Side Group Engineering of Small Molecular Acceptors for High-Performance Fullerene-Free Polymer Solar Cells: Thiophene Being Superior to Selenophene

Side group of ITIC-like small molecular acceptor (SMA) plays a critical role in crystallization property. In this article, two new SMAs with n-hexylthienyl and n-hexylselenophenyl as side chain, namely ITCPTC-Th and ITCPTC-Se, are designed and synthesized by employing newly developed thiophene-fused ending group (CPTCN). And thiophene and selenophene side group substituted effects of SMA-based fullerene-free polymer solar cells (PSCs) are investigated. A stronger s-inductive effect between selenophene side group and electron-donating backbone endows ITCPTC-Se with better optical absorption and higher LUMO level, ITCPTC-Th-based PSCs deliver a higher power conversion efficiency of 10.61%. Charge transport and collection, recombination loss mechanism, and morphology of blend films are intensively studied. These results confirm that side group substituted effects of SMAs are multiple and thiophene is a superior option to selenophene as aromatic side group of ITIC-like SMAs.