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Inuence of additives on Cu electrodeposition mechanisms in acid

solution: direct current study supported by non-electrochemical


measurements
L. Bonou
a
, M. Eyraud
b,
*, R. Denoyel
b
, Y. Massiani
b
a
Laboratoire de Chimie Physique et dElectrochimie, Universite de Ouagadougou, Ouagadougou 03 BP 7021, Burkina Faso
b
Laboratoire Materiaux Divises et Revetements Electroceramiques (MADIREL), UMR 6121, Universite de Provence-CNRS, case 26, 3 pl. V. Hugo,
13331 Marseille Cedex 03, France
Received 7 March 2002; received in revised form 6 June 2002
Abstract
The effect of polyethylene glycol (PEG) and chloride ions on copper electrodeposits is investigated by electrochemical
measurements (cyclic voltammetry, current and potential pulses) coupled with an ellipsometric study at open circuit. When PEG is
added to the Cu
2
solution, the modifications of the copper electrodeposition mechanism can be explained by a polymer-electrode
interaction instead of a complex formation in solution. Since ellipsometry has shown no PEG adsorption at least at open circuit, that
adsorption is assumed to be potential dependent. Moreover, the efficiency of PEG alone in solution, seems to be decreased when the
deposit grows. With Cl

alone, an activation of copper deposition is performed. The simultaneous addition of the two additives
induces a blocking effect of the copper reduction that continues on with time. X-ray diffraction, optical microscopy and atomic force
microscopy (AFM) carried out complementary results, on bulk deposits obtained from solution with and without these additives. It
has been found that a bright, compact and homogeneous coating is only obtained in presence of both additives. In that case, the
texture of the deposit is modified and the roughness is significantly decreased to 0.5 mm. # 2002 Elsevier Science Ltd. All rights
reserved.
Keywords: Cu electrodeposition; Additives; PEG/Cl

; Synergetic effect
1. Introduction
In modern electroplating practice, it is well known
that the addition of even small amounts of certain
substances in the plating bath leads to significant
changes in the properties and aspect of the deposit.
Recent reviews have tried to summarize their different
effects [1/5]:
/ Levelers have the ability to produce deposits rela-
tively thick in small recesses and relatively thin on
small protusions. They act by adsorption at points
where otherwise there would be a rapid deposition of
the metal.
/ Brighteners allow the microscopic roughness of the
deposit to be lower as the wavelength of the incident
light so that it is reflected rather than scattered. They
act by a modification of the nucleation process and,
therefore, change the Tafel slope.
/ Structure modifiers change the structure of the
deposit and maybe even the preferred orientation of
lattice.
/ Wetting agents accelerate the release of hydrogen gas
bubbles from the surface and avoid hydrogen embrit-
tlement.
/ Among the involved mechanisms, it is known that
many additives are usually capable of adsorption on
the cathodic substrate and even might trap in the
deposit. Some additives also increase the deposition
over-potential. This may be due to either the need for
the electron transfer to occur through the adsorbed
layer or to a complex formation at the electrode
surface. A complexation of the metal cation in
solution is also proposed.
* Corresponding author
E-mail address: m.eyraud@newsup.univ-mrs.fr (M. Eyraud).
Electrochimica Acta 47 (2002) 4139/4148
www.elsevier.com/locate/electacta
0013-4686/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 0 2 ) 0 0 3 5 6 - 0
But, although advances have been made, in many
cases the use of additives is still done in an empirical
way. Indeed, the number of these organic or non-
organic substances is very large. Moreover, their action
could be different in function of the substrate, the ion to
reduce and the electrolytic conditions. For example,
additive re-orientation on the electrode surface [1,2] has
been observed depending on the surface coverage or as a
function of pH. A synergetic effect, often noticed when
several additives are added to the solution even confuses
the issue.
In the case of copper, a very great number of
researches have already been undertaken, because of
the industrial interest. Indeed, electroplated copper has
various applications as contacts and circuitry in the
electronic industry, undercoating for Ni and Cr plating
and the decoration of consumer goods. Each will require
somewhat different properties and hence different bath
formulations or electrolytic conditions. Most copper
baths are made either from cyanide or sulfate salts, but
the first one is gradually given up due to environmental
problems related to the cyanide toxicity.
Addition of some components in the copper electro-
lyte has become quite usual to obtain a uniform deposit
with a high throwing power and a weak roughness. The
most common species added to obtain a bright copper
deposit are: dextrin, gelatin, urea, chloride ions, sulfur-
containing compounds or other organic molecules [6/
18]. Although it has been established that these sub-
stances lead to high changes in the morphology of the
deposit, the knowledge in the mechanism of action of
these additives is very poor. For example, recent years
have shown an increasing use of polyethylene glycol
(PEG) to sulfuric copper electrolytes with or without
Cl

