Journal of Electroanalytical Chemistry 791 (2017) 1–7

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Electrochemical nucleation and growth of Cu onto Au nanoparticles

supported on a Si (111) wafer electrode
M. Romero-Romo a, J. Aldana-González a, L.E. Botello a, M.G. Montes de Oca a, M.T. Ramírez-Silva b,
S. Corona-Avendaño a, M. Palomar-Pardavé a,⁎
a
Universidad Autónoma Metropolitana-Azcapotzalco, Departamento de Materiales, Área Ingeniería de Materiales, Av. San Pablo #180, Col. Reynosa-Tamaulipas, CDMX C.P. 02200, Mexico
b
Universidad Autónoma Metropolitana-Iztapalapa, Departamento de Química, Área de Química Analítica Av. San Rafael Atlixco #186, Col. Vicentina, CDMX C.P. 09340, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: This work showed that chemically-synthesized gold nanoparticles, AuNPs, supported onto a Si (111) wafer elec-
Received 12 January 2017 trode, can be selectively modified with a copper adlayer through underpotential deposition (upd) conditions,
Received in revised form 28 February 2017 using both: potentiodynamic or potentiostatic electrochemical means. From analysis of experimental
Accepted 2 March 2017
potentiostatic current density transients, it is shown that Cu upd onto the AuNPs occurs by a mechanism involv-
Available online 4 March 2017
ing the simultaneous presence of a Langmuir-type adsorption-desorption and an instantaneous two-dimension-
Keywords:
al, 2D, nucleation process. The influence of the applied potential on the Cu upd kinetics and on the extent of Cu
Gold nanoparticles atoms coverage over the AuNPs was also reported. Furthermore, it is shown that the Cu overpotential deposition,
Si (111) wafer electrode opd, onto these AuNPs, starting from a potential in the upd region where the AuNPs surface is free from Cu atoms,
Cu upd-opd occurs through a 2D-3D mechanism, where the 3D nucleation is mass-transfer controlled. Notwithstanding,
Nucleation when Cu opd started at the equilibrium potential the mechanism solely involved 3D nucleation.
Kinetics © 2017 Elsevier B.V. All rights reserved.

1. Introduction supported onto a Si (111) wafer electrode with 2D adlayers formed

The metallization of semiconductor surfaces for the formation of
Schottky barriers, ohmic contacts and diffusion barriers in electronic de-
vices can be performed, in vacuum, by evaporation and sputtering [1],
electrodeposition [2–8], or through charged particle beams [9], Si-C co-
valent bonds [10] and self-assembled method [11]. Recently, we have
shown that chemically synthesized gold nanoparticles, AuNPs, can be
electrostatically adsorbed onto an ITO substrate, previously modified
with Poly-L-Lysine, for its metallization [12–14] and that the resulting
ITO/AuNPs electrode can be used for dopamine selective quantification
[15]. Furthermore, we have also shown that these AuNPs surfaces can be
selectively covered with a copper full 2D monolayer via underpotential
deposition, Cu upd [16]. Some researchers have taken advantage of this
sort of adlayers to control the synthesis of platinum catalysts on AuNPs
towards methanol oxidation [17]. Since the amount of Cu upd coverage,
on the AuNPs, is susceptible to be modulated by controlling the elec-
trode potential [18–32], in this work the modification of AuNPs,
through Cu upd is considered, with specific attention to the formation
mechanism and kinetics, using both potentiodynamic and
potentiostatic electrochemical techniques. Moreover, the Cu 2D-3D
transition when varying the applied potential from the upd zone to
the overpotential deposition (opd) region, is also shown.
2. Experimental
2.1. Chemicals and solutions
All solutions were prepared with analytical grade reagents and deion-
ized water (18.2 MΩcm) from Millipore Milli-Q. HAuCl4·3H2O, 99.9%,
C2H5Na3O7·2H2O, 99.5%, CuSO4, 99.999%, H2SO4, 99.999%, Poly-L-Lysine
(Mw 30.000–70.000), NaCl, 99.5% and Si(111) wafer were purchased
from Sigma-Aldrich. CuSO4 and H2SO4, ultrapure grade, were from Merck.
2.2. Synthesis of AuNPs

