Fluorination Effects on Indacenodithienothiophene Acceptor Packing and Electronic Structure, End-Group Redistribution, and Solar Cell Photovoltaic Response

Indacenodithienothiophene (IDTT)-based postfullerene electron acceptors, such as ITIC (2,2′-[[6,6,12,12-tetrakis(4-hexylphenyl)-6,12-dihydrodithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene-2,8-diyl]-bis[methylidyne(3-oxo-1H-indene-2,1(3H)-diylidene)]]bis[propanedinitrile]), have become synonymous with high power conversion efficiencies (PCEs) in bulk heterojunction (BHJ) polymer solar cells (PSCs). Here we systematically investigate the influence of end-group fluorination density and positioning on the physicochemical properties, single-crystal packing, end-group redistribution propensity, and BHJ photovoltaic performance of a series of ITIC variants, ITIC-nF (n = 0, 2, 3, 4, and 6). Increasing n from 0 → 6 contracts the optical bandgap, but only marginally lowers the LUMO for n > 4. This yields enhanced photovoltaic short-circuit current density and good open-circuit voltage, so that ITIC-6F achieves the highest PCE of the series, approaching 12% in blends with the PBDB-TF donor polymer. Sing...