1632 Ind. Eng. Chem. Res.

1997, 36, 1632-1636

Effect of Cu(OH)2 on Electroless Copper Plating

J. Shu, B. P. A. Grandjean, and S. Kaliaguine*

Department of Chemical Engineering, Laval University, Ste-Foy, Quebec, Canada G1K 7P4

Although electroless copper deposition has been widely used in the electronic industry, the
selection of the bath solutions relies still on some empirical rules. This paper provides a further
exploration of the bath compositions for electroless copper plating. It was found that the
formation of Cu2O in electroless copper plating is associated with the presence of Cu(OH)2 in
the bath. A chemical equilibrium calculation was thus made for the avoidance of Cu(OH)2 in
an electroless copper bath. Sodium thiosulfate was found to be an effective stabilizer for
electroless copper plating. The plating was further optimized based on a statistical design of
sorts, namely, Taguchi’s approach. Effects of individual components on the plating rate were
discussed.

Introduction to increase the electroless copper bath stability. On the

Electroless copper plating has been widely used in the
manufacture of printed circuit and decorative platings
for over 4 decades and is now extended for ultralarge-
scale integration applications (Shacham-Diamand et al.,
1995). The plating solutions are often composed of
copper sulfate as the metal source, complexing agent
such as EDTA, reducing agent HCHO, stabilizer, and
NaOH to adjust the pH value. The selection of the bath
compositions relies on some empirical rules, mainly
established in the late 1950s (Beck, 1984). For example,
the ratio of EDTA/Cu should be set at about 2.5 to allow
complexing of all cupric ions, whereas pH values are
best adjusted between 12.5 and 13.5 (Graham, 1971).
So far, various attempts have been made to improve
plating quality as well as rate and bath stability (see,
for example, Paunovic and Arndt, 1983; Duffy et al.,
1983).
In electroless copper deposition, the formation of
cuprous oxide (Cu2O) in the plating bath or in the
deposit has often been a concern. It was proposed that
the instability of electroless copper baths mainly results
from disproportionation of Cu2O (Lowenheim, 1978;
Junginger, 1988). Indeed the presence of small amounts
of Cu2O would significantly affect the applicability of
copper deposits (Schneble et al., 1971). On the basis of
a cyclic voltammetry study, Beck (1984) suggested
previously that the formation of Cu2O is through a
cathodic partial reaction:
2Cu(OH)2 + 2H+ + 2e- f Cu2O + 3H2O (1)
The same partial reaction was also suggested by Bindra
et al. (1984). Another form of this side reaction during
electroless copper plating was also proposed by Sha-
cham-Diamand et al. (1995) and Matsuoka et al. (1995):
2Cu2+ + 5OH- + CH2O f Cu2O + HCOO- + 3H2O
(2)
It should be mentioned that both expressions (1) and
(2) do not take into account the complexation of Cu2+
ions. Practically, one has to add a stabilizer into the
plating solution to complex the cuprous species in order
* Author to whom correspondence should be addressed.
Fax: 1-418-656-5993. E-mail: kaliagui@gch.ulaval.ca.
S0888-5885(96)00091-7 CCC: $14.00
other hand, the presence of Cu2O in electroless copper
deposits needs confirmation since Nakahara and Oki-
naka (1975) once argued that Cu2O was not experimen-
tally observed in the copper deposit. The aim of this
work is to clarify the formation of Cu2O in relation with
the complexed Cu2+ concentration in the electroless
bath. A chemical equilibrium calculation was thus
made to determine the formation of Cu(OH)2 in the
plating solution. Further works on the optimization of
electroless copper deposition will also be presented in
this paper.
Experimental Section
The substrate used for copper deposition was 316 L
stainless steel disks with an effective surface area of 1
cm2. The specimens were first activated by an electro-
less Pd precoating to a Pd thickness of about 2 µm. The
detailed procedures as well as the physicochemical
properties of the Pd deposit were previously reported
(Shu et al., 1993a,b, 1994). Unlike the Pd seeds formed
by the sensitization procedure, the electrolessly depos-
ited Pd provided stable surface properties and was more
active to initiate the electroless copper deposition. The
use of this kind of active substrate allowed us to ignore
the effect of the activation procedure on the copper
deposition.
For copper deposition, Pd-deposited specimens were
immersed in electroless copper baths with magnetic
agitation (650 rpm) at ambient temperature. The
deposition was done in air. The baths consisted of
copper sulfate, Na2EDTA, formaldehyde, sodium hy-
droxide, and 10 ppm of sodium thiosulfate. In the
presence of catalytically active palladium species, cupric
ions could be reduced easily and deposited on the
substrate surface. The use of small amounts of sodium
thiosulfate in the baths was aimed at replacing the
conventional toxic cyanide stabilizer. This additive was
found to be effective in stabilizing the electroless Cu
bath. Equal volumes of solution A containing CuSO4
and HCHO and solution B containing EDTA and NaOH
were mixed to make up the electroless baths in order
to reduce the precipitation of copper hydroxide during
the bath preparation (Graham, 1971). The pH value of
the baths was measured using a pH meter (Fisher,
Accumet 810). The deposited Cu content was estimated
from the mass gain of the substrate.
© 1997 American Chemical Society

