Superatom Molecular Orbital as an Interfacial Charge Separation State

Hot electron cooling by energy loss to heat through electron-phonon (e-ph) interaction is an important mechanism that can limit the efficiency of solar energy conversion. To avoid such energy loss, sufficient charge separation needs to be realized by extracting hot carriers from the photoconverter before they cool, which requires fast interfacial charge transfer and slow internal hot carrier relaxation. Using ab initio time-dependent nonadiabatic molecular dynamics and taking C₆₀/MoS₂ as a prototype system, we show that the superatom molecular orbitals (SAMOs) of fullerenes, which are bound by the central potential of the whole molecule induced by the charge screening, are ideal media for charge separation. The diffuse character of SAMOs results in extremely weak e-ph interaction and therefore acts as a "phonon bottleneck" for hot electron cooling. Furthermore, it also leads to significant hybridization with other atoms at the interface that induces fast charge transfer. The interfacial charge-transfer rate at the C₆₀/MoS₂ interface is found to be 2 orders of magnitude faster than the hot electron cooling from s-SAMO in C₆₀. This conclusion is generally applicable for different carbon nanostructures that have SAMOs. The proposed SAMO-induced charge separation provides unique and essential insights into the material design and function for solar energy conversion.