Blue phosphorene, a two-dimensional, hexagonal-structured, semiconducting phosphorus, has gained attention as it is considered easier to synthesize on metal surfaces than its allotrope, black phosphorene. Recent studies report different structures of phosphorene, for example, on Cu(111), but the underlying mechanisms of their formation are not known. Here, using a combination of in situ ultrahigh vacuum low-energy electron microscopy and in vacuo scanning tunneling microscopy, we determine the time evolution of the surface structure and morphology during the deposition of phosphorus on single-crystalline Cu(111). We find that during the early stages of deposition phosphorus intermixes with Cu, resulting in copper phosphide structures. With the increasing surface concentration of phosphorus, the phosphide phase disappears, and a blue phosphorene layer forms, followed by the self-assembly of highly ordered phosphorus clusters that eventually grow into multilayer islands. We attribute the unexpected transformation of stable phosphide to a phosphorene layer to the presence of a large concentration of P2 dimers on the surface. Our results constitute direct evidence for a growth mode leading to a flat phosphorene layer via an intermediary phase, which could underpin the growth of other 2D materials on strongly interacting substrates.

CEITEC BUT Brno University of Technology Purkyňova 123 612 00 Brno Czech Republic

Department of Materials Science and Engineering Virginia Polytechnic Institute and State University Blacksburg Virginia 24061 United States

Department of Mechanical Engineering Materials Science Program Colorado School of Mines Golden Colorado 80401 United States

Institute of Physical Engineering Brno University of Technology Technická 2 616 69 Brno Czech Republic

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