The spin-orbit interaction controls photoinduced interfacial electron transfer in fullerene-perovskite...

Here, we used collinear and noncollinear density functional theory (DFT) methods to explore the interfacial properties of two heterojunctions between a fullerene (C₆₀ and C₇₀) and the MAPbI₃(110) surface. Methodologically, consideration of the spin-orbit interaction has been proven to be required to obtain accurate energy-level alignment and interfacial carrier dynamics between fullerenes and perovskites in hybrid perovskite solar cells including heavy atoms (such as Pb atoms). Both heterojunctions are predicted to be the same type-II heterojunction, but the interfacial electron transfer process from MAPbI₃ to C₆₀ is completely distinct from that to C₇₀. In the former, the interfacial electron transfer is slow because of the associated large energy gap, and the excited electrons are thus trapped in MAPbI₃ for a while. In contrast, in the latter, the smaller energy gap induces ultrafast electron transfer from MAPbI₃ to C₇₀. These points are further supported by DFT-based nonadiabatic dynamics simulations including the spin-orbit coupling (SOC) effects. These gained insights could help rationally design superior fullerene-perovskite interfaces to achieve high power conversion efficiencies of fullerene-perovskite solar cells.