Structure of the Crystalline Core of Fiber-like Polythiophene Block Copolymer Micelles

The internal structure and cross-sectional geometry of fiber-like poly­(3-hexylthiophene)-based block copolymer micelles has been determined using small- and wide-angle X-ray scattering (SAXS and WAXS, respectively) techniques alongside electron and atomic force microscopies. WAXS of concentrated micellar solutions demonstrated that the block copolymers form crystalline-core micelles in solvents selective for the corona-forming block. Furthermore, by generating macroscopic fibers from micellar solutions, it was possible to align the micelles and discern the type and orientation of the unit cell within the core. Using the unit cell information gained from the wide-angle measurements, in conjunction with the structural insights gained from the microscopy techniques, it was possible to form a complete picture of the cross-sectional geometry of the micelles, whereby the polymer chains lie perpendicular to the long axis of the micelle core and do not undergo chain folding. Finally, this information was used to propose a self-assembly mechanism and to construct and validate a model for the small-angle scattering data, revealing the inherent flexibility of the micelles.