AuNPs were synthesized following Turkevich and Frens method [33,

⁎ Corresponding author. 34], slowly adding C2H5Na3O7 to HAuCl4 under reflux and strong agita-
E-mail address: mepp@correo.azc.uam.mx (M. Palomar-Pardavé). tion, during 1 h. The reaction is ended when the solution turns red.

http://dx.doi.org/10.1016/j.jelechem.2017.03.003
1572-6657/© 2017 Elsevier B.V. All rights reserved.
2 M. Romero-Romo et al. / Journal of Electroanalytical Chemistry 791 (2017) 1–7
Fig. 1. UV–Vis spectrum of AuNPs.
2.3. AuNPs characterization
2.3.1. UV–Vis absorption spectroscopy
AuNPs UV–Vis spectra were obtained with a Perkin Elmer lambda 35
UV–Vis spectrometer with a 10 mm quartz cell, using Milli-Q water as
blank.
2.4. Si (111)-AuNPs electrodes preparation
The Si (111) wafer electrode was ultrasound-cleansed in acetone,
ethanol and deionized water, 15 min in each, and dried under pure
N2. The clean surfaces were modified by dipping in 1 mg cm−3 Poly-L-
Lysine, PLL, solution for 10 min, followed by deionized Milli-Q water
rinsing and drying under pure N2. For electrochemical experiments,
five layers were stacked on the modified PLL-Si (111) wafer electrode,
having the AuNPs electrostatically adsorbed. This allowed control of
the AuNPs number, dependent on the Si (111) wafer electrode immer-
sion time in the AuNPs solution [12–14]. The PLL cationic nature makes
it an intermediary between the negatively charged substrate's structure,
and the AuNPs enclosed in citrates' chains [14]. The electroactive surface
area of the Si (111)-AuNPs electrode was estimated as (0.285 ± 0.043)
cm2 following the methodology reported by Aldana-González et al. [16].
2.4.1. SEM characterization
The Si (111)-AuNPs was characterized through a SEM SUPRA PV
Zeiss instrument, using 10 kV accelerating voltage and 20 KX or
100 KX magnifications.
Fig. 2. SEM images of the AuNPs (one layer was stacked) electrostatically adsorbed on a Si (111) wafer electrode surface: a) 20,000× and b) 100,000×.
2.5. Electrochemical setup
Cyclic voltammetry and chronoamperometry served to study Cu
electrodeposition at Si (111)-AuNPs substrates from a 5.0 mM CuSO4
and 0.5 M H2SO4 solution. Electrochemical experiments were carried
out in a system using a Si (111)-AuNPs working electrode with a
0.071 cm2 geometric area, a Pt wire as counter electrode and a Cu
wire as pseudo-reference electrode, to which all potentials are herein
quoted. Before the experiments, solutions deaeration was done for
30 min using pure N2. Potentials were controlled by a PAR 273 (USA)
potentiostat-galvanostat coupled to a PC running the M270 electro-
chemical research software (EG&G PAR) for experimental control and
data acquisition. Before initiating the Cu upd experiments, the working
electrode was constantly maintained under the potential control
(400 mV), from initial contact with solution.
3. Results and discussion
3.1. AuNPs characterization
From analysis of the chemically synthesized AuNPs by means of XRD
[15] and UV–Visible spectroscopy, see Fig. 1, it was found they are poly-
crystalline, with a predominant Au(111) plane, see Fig. 4 in [15], and
display a 5–20 nm average diameter (a plasmon resonance peak ap-
peared around 520 nm), see Fig. 1, respectively.
3.2. Si (111)-AuNPs electrode characterization
3.2.1. SEM analysis
The AuNPs were supported onto a Si (111) wafer electrode, see
Section 2.4. Fig. 2 shows SEM images of the AuNPs electrostatically
adsorbed on a Si (111) wafer surface. It is possible to note that the
AuNPs are dispersed over the whole Si(111) wafer surface, see Fig. 2a,
and in spite that some of them agglomerated, their nanometric nature
was preserved, see Fig. 2b.
3.2.2. Cyclic voltammetry analysis
Fig. 3 shows typical CVs recorded using the bare Si (111) wafer elec-
trode, showing practically null faradaic activity in the potential range
considered (see the red CV), or that modified with AuNPs, Si (111)-
AuNPs (blue CV), immersed in a sulfuric acid aqueous solution. The lat-
ter shows the faradaic current associated with the oxidation of the
AuNPs to form gold oxides (O1) and its corresponding reduction to me-
tallic gold (R1). It is important to note that in the potential range:
0 ≤ E ≤ 400 mV there is not any faradaic activity and solely the capacity
current associated to the electrochemical double layer can barely be ob-
served, see the inset in Fig. 3.
 M. Romero-Romo et al. / Journal of Electroanalytical Chemistry 791 (2017) 1–7 3

