High-performance ternary polymer solar cells using wide-bandgap biaxially extended octithiophene-based conjugated polymers

Ternary organic photovoltaics (OPVs) have recently attracted intense research attention since they have been proven as an effective approach to enhance device performance. We herein describe a new strategy to realize high-performance ternary OPVs by using biaxially extended octithiophene (8T)-based wide-bandgap (E_g) conjugated polymers as the third photoactive component. Owing to the π-π transition of the biaxially extended conjugated side-chains, such polymers exhibit intense absorption in the near-ultraviolet region, in addition to the original intra-charge transfer (ICT) feature arising from the main backbone, revealing a new molecular design for wide-E_g polymers. By further tailoring the polymer backbone with p-type moieties such as thiophene (T) or thienothiphene (TT), two wide-E_g (∼2.0 eV) polymers, P8TT and P8TTT, with absorption wavelengths below 650 nm, were prepared, showing high complementary absorption to the spectra of both the state-of-the-art fullerene-(PTB7-Th:PC₇₁BM) and non-fullerene-based (PBDB-T:ITIC) bulk-heterojunction (BHJ) systems. By providing suitable energy levels, P8TTT was demonstrated to enhance the power conversion efficiency (PCE) of its derived fullerene- and non-fullerene-based ternary blends by 7.58% and 6.60%, respectively, with only a small loading amount (10 wt%). This study manifests a new perspective in wide-E_g material design for realizing efficient ternary BHJ systems.