A fast meniscus-guided coating for ultrahighly oriented thin films of a typical donor-acceptor π-conjugated polymer, poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno[3,2-b]thiophene)](PDPP-DTT) was realized. A coating speed higher than 100 mm/s, which was regarded as a Landau-Levich regime, was applicable. The 2D order parameter (S2) of the thin films changed by selecting the solvent and adjusting the initial concentration of the solution, and the large elongated rodlike preaggregates formed particularly in chlorobenzene contributed to the high orientation in the solid film state, resulting in the highest value of S2 = 0.87. Focused on the PDPP-DTT preaggregate formation in the solution, the SAXS analysis was carried out to investigate the shape and size of the preaggregates. The mechanism of the molecular orientation was discussed by taking the preaggregates and the solution flow under the coating process into account.
Keywords: bar-coating; molecular orientation; optical and electrical anisotropy; preaggregation; thin film fabrication; π-conjugated polymer.