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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
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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
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
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
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
(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
, remains unchanged:
they keep the same slope. It can be concluded that the
presence of 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
. It seems that 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
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
.
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
.
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
.
L. Bonou et al. / Electrochimica Acta 47 (2002) 4139/4148 4147
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