Circular Intensity Differential Scattering Reveals the Internal Structure of Polymer Fibrils

The optical and electronic properties of π-conjugated polymers in organic electronic devices depend on their intra- and interchain interactions, dictated by the internal arrangement of the polymer chains in an amorphous or semicrystalline aggregated state. Here, we discuss the utility of circular intensity differential scattering (CIDS) of circularly polarized light as a sensitive probe to identify the internal arrangement of the polymer chains in helical polymer aggregates. We advance existing theoretical models to utilize the CIDS response and extract structural properties such as the size, orientation, and periodicity of a polymer aggregate. As an example, we analyze the CIDS signatures of helically assembled fibrillar aggregates of a chiral polymer poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(benzothiadiazole)] (PFBT) in solution and reveal that PFBT fibrils incorporate at least five intertwined polymer chains. We anticipate our approach can be extended more generally to investigate the internal arrangement of supramolecular assemblies of a wide range of fibrillar aggregates of π-conjugated polymers.