Understanding Structure–Property Relationships in All-Small-Molecule Solar Cells Incorporating a Fullerene or Nonfullerene Acceptor

To investigate the influence of donor molecule crystallinity on photovoltaic performance in all-small-molecule solar cells, two dithieno­[2,3-d:2′,3′-d′]-benzo­[1,2-b:4,5-b′]­dithiophene (DTBDT)-based small molecules, denoted as DTBDT-Rho and DTBDT-S-Rho and incorporating different side chains, are synthesized and characterized. The photovoltaic properties of solar cells made of these DTBDT-based donor molecules are systemically studied with the [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) fullerene acceptor and the O-IDTBR nonfullerene acceptor to study the aggregation behavior and crystallinity of the donor molecules in both blends. Morphological analyses and a charge carrier dynamics study are carried out simultaneously to derive structure–property relationships and address the requirements of all-small-molecule solar cells. This study reveals exciton decay loss driven by large-scale phase separation of the DTBDT molecules to be a crucial factor limiting photocurrent generation in the all-small-molecule solar cells incorporating O-IDTBR. In the all-small-molecule blends, DTBDT domains with dimensions greater than 100 nm limit the exciton migration to the donor–acceptor interface, whereas blends with PC71BM exhibit homogeneous phase separation with smaller domains than in the O-IDTBR blends. The significant energy losses in nonfullerene-based devices lead to decreased Jsc and fill factor values and unusual decrease in Voc values. These results indicate the modulation of phase separation to be important for improving the photovoltaic performances of all-small-molecule blends. In addition, the enhanced molecular aggregation of DTBDT-S-Rho with the alkylthio side chain leads to higher degrees of phase separation and unfavorable charge transfer, which are mainly responsible for the relatively low photocurrent when using DTBDT-S-Rho compared with that when using DTBDT-Rho. On the other hand, this enhanced molecular aggregation improves the crystallinity of DTBDT-S-Rho and results in its increased hole mobility