Tuning Charge Generation Process of Rylene Imide-Based Solar Cells via Chalcogen-Atom-Annulation

A series of high-performance organic semiconductors, which are modulated by introducing heteroatoms to rationally control molecular packing and charge carrier transport, have been successfully reported. However, a fundamental physical understanding of the impact of chalcogen atoms on intermolecular interactions between donors and acceptors as well as photophysical process in photovoltaic cells is still lagging. Herein, a detailed investigation on rylene imide-based solar cells is carried out to reveal the role of chalcogen atoms in controlling intermolecular interactions, molecular orientation in bulk and at the donor–acceptor interface, and polaron-pair dissociation. Compared to their Se-atom-free assisted counterparts, poly­{[4,8-bis­[5-(2-ethylhexyl)-4-fluoro-2-thienyl]­benzo­[1,2-<i>b</i>:4,5-<i>b</i>′]­dithiophene2,6-diyl]-<i>alt</i>-[2,5-thiophenediyl­[5,7-bis­(2-ethylhexyl)-4,8-dioxo-4<i>H</i>,8<i>H</i>-benzo­[1,2-<i>c</i>:4,5-<i>c</i>′]­dithiophene-1,3-diyl]]} (PBDB-TF): selenium-annulated triperylene hexaimide (TPH-Se) bulk heterojunctions preserve face-on orientation and possess smaller domain size, which are partially attributed to the Se···O van der Waals contacts between the acceptor and polymer chain. This feature enables PBDB-TF:TPH-Se interfaces with enhanced π-orbital overlap, improved charge transfer, a narrowed charge-transfer band, and suppressed polaron-pair binding energy. Consequently, all of the Se-containing solar cells investigated in this manuscript exhibit higher short-circuit current densities and conversion efficiencies than those in Se-atom-free devices. Our results reveal an important molecular design strategy for high-performance rylene imide-based acceptors: efficiently improving the electronic interactions at the D–A interface to increase polaron-pair dissociation and suppress geminate recombination.