Synthesis of Silicene

The key issue for the first proof-of-principle synthesis of the two-dimensional Si allotrope, silicene, realized in 2012, was to find an appropriate substrate. Here, we give a background for the initial choice of silver single crystals, determined by decades of studies of the reverse system: silver deposited onto silicon (111) templates. Next, clever serendipity lead to another platform: ZrB2 thin films grown on Si(111). Clearly, non-metallic substrates would be preferred for many practical applications, they are currently searched for. A digest of this quest is presented in this chapter.