DYNAMICS AND TOPOGRAPHY OF QUASI-2D NEEDLE-LIKE SILVER ELECTROCHEMICAL DEPOSITS UNDER A QUASI-STEADY-STATE REGIME

The electrochemical formation of single silver needles from aqueous silver sulfate was studied under both potentiostatic and galvanostatic conditions utilizing different quasi-2D cells. Under potentiostatic conditions, four (I–IV) stages of growth were distinguished. Stage III involved single needle growth under a quasi-steady-state (q-ss) regime in which, at the millimeter scale, the tip profile remained almost unchanged. Fast growing needles exhibited a truncated quasi-conical tip, and slow growing ones approached prolate hemispheroids. At stage III, the almost constant q-ss silver deposition rate was evaluated from the tip front displacement (dL z /dt) perpendicularly to the tangential plane of the tip. For the cathode to anode potential difference in the range -1.00 ≤ E c-a ≤ -0.22 V , values of (dL z /dt) in the range 0.08–2.0 μm s-1 were obtained. At the needle stem, the q-ss radial silver deposition rate (dL x /dt) was about two orders of magnitude lower than (dL z /dt). The transition from stage III to IV was characterized by tip thickening, i.e. a change in the tip q-conical profile to that of a prolate hemispheroid, and eventual tip splitting. Scanning electron micrographs at the micrometer scale of single silver needle tips from potentiostatic runs showed either a defined crystallography or an irregular topography covered by a large number of tiny crystals. In contrast, stems were always faceted. This difference indicated that surface relaxation processes following silver ion mass transport and discharge played a relevant role in the needle growth mode. At stage III, the growth regime is described utilizing a dual diffusion (D) and migration (M) model consisting of a DM direct contribution that becomes dominant at the needle stem, and a space charge (SC)-assisted DM contribution that operates at the tip apex. This explanation is consistent with the local cathodic current density values, the concentration ratio of silver clusters at the stem and tip apex surface, and the distinct kinetic behavior of needles produced from potentiostatic and galvanostatic runs. The complex link between mass transport phenomena of silver ions from the binary solution side, the silver ion discharge at the interface and the surface relaxation of silver adatoms and clusters at the metal lattice shed new light on the aspects of single silver needle formation.