A Fused‐Ring Acceptor Unit in D–A Copolymers Benefits Photovoltaic Performance

Pentacyclic lactam acceptor unit TPTI invented by our group is proved to be a good building block for efficient D‐A copolymers used in organic solar cells. Here, two D‐A copolymers PBTTPTI and PTTTPTI are developed by copolymerizing TPTI with 2,2′‐bithiophene (BT) or thieno3,2‐b]thiophene (TT). PBTTPTI and PTTTPTI exhibit good solubility and strong interchain π–π interaction even in dilute solution. They possess deep HOMO levels (ca. ‐5.3 eV), partial crystallinity, and good hole mobilities. Blending with PC₇₁BM, PBTTPTI and PTTTPTI give decent power conversion efficiencies (PCE) up to 6.83% and 5.86%, with outstanding fill factors (FF) of 74.3% and 71.3%, respectively.