[2,8/18]. This additive appears as brightening or


leveling agent. But, while its influence on the copper
deposition is always observed, it has given rise to
contradictory explanations like:
/ Formation of complexes in solution between ethylene
oxide ligands (/CH
2
/CH
2
/O/)
n
and Cu

or Cu
2
cations [8]. As a result, the transport of copper ions
from the bulk electrolyte is impeded and the work for
the discharge of the copper complex ion increases.
/ Complex formation on the copper electrode surface
[9]: the adsorption of PEG on the Cu electrode during
electrorefining, involved by polarization curves, gives
rise to surface bonds between the ether oxygen of the
macromolecules and the Cu
2
, Cu

or Cu species.
In that case, the current is decreased and the potential
of copper oxidation becomes more positive. The same
authors have shown that, with Cl

species alone in
solution, the current is also decreased due to a
passivation of the surface related to the presence of
a copper chloride film. Nevertheless, in that case, the
potential of copper oxidation is shift toward a more
negative range. In presence of both PEG and Cl

,
the strongest effect is observed, showing a synergy
between the two additives.
/ Adsorbed glycol film that represents an uniform
barrier to electron transfer, which contributes to a
more uniform deposit [2,10,11].
Generally speaking, adsorption of PEG is often
involved but in different manners and in different forms
(film, monolayer, adsorption of rod-like PEG molecules,
adsorption of spherical PEG molecules. . .) [12/18]. For
example, different forms of adsorption as a function of
the potential range are involved [12,13]. It has been
established by Raman spectroscopy that PEG is ad-
sorbed on the copper surface in the potential range for
copper deposition, but not at the open circuit potential.
However, by comparison of the electrochemical and the
Raman results, the same authors concluded that quite
different PEG species are adsorbed on the surface at
open potential (not detected by Raman method) and in
the potential range where copper deposition occurred. It
is believed that a simple neutral PEG is adsorbed in the
most negative potential area, and a copper chloride
complex with PEG as a ligand close to the open circuit.
On the other hand, differential capacitance measure-
ments in H
2
SO
4
electrolyte have shown [14] that PEG is
very slightly adsorbed on the copper surface, and that
this additive on its own is not able to produce bright
coatings. Hope et al. [15], also involves the weak
adsorption of PEG on steel during copper deposition.
The macromolecules, being slightly adsorbed, are suffi-
ciently mobile and are entrapped in the deposit by
approaching atomic layer, leading to incorporation of
aggregates rather than individual molecules. A decrease
in the PEG concentration is in part due to its inclusion
during the copper deposition. West et al. [17,18] also
indicated a small effect on the electrode kinetics when
PEG is alone in solution, while Cl

only promotes the


copper deposition reaction. Using a quartz crystal
microbalance and electrochemical impedance spectro-
scopy, they suggested the adsorption of a monolayer of
PEG molecules that collapse into spheres provided Cl

is present. That adsorption leads to a blocking of


available surface sites for charge transfer. In contrary,
without Cl

there is a little PEG adsorption.


