Disparity in Photoexcitation Dynamics between Vertical and Lateral MoS2/WSe2 Heterojunctions: Time-Domain Simulation Emphasizes the Importance of Donor–Acceptor Interaction and Band Alignment

Two-dimensional transition metal dichalcogenides (TMDs) heterojunctions are appealing candidates for optoelectronics and photovoltaics. Using time-domain density functional theory combined with nonadiabatic (NA) molecular dynamics, we show that photoexcitation dynamics exhibit a significant difference in the vertical and lateral MoS2/WSe2 heterojunctions arising from the disparity in the donor–acceptor interaction and fundamental band alignment. The obtained electron transfer time scale in the vertical heterojunction shows excellent agreement with experiment. Hole transfer proceeds 1.5 times slower. The electron–hole recombination is 3 orders of magnitude longer than the charge separation, which favors solar cell applications. On the contrary, the lateral heterojunction shows no band offsets steering charge separation. The excited electron is localized at the interface that attracts holes to form an exciton-like state due to Coulomb interaction, suggesting potential applications in light-emitting devices. The coupled electron and hole wave functions increase NA coupling and the coherence time, accelerating electron–hole recombination by a factor of 3 compared with the vertical case. The atomistic studies advance our understanding of the photoinduced charge–phonon dynamics in TMDs heterojunctions.