D530 Journal of The Electrochemical Society, 160 (11) D530-D537 (2013)

0013-4651/2013/160(11)/D530/8/$31.00 © The Electrochemical Society

Study of Tin Electroplating Process Using Electrochemical

Impedance and Noise Techniques
Xianqiu Huang,a,b Yu Chen,a Taiwen Fu,c Zhao Zhang,a,z and Jianqing Zhanga,d
a Department of Chemistry, Yu-quan Campus, Zhejiang University, Hangzhou 310027, China
b Research Institute of Wuhan Iron and Steel Co., Wuhan 430080, China
c 92351 Military, Sanya 572016, China
d State Key Laboratory for Corrosion and Protection, Shenyang 110015, China

The tin electroplating process was studied by means of electrochemical impedance and noise (EN) technique. Scanning electron
microscopy (SEM) was used to investigate the morphology of tin electrodeposits. Electrochemical impedance results reveal that
charge transfer resistance of tin electroplating decreases with the potential bias η exponentially at this experimental condition. It
is found that the EN generated at high current density has large potential oscillation amplitude and positive potential drift, while
the EN show small noise amplitude at low current density. With the decrease of current density, the corresponding deposit changes
from large conglomerate particles to compact. New parameters are proposed to cultivate the relationship between the EN feature
and the structure of tin deposits. The variation trend of Parameter n2 was found to be in accordance with the crystallite size. For
different Sn2+ concentrations, the oscillation amplitude of the potential noise at low concentrations are much larger than that of
high concentrations, which may be correlated with that tin electroplating process is coupled with hydrogen evolution at low Sn2+
concentrations.
© 2013 The Electrochemical Society. [DOI: 10.1149/2.055311jes] All rights reserved.

Manuscript submitted August 7, 2013; revised manuscript received August 30, 2013. Published September 26, 2013.

Tin and Sn-based alloys have received widely interest in recent Experimental
years due to its relatively low cost, high electrical conductivity, good
316L steel substrates with geometric area of 0.50 cm2 were used
corrosion and non-toxic nature.1–4
as working electrode to electroplate tin films. Before electroplating,
Electroplating is a powerful technique to deposit different kinds
the working surfaces were polished to mirror using 2.5 μm diamond
of metals and alloys, and possesses many advantages, such as low
paste, rinsed with double distilled water, washed in acetone and then
processing temperature, normal handling pressure, high purity of de-
dried in air. A saturated calomel electrode (SCE) connected through
posits, etc. Tin has been commercially electrodeposited from several
a salt bridge was used as reference, and a large platinum foil as
acid and alkaline baths.5–8 The acid fluoride-based bath is one of the
counter electrode, respectively. The electroplating bath electrolyte was
most popular tin electroplating baths owing to its good solubility, wide
prepared with AR grade reagents and double distilled water according
electroplating current range, high current efficiency, good dispersion
to the fundamental compositions listed in Table I. A conventional glass
and so on,9 which has been widely used in large iron enterprises of
electrolysis cell with inlet and outlet to deaerate the solution with N2
China, such as Wuhan Iron and Steel Co. and Shanghai Bao Steel
gas was employed to make sure the experiments were done in an
Group. Recently, a few published studies have focused on the initial
oxygen-free electrolyte. The electrolyte was purged with nitrogen gas
nucleation process of Sn electrodeposits, which has been demon-
for about half an hour before experiment and then the nitrogen bubbler
strated to influence the obtained film qualities markedly.3,10 Han3 has
was pulled above the electrolyte surface during measurements.
studied the nucleation process of Sn onto Pt using current transient
Electrochemical impedance spectroscopic (EIS) measurements
technique, and found that the process followed the progressive nu-
were carried out using an impedance measurement unit (PARSTAT
cleation mechanism controlled by diffusion. Wen and Szpunar10 also
2273, Advanced Electrochemical System) over the frequency range
studied the initial stages of Sn electroplating onto low carbon steel with
of 0.1–10,000 Hz with the voltage amplitude of 20 mV at different
current step methods and found that 3D tin crystallites were formed
potential bias, and the frequency sweep always initiated from high to
preferentially on step edges, which was followed by fast covering of
low.
neighboring sites with much smaller and densely packed crystallites
EEN was recorded at different current density Jk and Sn(BF4 )2
of about 150–180 nm in size.
concentration with a commercial PowerLab coupled with GP Amp
It is well known that during metal electroplating, the electrochem-
(ADInstruments Pty Ltd., Australia) at a sampling rate of 10 Hz.
ical dynamical parameters, such as current and potential will fluctuate
After the EEN measurements, scanning electron microscopy (SEM)
spontaneously, which has been designated as electrocrystallization
was used to investigate the morphology of tin electrodeposits. All
electrochemical noise (EEN).11,12 EEN has been reported in the litera-
the measurements were performed in a quiescent solution. The solu-
ture for several electroplating systems.13–17 Our previous study15 also
tion temperature was controlled by a thermostatically water bath at
investigated the relationship between the EEN features and the zinc
30 ± 1◦ C and the experimental device was shielded in a faradaic cage.
electrodeposits structure, and found that the EEN generated during the
electroplating of dentritic or large conglomerate zinc deposit has large
potential oscillation amplitude and positive potential drift while the Results and Discussion
compact zinc deposit possesses small noise amplitude and little po-
tential drift, the EDP (relative energy distribution plot) obtained from Electrochemical impedance.— EIS diagrams were recorded at dif-
wavelet analysis of the EEN can be used as “fingerprints” to char- ferent potential bias η as shown in Fig. 1. It is apparent that the
acterize the electroplating process and the deposit structure, and the diameter of the high-frequency capacitive semicircle decreases with
electrochemical noise technique can give more information about the increasing the applied potential bias, and the impedance module value
deposit structure than other normal electrochemical measurements.
However, there is little research on tin electroplating from stannous Table I. Basic compositions of electroplating bath electrolyte.
fluoborate acid electrolyte by using EEN technique.
The current study focuses on tin electroplating process using EEN Component c/mol.l−1
technique, especially investigate the correlations between the EEN Sn(BF4 )2 0.02
features of tin deposits and the deposit structure phenomenologically. HBF4 0.04
H3 BO3 0.01
z
E-mail: eaglezzy@zjuem.zju.edu.cn pH 3.5

