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Electrochimica Acta 54 (2009) 58135817

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Electrochimica Acta
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Kinetics of Cu
O electrocrystallization under magnetic elds
Anne-Lise Daltin

, Frdric Bohr, Jean-Paul Chopart

LACM-DTI, LRC CEA, Universit de Reims, Moulin de la Housse, B.P. 1039, 51687 Reims Cedex 02, France
a r t i c l e i n f o
Article history:
Received 2 February 2009
Received in revised form 17 April 2009
Accepted 9 May 2009
Available online 19 May 2009
Cuprous oxide
Transient current
a b s t r a c t
The magnetic eld effects on cuprous oxide cathodic electrodeposition from alkaline cupric lactate solu-
tion have been investigated at 70

C by electrochemical and physical techniques.

Stationary analyses exhibit a tenuous decrease of the plateau electrolytic current as the magnetic eld
increases. Due to the limited diffusion process of the hydroxide species which reacts during the electro-
chemical process, a magnetically induced effect can be suspected but deposition of Cu
O that covers the
electrode and passivates the surface leads to antagonist effects that explain the current decrease.
For a cathodic applied potential corresponding to the current plateau, X-ray diffraction studies reveal
the formation of single phase cubic Cu
O lms with or without magnetic eld, but a change in elec-
trocrystallization kinetics of Cu
O is observed in the presence of the magnetic eld. Analyses of the
transient current curves reveal a convective effect of the magnetic eld from the very rst moments of
the electrocrystallization.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Cuprous oxide thin lms are non-toxic and suitable for numer-
ous applications such as photovoltaic tools and are used in
conversion of optical, electrical and chemical energy [19]. Cu
O is
also used as a photocatalyst for overall water splitting under light
irradiation [10].
The grain size of thin cuprous oxide lms is a key to improve
solar applicationdevices [11] andCu
Oelectrical properties depend
strongly on the preparation conditions [12], therefore many exper-
imental works have dealt with Cu
O lm synthesis by numerous
methods such as chemical deposition, solgel, sputtering, acti-
vated reactive evaporation, and thermal oxidation [46,9,13 and ref
Deposition of cuprous oxide by electrochemical technique from
aqueous solutions has attracted much research interest because it
is an inexpensive and convenient method [12,1416].
Pure Cu
O lms can be obtained in potentiostatic mode by
cathodic reduction of alkaline cupric lactate solution. Several
authors have reported electrodeposition of Cu
O on copper and tin
oxide [17], gold [18] and stainless steel [19] substrates and its char-
acterization. Some thin lms have been obtained with the same
electrolytic bath that Mahalingam et al. [17] used. In this last case,
it must be noticed that potential oscillations occur in galvanos-
tatic mode. This effect originates from modulations of the pH in
the vicinity of the working electrode. These oscillations led to elec-

Corresponding author. Tel.: +33 3 26 91 84 77; fax: +33 3 26 91 89 15.

E-mail address: al.daltin@univ-reims.fr (A.-L. Daltin).
trodeposition of copper and cuprous oxide multilayers instead of
pure Cu
O lm [20].
Due to the importance of the very rst electrodeposition
moments on material properties, we have undertaken experimen-
tal investigations on the cuprous oxide electronucleation process.
Directly related to the problemof nucleationand crystal growth,
electrochemical deposition process and more specially electrocrys-
tallization have attracted much interest. The study of nucleation via
potentiostatic current transient modelling is a convenient method
to explore these processes and has been extensively used to ana-
lyze metal deposition current transient curves. Large reviews on
this topic have been made by Budevski et al. [21] and more recently
by Hyde and Compton [22]. In this last paper, multiple nucleations
with diffusion controlled growth have been analyzed and different
models were reported for the current-time transients showing a
maximum followed by an exponential decay.
A classical treatment of the experimental data that leads to
numerous models [2326] considers that the nuclei are formed
according to the equation:
= AN
or N = N
(1 e
) (1)
where t is the time since the overpotential is applied to the elec-
trode, Nis the number of nuclei, N
is the saturationnucleus density
(i.e. the number of active sites) and A is the nucleation rate con-
stant. Totreat theoverlapof diffusionzones, authors generallyapply
the Avramis theorem that considers collisions and overlaps of the
growing centres in a process of multiple nucleations and growth.
According to this school, the Scharifker and Hills model [27]
in which two limiting nucleation mechanisms instantaneous
0013-4686/$ see front matter 2009 Elsevier Ltd. All rights reserved.
5814 A.-L. Daltin et al. / Electrochimica Acta 54 (2009) 58135817
and progressive are described is commonly used to discriminate
nucleation kinetics:
- An instantaneous nucleation corresponds to a slow growth of
nuclei with a quite small number of active sites appearing at the
same moment. In this case, nuclei are born before being affected
by the spreading of nucleation exclusion zones.
- During a progressive nucleation, corresponding to a fast growth
of nuclei on many active sites which are progressively born, the
break in nucleation process is dominated by spreading of nucle-
ation exclusion zones.
For these two limiting cases, it is possible to express the ratio of
the total current I per the maximum current I
versus the ratio of
the time t per the time t
corresponding to I
For an instantaneous nucleation, the theoretical reduced curve
obeys the relationship:
1 exp
For a progressive nucleation, the expression turns to:
1 exp
By developing the former situation, Scharifker and Mostany [23]
obtained a more general equation for the transient currenttime
curve in the case of a three-dimensional nucleation of hemispheri-
cal nuclei, followedbydiffusioncontrolledgrowth. Inthis case, they
expressed the current density I onto the electrode as a function of
the time t:
I =

