Silicene's pervasive surface alloy on Ag(111): a scaffold for two-dimensional growth

Silicene, the two-dimensional (2D) allotrope of silicon, is a promising material for electronics. So far, the most direct synthesis strategy has been to grow it epitaxially on metal surfaces; however, the effect of the strong silicon-metal interaction on the structure and electronic properties of the metal-supported silicene is generally poorly understood. In this work, we consider the (4 x 4)-silicene monolayer (ML) grown on Ag(111), probably the most illustrious representative of the 2D silicon family, and show that our experimental results refute the common interpretation of this system as a simple buckled, honeycomb ML with a sharp interface to the Ag substrate. Instead, the presented analysis demonstrates the pervasive presence of a second silicon species, which we conclude to be a Si-Ag alloy stacked between the 2D silicene and the silver substrate and scaffolding the 2D silicene layer. These findings question the current structural understanding of the silicene/Ag(111) interface and may raise expectations of analogous alloy systems in the stabilization of other 2D materials grown epitaxially on metal surfaces.