Herein, we investigate the role of processing solvent additives on the formation of polymer-perylene diimide bulk-heterojunction active layers for organic photovoltaics using both spin-coating and slot-die coating methods. We compare the effect of 1,8-diiodooctane (DIO) and diphenyl ether (DPE) as solvent additives on the aggregation behavior of the non-fullerene acceptor, N-annulated perylene diimide dimer (tPDI2N-EH), in neat films and blended films with the benzodithiophene-quinoxaline (BDT-QX, QX-3) donor polymer, processed from toluene in air. DIO processing crystallizes the tPDI2N-EH acceptor and leads to the decreased solar cell performance. DPE processing has a more subtle effect on the bulk-heterojunction morphology and leads to an improved solar cell performance. A comparison of the spin-coating vs slot-die coating methods shows that the effect of DPE is prominent for the slot-die coated active layers. While similar device power conversion efficiencies are achieved with active layers coated with both methods (ca. 7.3% vs 6.5%), the use of DPE improves the film quality when the slot-die coating method is employed.
Keywords: diphenyl ether; halogen-free processing; morphology control; organic photovoltaics; perylene diimide; quinoxaline; slot-die coating; solvent additive.