The employment of ellipsometry for the study of in
situ electrode process as oxidation of metals dates from
the sixties [19]. A few years later, ellipsometry was also
used in the measurement of adsorption of several species
on noble metal [20/22]. Such metals are often required
due to the need of the high stability of the surface: the
changes in optical parameters have not arisen from an
electrode oxidation. More recently, this method was
used to understand the effect of nicotinic acid on copper
layers electrodeposited on Pt [21].
L. Bonou et al. / Electrochimica Acta 47 (2002) 4139/4148 4140
Here, both electrochemical methods (cyclic voltam-
metry, potentiostatic and galvanostatic experiments) as
well as ellipsometric study at open potential have been
used to have a better insight in the role of PEG and Cl

during copper electrodeposition. This work was done


for each additive separately and together, to show the
evidence of a possible synergetic effect between the two
additives. Optic and atomic force microscopy (AFM) as
well as X-ray diffraction was carried out on the bulk
deposits obtained with or without additives, to support
the electrochemical study and for complementary results
(morphology, roughness, structure and preferential
orientation).
2. Experimental
A classic three-electrode cell was used for all electro-
chemistry experiments. The working electrode consisted
of a 0.28 cm
2
pure copper rod (99.999% purity). It was
prepared by extensive polishing using emery paper to a
grade of 1200, followed by a diamond paste polishing on
a polishing cloth. The counter electrode was a platinum
grid and all potentials were recorded with respect to a
saturated calomel electrode (SCE).
The study of the influence of PEG (CH
2
OH(CH
2
-
OCH
2
)
n
CH
2
OH average molar mass 10 000, supplied by
Merck) and chloride ions (added by using NaCl salt)
was carried out by introducing them in the common
formulation bath (pH 0): CuSO
4
/H
2
SO
4
. In the aim to
determine the influence of each additive, several solu-
tions were prepared with water treated by a millipore
system.
Blank experiments were carried out in electrolytes
referenced as followed:
S
o
: pure H
2
SO
4
2.2 M solution.
S
p
: S
o
/PEG1 g l
1
.
S
c
: S
o
/Cl

50 ppm.
S
pc
: S
o
/PEG1 g l
1
/Cl

50 ppm.
It is obvious that the weak concentration of additives
in solution do not lead to a change of pH. The copper
solutions are listed below:
Cu
o
: S
o
/CuSO
4
/5H
2
O 0.3 M.
Cu
p
: Cu
o
/PEG1 g l
1
.
Cu
c
: Cu
o
/Cl

50 ppm.
Cu
pc
: Cu
o
/PEG1 g l
1
/Cl

50 ppm.
Electrochemical experiments consisted of cyclic vol-
tammetry or linear sweep polarization, potential /time
and current /time transients. The equipment consisted
of a EG&G-PAR model 273 potentiostat /galvanostat.
The potential sweeps or steps started from the rest
potential of the substrate in the solution and continued
in the cathodic direction.
Ellipsometric measurements were made with a Ru-
dolph apparatus type 43603-200E, which has been
described in numerous papers [23,24]. It is a null
ellipsometer in a horizontal polarizer, compensatory,
sample analyzer (PCSA) arrangement. All details on
null procedure can be found in [25]. The sample was
maintained vertically in a trapezoid quartz cell (Thuet et
Bichelin, Strasbourg) allowing experiments at an inci-
dence angle of 688. The wavelength was 632.8 nm. The
optical parameters, D and C, were measured by the four
zones method.
The measurements were made on a copper sample,
glued on an isolated conductive sheet. Special care was
taken on polishing to obtain a flat, reproducible, and
mirror like surface. For that, the same polish procedure
as described before was employed, but it was pursued to
a 1 mm grade. To know if there is a PEG adsorption on
the copper surface, ellipsometric results obtained from
solution with or without PEG, were compared. The
blank electrolyte consisted on the S
o
bath, previously de-
aerated under an argon flow, to avoid the oxidation of
the copper surface with time. De-aeration was main-
tained during the experiment. To verify the ageing of the
surface with time in the blank solution, the time stability
of D and C values were controlled before the first
injection. Then, injections of a concentrate PEG solu-
tion were made so as to increase the PEG concentration
of about 1 g l
1
after each addition. The measurements
of the optical parameters were made twice immediately
and 20 min after each injection.
Bulk deposits were obtained under galvanostatic
conditions, from copper solutions with and without
the additives. In that case, the substrate consisted in a 2
cm
2
pure copper sample (99.9% purity), soldered on a
conductive sheet isolated from the solution by an
araldite film. In this way, the substrates were easily
released from the support to be analyzed. Morphology,
roughness and structure of the deposits were determined
by optical microscopy, AFM (CP Autoprobe provided
by Park Scientific Instruments) and X-rays diffraction
(Siemens D-5000).
3. Results and discussion
3.1. Blank experiments without Cu
2
in solution
Since the modification of the hydrogen evolution
reaction (HER) is dependent of an adsorbed layer, the
first experiments were made on blank solutions without
Cu
2
, containing or not the additives. Since the pH-
value is unchanged whatever the solution used, if a
change of HER. (E
eq,H

