The spin-orbit interaction controls photoinduced interfacial electron transfer in fullerene-perovskite heterojunctions: C60versus C70.

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.