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 Journal of The Electrochemical Society, 160 (11) D530-D537 (2013) D531

5000
-0.48
-0.52
4000 -0.56
-0.60
-0.64
3000 -0.68 Figure 2. EEC used for simulating the high-frequency impedance spectra
data.
Z, ohm

2000
ductive component (the shrinkage phenomenon of the real part at low
frequency domain) appears. The reason may be that tin electroplating
1000 process is coupled with hydrogen evolution at large potential bias.20,21
Potential bias η is defined as follows:

0
η = E − E eq [1]
where E is the applied cathodic potential, E eq is the electrode equilib-
0.1 1 10 100 1000 10000 100000 rium potential.
f,Hz The time-constant numbers of EIS plots in Fig. 1 have been de-
termined through both the features of the EIS diagrams (such as the
-70 number of the phase angle peak in Bode plot, the number of the slopes
-0.48 in Bode plot and the number of the capacitance in Nyquist plot), and
-0.52
-60
-0.56 the method developed by Wit22,23 simultaneously. The analyzed re-
-0.60 sults demonstrate that, only one time-constant for tin electroplating
-50 -0.64 process can be obtained above the real axis. Consequently, the high-
Phase angel, deg

-0.68 frequency EIS data shown in Fig. 1 are fitted with Z-view software
-40
and the equivalent electrical circuit (EEC) model shown in Fig. 2. The
-30 analyzed results are listed in Table II.
Fig. 2. EEC used for simulating the high-frequency impedance
-20 spectra data. Rs is the solution resistance, CPE represents the double
layer capacitance Cdl and Rt is the charge transfer resistance.
-10
The fitted results demonstrate that charge transfer resistance (Rt )
0
decreases from 1880  cm2 to 52  cm2 with increasing the potential
bias from −0.48 V to −0.68 V (Table II), which indicates that the
10 electroplating process of tin is much easier at higher cathodic po-
0.1 1 10 100 1000 10000 100000
tential bias. The fluctuation of CPE-P may be due to the changes of
f, Hz electrode surface roughness during tin electroplating and hydrogen
-5000
evolution process. Relationship between potential bias η and Rt is
plotted in Fig. 3, where Rt decreases with η exponentially. This phe-
-0.48
-0.52
nomenon has been found and explained by Chen24 with the following
-4000 -0.56 equation:
-0.60  
n Fη − H
-0.64 k = A exp [2]
-3000 -0.68 RT
where A is the pre-exponential factor, T is the absolute temperature,
Zima

