title: Cluster nucleation and growth from a highly supersaturated adatom phase: silver on magnetite.
abstract: The atomic-scale mechanisms underlying the growth of Ag on the (√2×√2)R45°-Fe3O4(001) surface were studied using scanning tunneling microscopy and density functional theory based calculations. For coverages up to 0.5 ML, Ag adatoms populate the surface exclusively; agglomeration into nanoparticles occurs only with the lifting of the reconstruction at 720 K. Above 0.5 ML, Ag clusters nucleate spontaneously and grow at the expense of the surrounding material with mild annealing. This unusual behavior results from a kinetic barrier associated with the (√2×√2)R45° reconstruction, which prevents adatoms from transitioning to the thermodynamically favorable 3D phase. The barrier is identified as the large separation between stable adsorption sites, which prevents homogeneous cluster nucleation and the instability of the Ag dimer against decay to two adatoms. Since the system is dominated by kinetics as long as the (√2×√2)R45° reconstruction exists, the growth is not well described by the traditional growth modes. It can be understood, however, as the result of supersaturation within an adsorption template system.
authors.affiliation: Institute of Applied Physics, Vienna University of Technology , Vienna, Austria.
authors.forename: Roland
authors.initials: R
authors.lastname: Bliem
authors.forename: Rukan
authors.initials: R
authors.lastname: Kosak
authors.forename: Lukas
authors.initials: L
authors.lastname: Perneczky
authors.forename: Zbynek
authors.initials: Z
authors.lastname: Novotny
authors.forename: Oscar
authors.initials: O
authors.lastname: Gamba
authors.forename: David
authors.initials: D
authors.lastname: Fobes
authors.forename: Zhiqiang
authors.initials: Z
authors.lastname: Mao
authors.forename: Michael
authors.initials: M
authors.lastname: Schmid
authors.forename: Peter
authors.initials: P
authors.lastname: Blaha
authors.forename: Ulrike
authors.initials: U
authors.lastname: Diebold
authors.forename: Gareth S
authors.initials: GS
authors.lastname: Parkinson