10.1007@0 306 47604 52
10.1007@0 306 47604 52
Stojan S.
The Westaim Corporation, Fort Saskatchewan, Alberta, T8L 3W4, Canada
I. INTRODUCTION
present, but it should be noted that there are reports on their deposition
in the published literature. For example, it has been reported that Cd
can be deposited using as a reducing agent5 and Pb can be
deposited using thiourea or titanium chloride7 as reducing agents. Bi8
6
Brenner and Riddell3,4 were the first authors to introduce the term
electroless metal deposition when describing an autocatalytic process
of depositing a metal in the absence of an external source of electrical
current. Since there are other metal depositions from aqueous solutions
that are carried out without an external current, this process can be
divided into three main groups:
1. displacement deposition
2. contact deposition
3. autocatalytic deposition
1. Displacement Deposition
after the reduced metal (more positive metal) covers the surface of the
immersed metal (more negative metal). Accordingly, the thickness of
the deposited metal is always limited. The time of immersion is
particularly critical for achieving a uniform coating layer. Very often,
the adhesion of the deposited films is not as good as that of films
prepared by electrodeposition or by autocatalytic deposition. The
displacement deposition differs from all other plating processes from
aqueous solutions without an external source of electrical current,
because it does not require a reducing agent. Similarly to autocatalytic
processes, displacement deposition has the advantage of nearly
unlimited throwing power. Because of lower quality and thinner
coatings, displacement deposition has found applications mainly in the
refining metals. To a certain extent, however, there are other
applications such as coatings for porcelain enamelling17, zincate
coatings18, decorative finishing, soldering19, etc.
2. Contact Deposition
(e.g. Ni on Cu). The metals that can be plated by the contact deposition
process include Ni, Co, Cu, brass, Ag, Pt, Sn.18
3. Autocatalytic Deposition
2. Complexing Agents
3. Reducing Agents
(i) Hypophosphite
or
On the other hand, when Cu or its alloys are plated with Ni, pre-
treatment with catalyst or contact deposition20 is required.
The most studied reaction among electroless processes is definitely
deposition of Ni with hypophosphite. The overall reaction for nickel
deposition with hypophosphite can be represented as:
S. Djokic 61
solution and operating conditions. The rest is usually boron and other
occluded reacting agents. The-boron containing reducing agents are
used for electroless deposition of common metals, such as Ni, Co, Pd,
Pt, Au, Ag and their alloys.
Borohydride ion
or
or
or
S. Djokic 65
and
and
Amine Boranes
Most authors believe that the major species supplying electrons for
67,68,71,72
metal-ion reduction is The investigation of hydrolysis
71
of DMAB shows that hydrolysis is pronounced at pH’s below 5. In
68 Electroless Deposition of Metals and Alloys
(iii) Formaldehyde
or
It seems that the last reaction is more probable, since the hydrogen
evolution reaction has not been observed during the electroless
deposition.
From other metals, as mentioned earlier, the electroless Co deposition
is carried out using formaldehyde as a reducing agent.81 The rate of
cobalt deposition increased in a linear way, with an increase in
concentration within the range to On the
other hand, the dependence of the rate of Co deposition on the
formaldehyde concentration is found to pass through a maximum for
the formaldehyde concentration at about In the alkaline
solution (NaOH concentration 7 to is
formed.81 Reduction to Co is accompanied by hydrogen gas evolution.
The overall reaction for Co deposition is described by the following
equation:
(iv) Hydrazine
and
However, this reaction does not account for the hydrogen evolution
reaction, which is unavoidable during electroless Ni deposition with
hydrazine. In order to explain the hydrogen production, Mallory20
proposed the following reaction:
and
4. Stabilizers
For the activation energy, the authors reported a value of 68.6 kJ/mol.
Lloyd and Mallory reported that the reaction order and the
activation energy depend on the nature of the complexing agent.129
Their results are summarized in Table 4.
The activation energy for all complexing agents had values between
50 and 100 kJ/mol. However, some differences in the reaction order, in
respect to the corresponding species, appeared. Differences in the
activation energy and reaction orders are obviously due to use of
different solutions (different complexing agents) in the experiments.
82 Electroless Deposition of Metals and Alloys
Glycolate:
Malate:
84 Electroless Deposition of Metals and Alloys
Citrate:
and
Anodic:
Recombination:
Two hydride ions from the above reactions can then react with
or one ion with either a hydrogen ion or water:
Acid solutions:
Alkaline solutions:
S. Djokic 91
with
with and
with
with
Cases 3 and 4 were not discussed by the authors; they explain that
in both cases mixed potential is independent of the rotation rate, and
that such cases are rarely encountered in electroless processes.
Measurements were performed in the complete electroless bath, as well
as in the catholyte and in the anolyte separately. The theory developed
by Bindra and Roldan154 was experimentally verified by a comparison
of mixed potentials for different rotation rates and concentrations.
As shown in Figures 12 and 13, there are linear relationships
between and and between and which is in
agreement with equations (84) and (85).
For the oxidation of formaldehyde in complete solution (with all
constituents), the polarization curve is illustrated in Figure 14. The
Tafel slope for formaldehyde oxidation obtained from Figure 14 has the
value +210 mV per decade at 70 °C. The large value of the Tafel slope
is attributed to the electrochemical oxidation of formaldehyde under
Temkin adsorption conditions. For electroless Cu deposition, they
showed that the formaldehyde partial reaction (oxidation) is
electrochemically-controlled, while the metal deposition partial
reaction is diffusion-controlled which is in an agreement with their
theoretically proposed model.
Mital et al.70 investigated the validity of mixed potential theory for
electroless Ni deposition. The results for Ni deposition with DMAB
show the predominance of an electrochemical mechanism. These
authors stated that the mixed potential theory is applicable only for
S. Djokic 99
and
or
Anodic:
Dehydrogenation: RH = R + H
Oxidation:
Recombination:
Oxidation:
Cathodic:
Metal Deposition:
Hydrogen Evolution:
cathodic
with
and anodic
with
and
(i)
(ii)
(iii)
the other hand, Abrantes and Correia250 found that the mixed potential
theory is unable to describe the electroless deposition of NiP alloys.
VIII. CONCLUSIONS
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