Following the Morphology Formation In Situ in Printed Active Layers for Organic Solar Cells

The device performance of organic polymer:fullerene bulk heterojunction solar cells strongly depends on the interpenetrating network of the involved donor and acceptor materials in the active layer. Since morphology formation depends on the conditions of film preparation, the final morphology varies for different deposition methods. In order to understand and optimize industrial coating processes and, therefore, the performance of the solar cells produced, a deeper understanding of structure formation is important. In situ measurements of slot‐die printed polymer:fullerene active layers are presented that reveal insights into the evolution of the structure. Polymer crystallization and ordering is monitored by in situ grazing incidence wide angle X‐ray scattering (GIWAXS), and in situ grazing incidence small‐angle X‐ray scattering (GISAXS). The development of the morphology exhibits five stages independent of the drying conditions. Two growth rates are observed, an initial slow formation of poly(3‐hexylthiophene‐2,5‐diyl) crystallites in well‐aligned edge‐on orientation followed by a rapid crystal growth. By combining the GIWAXS and GISAXS measurements, a five‐stage growth and assembly process is found and described in detail along with a proposed model of the structural evolution. The findings are an important step in tailoring the assembly process.