Alkoxy- and Alkyl-Side-Chain-Functionalized Terpolymer Acceptors for All-Polymer Photovoltaics Delivering High Open-Circuit Voltages and Efficiencies

A new terpolymer acceptor is presented, comprising various ratios of the same dithienothienopyrrolobenzothiadiazole (BTP) core with different side chains-alkoxy side chains (BTPO-IC) and alkyl side chains (BTP-IC)-and thiophene units, for use in all-polymer organic photovoltaics. Devices incorporating binary blends of this terpolymer and the polymer PM6 as the active layer displayed open-circuit voltages (V-OC) that increase linearly upon increasing the molar ratio of BTPO-IC. For example, the optimized device incorporating PM6:PY-0.2OBO (i.e., with 20 mol% of BTPO-IC) (1:1.2 wt.%) blend, with the smallest domain sizes but largest coherence length and combined face-on and edge-on orientation fractions among all blends, have a champion power conversion efficiency (PCE) of 16.7% (V-OC = 0.97 V; J(SC) = 25.2 mA cm(-2); FF = 0.68), whereas the device containing a similar blend ratio of the PM6:PY-OD:PY-OBO ternary blend (1:0.96:0.24 wt.%) displayed a PCE of 8.6% (V-OC = 0.969 V; J(SC) = 18.7 mA cm(-2); FF = 0.48). The device with PM6:PY-0.2OBO displays better thermal stability than the devices with PM6: PY-OD or PY-OBO. Thus, employing terpolymer acceptors with differently functionalized side-chain units can be an effective approach for simultaneously optimizing the aggregation domain and enhancing the PCEs and thermal stabilities of all-polymer devices.