-2000 R is the gas constant. H is a constant at certain temperature and

pressure. Thus, reaction rate constant (k) increases exponentially with
the applied potential bias, resulting in exponentially decay of Rt with
-1000 the applied potential bias.

Electrochemical noise.–Influence of electroplating current

0
density.— Fig. 4 shows the potential EEN in the initial short time
for tin electroplating onto 316L steel at different current densities. It
0 1000 2000 3000 4000 5000
is clear that the potential EEN curves are different at different elec-
Zreal troplating current density (Jk ). In the case of small Jk value (e.g.,
0.5 mA cm−2 and 1 mA cm−2 ), the potential curves initially show an
Figure 1. EIS plots for tin electroplating at different applied potential bias. abrupt potential drop corresponding to double layer capacitance charg-
ing process, then a quickly increase due to tin nucleation / growth

decreases sequentially as well. Meanwhile, the site of the phase-angle

peak statistically moves from low to high frequency domain, which Table II. EIS analyzed results for tin electroplating at different
means the electroplating process get faster as the high frequency ca- potential bias.
pacitive semicircle is related to charge transfer process. Nyquist plots
show that all centers of the high-frequency capacitive circles are be- η/V Rs / cm2 CPE1-T/μF cm−2 CPE1-P Rt / cm2
low the real axis, indicating that the charge-transfer process controls −0.48 11.9 101.2 0.844 1880
the tin electroplating process in our experimental conditions.18,19 The −0.52 13.4 68.4 0.844 841
highness of the phase-angle peak decreases with increasing the ap- −0.56 12.6 154.8 0.814 592
plied potential bias, which means that the nucleation / growth process −0.60 15.1 62.2 0.841 254
becomes more and more inhomogeneous. When the cathodic potential −0.64 11.8 48.9 0.869 65
bias is too large, the low-frequency EIS data becomes discrete and in- −0.68 13.4 76.8 0.811 52

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 D532 Journal of The Electrochemical Society, 160 (11) D530-D537 (2013)

2500 combined to H2 and then separated from the surface, the real active
surface area of the electrode during tin electroplating changes from
Rt=6.71E6*exp(17.1η) time to time, causing the large potential oscillation compared to that
2000 of low current density.
The EEN data containing 5120 points selected after the initial
10 ms (determined by chronoamperometry technique) of double layer
charging process are analyzed with wavelet technique using the or-
1500 thogonal Daubechies wavelets (FWT) of the fourth order (db4). For
FWT analysis, the interval range of each crystal is given by:
Rt /Ω cm2

(C1l , C2l ) = (2l t, 2l−1 t) [3]

1000
The overall energy (E) of the noise containing 5120 data points in
this experiment is calculated as follows:
500

N
E= Sn2 (n = 1, 2, ..., N , N = 5120) [4]
n=1
0 Then, the fraction of energy associated with each crystal (D and
-0.70 -0.65 -0.60 -0.55 -0.50 -0.45
S) can be calculated as:
η vs SCE/ V
N /2 l
1  2
Figure 3. Variation of Rt with the applied potential bias. ElD = D (l = 1, 2, ..., J, J = 8) [5]
E k=1 l,k

