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Cuprous Ion Mass Transport Limitations During Copper Electrodeposition
Author(s) -
Schmidt Ralf,
Gaida Josef
Publication year - 2017
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.201700208
Subject(s) - comproportionation , copper , inorganic chemistry , electrolyte , ion , limiting current , electrochemistry , sulfuric acid , copper plating , chemistry , polarization (electrochemistry) , diffusion , materials science , analytical chemistry (journal) , electrode , electroplating , metallurgy , thermodynamics , organic chemistry , physics , layer (electronics) , chromatography
Polarization experiments in sulfuric acid based copper plating electrolytes disclosed unique mass‐transport limitations at very small cathodic overpotentials. Determination of the bulk concentration of the species, which is correlated to the observed limiting current plateaus, by means of Levich plots indicated that these plateaus may be related to mass‐transport‐limited copper deposition from cuprous ions. This hypothesis was further supported by comparison of the equilibrium constant of the comproportionation of cupric ions and metallic copper to cuprous ions obtained from experiments with literature values. The results provide a simple technique to detect cuprous ions and support the view that cuprous ions are deposited at a diffusion‐limited rate, whereas cupric ions deposition is controlled by electrochemical kinetics. The method may be of relevance for superfilling, since the action of additives in industrial plating electrolytes involves interaction with cuprous ions.