Fig. 3. CVs recorded in the systems: Si (111) / 0.5 M H2SO4 (red line) and Si (111)-AuNPs /
0.5 M H2SO4 (blue line), in both cases the potential scan started at − 420 mV in the
positive direction at 5.0 mVs−1. The inset shows a close up of the region
(0 ≤ E ≤ 400 mV) of the CVs.

3.3. Cu upd onto AuNPs

3.3.1. Potentiodynamic study

Fig. 4 depicts an experimental CV recorded during Cu upd onto the
AuNPs supported on the Si (111) wafer electrode. Two well resolved
voltammetric peaks were formed. The cathodic one is associated with
the formation of a copper monolayer covering the whole electroactive
surfaces of the AuNPs, and the anodic one its electrochemical dissolu-
tion to form Cu(II) ions in solution. It is important to mention that Cu
electrodeposition onto Si(111) surface has been reported; however, it Fig. 5. Comparison of the experimental i-θ plots, corresponding to both: the anodic (Fig.
occurs at potential values more negative than − 1.0 V vs. Cu(II) / 5a) and cathodic (Fig. 5b) branches of the CV shown in Fig. 4, where the θ values where
obtained by integration of the respective voltammetric branch, with that obtained by
non-linear fitting of Eq. (2). The best fit parameters obtained were: for the anodic
branch P1 = (27 ± 0.1) μA and P2 = − 0.8 ± 0.1 and for the cathodic branch, P1 =
(27 ± 0.2) μA and P2 = −2.0 ± 0.3.

Cu(0) [2–6]. It is important to point out that the CV recorded during

Cu upd onto Au(111) single crystals extended surfaces [19,25,32], at
the same experimental conditions, showed two very well defined

Fig. 4. Cyclic voltammogram recorded in system: Si (111)-AuNPs / 5.0 mM CuSO4, 0.5 M
H2SO4. The potential scan started at 375 mV in the negative direction at 5.0 mVs−1.
Fig. 6. Comparison of the experimental (circles) i-t plots recorded in the system: Si (111)-
AuNPs / 5.0 mM CuSO4, 0.5 M H2SO4 stepping the potential from 400 mV to the different
potential values indicated in the Figure in mV, and the theoretical ones (solid lines)
obtained by non-linear fit of Eq. (3) to the experimental data. The inset shows the
individual contributions of the theoretical overall current, for the i-t plot recorded at
60 mV due to an adsorption process (iad) and an instantaneous 2D nucleation process,
limited by ad-atoms incorporation (i2Di-LI).
4 M. Romero-Romo et al. / Journal of Electroanalytical Chemistry 791 (2017) 1–7

Table 1
Current maxima coordinates and best fitting parameters obtained through non-linear fitting of Eq. (3) to the experimental transients shown in Fig. 6.

E tm a ima k1a k2a k3a 103 k4a qb im tm/q

/mV /s /μA /μA /s−1 /μAs−1 /s−2 /μC

100 6.05 ± 0.02 2.20 ± 0.04 8.65 + 0.31 1.02 ± 0.04 0.60 ± 0.01 11.6 ± 0.2 21.5 0.62
80 5.25 ± 0.01 5.53 ± 0.08 9.50 ± 0.39 0.91 ± 0.04 1.44 ± 0.02 13.9 ± 0.2 54.4 0.53
60 4.47 ± 0.04 9.21 ± 0.06 10.83 ± 0.68 0.90 ± 0.07 2.85 ± 0.05 19.2 ± 0.3 68.2 0.60
40 3.16 ± 0.02 19.92 ± 0.08 11.20 ± 0.44 0.71 ± 0.04 6.20 ± 0.02 40 ± 1 81.9 0.77
20 2.63 ± 0.01 24.82 ± 0.02 11.85 ± 0.56 0.32 ± 0.07 9.11 ± 0.27 55 ± 1 93.7 0.70
0 2.10 ± 0.02 29.58 ± 0.01 12.92 ± 0.52 0.30 ± 0.05 12.78 ± 0.30 72.6 ± 1.1 103.5 0.60
a
The uncertainty values were evaluated on the basis of 3 repetitions for each applied potential.
b
Obtained by integration of the cathodic branch of the CV reported in Fig. 4.

