Fine Structures in the Spherulites of Regioregular Poly(3-dodecylthiophene)

In this work, we employed various techniques to cooperatively characterize the crystalline structure and morphology of a regioregular poly(3‐dodecylthiophene). We observed the spherulites in casting films first by polarized light microscopy and then further studied the fine structures within the spherulites by scanning and transmission electron microscopy. These studies showed that the stripe‐like structures with a width of ≈20 nm and a length of 100–500 nm are the basic building blocks of the spherulites. The small‐angle X‐ray scattering and wide‐angle X‐ray diffraction studies further confirm the existence of such the structures. Considering the stiff and unfolding feature of the macromolecules, we believe that the stiff macromolecules may adopt a special way to form the fine structure: the orientation of stiff macromolecules parallel to the longitudinal direction of the stripes without any chain folding.