Mechanisms of Ultrafast Charge Separation in a PTB7/Monolayer MoS₂ van der Waals Heterojunction

Mixed-dimensional van der Waals heterojunctions comprising polymer and two-dimensional (2D) semiconductors have many characteristics of an ideal charge separation interface for optoelectronic and photonic applications. However, the photoelectron dynamics at polymer-2D semiconductor heterojunction interfaces are currently not sufficiently understood to guide the optimization of devices for these applications. This Letter reports a systematic exploration of the time-dependent photophysical processes that occur upon photoexcitation of a type-II heterojunction between the polymer PTB7 and monolayer MoS₂. In particular, photoinduced electron transfer from PTB7 to electronically hot states of MoS₂ occurs in less than 250 fs. This process is followed by a 1-5 ps exciton diffusion-limited electron transfer from PTB7 to MoS₂ and a sub-3 ps photoinduced hole transfer from MoS₂ to PTB7. The equilibrium between excitons and polaron pairs in PTB7 determines the charge separation yield, whereas the 3-4 ns lifetime of photogenerated carriers is probably limited by MoS₂ defects.