/H
2
//0.24 V per ECS) is
performed, that cannot be due to a complex formation
with the proton but rather to an adsorbed layer on the
electrode surface.
L. Bonou et al. / Electrochimica Acta 47 (2002) 4139/4148 4141
Fig. 1 reports the linear sweep polarization carried
out on copper at 20 mV s
1
, from open circuit to /1 V,
in S
o
, S
p
, S
c
, S
pc
solutions. For S
o
, no significant current
is performed until the potential reaches /700 mV,
corresponding to the HER. The over potential for the
proton reduction on the copper substrate is then about
450 mV. From the other solutions, it can be noticed
that:
/ No supplementary current is observed until the HER;
the PEG and Cl

additives are not electroactive, at


least in this potential range.
/ When the additives are added to the S
o
solution, a
supplementary over voltage for the HER is obtained
on the curves S
p
, S
c
and S
pc
in comparison to S
o
. This
increase in the over potential is more effective with
both additives in solution, as can be seen in Table 1.
It can be concluded that these two additives can
adsorb on the copper substrate, at least for the potential
range where the HER occurs.
The ellipsometric D and C data in function of time
are shown in Fig. 2. At first, to control the copper
surface stability with the immersion time, the D and C
parameters were monitored during 45 min before the
first PEG injection. That corresponds to the two first
points on the curves. A weak but significant decrease of
both the D and C values can be noticed, probably due to
a slow surface oxidation. Then, four Injections of PEG
were made during the 3 h of the experiment. These
injections are identified by i on the curves. The
measurements of the optical parameters were made
immediately and 20 min after each injection. It can be
seen from the curves, that no supplementary deviation
of the optical parameters was performed, neither shortly
after the injection nor after 20 min. This result seems to
point out that there is no PEG adsorption on the copper
surface.
At first sight, this conclusion might be considered as a
total contradiction to the first electrochemical experi-
ments described above. But, if the electrochemical and
the optical results are interpreted together, then the
conclusion must be that the PEG adsorption does not
occur at open circuit but at a more cathodic potential.
3.2. From Cu
2
solutions
3.2.1. Additive-free Cu
2
solution
Fig. 3 shows two cycles of the voltammograms from
the additive-free copper bath Cu
o
. The first cycle
corresponds to the copper deposition on polished
copper substrate and the second cycle to the copper
deposition on electrodeposited copper. On polished
substrate, no current is performed until Er//100
mV, that corresponds to the reduction of Cu
2
. From
that, there is an increase in the cathodic current, due to
the copper crystallization, followed by a current plateau,
at about 32 mA cm
2
, indicating a mass transfer control
of the process. By reversing the sweep, a cross-over is
observed between the cathodic and the anodic current,
that is characteristic of a mechanism of nucleation [26].
This shape of voltammogram was already obtained
from sulfuric acid solution, but on vitreous carbon
and not on coppers that is the substrate used for this
study [27]. The copper nucleation mechanism is more
surprising on copper substrate, where an epitaxial
growth seems to be more normal. Copper epitaxial
growth was obtained on electrodeposited copper, as it is
shown by the second cycle of the Fig. 3. In that case, the
nucleation loop has disappeared. That results emphasize
the importance of the surface state, its purity, pretreat-
ment conditions. . . on the deposition mechanisms.
Fig. 4 deals with a set of i /t transients for various
potential pulses, from Cu
o
solution, on polished copper
substrate. The shape of the transients depends on the
applied potential. For the highest over-potentials, they
present a maximum current i
m
which occurs at time t
m
,
related to the time at which full coalescence of the
crystallites occurs [28] indicating that a nucleation
mechanism is involved. After the ascending part, the
transients show a decrease followed by stabilization in
current at about 35 mA cm
2
.
The region of the rising part of the peak can be used
to determine the kinetics of nucleus growth [29]. In the
case of a mechanism controlled by mass-transfer, two
types of nucleation can occur: instantaneous nucleation
in which the nuclei are formed at the beginning of the
Fig. 1. Inuence of additives on the linear sweep polarizations for H

