Unravelling a Zigzag Pathway for Hot Carrier Collection with Graphene Electrode

The capture of photoexcited deep-band hot carriers, excited by photons with energies far above the bandgap, is of significant importance for photovoltaic and photoelectronic applications because it is directly related to the quantum efficiency of photon-to-electron conversion. By employing time-resolved photoluminescence and state-of-the-art time-domain density functional theory, we reveal that photoexcited hot carriers in organic–inorganic hybrid perovskites prefer a zigzag interfacial charge-transfer pathway, i.e., the hot carriers transfer back and forth between CH₃NH₃PbI₃ and graphene electrode, before they reach a charge-separated state. Driven by quantum coherence and interlayer vibrational modes, this pathway at the semiconductor–graphene interface takes about 400 fs, much faster than the relaxation process within CH₃NH₃PbI₃ (several picoseconds). Our work provides new insight into the fundamental understanding and precise manipulation of hot carrier dynamics at the complex interfaces, paving the way for highly efficient photovoltaic and photoelectric device optimization.