cathodic peaks which have been associated [32] with structural changes where θRe is the fractional area of Re, S is the electrode surface area, z is
on the Cu monolayer formation. The first one (occurring at more posi- the number of electrons transferred during the heterogeneous reaction,
tive potential values) to the transition from Cu randomly adsorbed to ð v is the potential scan rate, R, T and F are the universal gas constant, ab-
pffiffiffi pffiffiffi
3  3 ÞR30 ° , honeycomb-like superstructure, and the second one solute temperature and Faraday constant, respectively, Γο⁎ is the total
to the transition from the latter to that corresponding with the isomor- surface coverage, ε is the number of water molecules displaced from
phic (1 × 1) full Cu monolayer formation. Therefore, a plausible expla- the surfaces by absorption of Ox or Re, θT = θRe + θOx (with θOx being
nation in the case of Cu upd onto AuNPs is that it occurs through just the fractional area of Ox) and g = aOx + aRe − 2aOxRe (where aOxRe, aOx
one structural transition namely: from Cu randomly adsorbed to a and aRe are the Ox-Re, Ox-Ox and Re-Re interaction parameters
(1 × 1) adlayer structure. These features clearly indicate that the kinet- (dimensionless)).
ics and mechanism of the Cu upd onto Au are very sensitive to the struc- z2 F 2 Sv0
Eq. (2) is a parameterized form of Eq. (1) with P1 ¼ RT and
ture of the gold surfaces. The complexity of the Cu upd on Au flat P2 = 2εgθT
surfaces has been addressed by Rikvold and coworkers [26,27] and by
Oviedo et al. [31], by means of different simulations namely: numerical  
θRe ð1−θRe Þ
studies of lattice-gas [26,27] and quantum mechanical methods models i ¼ P1 ð2Þ
1−P 2 θRe ð1−θRe Þ
[31].

Fig. 5 shows a comparison of the experimental i-θ plots, correspond-

3.3.1.1. Voltammogram simulation. Considering the following: a) the
shape of the experimental CV recorded during Cu upd onto AuNPs sup-
ported onto the Si (111) wafer electrode, b) that the electroactive spe-
cies is adsorbed and c) that this process involves the formation of a
copper monolayer onto the surfaces of the AuNPs, it was decided to an-
alyze the CV shown in Fig. 4 in terms of surface coverage derived from
transient measurements as described in Eq. (1) [35]. When lateral inter-
actions exist between the oxidized, Ox, and the reduced, Re, form of the
atoms that will give rise to the two-dimensional, 2D, film, the shape of
the i-E curve depends upon the energies of the interactions of Ox with
Ox, Re with Re and Ox with Re. If a Frumkin-type isotherm is assumed,
the expression of the current as a function of the surface coverage, θ,
is given by Eq. (1). This methodology is similar to that described by
Barradas and Porter [36], for the analysis of two-dimensional nucle-
ation-growth processes in terms of surface coverage, derived from tran-
sient measurements, and also described by Noel and Vasu [37].
 
z2 F 2 SvΓ 0 θRe ð1−θRe Þ
i¼
RT 1−2εgθT θRe ð1−θRe Þ
ing to both: the anodic (Fig. 5a) and cathodic (Fig. 5b) branches of the
CV shown in Fig. 4, where the θ values were obtained by integration of
the respective voltammetric branch, with that obtained by non-linear
fitting of Eq. (2). It is possible to note that both cases can be adequately
described by the model of monolayers formation and dissolution
in terms of surface coverage, derived from transient measurements
[35–37] and furthermore, since the interaction parameter (P2) is differ-
ent to 0 in both cases, it means that lateral interactions between the
copper ad-atoms that form the monolayer are not negligible (as com-
pared with the interaction of these ad-atoms with the gold substrate);
this is congruent with the formation of a Cu monolayer throughout a
nucleation mechanisms [36].
3.3.2. Potentiostatic study
3.3.2.1. upd. Hölzle et al. [25], studied the mechanisms and kinetics of Cu
upd onto Au(111) and Palomar-Pardavé et al., in both Au(111) [19–21]
and polycrystalline gold [21] extended surfaces by means of
potentiostatic current transients, i(t). In these works, it was shown
ð1Þ
that regardless of the crystalline nature of the Au surface, the

