Photoinduced charge generation rates in soluble P3HT: PCBM nano-aggregates predict the solvent-dependent film morphology

The device efficiency of bulk heterojunction (BHJ) solar cells is critically dependent on the nano-morphology of the solution-processed polymer : fullerene blend. Active control on blend morphology can only emanate from a detailed understanding of solution structures during the film casting process. Here we use photoinduced charge transfer (CT) rates to probe the effective length scale of the pre-formed solution structures and their energy disorder arising from a mixture of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in three different organic solvents. The observed solvent-dependent ultrafast biphasic rise of the transient polaron state in solution along with changes detected in the C=C stretching frequency of bound PCBM provides direct evidence for film-like P3HT : PCBM interfaces in solution. Using the diffusive component of the charge transfer rate, we deduce similar to 3-times larger functional nano-domain size in toluene than in chlorobenzene thereby correctly predicting the relative polymer nanofiber widths observed in annealed films. We thus provide first experimental evidence for the postulated polymer : fullerene : solvent ternary phase that seeds the eventual morphology in spin-cast films. Our work motivates the design of new chemical additives to tune the grain size of the evolving polymer : fullerene domains within the solution phase.