(1 exp{N
kD[t (1 e
)/A]}) (4)
where z is the electron number involved in the reaction, Dand C are
respectively the diffusion coefcient and the bulk concentration of
the electroactive species that are under diffusion control.
k is equal to (8CM/)
where M and are respectively the
molar weight and mass density of the deposit.
While numerous papers deal with diffusion limited three-
dimensional growth of metals, only few investigations have been
reported on mechanismand kinetics of electrochemical nucleation
and growth of oxide materials [2832].
When a magnetic eld is applied onto an electrochemical cell in
a direction parallel to the electrode surface, the MHD Lorentz force
creates liquid motion in the vicinity of the electrode that reduces
diffusionlayer thickness and enhances limiting currents. Therefore,
growth processes and deposit morphologies are changed for met-
als, alloys and oxide [3340] but not as much as forced mechanical
convection case (e.g. rotating electrode) that deeply modies the
nucleation process [22,41].
In this paper we analyze some experiments on the mechanism
of Cu
O nucleation on stainless steel electrode with or without a
surimposed magnetic eld on the electrochemical cell.
2. Experimental
The copper(I) oxide has been obtained by cathodic reduction of
copper(II) lactate species. The electrochemical experiments were
carried out in a conventional three-electrode cell. The reference
electrode was a saturated mercury sulphate electrode (SSE), the
counter-electrode was made of platinum wire. The working elec-
trode was a 1-cm
stainless steel substrate; it was polished before
each experiment with different grades of SiC papers, up to 4000.
The 100-cm
cell was plunged into the gap of an electromagnet
(DruschEAM20G) that delivers a uniformhorizontal magnetic eld
B (up to 1T) parallel to the upward electrode surface. The elec-
trolytic solution was a Cu(II) lactate solution (CuSO
0.45mol L
lactic acid 3.25mol L
). The bath pH was adjusted to 89 by addi-
tion of sodium hydroxide pellets. The solution was stirred 8h, and
the pH was adjusted to its nal value 9.5 with further addition of
NaOH. The potential of the working electrode was controlled by
means of a potentiostatgalvanostat (PGZ 100, Radiometer Analyt-
ical), interfaced with a personal computer.
Odeposits have beenanalyzedby X-ray diffractionby means
of a Bruker D8 diffractometer using Cu K

radiation. The surface

morphology has been studied by means of a Jeol JSM-6460 LAscan-
ning electron microscope (SEM).
3. Results and discussion
Linear sweep voltammograms of Cu
O deposition on stainless
steel fromlactate solution at pH=9.5 are shown in Fig. 1 for various
magnetic eld amplitudes. The potential sweep started at an open
circuit potential and was scanned cathodically at 700mV/s scan
rate. In these experimental conditions the coverage of the electrode
Ois not efcient for total passivationbut effect of Bis intricate
because several processes as diffusion, uid motion and nucleation
occur during the transient phenomena due to the high scan rate. A
curve change is observed for potential values between 0.8V/SSE,
and 0.9V/SSE, corresponding to the deposition of Cu
O [18].
As reported by Mahalingam et al. [17], for low cathodic overpo-
tential, a very weak current can be attributed to the reaction:

. (5)
When the cathodic potential is increased (0.8V/SSE) Fig. 1, a wave
depending on the magnetic eld is due to the formation of:

