Controlling Crystal Orientation in Films of Conjugated Polymers by Tuning the Surface Energy

It has been a long-term goal to understand the molecular orientation in films of conjugated polymers, which is crucial to their efficient exploitation. Here, we show that the surface energies determine the crystal orientation in films of model conjugated polymers, substituted polythiophenes crystallized on substrates. We systematically increase the surface energy of edge-on crystals formed at the vacuum interface by attaching polar groups to the ends of the polymer side chains. This suppresses crystallization at the vacuum interface, resulting in a uniform face-on crystal orientation induced by the graphene substrate in polythiophene films as thick as 200 nm, which is relevant for devices. Surprisingly, face-on crystal orientation is attained in the modified polythiophenes crystallized even on amorphous surfaces. Furthermore, for the samples with still competing interfacial interactions, the crystal orientation can be switched in the same sample, depending on the crystallization conditions. Thus, we report a fundamental understanding and control of the equilibrium crystal orientation in films of conjugated polymers.