Photoinduced Carrier Dynamics at the Interface of Pentacene and Molybdenum Disulfide

Understanding of photoinduced interfacial carrier dynamics in organic-transition metal dichalcogenides heterostructures is very important for the enhancement of their potential photoelectronic conversion efficiencies. In this work we have used density functional theory (DFT) calculations and DFT-based fewest-switches surface-hopping dynamics simulations to explore the photoinduced hole transfer and subsequent nonadiabatic electron-hole recombination dynamics taking place at the interface of pentacene and MoS₂ in pentacene@MoS₂. Upon photoexcitation the electronic transition mainly occurs on the MoS₂ monolayer, which corresponds to moving an electron to the MoS₂ conduction band. As a result, a hole is left in the valence band. This hole state is energetically lower than certain occupied states of the pentacene molecule; thus, the interfacial hole transfer from MoS₂ to pentacene is favorable in energy. In terms of nonadiabatic dynamics simulations, the hole transfer time to the HOMO-1 state of the pentacene is estimated to be about 600 fs; however, the following hole relaxation process from HOMO-1 to HOMO takes much longer time of ca. 15 ps due to the large energy gap between HOMO-1 and HOMO. Moreover, our results also show that the subsequent radiationless recombination process between the hole transferred to the pentacene molecule and the remaining electron on the MoS₂ CBM needs about 10.2 ns. The computational results shed important mechanistic insights on the interfacial carrier dynamics of mixed-dimensional pentacene@MoS₂. These insights could help to design excellent interfaces for organic-TMDs heterostructures.