process, and lastly almost remain at a certain constant value. This
phenomenon may be explained by that small Jk requires small con-
centration overpotential3 and initiates few crystal nucleis. In the case
of much larger Jk value, such as 10 mA cm−2 and 20 mA cm−2 , a
sudden potential drop directly to below −1.8 V appears which may
be due to the large concentration overpotential required to maintain
the high current density. The subsequent increase of potential results
from nucleation / growth of Sn which increases the effective electrode
surface area and, therefore, decrease both the real current density and
electrochemical polarization. The higher the electroplating (or appar-
ent) current density Jk , the sooner the Sn2+ consumes at the electrode
surface and the larger the diffusion overpotential required, resulting
in the diffusion-control of tin electroplating process. For the reason
that the nucleation / growth processes of tin particles onto homostruc-
ture is much easier than onto foreign material, tin deposit structure
changes to conglomerate particles under the conditions of diffusion
control (i.e., larger Jk value), which is also the main reason why the
height of the phase-angle peak decreases with increasing the applied
potential bias (Fig. 1).
Meanwhile, when Jk value is high enough, the H+ ions from bulk
solution discharge to form hydrogen atom on the substrate surface,
-0.4
a a: 0.5 mA cm-2
-0.6 b: 1 mA cm-2
b c: 2 mA cm-2
c d: 2.5 mA cm-2
-0.8
e: 3 mA cm-2
d f: 3.5 mA cm-2
-1.0
e g: 4 mA cm-2
E/v vs. SCE
N /2l
1  2
E JS = S (l = 1, 2, ..., J ) [6]
E k=1 J,k
Since the chosen wavelets are orthogonal, the following equation
is satisfied:25

J
E = E JS + ElD [7]
l=1
Energy distribution plot (EDP) is used to describe the relation-
ship between the relative energy accumulated by each crystal and the
crystal name. Furthermore, the EDP is re-plotted by discounting the
contribution of S8 crystal from the ensemble signal energy in order
to eliminate the energy contribution of dc drift from the ensemble
energy of the noise (the re-plotted EDP is named as RP-EDP). Ac-
cording to our previous studies,15 the RP-EDP can be divided into
three segments: 1) region A between D1 and D3 mainly characterizes
the nucleation process, 2) region B between D3 and D6 mainly charac-
terizes the growth process, and 3) region C between D6 and D8 mainly
reflects the information about the diffusion process.
In order to investigate the correlations between the EEN features
of tin deposits and their structure phenomenologically, the obtained
RP-EDP plots and the corresponding tin deposit morphologies of
720 s deposition (for better observation) at different Jk are plotted in
Figs. 5 and Figs. 6.
From Fig. 5a and Fig. 5b, it can be seen that the energy accumulated
in region A is almost zero at small Jk value (0.5 mA cm−2 and 1 mA
cm−2 ), which means that few nuclei are formed onto the heterogeneous
or foreign substrate. The result tallies tightly with the SEM observation
of the corresponding tin deposit surface (Fig. 6a) and Fig. 6b).

h: 7 mA cm-2
-1.2 i: 10 mA cm-2 Unfortunately, when Jk is higher than 1 mA cm−2 (Figs. 5c–5j), it is
f j: 20 mA cm-2 difficult to analyze the relationship between the RP-EDP features and
-1.4
the corresponding deposit morphologies, only the influence of Jk on
g tin deposit morphology can be easily obtained phenomenologically.
-1.6 h
When Jk increases to 2 mA cm−2 , a layer of tin deposits with some
cracks forms and fully covers the substrate (Fig. 6c). With the contin-
-1.8
i uous increase of Jk value from 2.5 to 3.5 mA cm−2 , the tin deposits
j layer becomes integrated and compact (Figs. 6d–6f). However, when
-2.0
Jk value reaches 4 mA cm−2 , both the H2 evolution and the higher con-
centration polarization make the deposits being increasingly porous or
-100 0 100 200 300 400 500 600 700 800 900 1000 rough (Figs. 6g–6j). It is observed that the tin deposit contains much
t/s larger conglomerate particles at 10 mA cm−2 (Fig. 6i) or dentritic
crystals at 20 mA cm−2 (Fig. 6j). The growth of conglomerate or den-
Figure 4. Potential EEN for tin electroplating at different Jk value tritic particles will change the surface structure and the active surface
(c = 20 mM). area of the electrode, cause the large potential oscillation amplitude

