Stimulating Phonon Bottleneck Effect in Organic Semiconductors by Charge-Transfer-Mediated J-Aggregation

Abstract

Hot carriers rapidly lose kinetic energies on a subpicosecond time scale, posing significant limitations on semiconductors' photon-conversion efficiencies. To slow the hot carrier cooling, the phonon bottleneck effect is constructed prevalently in quantum-confined structures with discrete energy levels. However, the maximum energy separation (ΔE ES ) between the energy levels is in a range of several hundred meV, leading to unsatisfactory cooling time. To address this, we design a novel organic semiconductor capable of forming intermolecular charge transfer (CT) in J-aggregates, where the lowest singlet excited state (S 1 ) splits into two states due to the significant interplay between the Coulomb interaction and intermolecular CT coupling. The ΔE ES between the two states can be adjusted up to 1.02 eV, and an extremely slow carrier cooling process of ∼72.3 ps was observed by femtosecond transient absorption spectroscopy. Moreover, the phonon bottleneck effect was identified in organic materials for the first time, and CT-mediated J-aggregation with short-range interactions was found to be the key to achieving large ΔE ES . The significantly prolonged carrier cooling time, compared to <100 fs in the isolated molecule (10 −6 M), highlights the potential of organic molecules with diversified aggregation structures in achieving long-lived hot carriers. These findings provide valuable insights into the intrinsic photophysics of electron−phonon scattering in organic semiconductors.