Phase behaviour of liquid-crystalline polymer/fullerene organic photovoltaic blends: thermal stability and miscibility

The thermal behaviour of an organic photovoltaic (OPV) binary system comprised of a liquid-crystalline fluorene-based polymer and a fullerene derivative is investigated. We employ variable-temperature ellipsometry complemented by photo-and electroluminescence spectroscopy as well as optical microscopy and scanning force nanoscopy to explore phase transitions of blend thin films. The high glass transition temperature correlates with the good thermal stability of solar cells based on these materials. Furthermore, we observe partial miscibility of the donor and acceptor together with the tendency of excess fullerene derivative to segregate into exceedingly large domains. Thus, for charge generation less adequate bulk-heterojunction nanostructures are poised to develop if this mixture is exposed to more elevated temperatures. Gratifyingly, the solubility of the fullerene derivative in the polymer phase is found to decrease if a higher molecular-weight polymer fraction is employed, which offers routes towards improving the photovoltaic performance of non-crystalline OPV blends.