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 Journal of The Electrochemical Society, 160 (11) D530-D537 (2013) D533

and positive potential drift, which is in accord with the EEN features face structures are also characterized using XRD (X-ray diffraction)
(Fig. 4). technique, and two new parameters (n 1 or n 1 and n 2 ) are defined to
In order to analyze the relationship between the RP-EDP features differentiate the nucleation and growth processes:
and the surface structure of tin deposits, and probe into the evolution Ed1 + Ed2 + Ed3
features of the energy defined in regions A and B, the deposit sur- n1 = [8]
Ed4 + Ed5 + Ed6

0.7 0.7

0.6 (a) 0.6 (b)

0.5 0.5

0.4 0.4
EDP

EDP
0.3 0.3

0.2 0.2

0.1 0.1

0 0
1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8
J J

0.5 0.9

0.45 0.8

0.4
(c) (d)
0.7
0.35
0.6
0.3
0.5
EDP

EDP

0.25
0.4
0.2
0.3
0.15

0.2
0.1

0.05 0.1

0 0 Figure 5. RP-EDP generated during tin electroplat-

1 2 3 4
J
5 6 7 8 1 2 3 4
J
5 6 7 8
ing at different Jk . (a) 0.5 mA.cm−2 ; (b)1 mA.cm−2 ;
(c) 2 mA.cm−2 ; (d) 2.5 mA.cm−2 ; (e) 3 mA.cm−2 ;
0.8 0.5 (f) 3.5 mA.cm−2 ; (g) 4 mA.cm−2 ; (h) 7 mA.cm−2 ;
(i) 10 mA.cm−2 ; (j) 20 mA.cm−2 . t = 720 s.
0.45
0.7
(e) 0.4
(f)
0.6
0.35
0.5
0.3
EDP

EDP

0.4 0.25

0.2
0.3

0.15
0.2
0.1
0.1
0.05

0 0
1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8
J J

0.7 0.45

0.4
0.6 (g) (h)
0.35
0.5
0.3

0.4 0.25
EDP

EDP

0.3 0.2

0.15
0.2
0.1

0.1
0.05

0 0
1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8
J J

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 D534 Journal of The Electrochemical Society, 160 (11) D530-D537 (2013)

0.45 0.7

0.4
(i) 0.6 (j)
0.35
0.5
0.3

0.25 0.4
EDP

EDP
Figure 5. (Continued.)
0.2 0.3

0.15
0.2
0.1

0.1
0.05

0 0
1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8
J J

(a) (b)
Ed1 + Ed2 + Ed3
n 1 = [9]
Ed1 + Ed2 + Ed3 + Ed4 + Ed5 + Ed6

Ed4 + Ed5 + Ed6

n2 = [10]
Ed1 + Ed2 + Ed3 + Ed4 + Ed5 + Ed6
where Ed1 + Ed2 + Ed3 is the nucleation energy defined in region
A, Ed4 + Ed5 + Ed6 corresponds to the growth energy in region B.
The relationship of the three new parameters n 1 (n 1 ) and n 2 with
(c) (d) Jk value is plotted in Fig. 7. Apparently, the dependences of the two
parameters (n 1 or n 1 and n 2 ) on Jk can be classified into three parts
(Fig. 7): (a) In the first part of low Jk value region, both n 1 and n 1
increase with increasing Jk , and reach their maximum value at 3 mA
cm−2 . (b) In the second part with Jk value increasing from 3 to 4 mA
cm−2 , both n 1 and n 1 decrease to smaller values. (c) Finally, n 1 and
n 1 increase slowly with the increase of Jk value from 4 to 20 mA
cm−2 . During the above three parts, the variation trend of n 2 is always
opposite to both n 1 and n 1 .
(e) (f) Fig. 8 shows the typical XRD patterns of tin deposits of 720 s
deposition at different Jk values. Most of the peaks can be assigned to
those of β-Sn (JCPDS no.04–0673). It can be seen that the peak for
(2 0 0) plane is the most intense one when the electroplating current
density is relatively low or much higher, followed by the peaks for (1
0 1), (2 2 0) and (2 1 1) planes, indicating that β-Sn in the deposits
is in the preferred orientation of (2 0 0) plane in this current density
range. Peaks for (2 2 0) and (2 1 1) planes are much stronger than

(g) (h)

1.2
n1
1.0 n2

0.8

nj 0.6
(i) (j)