O + H
O (6)
To be sure that only Cu
O deposition took place and no cop-
per was included in the reduction product, we have achieved
cuprous oxide electrodeposition at a xed potential value equal to
0.8V/SSE. For this potential value and all magnetic eld ampli-
tudes, only Cu
O peaks have been identied on X-ray diffraction
patterns in accordance to the JCPDS (05-0667) data (Fig. 2). The
(100) preferential orientation that has been obtained is similar to
the results that Switzer et al. [18] have reported.
Chronamperometry experiments were carried out in order to
investigate the copper oxide nucleation growth kinetics. Typi-
cal currenttime transients obtained at a cathodic potential of
0.8V/SSE are shown in Fig. 3. These transients exhibit the classic
shape of a nucleation process. After a rapid decay correspond-
ing to the double-layer charging, the current increased due to the
nucleation and growth of copper oxide nuclei. This rising current
reached quickly a maximum value (I
) as the discrete diffusion
zones for each growing crystallites began to overlap at time t
Fig. 1. Current densitypotential curves for Cu(II) lactate reduction and different
magnetic elds; scanning rate =700mV/s.
A.-L. Daltin et al. / Electrochimica Acta 54 (2009) 58135817 5815
Fig. 2. X-raydiffractionpatternof cuprous oxideelectrodepositedat cathodic poten-
tial (0.8V/SSE) during 1200s with a superimposed 1T magnetic eld.
Fig. 3. Cathodic transient current density during copper oxide electrodeposition at
a cathodic potential (0.8V/SSE) on a stainless steel substrate for different magnetic
After this maximum value, the current decayed as the diffusion
layer increased, to reach a stationary value. When magnetic eld
B up to 1T was superimposed, t
decreased, while i
increased up
to a maximumvalue for B=1T. For all experiments realizedwithout
superimposedmagnetic induction, thet
valueis always morethan
100s whenit is less than50s with1Tmagnetic eld. Morphologyof
Olayers obtainedwithandwithout Bhas beenobservedby SEM
technique and the microphotographies showed that the magnetic
eld does not alter the deposit.
We have analyzed the experimental curves by means of the
model proposed by Scharifker and Hills [27] and data have been
compared to the behavior for three-dimensional (3D) nucleation
and have been plotted in reduced variable form(I/I
versus (t/t
when no magnetic eld was applied onto the electrochemical cell
(Fig. 4) and with magnetic elds superimposed with values up to
1T (Fig. 5).
For the very rst moments, during the formation of critical
nuclei and before the curve maximum, the experimental data
obtained without magnetic eld (B=0T) are in agreement with a
progressive 3D nucleation mechanism (Fig. 4). After the maximum
value, deviation from progressive model curve and lower
Fig. 4. Normalized potentiostatic transient curves I(t). (a) Instantaneous mode, (b)
progressive mode, (c) and (d) experimental B=0T. Same electrolytic conditions as
Fig. 3.
Fig. 5. Normalized potentiostatic transient curves I(t). (a) Instantaneous mode, (b)
progressive mode, (e) and (f) experimental B=1T. Same electrolytic conditions as
Fig. 3.
current values indicate that the electrode is partly passivatedby the
Odeposit. Whenamagnetic eldis superimposedontotheelec-
trochemical cell in a direction parallel to the electrode surface, the
experimental data are in a good accordance with the instantaneous
nucleation process (Fig. 5). Once more after the current maximum
time (I/I
value decreases as it is without magnetic eld, indi-
cating a passivation of the electrode with oxide growth. For some
experiments realizedwiththe highest Bvalue (1T), the whole curve
is in accordance with the model. In fact, the mean electrical charge
involved in the deposition process that can be calculated up to the
maximumcurrent is decreasing when the magnetic eld is applied,
so for an equivalent reduced time value (t/t
), higher is the mag-
netic eld amplitude thinner is the deposited Cu
O thickness. The
meanthickness is 0.27mwithno magnetic eldand0.14mwith
1T-magnetic eld; therefore the passivation phenomenon is less
From the experimental data, the diffusive species which are
involved in the electrochemical reaction can be determined.
The I
products that result from Scharifker and Hills [27]
model are:for an instantaneous nucleation
= 0.1629(zFc)
D (7)
and for a progressive nucleation
= 0.2598(zFc)
D (8)
where D, zF and c are respectively the diffusion coefcient, the
molar charge and the bulk concentration of the reactive species.
The species that are involvedinthe Cu
Oelectrodepositionare cop-
per(II) and hydroxide ions. The copper(II) and OH

