Filament Growth and Related Instabilities during Adsorbate Suppressed Electrodeposition

Abstract

Anisotropic growth of a single filament on a microelectrode is demonstrated by galvanostatic electrodeposition in a bistable passive−active critical system. Specifically, a Cu filament is formed by disruption of a passivating polyether-halide bilayer triggered by metal deposition with positive feedback guiding highly localized deposition. For macroscale electrodes, complex passive−active Turing patterns develop, while for micrometer-sized electrodes, bifurcation is frustrated and a single active zone develops, which is reinforced by hemispherical transport. As deposition proceeds, hemispherical symmetry is broken with lateral propagation of a single filament while an increasing fraction of the applied current supports expansion of the passive sidewall area that eventually leads to termination of anisotropic growth. Different polyether suppressors alter the dynamic range between passive and active growth that determines the shape and extent of filament formation. The impact of electrode area, geometry, and applied current on morphological evolution was also briefly examined. The results highlight the utility of appropriately scaled microelectrodes in the study of growth instabilities during breakdown of additive suppressed layers in critical electrodeposition systems.