Molecular Considerations for Mesophase Interaction and Alignment of Lyotropic Liquid Crystalline Semiconducting Polymers

Intermolecular interactions in conjugated polymers influence crystallinity, self-assembly, and packing motif, factors which in turn crucially impact charge transport properties such as carrier mobility in organic electronic devices. Correlated alignment of molecular and crystalline morphologies provides direct pathways for charge carriers to follow; however, the role of intermolecular interactions in achieving this is unexplored. Herein, we synthesize a series of lyotropic liquid crystalline conjugated polymers with variable side-chain structure to lend distinct steric repulsion and van der Waals attractive forces to each mesophase. We use this to investigate the role of intermolecular interactions on mesophase alignment. The strength of intermolecular interaction for each mesophase is compared by measuring melting temperature, π-stacking distance, and the Maier-Saupe interaction parameter. In general we find that side-chain structure can impact interaction strength by varying steric repulsion and backbone attractions and that the Maier-Saupe interaction parameters correlate with higher degrees of alignment after shearing, achieving a dichroic absorbance ratio of up to 2. This observation is used to develop equilibrium processing methods for fabricating macroscopically aligned polymer substrates used in transistors, improving mobility by a factor of 3 compared to spin-coated devices.