Reducing the Singlet−Triplet Energy Gap by End‐Group π−π Stacking Toward High‐Efficiency Organic Photovoltaics

Abstract To improve the power conversion efficiencies for organic solar cells, it is necessary to enhance light absorption and reduce energy loss simultaneously. Both the lowest singlet (S1) and triplet (T1) excited states need to energertically approach the charge‐transfer state to reduce the energy loss in exciton dissociation and by triplet recombination. Meanwhile, the S1 energy needs to be decreased to broaden light absorption. Therefore, it is imperative to reduce the singlet−triplet energy gap (ΔE_ST), particularly for the narrow‐bandgap materials that determine the device T1 energy. Although maximizing intramolecular push−pull effect can drastically decrease ΔE_ST, it inevitably results in weak oscillator strength and light absorption. Herein, large oscillator strength (≈3) and a moderate ΔE_ST (0.4−0.5 eV) are found for state‐of‐the‐art A−D−A small‐molecule acceptors (ITIC, IT‐4F, and Y6) owing to modest push−pull effect. Importantly, end‐group π−π stacking commonly in the films can substantially decrease the S1 energy by nearly 0.1 eV, but the T1 energy is hardly changed. The obtained reduction of ΔE_ST is crucial to effectively suppress triplet recombination and acquire small exciton dissociation driving force. Thus, end‐group π−π stacking is an effective way to achieve both small energy loss and efficient light absorption for high‐efficiency organic photovoltaics.