Figure 1. Factorial effects in electroless copper plating (concentrations in mol/L).
Results and Discussion
An electroless plating bath is composed of several
components which are necessary to form a metallic
coating while maintaining the stability of the bath. In
this study, effects of individual bath components on the
electroless copper deposition rate were examined in an
optimization experiment based on a statistical design
of sorts, namely, Taguchi’s approach (1987). An L9
orthogonal array was used for the selection of various
concentration variables, as shown in Table 1. The
deposition results after 3 h of plating are also included
in the table. The results were further analyzed statisti-
cally, as shown in the table, where Ki is the summation
of corresponding testing results at level i, ki ) Ki/3, and
∆k ) ki,max - ki,min. According to statistics, the param-
eter ∆k is a measure of the effect of the corresponding
factor on the deposition rate (Montgomery, 1991).
Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997 1633
Figure 1 shows the dependence of the deposited copper
content on each concentration variable. It can be seen
that concentrations of Na2EDTA and NaOH are the
most important factors controlling the deposition rate
of Cu under the present chemical conditions. The Cu
deposition was enhanced by increases of [NaOH], [Cu-
SO4], and [HCHO] and a decrease of [Na2EDTA]. This
is reasonable since raising [NaOH], [CuSO4], or [HCHO]
increases the concentration of reactant species (see
below reaction (5)), whereas an excess of EDTA inhibits
the reactivity of Cu2+ via complexation. The slight
deviation of [CuSO4] and [HCHO] curves from mono-
tonic relationships indicates that there are minor com-
plexing effects among these concentration variables.
Indeed, as pointed out by Shacham-Diamond et al.
(1995), the reaction orders of the reactants in electroless
copper plating depend on the chemical conditions, i.e.,
the bath composition.
1634 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997

Table 1. L9 Orthogonal Array of Experiments (Concentration in M) and the Results of Mass Deposited after 3 h
results
test no. A [CuSO4] B [Na2EDTA] C [HCHO] D [NaOH] pH value kg of Cu/m2 remark
1 0.0251 0.0537 0.107 0.300 12.73 27.5
2 0.0251 0.0806 0.160 0.400 12.75 17.5
3 0.0251 0.1075 0.187 0.500 12.80 35.1
4 0.0502 0.0537 0.160 0.500 12.94 39.0 ppta
5 0.0502 0.0806 0.187 0.300 12.42 24.7
6 0.0502 0.1075 0.107 0.400 12.72 13.8
7 0.0752 0.0537 0.187 0.400 12.87 58.3 ppta
8 0.0752 0.0806 0.107 0.500 12.92 49.8 ppta
9 0.0752 0.1075 0.160 0.300 11.93 12.5
∑ 278.2
K1 80.1 124.8 91.1 64.7
K2 77.5 92.0 69.0 89.6
K3 120.6 61.4 118.1 123.9
k1 26.7 41.6 30.4 21.6
k2 25.8 30.7 23.0 29.9
k3 40.2 20.5 39.4 41.3
∆k 14.4 21.1 16.4 19.7
a ppt denotes precipitate in solutions.

