π‑Bridge-Independent 2‑(Benzo[c][1,2,5]thiadiazol-4-ylmethylene)malononitrile-Substituted Nonfullerene Acceptors for Efficient Bulk Heterojunction Solar Cells

Molecular acceptors are promising alternatives to fullerenes (e.g., PC₆₁/₇₁BM) in the fabrication of high-efficiency bulk-heterojunction (BHJ) solar cells. While solution-processed polymer–fullerene BHJ devices have recently met the 10% efficiency threshold, molecular acceptors have yet to prove comparably efficient with polymer donors. At this point in time, it is important to forge a better understanding of the design parameters that directly impact small-molecule (SM) acceptor performance in BHJ solar cells. In this report, we show that 2-(benzo­[c]­[1,2,5]­thiadiazol-4-ylmethylene)­malononitrile (BM)-terminated SM acceptors can achieve efficiencies as high as 5.3% in BHJ solar cells with the polymer donor PCE10. Through systematic device optimization and characterization studies, we find that the nonfullerene analogues (FBM, CBM, and CDTBM) all perform comparably well, independent of the molecular structure and electronics of the π-bridge that links the two electron-deficient BM end groups. With estimated electron affinities within range of those of common fullerenes (4.0–4.3 eV), and a wider range of ionization potentials (6.2–5.6 eV), the SM acceptors absorb in the visible spectrum and effectively contribute to the BHJ device photocurrent. BM-substituted SM acceptors are promising alternatives to fullerenes in solution-processed BHJ solar cells.