We have used low energy electron microscopy to directly visualize the formation and stability of silicene layers on a Ag(111) substrate. Theoretical calculations call into question the stability of this graphene-like analog of silicon. We find that silicene layers are intrinsically unstable against the formation of an “sp3-like” hybridized, bulk-like silicon structure. The irreversible formation of this bulk-like structure is triggered by thermal Si adatoms that are created by the silicene layer itself. To add injury to insult, this same instability prevents the formation of a fully closed silicene layer or a thicker bilayer, rendering the future large-scale fabrication of silicene layers on Ag substrates unlikely.

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