Crystallinity Effects in Sequentially Processed and Blend-Cast Bulk-Heterojunction Polymer/Fullerene Photovoltaics

Although most polymer/fullerene-based solar cells are cast from a blend of the components in solution, it is also possible to sequentially process the polymer and fullerene layers from quasi-orthogonal solvents. Sequential processing (SqP) not only produces photovoltaic devices with efficiencies comparable to the more traditional bulk heterojunction (BHJ) solar cells produced by blend casting (BC) but also offers the advantage that the polymer and fullerene layers can be optimized separately. In this paper, we explore the morphology produced when sequentially processing polymer/fullerene solar cells and compare it to the BC morphology. We find that increasing polymer regioregularity leads to the opposite effect in SqP and BC BHJ solar cells. We start by constructing a series of SqP and BC solar cells using different types of poly(3-hexylthiophene) (P3HT) that vary in regioregulary and polydispersity combined with [6,6]-phenyl-C-61-butyric-acid-methyl-ester (PCBM). We use grazing incidence wide-angle X-ray scattering to demonstrate how strongly changes in the P3HT and PCBM crystallinity upon thermal annealing of SqP and BC BHJ films depend on polymer regioregularity. For SqP devices, low regioregularity P3HT films that possess more amorphous regions allow for more PCBM crystallite growth and thus show better photovoltaic device efficiency. On the other hand, highly regioregular P3HT leads to a more favorable morphology and better device efficiency for BC BHJ films. Comparing the photovoltaic performance and structural characterization indicates that the mechanisms controlling morphology in the active layers are fundamentally different for BHJs formed via SqP and BC. Most importantly, we find that nanoscale morphology in both SqP and BC BHJs can be systematically controlled by tuning the amorphous fraction of polymer in the active layer.