Ultrafast Electron-Transfer Via Hybrid States at Perovskite/Fullerene Interface

Interfacial charge-transfer between perovskite and charge-transport layers plays a key role in determining performance of perovskite solar cells. The conventional viewpoint emphases the necessity of favorable energy-level alignment of the two components. In recent reports, efficient electron-transfer is observed from perovskite to fullerene-based electron-transport layers even when there are unfavorable energy-level alignments, but the mechanism is still unclear. Here, using an ultrafast in situ two-photon photoelectron spectroscopy, real-time observations of electron-transfer processes at CsPbI₃/C₆₀ interface in both temporal and energetic dimensions are reported. Due to strong electronic coupling, a large amount of interfacial hybrid states is generated at the interfaces, aiding fast photoinduced electron-transfer in ≈124 fs. This process is further verified by nonadiabatic molecular dynamics simulations and transient absorption experiments. The short timescale explains why electron-transfer can overcome unfavorable energy-level alignments, providing a guideline for device design. © 2024 The Author(s). Advanced Materials published by Wiley-VCH GmbH.