  State-of-the-art Y6-type molecular acceptors exhibit nanosecond excited-state
lifetimes despite their low optical gaps (~1.4 eV), thus allowing organic solar
cells (OSCs) to achieve highly efficient charge generation with extended
near-infrared (NIR) absorption range (up to ~1000 nm). However, the precise
molecular-level mechanism that enables low-energy excited states in Y6-type
acceptors to achieve nanosecond lifetimes has remained elusive. Here, we
demonstrate that the distinct packing of Y6 molecules in film leads to a strong
intermolecular charge-transfer (iCT) character of the lowest excited state in
Y6 aggregates, which is absent in other low-gap acceptors such as ITIC. Due to
strong electronic couplings between the adjacent Y6 molecules, the iCT-exciton
energies are greatly reduced by up to ~0.25 eV with respect to excitons formed
in separated molecules. Importantly, despite their low energies, the iCT
excitons have reduced non-adiabatic electron-vibration couplings with the
electronic ground state, thus suppressing non-radiative recombination and
allowing Y6 to overcome the well-known energy gap law. Our results reveal the
fundamental relationship between molecular packing and nanosecond excited-state
lifetimes in NIR-absorbing Y6-type acceptors underlying the outstanding
performance of Y6-based OSCs.
