Small-Molecule Bulk Heterojunctions: Distinguishing Between Effects of Energy Offsets and Molecular Packing on Optoelectronic Properties

ABSTRACT: We report on the dependence of time-resolved photoluminescence (PL) and photocurrent in small-molecule bulk heterojunctions on the donor− acceptor (D/A) LUMO offset, D/A separation, and acceptor domain structure. We chose a high-performance functionalized fluorinated anthradithiophene (ADT) derivative, ADT-TES-F, as the donor and two other fluorinated ADT derivatives, ADT-R-F (where R is a variable side group), as well as two functionalized fluorinated pentacene (Pn) derivatives, Pn-R-F8, as acceptors. The choice of ADT and Pn acceptors enabled us to separate the effects of the D/A LUMO offset, which was approximately zero in the case of ADT acceptors and ∼0.55 eV in the case of Pn acceptors, from those of molecular packing on the optoelectronic properties. The acceptor side groups R were chosen based on (i) packing motifs in the solid state and (ii) size, to achieve different D/A separations at the D/A interface. Addition of an ADT-R-F acceptor to the ADT-TES-F donor introduced disorder, which resulted in increased PL emission, depending on the acceptor’s packing motif, and in reduced photocurrents. In ADT-TES-F/Pn-R-F8 films, charge transfer from ADT-TES-F to Pn-R-F8 was observed with an acceptor packing-dependent formation of an exciplex, which dissociated under applied electric field, contributing to charge carrier photogeneration. However, this contribution was not sufficient to compensate for a photocurrent reduction due to an increased disorder at Pn-R-F8 concentrations of 7 wt % and above, regardless of the acceptor’s R-groups and packing motifs. 1