Novel Surface Molecular Functionalization Route to Enhance Environmental Stability of Tellurium-Containing 2D Layers

Recent studies have shown that tellurium-based two-dimensional (2D) crystals undergo dramatic structural, physical, and chemical changes under ambient conditions, which adversely impact their much desired properties. Here, we introduce a diazonium molecule functionalization-based surface engineering route that greatly enhances their environmental stability without sacrificing their much desired properties. Spectroscopy and microscopy results show that diazonium groups significantly slow down the surface reactions, and consequently, gallium telluride (GaTe), zirconium telluride (ZrTe₃), and molybdenum ditelluride (MoTe₂) gain strong resistance to surface transformation in air or when immersed under water. Density functional theory calculations show that functionalizing molecules reduce surface reactivity of Te-containing 2D surfaces by chemical binding followed by an electron withdrawal process. While pristine surfaces structurally decompose because of strong reactivity of Te surface atoms, passivated functionalized surfaces retain their structural anisotropy, optical band gap, and emission characteristics as evidenced by our conductive atomic force microscopy, photoluminescence, and absorption spectroscopy measurements. Overall, our findings offer an effective method to increase the stability of these environmentally sensitive materials without impacting much of their physical properties.