Tuning the order of poly(3-alkylthiophene) derivatives ultrathin films through side-chain polarity: From a short-range ordered monolayer to a highly crystalline bilayer

In order to pave the way for the formation of ultrathin electronically conductive organic films, we explored the structure and morphology of polythiophene derivatives in situ on the water surface. By changing the side chain end-group of poly(3-hexylthiophene) (P3HT) from methyl to carboxylic acid potassium salt, we showed that the film structure is drastically changed from a highly ordered bilayer to a short -range organized monolayer. Using a comprehensive experimental approach from macroscopic length scale to molecular organization as well as simulations of diffraction patterns, the detailed structure of the crystalline P3HT bilayer was determined. Some similarities with the structure measured on thicker films deposited on solid substrates were evidenced such as the pi-stacking distance, the interlayer spacing, and the edge-on conformation. Some differences were also pointed out, in particular the in -plane packing along the polymer backbones and the shift of the upper monolayer with respect to the bottom one in this direction. Such observations highlighted the influence of both the forced twodimensional confinement and the nature of the substrate (water) on the P3HT film structure. The presence of a carboxylic acid potassium salt at the end of the side chain induced completely different behavior. Indeed, high pressures were necessary to observe a pi-stacking of the thiophene units, but only short -range, and although the polymer keeps a monolayer organization independently of the pressure, a deep change in the polymer conformation was evidenced with the pressure.