Modulation of End Groups for Low‐Bandgap Nonfullerene Acceptors Enabling High‐Performance Organic Solar Cells

Abstract The field of nonfullerene organic solar cells (OSCs) has seen an impressive progress, largely due to advances in high‐performance small molecule acceptors (SMAs). As a large portion of the solar energy is located in the near‐infrared region, it is important to develop ultralow‐bandgap SMAs that have extended absorption in the spectral range of 800–1000 nm to maximize light absorption and efficiencies. In this work, three low‐bandgap SMAs, namely, IXIC, IXIC‐2Cl, and IXIC‐4Cl, are designed and synthesized with same fused terthieno[3,2‐b]thiophene donor unit and different end groups (EGs). The three SMAs all have low optical bandgap (Eg) of 1.35, 1.30, and 1.25 eV, respectively. The chlorination on EGs can lower the energy level and broaden absorption range of the SMAs. As a result, the Voc of the devices is reduced but the Jsc is significantly increased. In addition, the addition of chlorine atoms can enhance π–π stacking and crystallinity of the SMAs, which result in high fill factors. Overall, the optimum EGs are monochlorine‐substituted IC and OSCs based on PBDB‐T:IXIC‐2Cl that can achieve remarkable power conversion efficiencies (PCEs) of 12.2%, which is one of the highest PCEs for nonfullerene organic solar cells based on low‐bandgap SMAs.