Conjugation‐Curtailing of Benzodithionopyran‐Cored Molecular Acceptor Enables Efficient Air‐Processed Small Molecule Solar Cells

Abstract Small molecule solar cells (SMSCs) lag a long way behind polymer solar cells. A key limit is the less controllable morphology of small molecule materials, which can be aggravated when incorporating anisotropic nonfullerene acceptors. To fine‐tune the blending morphology within SMSCs, a π‐conjunction curtailing design is applied, which produces a efficient benzodithionopyran‐cored molecular acceptor for nonfullerene SMSCs (NF‐SMSCs). When blended with a molecular donor BDT3TR‐SF to fabricate NF‐SMSCs, the π‐conjunction curtailed molecular acceptor NBDTP‐M obtains an optimal power conversion efficiency (PCE) of up to 10.23%, which is much higher than that of NBDTTP‐M of longer π‐conjunction. It retains 93% of the PCE of devices fabricated in a glove box when all spin‐coating and post‐treating procedures are conducted in ambient air with relative humidity of 25%, which suggests the good air‐processing capability of π‐conjunction curtailed molecules. Detailed X‐ray scattering investigations indicate that the BDT3TR‐SF:NBDTP‐M blend exhibits a blend morphology featuring fine interpenetrating networks with smaller domains and higher phase purity, which results in more efficient charge generation, more balanced charge transport, and less recombination compared to the low‐performance BDT3TR‐SF:NBDTTP‐M blend. This work provides a guideline for molecular acceptors' design toward efficient, low‐cost, air‐processed NF‐SMSCs.