Fig. 7. Potential variation of a) the current time's maxima (tm) of the experimental i-t transients reported in Fig. 5 and b) parameter k4 obtained by non-linear fit of Eq. (3) to the
experimental potentiostatic current transients. The lines and the equations correspond to the linear fitting of the data obtained (points).
 M. Romero-Romo et al. / Journal of Electroanalytical Chemistry 791 (2017) 1–7 5

mechanism that described the experimental potentiostatic current

transients, see Eq. (3), involves the simultaneous presence of the double
layer charge process, a Langmuir-type adsorption-desorption equilibri-
um, iad (t), Eq. (4) and at least an instantaneous 2D nucleation process
limited by the lattice incorporation, i2Di-LI (t), of Cu ad-atoms to the 2D
nuclei Eq. (5).

iðt Þ ¼ iad ðt Þ þ i2Di−LI ðt Þ ð3Þ

with:

iad ðt Þ ¼ k1 expð−k2 t Þ ð4Þ

where t is the potential perturbation time, k1 ¼ SE

Rs , k2 ¼ Rs C
1

and
Fig. 8. Potential variation of the charge density (left y-axis) and the corresponding AuNPs
  surface coverage with Cu atoms (right y-axis). The individual contributions to the total Cu
i2Di−LI ðt Þ ¼ k3 t exp −k4 t 2 ð5Þ
upd process (circles) due to 2D nucleation (squares) and the adsorption process
(triangles) were obtained from Eqs. (8) and (9) using the parameters reported in Table 1.
2πzSFMhN0 K 2g πM2 N0 K 2g
with k3 ¼ ρ and k4 ¼ ρ2
fitting of the Eq. (3) gives a good support to the model used to describe
where E is the applied potential, Rs is the solution's resistance, C the dou-
the mechanisms and kinetics of Cu upd on AuNPs. Moreover, for instan-
ble layer capacitance, Kg is the nuclei growth rate constant (mol cm−2- taneous 2D nucleation [38–39] the product im tm must be equal to 0.606
s− 1), M and ρ are the molecular mass and the deposit density,
respectively; h is the layer formed height and N0 is the overall number
density of active sites available for the nucleation process on the sub-
strate surface.

3.3.2.2. Influence of the applied potential on Cu upd onto AuNPs. Fig. 6 com-
pares the experimental potentiostatic current density transients obtain-
ed during Cu upd on the AuNPs surfaces, supported onto Si (111) wafer
electrode, for different applied potentials and those resulting from Eq.
(3) fitting to the respective experimental data. The best fitting parame-
ters are shown in Table 1. Note that Eq. (3) describes adequately the ex-
perimental evidence in all cases. Moreover, it is plain from the inset in
Fig. 6 that at very short times the adsorption process is the dominant
contribution. However, after a few seconds the 2D instantaneous nucle-
ation becomes the more important contribution to the total current.
This transition can be related to the structural changes observed during
Cu upd on Au(111) extended surfaces, namely: random adsorption of
pffiffiffi pffiffiffi
Cu atoms to ð 3  3ÞR30 ° or honeycomb structure, and eventually,
if the applied potential corresponds to the equilibrium potential, to a
(1 × 1) isomorphic structure corresponding to the formation of a full
monolayer [18].
As can be noted from Fig. 6 all these current transients possess well-
resolved current maxima with tm, im coordinates, see Table 1. At this
current maximum, see inset in Fig. 6, the contribution associated to
the double layer charging is negligible, thus at this point the current is
practically due to the 2D nucleation process and then the temporal de-
rivative of Eq. (5) must be equal to zero. Thus, differentiation of Eq. (5)
with respect to time yields:
 1=2
1 ρ
tm ¼ ¼ ð6Þ
2k4 ð2πN0 Þ1=2 MK 2g