Figure 2. XRD patterns of copper deposits on Pd/SS: (a) from bath 3, (b) from bath 4, and (c) from bath 10.

The above trends provide the basis for predicting
concentration effects on the electroless copper deposi-
tion. Bright Cu deposits were obtained from homoge-
neous baths where no Cu(OH)2 precipitate could be
observed. In these cases the phase purity of the Cu
deposited was confirmed by XRD, as illustrated by the
XRD pattern of the Cu deposit from bath 3, shown in
Figure 2a. Precipitates of Cu(OH)2 were observed in
baths 4, 7, and 8, resulting in deposited copper with a
slightly gray color. Small amounts of Cu2O were
detected by XRD in the corresponding deposits (Figure
2b), indicating a relation with the presence of Cu(OH)2
in the bath. Cu2O was previously found in the copper
deposit from a bath with pH ) 13.0 by Duffy et al. (1983)
using Auger spectra. It is known that Cu2O is normally
red in color. The present gray appearance might be
attributed to the very fine Cu2O particles. Cu2O is
catalytically inactive toward further copper deposition
(Bindra et al., 1984). Thus, the codeposited Cu2O would
exist in the form of isolated small particles. The
presence of Cu2O would significantly affect the proper-
ties of Cu deposits, for example, the film ductility. Our
experience also showed that the codeposited Cu2O,
though in a very small portion, would prevent the
formation of Pd-Cu alloys via atomic diffusion at
elevated temperature (Shu, 1994). Therefore, Cu(OH)2
precipitation should be avoided in the bath in order to
improve the deposit quality.
The electroless copper bath is a metastable system
where several equilibria exist simultaneously. First,
cupric ions should be complexed (reaction (3)) in order
to prevent its spontaneous reduction by the reducing
agent formaldehyde. Second, the copper deposition
needs to be performed in an alkaline medium. Copper
hydroxide precipitate might form under certain condi-

