Vitality of Intralayer Vibration in hBN for Effective Long-Range Interlayer Hole Transfer across High Barriers in MoSe2/hBN/WSe2 Heterostructures

Introducing the two-dimensional (2D) hexagonal boron nitride (hBN) between 2D transition metal dichalcogenide (TMD) layers promises convenient manipulation of the interlayer exciton (IX) and interlayer charge transfer in TMD/hBN/TMD heterostructures, while the role of inserted hBN layers during IX formation is controversial. Employing ab initio nonadiabatic molecular dynamics (NAMD) simulations and the electron-phonon coupling model, we systematically investigate interlayer hole transfer in MoSe2/WSe2 bilayers intercalated by hBN layers with various thicknesses. The conventional direct hole transfer from MoSe2 to WSe2 is decelerated by 2-3 orders of magnitude after the hBN insertion. Meanwhile, a novel channel intermediated by a deeper hole of WSe2 becomes dominant, where the intralayer shear mode of hBN plays a crucial role by reducing the energy barriers for this new channel. The unique role of hBN layers is revealed for the first time, enriching the knowledge of the underlying microscopic mechanisms and providing instructive guidance to practical van der Waals optoelectronic devices.