reduction from: (S
o
): 2.2 M H
2
SO
4
; (S
p
) is S
o
/1 g l
1
PEG; (S
c
) is
S
o
/50 ppm Cl

; (S
pc
) is S
o
/1 g l
1
PEG/50 ppm Cl

.
Table 1
Supplementary overpotential for the HER induced by PEG and/or
Cl

in comparison with the blank solution


Solutions S
p
S
c
S
pc
Supplementary overvoltage for HER per S
o
(mV) 82 60 105
L. Bonou et al. / Electrochimica Acta 47 (2002) 4139/4148 4142
pulse (i #kt
1/2
) and progressive nucleation in which the
formation of the nuclei goes on with the growth
(i #kt
3/2
). By plotting log i /f (log t) the slope can allow
to determine the nucleation and growth model. How-
ever, in our case, the ascending part of the transients
does not fit with a classical model.
Even if no classical nucleation and growth could be
determined, the shape of the transients confirms the
nucleation of copper deposit on copper substrate and
the mass-transfer control, in agreement with the voltam-
metric experiments.
3.2.2. Cu
2
in presence of additives
Fig. 5 presents the voltammograms obtained in
presence of the various additives, from Cu
p
, Cu
Cl
and
Cu
pc
solutions, on the copper substrate. For compar-
ison, the curve Cu
o
is also plotted.
3.2.2.1. With PEG. In the presence of the only PEG
(solution Cu
p
), the shape of the voltammogram ob-
tained is modied with regards to the precedent. A
strong inhibiting effect can be noticed because the
additive promoted a shift of the deposition potential
to more negative values creating an over-voltage of 220
mV. The slope of reduction is not the same as before,
but stronger. In this way, a new kinetic constant is
introduced. It is necessary to note that the limiting
current is the same with or without PEG that removes
the possibility of the complex formation in solution
between PEG and the Cu
2
species. Indeed, in this case
the diffusion coefcient of Cu
2
in solution would have
Fig. 2. Change in the ellipsometric parameters D and C in function of time, from So solution (2.2 M H
2
SO
4
), on copper surface. PEG Injections
were identied by i on curves.
Fig. 3. Successive voltammograms performed from Cu
o
bath: CuSO
4
0.3 M/2.2 M H
2
SO
4
. First cycle corresponds to copper deposition on
polished copper substrate. Second cycle corresponds to copper
deposition on electrodeposited copper.
Fig. 4. Potentiostatic i /t transients for Cu
o
bath: CuSO
4
0.3 M/2.2
M H
2
SO
4
.
L. Bonou et al. / Electrochimica Acta 47 (2002) 4139/4148 4143
been modied, and consequently the limiting current
[30]. Anyway, the complexation of 0.3 M of Cu ions by a
small PEG quantity seems unlikely. By reversing the
scan, it appears that the backward currents with and
without the additive are very close. This result may
suggest that the change at the copper surface due to the
additive adsorption is irreversible: once copper deposi-
tion has begun, PEG lost its ability to inhibit the
deposit. A similar conclusion was already proposed in
[12]. The observations about the other solutions will be
shown in the following page.
To confirm this result, two successive voltammograms
are performed with PEG in solution (Fig. 6). The second
cycle corresponds to copper deposition on electrode-
posited copper. It clearly presents an increase in the
cathodic current in two steps, with a decrease in the
over-voltage and in the slope values initially induced by
PEG. In this case, the increase in current is slower,
getting closer to that obtained without additive in
solution. On the contrary, by stopping the experiment
during a few minutes and starting it again, we find the
first over-voltage again. Even if PEGs finger print is
still visible, there is a release of the effect of PEG during
the growth of the deposit that could be due to a
competition for the sites in surface among PEG and
copper ions.
Fig. 7 deals with the transients obtained with (Cu
p
)
and without (Cu
o
) PEG in solution, for the same
cathodic pulse at /250 mV. Once again, with PEG,
no deposition law could be established. Nevertheless,
the two curves present a rising part that indicates a
nucleation mechanism. Then, the current stabilizes at
the same value: the diffusion of Cu
2
in solution is not
influenced by a PEG addition. The more important
difference between the transients comes from the
coalescence speed of the crystallites, which is decreased
with PEG. This induction time could be related to the
PEG adsorption on the copper surface that hinders the
formation of the first copper nuclei.
3.2.2.2. With Cl