Taking the logarithm of Eq. (6) and then its partial differentiation
with respect to E yields:
Fig. 9. a) Comparison of the experimental (circles) j-t plot recorded in the system: Si
    (111)-AuNPs / 5.0 mM CuSO4, 0.5 M H2SO4 stepping the potential from 400 to −60 mV
∂ logt m 1 ∂ logk4
≅− ð7Þ (upd-opd), and the theoretical one (solid line) obtained by non-linear fit of Eq. (10) to
∂E 2 ∂E the experimental data. The individual contributions of the theoretical overall current
density due to adsorption (iad), instantaneous (i2Di-LI) and progressive (i2Dp-LI) 2D
Fig. 7 shows the potential dependence of the logarithm of current nucleation, limited by ad-atoms incorporation and a 3D nucleation process mass
time's maxima (tm), Fig. 7a, and the logarithm of parameter k4, Fig. 7b. transfer-controlled (i3D-dc) are also shown. b) Comparison of experimental (points) j-t
plots recorded in the system: Si (111)-AuNPs / 5.0 mM CuSO4, 0.5 M H2SO4 stepping the
In both cases, the observed behaviors were linear. The slopes were potential from 400 to −60 mV (upd-opd) (triangles) and from 0 to −60 mV (points)
0.004 (for log (tm) vs. E) and −0.008 (for log (k4) vs. E). This agreement with the theoretical j-t traces generated by Eq. (10) and (17), respectively. For both
between direct experimental evidence (tm) and that (k4) obtained by cases the best fit parameters obtained are reported in Table 2.
6 M. Romero-Romo et al. / Journal of Electroanalytical Chemistry 791 (2017) 1–7

Table 2
Adsorption and nucleation parameters obtained through non-linear fitting of Eqs. (10) or (17) to the experimental transients shown in Fig. 9.

Potential perturbationa jad(t) j2Di−LI(t) j2Dp −LI(t) j3D−DC(t)

k1 k2 N0K2g AN0K2g 105 D A 10−6 N0

/mA cm− 2 /s− 1 /mol2 cm− 6 s− 1 /mol2 cm− 6 s− 3 /cm2 s− 1 /s− 1 /cm− 2

400 to −60 mV 0.81 ± 0.02 6.6 ± 0.3 0.002 ± 0.001 0.00005 ± 0.00002 1.3 ± 0.2 0.00004 ± 0.00001 1582 ± 8
0 to −60 mV 1.56 ± 0.05 4.0 ± 0.3 – – 1.3 ± 0.1 0.27 ± 0.01 4.45 ± 0.01
a
The uncertainty values were evaluated on the basis of 3 repetitions for each applied potential.

qM, where qM is the monolayer charge. As can be noted from Table 1, the with
value of this product, calculated from the experimental transients, and
divided by the charge of the monolayer, obtained by integration of the
2FD1=2 c0
cathodic branch of the CV reported in Fig. 4, adequately agrees with P1 ¼ ð13Þ
the theoretical value of 0.606, for any of the applied potentials π1=2
considered.
From analysis of Eqs. (4) and (5) it is possible to estimate the charge P 2 ¼ N 0 πkD ð14Þ
densities due to adsorption, qad and 2D nucleation, q2D, processes re-
spectively as:
P3 ¼ A ð15Þ

