Effect of the Interfacial Energy Landscape on Photo-induced Charge Generation at the ZnPc-MoS2 Interface

Monolayer transition-metal dichalcogenide crystals (TMDC) can be combined with other functional materials, such as organic molecules, to form a wide range of heterostructures with tailorable properties. Although a number of works have shown that ultrafast charge transfer (CT) can occur at organic/TMDC interfaces, conditions that would facilitate the separation of interfacial CT excitons into free carriers remain unclear. Here, time-resolved and steady-state photoemission spectroscopy are used to study the potential energy landscape, charge transfer, and exciton dynamics at the zinc phthalocyanine (ZnPc)/monolayer (ML) MoS2 and ZnPc/bulk MoS2 interfaces. Surprisingly, although both interfaces have a type-II band alignment and exhibit sub-100 fs CT, the CT excitons formed at the two interfaces show drastically different evolution dynamics. The ZnPc/ML-MoS2 behaves like typical donor–acceptor interfaces in which CT excitons dissociate into electron–hole pairs. On the contrary, back electron transfer occur at...