Silicene is an atom thick, honeycomb layer made from Si atoms, and thus the silicon counterpart of graphene. Epitaxial silicene forms spontaneously on single-crystalline zirconium diboride thin films grown on Si(111) wafers through surface segregation. The results of structural as well as electronic structure characterizations, which reveal the silicene nature of this surfactant layer, will be reported, and the possibility to synthesize two-dimensional materials in a similar way will be discussed. 

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