Lawrence Berkeley National Laboratory

The electronic properties of organic semiconductors are strongly influenced by intermolecular packing. When cast as thin films, crystalline π-conjugated molecules are strongly textured, potentially leading to anisotropic charge transport. Consequently, it is hypothesized that the orientation of crystallites in the active layer plays an important role in charge extraction and organic photovoltaic device performance. Here we demonstrate orientation control of molecular packing from mostly face-on to edge-on configurations in the active layer of P3HT-b-PFTBT block copolymer photovoltaics using 1-chloronaphthalene as a solvent additive. The effect of molecular orientations in P3HT crystals on charge transport and solar cell performance is examined. We find that optimized photovoltaic device performance is independent of the crystalline texture of P3HT. Our observations provide further insights into the molecular organization required for efficient charge transport and overall device efficiencies. The dominant crystal orientation, whether face-on or edge-on, is not critical to block copolymer solar cells. Instead, a broad distribution of crystallite orientations ensures pathways for charge transport in any direction and enables efficient charge extraction in photovoltaic devices.