Abstract : Mechanical rubbing of polymer films has been widely used in the liquid crystal display industry to prepare oriented alignment layers of polyimides. We show that this fast orientation method can be successfully applied to a large palette of different π-conjugated systems, i.e., p- and n-type semiconducting homopolymers and alternating copolymers. Transmission electron microscopy, grazing incidence X-ray diffraction and UV-vis absorption spectroscopy reveal that both, the temperature of the films during rubbing and the molecular weight of the polymer strongly influence the level of orientation. For polythiophenes and polyfluorenes, the dependence of the orientational order parameter on the rubbing temperature (Trub) was determined. A strong increase of alignment with Trub is explained by the progressive alignment of higher molecular weight fractions at higher Trub. The disordering of alkyl side chains allows the hairy-rod shaped macromolecules to disentangle and align during rubbing. In addition, for certain conjugated polymers, the in-plane orientation, crystallinity, and polymorphism of the rubbed films can be substantially improved/modified by postdeposition thermal or solvent vapor annealing. This high level of orientation results in highly anisotropic optical and electronic properties (UV-vis absorption, fluorescence, charge transport).
