene) (P3HT) nanofibers by using zone-casting approach is reported. The length and the orientation of the nanofibers are defined by the solubility of the solvent

the P3HT molecular weight and the substrate temperature. The length of the oriented nanofibers could be increased from 1 μm to more than 10 μm by adding poor solvent into the P3HT solution. It is found that for P3HT of relatively low molecular weight

a solvent with relatively low solubility has to be chosen to get the oriented film. While for the high molecular weight P3HT

the solvent with a relatively high solubility has to be used. The well-aligned film could be obtained because of the solute concentration gradient in the region where the critical concentration is reached during the zone-casting process. Particularly

the solvent evaporation rate and crystallization rate must be chosen properly to satisfy the stationary conditions above

which were controlled by an appropriate choice of solvent and substrate temperature. The film prepared by zone-casting approach had microcrystalline P3HT domains with more inter-chain order than spin-coating film. Meanwhile

the P3HT π-π stacking direction was parallel to the alignment direction of the nanofibers.