Interfacial width and phase equilibrium in polymer-fullerene thin-films

Domain composition and interfacial structure are critical factors in organic photovoltaic performance. Here, we report neutron reflectivity, grazing-incidence X-ray diffraction and atomic force microscopy measurements of polymer/fullerene thin-films to test a hypothesis that these partially miscible blends rapidly develop composition profiles consisting of co-existing phases in liquid-liquid equilibrium. We study a range of polymer molecular weights between 2 and 300 kg mol(-1), annealing temperatures between 120 and 170 degrees C, and timescales up to 10 min, yielding over 50 distinct measurement conditions. Model bilayers of fullerene-derivatives and polystyrene enable a rigorous examination of theoretical predictions of the effect of polymer mass and interaction parameter on the compositions, phi, and interfacial width, w, of the coexistent phases. We independently measure phi and w and find that both Flory-Huggins mean-field-theory and key aspects of self-consistent-field-theory are remarkably consistent with experiment. Our findings pave the way for predictive composition and interface design in organic photovoltaics based on simple experimental measurements and equilibrium thermodynamic theory.