. Fig. 5 also shows the inuence of


Cl

(solution Cu
Cl
) on the copper reduction mechan-
ism. In that case, the reaction of Cu
2
reduction is
moved towards more positive potential. An inverse
effect is thus obtained with Cl

with regard to that


obtained with PEG, already underlined in references
[9,17]. On the other hand the shape of the curves Cu
Cl
and Cu
o
with and without Cl

, remains unchanged:
they keep the same slope. It can be concluded that the
presence of Cl

leads to an acceleration of the copper


reduction but without modication of the mechanism.
Besides this, Cl

is known for its high adsorption power


[20,31,32], the formation of a cuprous chloride layer
adsorbed on the copper surface was already involved [9].
Fig. 5. Inuence of additives on voltammograms from several solu-
tions: (Cu
o
): CuSO
4
0.3 M/2.2 M H
2
SO
4
; (Cu
p
) is Cu
o
/1 g l
1
PEG;
(Cu
Cl
) is Cu
o
/50 ppm Cl

; (Cu
pc
) is Cu
o
/1 g l
1
PEG/50 ppm
Cl

.
Fig. 6. Successive voltammograms performed from Cu
p
bath: CuSO
4
0.3 M/2.2 M H
2
SO
4
/1 g l
1
PEG. First cycle corresponds to copper
deposition on polished copper substrate. Second cycle corresponds to
copper deposition on electrodeposited copper.
Fig. 7. PEG effect on the i /t transients obtained at /250 mV, from
Cu
o
and Cu
p
bath: (Cu
o
): CuSO
4
0.3 M/2.2 M H
2
SO
4
; (Cu
p
) is Cu
o
/
1 g l
1
PEG.
L. Bonou et al. / Electrochimica Acta 47 (2002) 4139/4148 4144
The mechanism of ion bridging was introduced by T.C.
Franklin [4,33]. It consists of the ability of a complexed
ion to accelerate the rate of ow of electrons through the
additive from the electrode to the metal ion. Indeed,
there is no electron transfer through the primary water
molecules bound to the ion. Thus, reduction of aqueous
complexes requires either partial desolvatation during
the adsorption process or substitution of the water with
an ion bridge as Cl

.
3.2.2.3. With PEG/Cl

. On Fig. 5, the curve Cu


pc
is
performed from the bath containing the both additives
PEG/Cl

. It seems that Cl

s addition in the PEG


solution leads to the same over-voltage than PEG alone
(curve Cu
p
) but with a slowing down of the deposition
speed of the copper. One nds the same reduction slope
than for copper alone (curve Cu
o
) and in the presence of
Cl