0.4

0.2
n'1
0.0

0 5 10 15 20
2
Figure 6. The corresponding SEM image of tin deposit at different Jk . j/mA cm
(a) 0.5 mA.cm−2 ; (b)1 mA.cm−2 ; (c) 2 mA.cm−2 ; (d) 2.5 mA.cm−2 ;
(e) 3 mA.cm−2 ; (f) 3.5 mA.cm−2 ; (g) 4 mA.cm−2 ; (h) 7 mA.cm−2 ; Figure 7. Dependence of three parameters n 1 , n 1 and n 2 on deposition current
(i) 10 mA.cm−2 ; (j) 20 mA.cm−2 . t = 720 s. density.

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 Journal of The Electrochemical Society, 160 (11) D530-D537 (2013) D535

(200)
-0.4

(211)
(220)
(101)

(112)
(400)
a: 2mA/cm2

(321)
h b: 2.5mA/cm2 d
-0.6
c: 3mA/cm2
g
d: 3.5mA/cm2
-0.8 c
f e: 4mA/cm2
f: 7mA/cm2

E/v vs.SCE
intensity/cps

e g: 10mA/cm2 -1.0 a: 5mM

h: 20mA/cm2 b: 10mM
d
c: 20mM
-1.2
d: 50mM
c
-1.4
b
b
a -1.6

a
20 30 40 50 60 70 80
-1.8
Two theta/deg -100 0 100 200 300 400 500 600 700 800
t/s
Figure 8. X-ray diffraction patterns of tin films formed at different Jk
(c = 20 mM, t = 720 s). Figure 9. Potential EEN for tin electroplating at different Sn2+
concentrations.

