Modulating phase segregation during spin‐casting of fullerene‐based polymer solar‐cell thin films upon minor addition of a high‐boiling co‐solvent

The impact of additives on the nanoscale structures of spin‐cast polymer composite films, particularly in polymer solar cells, is a topic of significant interest. This study focuses on the blend film comprising poly(thieno[3,4‐b]thiophene‐alt‐benzodithiophene) (PTB7) and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM), exploring how additives like 1,8‐diiodooctane (DIO) influence the film structures spin‐cast from chlorobenzene solution. Combined results of specular X‐ray and neutron reflectivity, grazing‐incidence small‐ and wide‐angle X‐ray scattering (GISAXS and GIWAXS), and X‐ray photoelectron spectroscopy indicate that DIO could significantly enhance the dispersion of PC71BM and reduce composition inhomogeneity in the film. Time‐resolved GISAXS–GIWAXS with 100 ms resolution further captures a rapid spinodal decomposition of the mixture within 1 s in the constant‐evaporation stage of spin‐casting. Further combined with parallel analysis of time‐resolved UV–Vis reflectance, these findings reveal that DIO mitigates the spinodal decomposition process by accelerating solvent evaporation, which, in turn, decelerates phase segregation, leading to a nucleation‐driven process. These observations provide mechanistic insights into the role of additives in controlling the nanostructural evolution of spin‐cast films by altering the kinetics of solvent evaporation and phase separation during the spin‐coating process. Combined 100 ms‐resolved grazing‐incidence small/wide‐angle X‐ray scattering and optical interferometry reveal that the additive diiodooctane can double the solvent evaporation rate, thereby effectively suppressing the rapid spinodal decomposition process in the early stage of spin‐coating, favouring slow phase segregation kinetics with nucleation and growth.