(curve Cu
Cl
). Besides, the current limit remains
always the same with or without additive. That conrms
that the mechanism of reduction stays under mass-
transfer control and that the effect of additives does not
intervene through a complex formation of copper in
solution.
An important difference is recorded on the backward
scan of the curve Cu
pc
, where in that case the backward
current is smaller than the forward current, without
nucleation loop. This is the finger print that the
influence of the two additives continues during the
growth of the copper deposit while, with only PEG in
solution, there is a release of the PEG effect during the
thickening of the deposit. Therefore, it may be con-
cluded that PEG and Cl

can act in a synergistic way,


leading to a strong inhibition of the deposit with the
change in deposition mechanism.
Fig. 8 deals with potential step experiments were
realized from the solution Cu
pc
in presence of the two
additives. In that case, the i /t transients present a
monotonous decrease in current followed by a stabiliza-
tion, which confirms that the copper deposit is made
without nucleation. This figure can be compared with
Fig. 7 obtained with Cu
o
and Cu
p
, where the rising part
indicated a copper nucleation step. With PEG/Cl

the
mechanism of copper deposition is thus different than
that obtained with PEG alone or without additive.
3.2.3. Bulk deposits characterization
To support the electrochemical and ellipsometric
study, bulk copper coatings were obtained on a 2 cm
2
copper substrate under galvanostatic conditions (j /10
mA cm
2
), with a theoretical thickness of 10 mm.
Depending on the Cu
2
bath used, Cu
o
without any
additive, Cu
p
with PEG only or Cu
pc
with PEG and
Cl

, these deposits are, respectively, identified by I


o
, I
p
and I
pc
.
To determine the influence of the additives under
galvanostatic conditions, the E/t curves obtained from
the three solutions at 10 mA cm
2
were brought
together on Fig. 9. Without additive, the potential
rapidly stabilizes at /120 mV. Addition of additives
in the bath induces a more negative potential, showing
again the blocking effect of additives. Nevertheless, with
PEG alone in solution, the potential quickly evolves
towards that obtained without additive underlining the
release of the effect of PEG during the growth of the
deposit. On the other hand, in the presence of two
additives, the initial over-potential is preserved, con-
firming the efficiency of additives with time. Therefore,
the conclusions relative to the effects of the additives are
the same under potential or under current polarization.
Morphological examination of the deposits was
achieved by optical microscopy and AFM. In the case
of the additive-free solution, the sample I
o
appears like a
dull and powdery coating, with a poor aspect and coarse
grains (Fig. 10). AFM observations were not possible
because of the too high roughness of I
o
. The presence of
Fig. 8. Potentiostatic i /t transients for Cu
pc
bath: CuSO
4
0.3 M/2.2
M H
2
SO
4
/1 g l
1
PEG/50 ppm Cl

.
Fig. 9. Galvanostatic E /t transients obtained at 10 mA cm
2
from
several solutions: (Cu
o
): CuSO
4
0.3 M/2.2 M H
2
SO
4
; (Cu
p
) is Cu
o
/1
g l
1
PEG; (Cu
pc
) is Cu
o
/1 g l
1
PEG/50 ppm Cl

.
L. Bonou et al. / Electrochimica Acta 47 (2002) 4139/4148 4145
PEGS in the bath smoothes the deposit (Figs. 11 and
12). The quality of the I
p
and I
pc
samples is improved,
with a comparable grain size between these deposits but
reduced in comparison to I
o
. However, The I
p
deposit is
not uniform and presents some big protuberances on the
surface (fuzzy area in Fig. 11). We do not know the
reason for the presence of these protuberances, but they
are always on the surface when PEG is alone in solution
and they disappear in the presence of the two additives
(Fig. 12). In our opinion, they can represent the finger
print of the release effect of the additive with the
deposition time, already mentioned, when PEG is alone
in solution. Some analyses have been made by AFM.
For I
p
, the size of crystallites varies from 1 to 6 mm, in
function of the analyzed zone. The roughness of the
surface is almost 0.6 mm. In the case of I
pc
, the AFM
result is shown in Fig. 12b. The micro-structure of the
coating is obvious with large grains (3/6 mm), put on a
compact and thin under-layer (crystallite size about 1
mm). In comparison to the results obtained from Cu
p
solution, the mean roughness is closed but reduced in a
significant way to 0.5 mm. The protuberances obtained
on I
p
represent the major difference between I
p
and I
pc
deposits, respectively, obtained with PEG or PEG/
Cl

