Intercalating
a foreign atom into the van der Waals (vdW) gap of
layered low-dimensional materials is an appealing strategy for material
optimization, while a thorough understanding of the interaction between
the intercalated atom and the inevitable intrinsic defect in the parent
material should be one of the prerequisites for intercalation techniques.
Here, using the extensively studied MoS2 as an example,
strong couplings between 5 representative intercalated atoms (Li,
Ge, Mo, Ag, and W) and the S vacancy in the MoS2 bilayer
are revealed. It is found that the intercalated atoms can partially
fill their nearest-neighboring S vacancy, which changes the spacing
of the vdW gap and the binding strength between two MoS2 monolayers dramatically. Magnetism can be induced and tailored as
the interaction between the inserted specie (especially for Mo/W)
and the vacancy varies. Furthermore, it is noted that the intercalated
atoms, in particular Mo and W, can significantly modulate the energy
landscape of the S vacancy diffusion in the MoS2 bilayer
by decreasing the diffusion barrier across the vdW gap, contrasting
the strongly anisotropic diffusion in the pristine layered material.
More importantly, it is observed that with the assistance of the intercalated
atom, the S vacancy/ion diffusion can be realized via the swap mechanism
and kick-out mechanism in addition to the classical vacancy mechanism
in clean MoS2. The strong energetic and kinetic coupling
between the inserted specie and the intrinsic vacancy presented here
provides valuable guidelines for the design of layered intercalation
materials for various applications.