Low-energy intralayer phonon assisted carrier recombination in Z-scheme van der Waals heterostructures for photocatalysis†
Abstract
Establishing the coupling mechanism of hot carriers and phonons is at the heart of nanoelectronics and photocatalysis of vdW heterostructures. Herein, via ab initio simulations, we endeavor to examine the intralayer phononic assisted recombination in a designed Z-scheme vdW heterostructure based on an emerging WSi2N4 material and transition metal dichalcogenides. Through integrating WSi2N4 with MoS2 (or its isoelectric cousin MoSe2), an intralayer phonon assisted electron–hole emission is revealed via nonadiabatic molecular dynamics calculations. Accompanied by weaker intralayer phonon modes, the WSi2N4/MoS2 interface shows a weaker nonadiabatic coupling and a longer electron–hole recombination time of up to 9.41 ns than the WSi2N4/MoSe2 heterolayer. Moreover, the staggered and appropriate band alignment in WSi2N4/MoS2 suggests its promising applications in photocatalysis such as water splitting. By comparing MoS2 and MoSe2, our time-domain simulations suggest that vdW heterostructures with a facile intralayer sliding and softening intralayer phonon would be beneficial for prolonging the lifetime of carriers.