, while the roughness of the two deposits is


approximately the same (only slightly smaller for I
pc
).
To characterize the influence of the additives on the
crystallographic structure of the deposits, XRD patterns
were made. Fig. 13 presents the diffractograms obtained
for the bare copper substrate and for the three deposits.
The experimental diffractograms were compared with
the powder standard file JCPDS (vertical line on the
figure) to display preferential orientations. All the
patterns are characteristics for a pure crystalline fcc
copper, with sharp peaks. However, there are some
noticeable differences in intensity with regards to the
powder spectrum. Without additive, the I
o
sample
Fig. 10. Optic micrograph of the sample I
o
(g/600). I
o
is obtained on
Cu substrate, at 10 mA cm
2
from Cu
o
solution: CuSO
4
0.3 M/2.2 M
H
2
SO
4
.
Fig. 11. Optic micrograph of the sample I
p
(g/600). I
p
is obtained on
Cu substrate, at 10 mA cm
2
from Cu
p
solution: CuSO
4
0.3/2.2 M
H
2
SO
4
/1 g l
1
PEG.
Fig. 12. (a) Optic micrograph of the sample I
pc
(g/600), obtained at
10 mA cm
2
from Cu
pc
bath: CuSO
4
0.3/2.2 M H
2
SO
4
/1 g l
1
PEG/50 ppm Cl

. (b) AFM 3D image of the sample I


pc
(10/10
mm). I
pc
is obtained on Cu substrate, at 10 mA cm
2
from Cu
pc
solution: CuSO
4
0.3/2.2 M H
2
SO
4
/1 g l
1
PEG/50 ppm Cl

.
L. Bonou et al. / Electrochimica Acta 47 (2002) 4139/4148 4146
presents the same (220) preferential orientation as the
bare substrate that differs from the more intense (111)
peak of the powder spectrum. In this case, the coating
seems to follow the substrate texture. With PEG, there is
a decrease of the (220) peak on behalf of the (111) peak.
This phenomenon is even more marked when both
additives are present in solution. All the patterns keep
their textural aspect.
4. Conclusion
Electrochemical methods supplied by non-electroche-
mical investigations were used to have an insight in the
mechanism of action of PEG and Cl

/PEG during
copper electrodeposition. The electrochemical evalua-
tion made on the proton reduction showed an adsorp-
tion of the additives on the copper surface. However,
ellipsometric and electrochemical results suggested that
this adsorption was obvious under cathodic polariza-
tion. These additives promoted a shift of deposition
potential to more negative values during copper deposi-
tion. The copper reduction process was then hindered
and a decrease in potential value was required.
PEG on its own, was not able to produce a bright
coating, owing to the release effect during the copper
growth. The addition of small amounts of Cl

to the
copper/PEG electrolyte had a substantial effect on the
polarization curves, with changes in deposition mechan-
ism. The nucleation mechanism of Cu
2
on the copper
substrate was no more involved, probably due to a
bridging effect of Cl

. In that case, the influence kept


on with time, showing a synergetic effect between the
two additives. This resulted in a quite good compact
copper deposit, with disappearing of large grains
obtained from the additive-free bath, and protuberances
obtained with PEG alone in solution. The additive
effects were also shown by XRD experiments, the
structure of the coating being modified in presence of
additives.
Complementary results obtained by alternative cur-
rent methods should improve the knowledge in the
action of these additives mechanism.
Acknowledgements
We thank Professor J. Crousier, who initiated this
work, for various and helpful discussions.
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