Spectroscopic Evidence for Interfacial Charge Separation and Recombination in Graphene-MoS2 Vertical Heterostructures

Abstract: Vertical van der Waals (vdW) heterostructures consisting of graphene (Gr) and transition metal dichalcogenides (TMDs) have created a fascinating platform for exploring optical and electronic properties in the two-dimensional limit. Previous study has revealed the ultrafast formation of interfacial excitons and the exciton dynamics in the Gr/MoS2 heterostructure. However, a fully understanding of interfacial charge separation and the subsequent dynamics in graphene-based heterostructures remains elusive. Here, we investigate the carrier dynamics of Gr-MoS2 (including Gr/MoS2 and MoS2/Gr stacking sequences) heterostructures under different photoexcitation energies and stacking sequences by comprehensive ultrafast means, including time-resolved terahertz spectroscopy (TRTS), terahertz emission spectroscopy (TES) and transient absorption spectroscopy (TAS). We demonstrate that the Gr/MoS2 heterostructure generates hot electron injection from graphene into the MoS2 layer with photoexcitation of sub-A-exciton of MoS2, while the interfacial charge separation in the MoS2/Gr could be partially blocked by the electric field of substrate. Charge transfer (CT) occurs in same directions for the Gr-MoS2 heterostructures with opposite stacking order, resulting in the opposite orientations of the interfacial photocurrent, as directly demonstrated by the terahertz (THz) emission. Moreover, we demonstrate that the recombination time of interfacial charges after CT is on a timescale of 18 ps to 1 ns, depending on the density of defect states in MoS2 layer. This work provides a comprehensive and unambiguous picture of the interfacial charge dynamics of graphene-based heterostructures, which is essential for developing Gr/TMDs based optoelectronic devices.