Effect of Number and Position of Chlorine Atoms on the Photovoltaic Performance of Asymmetric Nonfullerene Acceptors.

It has been well proved that the introduction of halogen can effectively modify the optoelectronic properties of classic symmetric nonfullerene acceptors (NFAs). However, the relevant studies for asymmetric NFAs are limited, especially the effect of halogen substitution number and position on the photovoltaic performance is not clear. In this work, four asymmetric NFAs with A-D-A 1 -A 2 structure are developed by tuning the number and position of chlorine atoms on the 1,1-dicyanomethylene-3-indanone end groups, namely, A303, A304, A305, and A306. The related NFAs show progressively deeper energy levels and red-shifted absorption spectra as the degree of chlorination increases. The PM6:A306-constructed organic solar cells (OSCs) give a champion power conversion efficiency (PCE) of 13.03%. This is mainly ascribed to the most efficient exciton dissociation and collection, suppressed charge recombination, and optimal morphology. Moreover, by alternating the substitution position, the PM6:A305-based device yielded a higher PCE of 12.53% than that of PM6:A304 (12.05%). This work offers fresh insights into establishing excellent asymmetric NFAs for OSCs.