From metastability to equilibrium during the sequential growth of Co–Ag supported clusters: a real-time investigation

Atomic motions and morphological evolution of growing Co-Ag nanoparticles are followed in situ and in real time, by wide and small angle X-ray scattering obtained simultaneously in grazing incidence geometry (GISAXS and GIWAXS), in single or multi-wavelength anomalous modes. The structural analysis of the experimental data is performed with the aid of equilibrium Monte Carlo simulations and of molecular-dynamics simulations of nanoparticle growth. Growth is performed by depositing Co atoms above preformed Ag nanoparticles. This growth procedure is strongly out of equilibrium, because Ag tends to surface segregation, and generates complex growth sequences. The real time analysis of the growth allows to follow the nanoparticle evolution pathways almost atom-by-atom, determining the key mechanisms during Co deposition: starting with the incorporation of Co atoms in sub-surface positions, to the off-center Co domain formation, then by which the nanoparticles finally approach their equilibrium quasi-Janus then core-shell structures.