Designing Benzodithiophene-Based Small Molecule Donors for Organic Solar Cells by Regulation of Halogenation Effects

The donors are key components of organic solar cells (OSCs) and play crucial roles in their photovoltaic performance. Herein, we designed two new donors (BTR-gamma-Cl and BTR-gamma-F) by finely optimizing small molecule donors (BTR-Cl and BTR-F) with a high performance. The optoelectronic properties of the four donors and their interfacial properties with the well-known acceptor Y6 were studied by density functional theory and time-dependent density functional theory. Our calculations show that the studied four donors have large hole mobility and strong interactions with Y6, where the BTR-gamma-Cl/Y6 has the largest binding energy. Importantly, the proportion of charge transfer (CT) states increases at the BTR-gamma-Cl/Y6 (50%) and BTR-gamma-F/Y6 (45%) interfaces. The newly designed donors are more likely to achieve CT states through intermolecular electric field (IEF) and hot exciton mechanisms than the parent molecules; meanwhile, donors containing Cl atoms are more inclined to produce CT states through the direct excitation mechanism than those containing F atoms. Our results not only provided two promising donors but also shed light on the halogenation effects on donors in OSCs, which might be important to design efficient photovoltaic materials.