ECS Transactions, 16 (22) 49-57 (2009)

10.1149/1.3115650 The Electrochemical Society

Formation Factor of Nodule by Copper Electrodeposition

N. Okamoto, S. Takahashi, T. Saito and K. Kondo

Department of Chemical Engineering, Osaka Prefecture University, 1-1 Gakuen-cho,

Naka-ku, Sakai, OSAKA 599-8531, Japan

Copper electrodeposition has been used in the formation of the

signal line in cellular phones, liquid crystal TVs and digital
cameras. Recently, the formation of nodules and large knot
deposits became a serious problem because of the downsizing of
signal lines pitch in electronic devices. The nodules cause short
circuits in the signal lines.
In our previous work, we have investigated the origins of the
nodules formation. The nodules grow as the growth of the copper
electrodeposits and tiny hemispherical deposits are the nucleuses
of the nodules. However, numerous unknown factors remain, such
as the formation mechanism of the nodules nucleuses. In this
report, we further discuss the factors of the nodule formation.

Introduction

Nodule is one kind of default of electrodeposited films. It looks like a large knot and
nodular deposits which has larger in size comparing to the normal deposits. Normally, the
size of a nodule is much larger than normal deposits. The nodule often causes a short
circuit in various electronic devices because the size of the nodule is larger than the
signal line pitch. Recently, the signal line pitch in electronic devices is downsizing.
Therefore, the problem of the nodule formation became more serious than before.
The anode sludge was commonly thought as the key cause of the nodule formation.
However, the experimental results do not always coincide with this general concept;
since sometimes the nodule was formed on the deposited films under the environment
without anode sludge in the plating bath. Up to now, no reasonable explanation on the
nodule formation exists, which can be widely accepted.
In this study, we propose that the formation of a nodule on Cu electrodeposited films
should correlate with the surface morphologies of the Cu electrodeposited films. In order
to verify this hypothesis, we made various surface morphologies of the Cu
electrodeposited films by changing the electrodeposition conditions, such as the bath
temperature, film thickness and the concentration of additives, for investigating the effect
of the surface morphologies to the nodule formation. We also counted the number of the
nodules with multiple repetition number of electrodeposition when the same bath was
used continuously. Here, it has been assumed that the nodule formation has occurred
easily in these multiple plating repetition cases. In this study, we investigate the condition
of nodule formation.

Experimental Method

The compositions of deposition bath and electrodeposition conditions are shown in

Table I. The basic bath consisted of CuSO45H2O 230 g/L , H2SO4 100 g/L and additives.

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50 ppm gelatin was added to the basic bath as an additive. Tough-pitch Cu board (99.5 %
in purity) was used for the anode, which was covered by the anode bag for inhibiting the
contamination with anode sludge. The Ti board was used for the cathode. The anode and
cathode were placed in parallel. The Cu electrodeposited films, which had about 25 m
in the average film thickness, were made by the galvanostatic electrolysis of 100 mA/cm2
in the current density while stirring electrolysis by 1000 rpm. The copper
electrodeposited film was removed from the Ti cathode and repeated these procedures for
multiple times. These repetition numbers will be named as the electrodeposition
number. Two types of plating condition (A and B) were used (see Table I).The area of
plating is 22 cm2 and 1010 cm2. The bath volume is 200 cm3 and 3000 cm3, and the
bath temperature is 25. The nodular and knot shaped deposits, which was over 50 m
in height and diameter, were counted among a nodule by man-eye observation. The
counted area was 22 cm2.
In each plating condition, we electrodeposited a Cu film and counted the change in the
number of nodules. The surface morphology of the deposited films and the nodules were
observed by using FESEM (Hitachi, S-4300). Linear sweep voltammetry was carried out
at room temperature under stirred conditions by using a potentio/galvanostat (Hokuto-
Denko HZ-3000). Counter electrode was Tough-pitch Cu board and reference electrode
was saturated calomel electrode (SCE).

TABLE I Plating conditions

Results and Discussions

Figure 1 shows the number of nodules formed on Cu electrodeposits. The x-axis in

Figure1 is the electrodeposition number by using one same bath continuously. With
gelatin 50 ppm additive and gelatin and Cl- ions both 50 ppm additive, the number of
nodules monotonously increases by increasing the electrodeposition number. However,
no nodule was observed with no gelatin additives.
Figure 2 shows the surface morphologies of the Cu electrodeposited films with gelatin
and Cl- ions both 50 ppm additives. The hemispherical deposits (about 10 m in
diameter), which were circled by the white dotted line, were observed with the
electrodeposition number of 40 (Fig. 2 (b)). The hemispherical deposits (about less than 5
m in diameter) were also observed with the electrodeposition number of 1 (Fig. 2(a)). It

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can be inferred that the surface morphologies, which have the hemispherical deposits,
correlate with the nodule formation.

Figure 1. The number of nodules which was formed on the Cu electrodeposited films.
: with gelatin 50 ppm additive, : with gelatin + Cl- both 50 ppm additive, no
additive Electrodeposition condition (A)

Figure 2. The surface morphologies of the Cu electrodeposited films with gelatin and Cl-
ions both 50 ppm additive. The electrodeposition number is (a) 1 and (b) 40 respectively.
Electrodeposition condition (A)

We further observed the surface morphologies of the nodule by changing the Cu

electrodeposited film thicknesses. Figure 3 shows the surface morphologies of the
nodules with film thicknesses (a) 6 m, (b) 12 m, (c) 18 m and (d) 25 m. In the
center of micrograph (a), the small nodule was observed. The size of nodules increased
by increasing the film thickness of the Cu deposited films as (b), (c), (d). This result
indicated that the nodule was not formed instantaneously by absorbing the nodular
deposits or contaminants. It was formed progressively by increasing the size of the
nodule, which are the convex deposits.

