How the Stacking Pattern Influences the Charge Transfer Dynamics of van der Waals Heterostructures: An Answer from a Time-Domain Ab Initio Study

Here, we perform a time domain densityfunctional studyin conjunctionwith a non-adiabatic molecular dynamics (NAMD) simulation to investigatethe charge carrier dynamics in a series of van der Waals heterostructuresmade of two-dimensional (2D) SnX2 (X = S or Se)-supportedZrS(2), ZrSe2, and ZrSSe monolayers. Results fromNAMD simulation reveal delayed electron-hole recombination(in the range of 0.53-2.13 ns) and ultrafast electron/holetransfer processes (electron transfer within 108.3-321.5 fsand hole transfer between 107.6 and 258.8 fs). The most interestingfinding of our study is that switching from AB to AA stacking in theheterostructures extends the carrier lifespan by a significant amount.The delayed electron-hole recombination because of the switchingstacking pattern can be rationalized by weak electron-phononcoupling, lower non-adiabatic coupling (NAC), and fast decoherencetime. Thus, these insightful NAMD studies of excited charge carriersreveal that the stacking pattern variation is an effective tool todevelop efficient photovoltaic devices based on 2D van der Waals heterostructures.