Strengthening the Intermolecular Interaction of Prototypical Semicrystalline Conjugated Polymer Enables Improved Photocurrent Generation at the Heterojunction.

The intra and intermolecular interactions (J‐ and H‐type aggregation) in the conjugated polymer films are found to readily facilitate the electron and hole transport, respectively. However, how those different aggregation types influence the photocurrent generation at the heterojunction is still mysterious, especially for the newly developed semicrystalline conjugated polymers. Here, the prototypical copolymer PM6 is used to tune the relative content of aggregation types with various halogen‐free processing solvents. Various measurements reveal that the toluene‐processed PM6 film exhibits the increased H‐aggregates and crystallinity in the π–π stacking direction compared to its o‐xylene‐ and trimethylbenzene (TMB)‐processed counterparts. This is partly resulted from the weak steric effect and good solubility in the PM6 solution prepared with toluene, which strengthens the intermolecular interaction of adjacent polymer segments. After analyzing the photovoltaic properties of PM6/Y6 bilayer devices, the faster charge carrier transport, smaller charge recombination, lower energy losses, and interfacial energetic disorder can be observed in the toluene‐processed device, leading to the synergistically improved short‐circuit current density (JSC) and open‐circuit voltage (VOC). These findings indicate the control of the molecular packing structure in terms of aggregation types is a powerful strategy to promote the photocurrent generation process at the conjugated polymer‐based heterojunction. [ABSTRACT FROM AUTHOR]