Modeling electrodeposition of thin films with compact, dendritic, and random morphologies

Abstract

We summarize previously published computer simulation studies of a metal electrodeposition model that considers diffusive cation flux, a fast reaction in contact with the electrode or with the growing deposit, and adsorbed atom diffusion in finite time windows. Simulations with various parameters show compact, fractal, dendritic deposits, and dynamic transitions between different morphologies during the growth of individual samples. The dendritic shapes are characterized by hierarchical organizations in which branches of a given order reproduce the shape and crystalline orientation of the branches of the previous order, in contrast to the random branching of the fractal deposits formed by DLA and related models. The simulations show dendrites with maple leaf shape in SC lattices, pine tree shape in FCC lattices, and flower-like shape in HCP lattices, with surfaces predominantly oriented in the lowest-energy configurations of each lattice. Simulations with nucleation restricted to a nanoscale seed show the initial formation of faceted particles followed by dendrite formation, in agreement with silver electrodeposition on substrates patterned with gold nanoparticles. A quantitative application to faceted and dendritic silver obtained in the same experiment provides values of the model parameters which are consistent with the characteristic widths of these structures being of the same order of magnitude of the diffusion lengths of atoms on (111) and (001) surfaces. Using an extended model for iron electrodeposition on Si(100), the simulations qualitatively reproduce the initial formation of multilayer islands, small oscillations of the roughness of a polycrystalline compact film after island coalescence, and instability development. Possible directions for applying this modeling to the electrodeposition of other materials are suggested.