qad ¼ k1 =k2 ð8Þ

q2D ¼ k3 =2 k4
Fig. 8 shows the potential dependencies of the total charge density,
q, (q = qad + q2D) along with those corresponding to the individual con-
tributions due to adsorption (Cu and co-adsorption of bisulfate and/or
sulfate anions) and Cu nucleation. It is possible to note that the surface
coverage can be modulated by controlling the electrode potential and
that even when the 2D nucleation contribution always predominates,
as the applied potential approaches the equilibrium one, the adsorption
contribution becomes more notorious. Furthermore, from the data in
Table 1, k1 increases linearly with the potential excursion, as expected,
and the rate of adsorption k2 decreases significantly as the potential is
varied from 100 to 0 mV. This is probably related to the drop in adsorp-
tion capacity as the copper monolayer is completed.
3.3.2.3. upd-opd transition. Fig. 9a shows a comparison of an experimen-
tal potentiostatic current density transient, j(t), recorded during the
copper electrodeposition onto the Si(111)/AuNPs electrode, starting
the potential (Ei) at 0.4 V, where the AuNPs surfaces are copper-free,
and then stepped the potential (Ef) to a value within the opd zone
(Ef b Eeq), with the theoretical one generated by non-linear fit of Eq.
(10) proposed by Palomar-Pardavé et al. [19,40], in order to describe
the potentiostatic current transients involving 2D-2D and 2D-3D nucle-
ation transitions, where the three-dimensional nucleation contribution,
j3D-dc(t), see Eq. (12), is a mass transfer-controlled process described by
Scharifker and Mostany [41].
k ¼ ð8πc0 =ρÞ1=2 ð16Þ
ð9Þ
where A is the nucleation rate, and c0 and D are the concentration and
diffusion coefficient of the metal ion in the solution's bulk, respectively.
From Fig. 9a it becomes plain that when Cu deposition onto the
AuNPs is carried out from an Ei value, where the AuNPs are free from
Cu atoms, Ei N Eeq, to a final potential value within the opd zone,
Ef b Eeq, where the 3D nuclei are thermodynamically favored, the copper
nucleation occurs. At the early stages, t b 2 s, the potentiostatic current
density transient is mainly formed by instantaneous 2D nucleation
however, for longer times, t N 2, the diffusion-controlled 3D nucleation,
is the main contribution to the total current density. Notwithstanding,
the participation of a 2D progressive nucleation was observed. The ori-
gin and nature of this second monolayer is unclear and further research
on this matter would be required. Nevertheless, if the potentiostatic Cu
opd is started at the Eeq (where the Cu full monolayer is already formed,
see Fig. 8) the experimental current density transient, see Fig. 9b, is
formed by a single current density maximum that can be adequately de-
scribed by Eq. (17) which solely involves a single 3D nucleation process.
Furthermore, from Fig. 9b and Table 2, it is possible to note that when
the 2D–3D nucleation transition is occurring, the 3D nucleation be-
comes slower (its maximum occurs a longer times with a lower nucle-
ation rate values); however, the 3D nuclei always are formed on top
of a 2D layer, this crystal growth model is known as the Stranski-
Krastanov mechanism [24]. The influences of the applied potential on
both experimental cases namely 2D-3D and·3D nucleation can be
found as supporting material of this work.

jðt Þ ¼ jad ðt Þ þ j2Di−LI ðt Þ þ j2Dp−LI ðt Þ þ j3D−DC ðt Þ ð10Þ jðt Þ ¼ jad ðt Þ þ j3D−DC ðt Þ ð17Þ

where the progressive 2D nucleation is given by Eq. (11)

4. Conclusions
 
j2Dp−LI ðt Þ ¼ k5 t 2 exp −k6 t 3 ð11Þ
It has been demonstrated that the electrochemical formation of a Cu
adlayer, under upd conditions, onto the AuNPs, supported onto a Si
πzFMhAN0 K 2g πM2 AN0 K 2g
with k5 ¼ ρ and k6 ¼ 3ρ2
(111) wafer electrode, followed a mechanism involving the simulta-
neous presence of an adsorption process and an instantaneous 2D nu-
And the mass transfer-controlled 3D nucleation contribution is rep-
cleation processes. From the theoretical model herein described, both
resented by Eq. (12)
contributions can be deconvoluted, where the individual contribution
to the Cu 2D layer, as a function of the applied potential, was also report-
  
1− expð−P 3 t Þ


jðt Þ ¼ P 1 t −1=2 1− exp −P 2 t− ð12Þ ed. Moreover, it was also shown that Cu opd on the AuNPs always in-
P3 volves the formation of 3D nuclei onto a 2D Cu monolayer.
 M. Romero-Romo et al. / Journal of Electroanalytical Chemistry 791 (2017) 1–7
Acknowledgements
The authors like to thank CONACyT for projects 258487 and 237327
and SEP-PRODEP for RedNIQAE. MTRS thank CONACyT for the cathedra
2159. JAG and LEB thanks CONACyT for the support given to undertake a
postdoctoral stay at UAMA and the scholarship granted to pursue post-
graduate studies at UAMA, respectively. JAG, MGMY, MTRS, SCA, MRR
and MPP wish to thank the SNI for the distinction of their membership
and the stipend received. MGMY is indebted to Bristol University and its
Electrochemistry group for her Ph.D. formation, CONACyT for paying the
corresponding tuition fees and L'oreál-UNESCO-CONACyT-AMC for the
grant Woman in Science 2016. We also like to express our gratitude to
the anonymous reviewers of this paper for their criticisms and sugges-
tions that contributed to improve our work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.jelechem.2017.03.003.
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