Exciton-Phonon Coupling Induces a New Pathway for Ultrafast Intralayer-to-Interlayer Exciton Transition and...

Despite the weak, van der Waals interlayer coupling, photoinduced charge transfer vertically across atomically thin interfaces can occur within surprisingly fast, sub-50 fs time scales. An early theoretical understanding of charge transfer is based on a noninteracting picture, neglecting excitonic effects that dominate optical properties of such materials. We employ an ab initio many-body perturbation theory approach, which explicitly accounts for the excitons and phonons in the heterostructure. Our large-scale first-principles calculations directly probe the role of exciton-phonon coupling in the charge dynamics of the WS₂/MoS₂ heterobilayer. We find that the exciton-phonon interaction induced relaxation time of photoexcited excitons at the K valley of MoS₂ and WS₂ is 67 and 15 fs at 300 K, respectively, which sets a lower bound to the intralayer-to-interlayer exciton transfer time and is consistent with experiment reports. We further show that electron-hole correlations facilitate novel transfer pathways that are otherwise inaccessible to noninteracting electrons and holes.