Ideal spread monolayer and multilayer formation of fully hydrophobic polythiophenes via liquid crystal hybridization on water

The spread monolayer formation of hydrophobic poly (3-alkylthiophene)s (P3ATs), regioregular poly(3-hexylthiophene) (HT-P3HT), regioregular poly(3-dodecylthiophene) (HT-P3DT), and regioirregular poly(3-hexylthiophene) (RI-P3HT), were attained on the water surface via cospreading with a liquid-crystal molecule, 4'-pentyl-4-cyanobiphenyl (5CB). The spread monolayers were characterized by R-A isotherms, Brewster angle microscopy (BAM), and atomic force microscopy (AFM). The molecular area for the cospread mixtures of P3ATs and 5CB expanded more than that of pure P3ATs as shown from the pi-A isotherms. BAM revealed that the mixed film forms the monomolecularly uniform and flat films on water. AFM elucidated that the spread monolayer of the hydrophobic P3ATs formed on the top of the 5CB monolayer on water with thicknesses of ca. 1.6 and ca. 2.6 nm for the two P3HTs and HT-P3DT, respectively. The P3AT/5CB hybrid monolayers could be fully transferred onto a solid substrate, and pure P3AT monolayers were obtained after volatilization of 5CB by gentle heating. The multilayer formation of pure MAT monolayers was prepared by layer-by-layer deposition involving repeating horizontal deposition and successive volatilization of 5CB. Grazing angle incidence X-ray diffraction measurements showed that the lamella plane of the P3ATs is perfectly oriented parallel to the substrate plane in the resulting thin films. This shows a marked contrast with those obtained by spin casting using the identical polymer, where both in-plane and out-of-plane lamellae are involved. These thin films with perfectly controlled lamella orientation should be of great significance as the model system for evaluating the charge mobility for organic polymer electric devices.