Metal Deposition and the Electrocrystallization Process

INTRODUCTION Metal electrodeposition processes are of fundamental technological importance to a number of fields. Electrorefining, electrowinning, electroplating, and electrogalvanizing have all been the subject of intense study for over a century. More recently, electrochem- ical deposition has played a critical role in advances in microelectronics and lately has been an enabling technology for the production of certain nanostructured materials. Electrometallurgists have most frequently been concerned with the structure and morphology of massive deposits. For example, in metal recovery steps such as electrorefining and electrowinning, deposits demonstrating adherent coarse-grained characteristics are most desirable. In the case of electroplating, a bright fine-grained, tenacious and strongly adherent deposit is required. The fabrication of microelectronic devices and the production of nanoscale structures such as nanoparticles, nanowires, and nanorods requires a keen understanding of early stage deposition effects. The initial stages of metal deposition, usually referred to as electroclystallization, are fundamentally linked to nucleation and growth phenomena. Early stage deposits are typically very ordered. Whereas, bulk metal deposition structures are much more ran- dom. In both cases, the discharge of a metal ion at an electrified interface is represented by simple cathodic reduction as follows: [ ] Me(H2O)xn[ ] is a hydrated metal ion residing in the bulk solution and Me is the metal atom occupying a crystallographic lattice position. A similar reduction reaction can be