Bulk heterojunction (BHJ) photovoltaics based on blends of conjugated polymers and fullerenes require an optimized nanoscale morphology. Casting BHJ films using solvent additives such as 1,8-diiodooctane (DIO), 1,8-octanedithiol (ODT), chloronapthalene (CN), or diphenyl ether (DPE) often helps achieve this proper morphology: adding just a few volume percent of additive to the casting solution can improve polymer/fullerene mixing or phase separation, so that solvent additives have become staples in producing high-efficiency BHJ solar cells. The mechanism by which these additives improve BHJ morphology, however, is poorly understood. Here, we investigate how these additives control polymer/fullerene mixing by taking advantage of sequential processing (SqP), in which the polymer is deposited first and then the fullerene is intercalated into the polymer underlayer in a second processing step using a quasi-orthogonal solvent. In this way, SqP isolates the role of the additives’ interactions with the polymer an...
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