Polarized Soft X-Ray Scattering Reveals Chain Orientation Within Nanoscale Polymer Domains

Fully conjugated donor acceptor block copolymers can serve as the active layer in organic photovoltaics and other organic electronic devices. Self-assembly into periodic domains and crystallization of the constituent blocks are crucial to enable control of the multiscale structure and consequently electronic properties. Resonant soft X-ray scattering (RSoXS) is an invaluable tool to characterize such materials, where tuning the X-ray energy and polarization reveals molecular orientation and domain spacing. Here, anisotropic soft X-ray scattering data reveal the type and degree of orientation within conjugated block copolymers composed of poly(3-hexylthiophene-2,5-diy1) and various push pull copolymers. The maximum anisotropy is observed at the scattering vector corresponding to the spacing between block copolymer domains, which scales with the end-to-end distance of the blocks, as expected. Furthermore, the anisotropy in RSoXS data reveals that the crystalline P3HT blocks orient, on average, parallel or nearly parallel to the block copolymer interface; the average tilt angle between P3HT chains and domain interfaces can be extracted from the dependence of the anisotropy with polar angle. We interpret this angle to correspond to the average tilt of rings in the unit cell, potentially within a chiral mesostructure. Results are corroborated with scattering calculations based on simple model structures.