Controlled dynamic variation of interfacial electronic and optical properties of lithium intercalated ZrO2/MoS2 vdW heterostructure

Abstract

Efficient strategies for modifying the characteristics of van der Waals (vdW) layered materials in a precise and reversible mode remain challenging. Our suggested method for customization entails the implementation of layer-sliding and intercalation. In this work, a norm-conserving approach within the context of density functional theory has been used to examine the electronic and optical properties of two-dimensional (2D) van der Waals heterostructure (vdWHS), which is modeled by using 2D zirconium dioxide (1T-ZrO2) and molybdenum disulfide (1T-MoS2) monolayers of similar phase. Both contributing monolayers have similar lattice structures, with a minimum lattice mismatch of 0.83 %, and have corrugation on both sides that can successfully retain foreign species at the vdW-gap. In the next step, interfacial engineering through Li-intercalation and layer-sliding was employed to modify physical properties of the vdWHS. It is the worth mentioning that a narrow bandgap of 0.102 eV (0.22 eV) has been observed in the unintercalated ZrO2/MoS2 vdWHS when employing PW-LDA (hybrid-functional). Li-intercalation and sliding process significantly influenced the electronic properties of the studied vdWHS. Furthermore, un-slided and fully-slided Li-intercalated vdWHS exhibit an increase in the vdW-gap by 3.78 % and 27.14 %, respectively, as compared to unintercalated vdWHS. To further understand the electrical behaviour at the interface of contributing monolayers, a comparative study has also been made for the variation in the planar average charge density difference, charge transfer, and interface dipole moment for unintercalated and intercalated vdWHS. In the unintercalated vdWHS, the calculated values of ΔQ and μ(z) provide evidence of significant charge transfer from 1T-ZrO2 to 1T-MoS2 before sliding, whereas in the fully-slided vdWHS, there is 80.11 % more charge transfer from 1T-MoS2 to 1T-ZrO2. Li-intercalation increases the magnitude of ΔQ (by 90.27 %) near 1T-MoS2, indicating a sufficient quantity of charge transfer from the 1T-MoS2 monolayer. The results of the anisotropic analysis show that the calculated in-plane and out-of-plane components of the real and imaginary parts of the dielectric function differ significantly. The optical absorption and energy losses of Li-intercalated vdWHS experience a substantial decrease of about 90 % and 50 %, respectively, as compared to unintercalated vdWHS. Our employed method promotes the notion that interfacial engineering through simultaneous layer-sliding and intercalation approach can be used to regulate and modify the physical properties of 2D insulator/metal based vdWHS.