Blending Donors with Different Molecular Weights: An Efficient Strategy to Resolve the Conflict between Coherence Length and Intermixed Phase in Polymer/Nonfullerene Solar Cells

Abstract Long coherence lengths (CLs) of crystals and proper intermixed phase amount guarantee charge transport and exciton dissociate efficiently, which is crucial for organic solar cells (OSCs) to achieve high device performance. However, extending CLs usually reduces the intermixed phase, leading to an insufficient interface for exciton dissociation. Herein, a strategy using a binary polymer with different molecular weights as donor is employed, that is, poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) with high (P3HT‐H) and low (P3HT‐L) molecular weight are blended as donor, and (5Z,5′Z)‐5,5′‐(((4,4,9,9‐tetraoctyl‐4,9‐dihydro‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐2,7‐diyl)bis(benzo[c][1,2,5]thiadiazole‐7,4‐diyl))bis(methanylylidene))bis(3‐ethyl‐2‐thioxothiazolidin‐4‐one) (O‐IDTBR) is used as acceptor. In kinetics, the entanglements of P3HT‐H are relieved due to the higher molecular diffusivity of P3HT‐L. In thermodynamics, the miscibility of P3HT‐L/O‐IDTBR, P3HT‐H/O‐IDTBR, and P3HT‐L/P3HT‐H blends increases in turn. Hence, P3HT forms a more ordered structure with longer CLs after adding P3HT‐L, which also drives O‐IDTBR dispersed in P3HT crystalline regions diffuse to the O‐IDTBR crystalline regions to further self‐organize. Consequently, the CLs of both P3HT and O‐IDTBR are extended, while keeping the intermixed phase amount proper. The optimized microstructure boosts device performance from 7.03% to 7.80%, which is one of the highest values reported for P3HT/O‐IDTBR blends. This is a novel way to solve the conflict mentioned above, which may provide guidance to finely regulating the morphology of the active layer.