Figure 3. Possibility of Cu(OH)2 precipitate formation in elec-
troless copper baths
tions (reaction (4)). The target electroless reaction is
the autocatalytic deposition (reaction (5)).
Cu2+ + EDTA4- h [CuEDTA]2- (log KMY )
18.80; Skoog and West, 1976) (3)
Cu2+ + 2OH- f Cu(OH)2
(Ksp ) 5.6 × 10-20; Linke, 1958) (4)
[CuEDTA]2- + 2HCHO + 4OH- h
Cu0 + 2H2O + H2 + 2HCOO- + EDTA4- (5)
The conditions of Cu(OH)2 precipitation are related
to the simultaneous equilibria of reactions (3) and (4)
in the absence of reducing agent:
x[Cu2+]0
)
(1 - x - y)[Cu2+]0([EDTA]0 - x[Cu2+]0)
1 × 1018.8 (mol/L)-1 (6)
and
(1 - x - y)[Cu]02+([OH]0 - 2y[Cu2+]0)2 )
5.6 × 10-20 (mol/L)3 (7)
where x and y are the equilibrium conversions for
reactions (3) and (4), respectively. [i]0 is the initial
concentration of component i. The combined equations
(6) and (7) have been solved numerically. The results
corresponding to various composition conditions are
drawn in Figure 3 as a diagram of [NaOH]/[CuSO4]vs
[EDTA]/[CuSO4]. As can be seen, at a constant concen-
tration of CuSO4, there is a boundary between the
precipitate region and the homogeneous region in the
electroless solution. At the left of each curve, the
precipitate of copper hydroxide would form in the
electroless bath. The boundary shifts toward the right
side with the increase of [CuSO4] in the baths, which
means that higher [EDTA]/[CuSO4] ratios should be
satisfied with increasing [CuSO4], in order to ensure a
homogeneous solution.
Figure 3 also reveals that, at any concentration of
CuSO4, [EDTA]/[CuSO4] must be more than 1.0 to
prevent cupric ions from precipitating. It is known that
copper hydroxide could precipitate at pH above 5 in the
absence of complexing agent. Another widely accepted
fact is that EDTA usually forms 1:1 complexes with
most metal ions such as Cu2+. Thus, the value 1.0 of
Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997 1635
[EDTA]/[CuSO4] seems to indicate that all Cu2+ must
be complexed to avoid precipitation. With the increase
of [NaOH] in the baths, this ratio should, therefore, be
higher than 1.
The calculated results shown in Figure 3 are in good
agreement with our experimental observations. Those
compositions indicated as a dot in Figure 3 actually
correspond to the baths listed in Table 1. It is note-
worthy that precipitates were only observed in baths 4,
7, and 8, which are described by dots actually located
at the left of their respective curves at [CuSO4] ) 0.05
and 0.075 M. Thus, Figure 3 gives a detailed descrip-
tion of Cu(OH)2 formation conditions in electroless
copper baths.
In the literature, some authors pointed out empiri-
cally that the molar ratio of [EDTA]/[Cu] should be set
at about 2.5 to complex all cupric ions. From Figure 3,
it can be seen that this ratio depends on the concentra-
tions of NaOH and Cu2+. At a low Cu2+ concentration,
[EDTA]/[Cu] could be near 1. In contrast, when Cu2+
concentration is very high, even the EDTA/Cu ratio of
2.5 is not sufficient to obtain a homogeneous solution.
From the optimization experiment, the bath composi-
tion with the highest plating rate should consist of 0.075
M of CuSO4, 0.054 M of Na2EDTA, 0.50 M of NaOH,
and 0.187 M of 37% HCHO. However, upon checking
with Figure 3, Cu(OH)2 precipitate could appear in such
a bath. Thus, we adjusted the less sensitive factor,
[CuSO4], to meet with the condition of no Cu(OH)2
precipitate. Finally, a compromised electroless Cu
deposition bath composition was selected, containing
0.025 M of CuSO4, 0.054 M of Na2EDTA, 0.50 M of
NaOH, and 0.187 M of 37% HCHO (designated as bath
10). A total of 5 ppm of Na2S2O3‚5H2O was found
effective enough to stabilize this bath. A typical copper
deposit was obtained and characterized by XRD (Figure
2c), showing an fcc structure with a usual (111) orienta-
tion.
In summary, this work provides a further under-
standing of the electroless copper bath composition. The
experiment based on Taguchi’s statistical design ap-
proach indicates that the concentrations of EDTA and
NaOH are the two most pronounced factors affecting
the copper deposition rate under the present chemical
conditions. Sodium thiosulfate was found to be an
effective stabilizer for electroless copper plating. Un-
desired Cu2O was codeposited from electroless copper
baths containing Cu(OH)2 precipitate. To optimize
electroless Cu deposition, the favorable combination of
components must meet with the condition of no Cu(OH)2
precipitate in the system since the resultant Cu2O
codeposit would limit the applicability of the electroless
copper deposits.
Acknowledgment
This work was supported by the Natural Sciences and
Engineering Research Council of Canada (NSERC). The
authors thank Mr. Y. Lacombe for experimental as-
sistance.
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Received for review February 8, 1996
Revised manuscript received January 27, 1997
Accepted February 3, 1997X
IE9600912
X Abstract published in Advance ACS Abstracts, March 15,
1997.