Efficient Hot Electron Capture in CuPc/MoSe₂ Heterostructure Assisted by Intersystem Crossing

Efficient hot electron extraction is a promising approach to develop photovoltaic devices that exceed the Shockley-Queisser limit. However, experimental evidence of hot electron harvesting employing an organic-inorganic interface is still elusive. Here, we reveal the hot electron dynamics at a CuPc/MoSe₂ interface using steady-state spectroscopy and transient absorption spectroscopy. A hot electron transfer efficiency of greater than 78% from MoSe₂ to CuPc is observed, comparable to that achieved in quantum dot hybrid systems. The mechanism is proposed as follows: the photogenerated hot electrons in MoSe₂ transfer to CuPc and form singlet charge transfer states, which subsequently transform into triplet charge transfer states assisted by the rapid intersystem crossing, inhibiting back-donation of electrons and facilitating exciton dissociation into CuPc polarons with a nanosecond lifetime. Our results demonstrate that the intersystem crossing of the hybrid electronic state at organic-inorganic interfaces may serve as a scheme to enable efficient hot electron extraction in photovoltaic devices.