Abstract
Electroless plating reactions are classified according to four overall reaction schemes in which each partial reaction is either under diffusion control or electrochemical control. The theory of a technique based on the observation of the mixed potential as a function of agitation, concentration of the reducing agent and concentration of metal ions is presented. Using this technique it is shown that in electroless copper plating the copper deposition reaction is diffusion-controlled while the formaldehyde decomposition reaction is activation-controlled. Values of the kinetic and mechanistic parameters for the partial reactions obtained by this method and by other electrochemical methods indicate that the two partial reactions are not independent of each other.
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Abbreviations
- a :
-
Tafel slope intercept
- A :
-
electrode area
- b M :
-
Tafel slope for cathodic partial reaction
- b R :
-
Tafel slope for anodic partial reaction
- B′ M :
-
diffusion parameter for CuEDTA2− complex
- \(B_{O_2 }^\prime \) :
-
diffusion parameter for dissolved oxygen
- B′ R :
-
diffusion parameter for HCHO
- C ∞M :
-
bulk concentration of copper ions
- \(C_{O_2 }^\infty \) :
-
bulk concentration of dissolved oxygen
- C aR :
-
surface concentration of HCHO
- C ∞R :
-
bulk concentration of HCHO
- D R :
-
diffusion coefficient of HCHO
- E :
-
electrode potential
- E M :
-
thermodynamic reversible potential for the metal deposition reaction
- E 0M :
-
standard electrode potential for copper deposition
- E MP :
-
mixed potential
- E R :
-
thermodynamic reversible potential for reducing agent reaction
- E 0R :
-
standard electrode potential for HCHO
- F :
-
Faraday constant
- i M :
-
current density for metal deposition
- i′ M :
-
total cathodic current density
- i kM :
-
kinetic controlled current density for metal deposition
- i 0M :
-
exchange current density for metal deposition
- i DM :
-
diffusion-limited current density for metal deposition
- i D′M :
-
diffusion-limited current density for total cathodic reactions
- \(i_{O_2 } \) :
-
current density for oxygen reduction
- i plat :
-
plating current density
- i R :
-
current density for HCHO oxidation
- i 0R :
-
exchange current density for HCHO oxidation
- i DR :
-
diffusion-limited current density for HCHO oxidation
- n M :
-
number of electrons transferred in metal deposition reaction
- n R :
-
number of electrons transferred in the HCHO oxidation reaction
- R :
-
gas constant
- T :
-
absolute temperature
- ν:
-
stoichiometric number
- αM :
-
transfer coefficient for metal deposition
- αR :
-
transfer coefficient for HCHO oxidation
- βM :
-
symmetry factor
- γ:
-
number of steps prior to rate determining step
- ηM :
-
overpotential for metal deposition
- ηR :
-
overpotential for HCHO oxidation
- v :
-
kinematic viscosity
- ω:
-
rotation rate of electrode
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Bindra, P., Roldan, J. Mechanisms of electroless metal plating. III. Mixed potential theory and the interdependence of partial reactions. J Appl Electrochem 17, 1254–1266 (1987). https://doi.org/10.1007/BF01023610
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DOI: https://doi.org/10.1007/BF01023610