Cluster Nucleation and Growth from a Highly Supersaturated Adatom Phase: Silver on Magnetite

The atomic-scale mechanisms underlying the growth of Ag on the (root 2x root 2)R45 degrees-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 03 ML, Ag dusters 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 (root 2x root 2)R45 degrees 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 duster nucleation and the instability of the Ag dimer against decay to two adatonis. Since the system is dominated by kinetics as long as the (root 2x root 2)R45 degrees 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.