that are respectively equal to 0.45mol L
and 3.210
mol L
(pH=9.5), the current efciency that is equal to 1 and the exper-
imental values for I
and t
allow to calculate the diffusion
coefcient of the diffusive species.
- Considering hydroxide ions as diffusive species, calculations lead
to an average diffusion coefcient equal to 0.2m
, that is an
absurd value.
- Considering the Cu(II) ions as diffusive species, a diffusion coef-
cient value included between 1.310
and 2.610
is obtained for B=0T and progressive nucleation relation.
- Considering the Cu(II) ions as diffusive species, a diffusion coef-
cient value included between1.710
and 1.910
obtainedfor B=1T andinstantaneous nucleationrelation. For this
last case, the value is very accurate because there is no scattering
for experimental data when a 1T-magnetic eld is applied.
For time larger than t
, in spite of the passivation process, a
Cottrells law is roughly valid (Fig. 6) and the apparent diffusion
coefcient value that can be obtained is in accordance with the
previous ones.
5816 A.-L. Daltin et al. / Electrochimica Acta 54 (2009) 58135817
Fig. 6. Transient current versus 1/t
for Cu
O electrocrystallization for different
magnetic elds. Same electrolytic conditions as Fig. 3.
Therefore, it can be obviously conclude that Cu(II) ions control
the limiteddiffusioncurrent. These results conrmthat the limiting
rate step is the rst one of the process which corresponds to the
reduction of the copper ion: Cu

All these results give the evidence that magnetic eld induction
alters electrodeposition kinetics in the same way that overpoten-
tial can act. Such modication can be induced by a change of the
number of active sites N
, but this change needs an actual energy
level that cannot be obtained by the involved magnetic eld ampli-
tude. To get a better understanding of this magnetic eld effect, we
have undertakennumerical ts of current transient curves for many
magnetic eld amplitudes.
Numerical ts havebeencarriedout usingtheLSMprogram[42].
LSM program carries computation with the Least Square Method
(non-linear regression), i.e., t parameters given in analytic way
function (Eq. (4)) for given points. Examples are given in Fig. 7.
Thesenumerical ts reveal that thenumber of activesites N
the nucleation rate constant A have values with a constant order
of magnitude and which are not depending on the magnetic eld
amplitude (Table 1). In fact N
is imposed by the substrate surface
pretreatment which is kept as similar as possible and the nucle-
ation rate constant mainly depends on the applied overpotential
that is always the same for all our experiments. It is obvious that
the scattering of these values obtained for B=0T is larger than for
magnetic eld up to 1T.
Therefore, only a mass transport effect induced by the mag-
netic eld can be considered as the effective cause that acts on the
electrodeposition kinetics. As it has been proved in previous paper
[43], magnetic elds are efcient on ultramicroelectrodes down to
10m diameter. If we consider the equivalent surface as the dif-
fusion zone around a nucleus, we obtain the age t of the nucleus
when magnetic eld begins to be effective; this t value is given by
t =
Table 1
Saturation nucleus density (N
) and nucleation rate constant (A) deduced by numer-
ical t (Eq. (4)) for various magnetic elds B.
B (T) N
) A (10
0 13.0 0.2 5.0 0.6
0 1.94 0.02 88 4
0.25 5.1 0.6 65 3
0.5 12.6 0.3 14.5 0.5
1 3.47 0.04 67 3
Fig. 7. Comparison between experimental current transients (thin) (a) 0T; (b) 0.5T;
and (c) 1T with theorical (Eq. (4)) transients (bold).
with r =510
m, D=1.810
and k =0.52, the age t is
found to be equal to 0.3s, that is about one-hundredth of t
when a
magnetic eld is applied. This value highlights that magnetic eld
is efcient at the very rst moments of the electronucleation pro-
cess. In this case, the growth of the nuclei is highly enhanced and
overlappinghappens more rapidlytherefore progressive nucleation
turns to instantaneous process. The magnetic eld phenomenon
that leads to mass transport enhancement is not a classical MHD
convective effect. The current density in the bulk of the solution is
very weak and therefore the Lorentz force in the solution cannot be
efcient. In return, the 3D nucleation creates a hemispherical dif-
fusion zone around the nuclei in which a microMHD effect can be
expected as mentioned by Aogaki and coworkers [4446]. A MHD
ow is created in the diffusion layer that decreases its thickness.
4. Conclusion
The initial stages of the electrochemical Cu
O deposition have
been analyzed by means of transient currenttime curves. With
A.-L. Daltin et al. / Electrochimica Acta 54 (2009) 58135817 5817
an applied overpotential that induces a pure Cu
O with (100)
preferential orientation, a magnetic eld applied in a parallel direc-
tion to the electrode, modies the electrocrystallization kinetics.
The apparent progressive mode which was highlighted when no
magnetic eld was applied on the electrochemical cell turns to an
instantaneous regimewitha1T-magnetic eld. Bymeans of numer-
ical ts of the transient curves, the saturation nucleus density and
the nucleation rate constant are proved to be not depending on
the magnetic eld amplitude. The effects that are brought out are
only due to the magnetically induced effect that is effective on the
mass transport process from the very beginning of the nucleation
process and that favours a more rapid overlapping of the diffusion
zones around the nuclei.
Authors thank the Conseil Rgional de Champagne-Ardenne
for nancial support. This study has beendone inthe frame of GDRE
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