Interplay between Thermal Stress and Interface Binding on Fracture of WS₂ Monolayer with Triangular Voids

The defect engineering of two-dimensional (2D) materials has become a pivotal strategy for tuning the electrical and optical properties of the material. However, the reliable application of these atomically thin materials in practical devices require careful control of structural defects to avoid premature failure. Herein, a systematic investigation is presented to delineate the complex interactions among structural defects, the role of thermal mismatch between WS₂ monolayer and different substrates, and their consequent effect on the fracture behavior of the monolayer. Detailed microscopic and Raman/PL spectroscopic observations enabled a direct correlation between thermal mismatch stress and crack patterns originating from the corner of faceted voids in the WS₂ monolayer. Aberration-corrected STEM-HAADF imaging reveals the tensile strain localization around the faceted void corners. Density functional theory (DFT) simulations on interfacial interaction between the substrate (Silicon and sapphire -Al₂O₃) and monolayer WS₂ revealed a binding energy between WS₂ and Si substrate is 20 times higher than that with a sapphire substrate. This increased interfacial interaction in WS₂ and substrate-aided thermal mismatch stress arising due to difference in thermal expansion coefficient to a maximum extent leading to fracture in monolayer WS₂. Finite element simulations revealed the stress distribution near the void in the WS₂ monolayer, where the maximum stress was concentrated at the void tip.