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Figure 3. The surface morphologies of the nodule that formed on the Cu electrodeposited
films with using the with gelatin 50 ppm additive.
The film thickness is (a) 6 m, (b) 12 m, (c) 18m and (d) 25 m.
Electrodeposition condition (A)

In order to investigate the differences in the surface morphologies and the number of
nodules between the electrodeposition number of 1 and that with the electrodeposition
number of 40, we applied the linear sweep voltammetry. Figure 4 shows the current-
potential curves by changing the electrodeposition number. The bath was with gelatin 50
ppm additive. The current-potential curve with the electrodeposition number of 40 was
shifted to a lower potential than that with the electrodeposition number of 1. Figure 5
shows the current-potential curves by changing the gelatin concentration in the bath. All
of the measurements in Figure 5 were done by using fresh baths. It was observed that the
current-potential curve was shifted gradually to lower potential by decreasing the
concentrations of gelatin. From these results, the deposition potential was changed by
increasing the electrodeposition number and gelatin concentration (Fig. 5).

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Figure 4. Current-potential curves which were obtain from with gelatin 50 ppm additive
bath.
The electrodeposition number of 40 and that of 1 are compared.

Figure 5. Current-potential curves with changing the concentration of gelatin 5 ppm, 25

ppm and 50 ppm.

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Figure 6 shows the number of nodules formed on Cu electrodeposits. For the

electrodeposited number less than 6, no nodule was observed with gelatin 0, 5 and 50
ppm. With gelatin 50 ppm, the number of nodules monotonously increases by increasing
the electrodeposition number. With gelatin 5 ppm, the number of nodules increases by
increasing the electrodeposition number less than 10, but after the electrodeposition
number of more than 10, the number of nodules decreases. With gelatin 0 ppm, no nodule
was observed after the electrodeposiion number less than 10.
As a already mentioned in introduction, the anode sludge formed from anode is
commonly thought as the causes of the nodule formation. It was assumed that the amount
of anode sludge should increase as the increase in the electrodeposition number, because
the anode sludge was formed by the electrode reaction. The nodule number did not
increase monotonously with the electrodeposition number for the case of 5 ppm gelatin.
Accordingly, we insist that there are other factors of nodule formation besides the anode
sludge. We further discuss the relationship between the nodule formation and the surface
morphologies of the electrodeposited films.

Figure 6. The number of nodules which was formed on the Cu electrodeposited films.
: with gelatin 50 ppm additive, : with gelatin 5 ppm, no gelatin
Electrodeposition condition (B)

Figure 7 shows the surface morphologies of the Cu electrodeposits films by changing

the electrodeposition number and the gelatin concentrations. The gelatin concentrations
were 0, 5, and 50 ppm. With gelatin 50 ppm with the electrodeposition number of 20 (Fig.
7 (c), Fig. 6 (I)), SEM micrograph shows hemispherical morphology. With gelatin 5 ppm
with the electrodeposition number of 20 (Fig. 7(b), Fig. 6(II)), hemispherical deposits
were not observed. With gelatin 0 ppm with the electrodeposition number of 10 (Fig. 7
(a), Fig. 6 (III)), hemispherical deposits were not observed. With gelatin 50 ppm of
electrodeposition number of 20, 15 nodules /4 cm2 was formed (Fig. 6 (I)) and
hemispherical deposits appeared on the surface (Fig. 7 (c)). With gelatin 5 and 0 ppm, no
nodule was observed (Fig.6 (II), (III) ), and hemispherical deposits were not observed

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(Fig. 7 (a), (b)). The number of nodules was determined by whether or not the
hemispherical deposits existed on the surface of the electrodeposited films. Therefore, the
surface morphology of the electrodeposited film have strong relation with the nodules
formation.

Figure 7. The surface morphologies of the nodule that formed on the Cu deposited films
with gelatin (a) 0, (b) 5 and (c) 50 ppm additive.
The electrodeposition number is (a) 10, (b) 20 and (c) 20.
Electrodeposition condition (B)

Figure 8 shows the surface morphologies of the deposited films with changing
deposition bath temperature of (a) 22.7 , (b) 25 , (c) 28 , (d) 35 , (e) 38 and
(f) 43 . With the deposition bath temperature less than 30 , hemispherical deposits
were observed on the surface (Fig. 8 (a), (b), (c)). With the deposition bath temperature
more than 30 , the blocky deposits were observed on the surface instead of the
hemispherical deposits (Fig. 8 (d), (e), (f)). As shown in Figure 9, the number of nodules
increases by decreasing the bath temperature. There is no nodule with the bath
temperature over 35 .
The nodule formation always coincides with the hemispherical deposits. This fact
strongly supported our assumption that the formation of the nodule on Cu
electrodeposited films should correlate with the surface morphologies.

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Figure 8. The surface morphologies of the nodule that formed on the Cu deposited films
with changing the deposition bath temperature to (a) 22.7 , (b) 25 , (c) 28 , (d)
35 , (e) 38 and (f) 43 .
The deposition bath was with gelatin 50 ppm additive.
Electrodeposition condition (B)

Figure 9. The number of nodules which was formed on the Cu deposited films with
changing the deposition bath temperature.
Electrodeposition condition (B)

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Conclusions

The number of nodules increased with increasing the electrodeposition number, gelatin
concentration and lower bath temperature of less than 35 . The Cu electrodeposited
films having hemispherical deposits, many nodules were always observed. The results
clearly indicate that the formation of hemispherical deposits have strong correlation with
the nodule formation.

Acknowledgments

Thank you for RAYTECH, INC. M. Kaneko, H. Uehara, Y. Kuramoto and M.

Oyama for the instructive suggestions.

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