that of (2 0 0) plane while the electroplating current density ranges

from 2.5 mA cm−2 to 3.5 mA cm−2 . In addition, Peaks corresponding
to any oxide phases are not found, which suggests that Sn2+ was not
oxidized in the electroplating process. The mean crystallite size of the
deposits is calculated using the Scherrer’s formula:26
kλ
D=
β cos θ
where D is the crystallite size, k is a constant (0.9 for Gaussian line
profiles and small cubic crystals of uniform size), λ is the wavelength
of the X-rays, θ is the diffraction angle, and β is FWHM in radians
(corrected for the instrumental broadening). The analyzed average
crystallite size (D) of tin deposits are listed in Table III.
Interestingly, when compared Jk dependence of n 1 or n 1 and n 2
(Fig. 7) with that of D (Table III), the same variation trend of n2 with
D in the low and middle Jk range can be found. Briefly, the value of D
first decreases with increasing the Jk value from 2 to 3 mA.cm−2 , then
increases when Jk increases from 3.0 mA cm−2 to 4.0 mA cm−2 . How-
ever, when Jk value is higher than 4.0 mA.cm−2 , although D shows the
decreasing trend but with some oscillation, which may be attributed to
the influence of hydrogen evolution. The above synchronous change
may be explained by the fact that, the formation process of deposit
simultaneously consist both the nucleation and growth reactions, the
latter always competes with the former, their relative rate play an im-
portant effect on the value of D. Generally, higher nucleation rate and
lower growth rate of crystallites result in smaller D.
In the low Jk range (0.5–3 mA cm−2 ), tin deposition is mainly
electrochemically controlled, few nuclei can be formed onto the het-
erogeneous or foreign substrate that requires much higher activation
energy, and tin ions (Sn2+ ) will discharge preferentially on the pre-
viously formed homogeneous Sn crystallites or the inhomogeneous
sites on the substrate, the above reasons result in that the relative en-
ergy accumulated in region A of RP-EDP is higher than that in region
B (Fig. 7) and consequently the value of D is smaller; Meanwhile,
with the increase of Jk , the active points on the substrate increases and
Table III. Crystallite size of tin deposits at different current
densities (Jk ).
Jk (mAcm−2 ) 2 2.5 3 3.5 4 7
D (nm) 73.6 61.2 58.8 72.1 74.3 74.2
results in the increase of nucleation rate, the decrease of D (Table III)
and the smoothing of deposit surface (Figs. 6a–6e).
In the middle Jk value range (3.0 mA cm−2 < Jk ≤ 4.0 mA cm−2 ),
the active points on the substrate is much larger, and Sn crystallites
can easily nucleate on the whole substrate surface instantaneously,
the initially fast nucleation causes the depletion of Sn2+ adjacent to
[11]
the cathode especially in the double layer, and the deposition pro-
cess is mainly diffusion controlled. In this case, Sn2+ ions arrived at
the cathode surface mainly discharge on the previously formed ho-
mogeneous Sn crystallites, which consequently improves the growth
rate of already formed Sn crystallites, results in that the relative en-
ergy accumulated in region B of RP-EDP is higher than that in re-
gion A (Fig. 7), and therefore both D and surface roughness increase
(Table III, Figs. 6e–6g).
When the electroplating current density is high enough (larger
than 4 mA.cm−2 ), the crystallite size oscillates due to the hydrogen
evolution (SEM graphs in Figs. 6g–6j) in the electroplating process,
the nucleation energy is therefore composed of both the Sn nucle-
ation energy and hydrogen nucleation energy, thus, values of n 1 and
n 1 increase while n 2 decreases slightly with increasing the current
density.
Influence of Sn2+ on the structure of tin electrodeposits.— Fig. 9
shows potential EEN for tin electroplating at different Sn2+ concen-
trations. It is clear that the potential EN curves can be classified into
two types. When the Sn2+ concentration is high (e.g., 20 mM and 50
mM), potential arrives at a relative steady state above −0.8 V after
initial double layer charging process. While the potential decreases
to much lower value below −1.5 V when Sn2+ concentration is low
due to that, larger overpotential is required by concentration polariza-
tion. In addition, the oscillation amplitude of the potential noise in the
electroplating bath containing low Sn2+ concentration is much larger
than that containing high Sn2+ concentration.
New parameter n 1 , n 1 and n 2 are also used (Fig. 10) here to inves-
tigate the correlations between the RP-EDP features of EEN and the
tin deposit structure at different Sn2+ concentrations (Figs. 11–13).
From Fig. 10, it can be seen that both n 1 and n 1 increase first then
decrease slightly with the increasing of Sn2+ concentrations, while n 2
changes oppositely. The increase of n 1 or n 1 and the decrease of n 2
indicate the smoothing of the deposit surface according to the above
investigation (Fig. 7 and Figs. 6a–6e).
10 20
Compare the Sn2+ concentration dependence of n 1 , n 1 and
68.5 62.8 n 2 (Fig. 10) with the corresponding deposit surface roughness

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 D536 Journal of The Electrochemical Society, 160 (11) D530-D537 (2013)

10 (Figs. 11–13), it is easily observed that the ensemble deposit sur-

face is of higher roughness and consists lots of small holes at 5 mM
(Fig. 11B), or many filose and conglomerate particles at 10 mM
(Fig. 12B). The formation of the holes may be partially attributed
n2
1 to the fact that tin electroplating process is competitively coupled
with hydrogen evolution especially at low Sn2+ concentrations. When
the concentration of Sn2+ increases to 20 mM, the surface becomes
relatively compact and smooth (Fig. 6c). However, the deposit surface
nj 0.1 roughness increases when Sn2+ concentration increases from 20 mM
n'1 to 50 mM (Fig. 13B), the result may be mainly result from the follow-
ing synergetic factors. First, Sn2+ ions arrived at the cathode surface
n1 mainly discharge on the previously formed homogeneous Sn grains,
0.01 especially on their emergent sites and accelerates the growth rate of
larger Sn grains (Fig. 10). Secondly, hydrogen evolution interferes
or modulates the migratory paths of Sn2+ from solution to cathode
surface.
1E-3
0 10 20 30 40 50
c/mM

Figure 10. Crystal parameter n 1 , n 1 and n 2 at different Sn2+ concentrations.

0.8

0.7

0.6

0.5
EDP

0.4

0.3

0.2

0.1

0
1 2 3 4 5 6 7 8
J

Figure 11. RP-EDP generated during tin electroplating and the corresponding SEM image of deposit (Jk = 2 mA.cm−2 , c = 5 mM, t = 720 s). A–RP-EDP,
B–SEM image.

0.9

0.8

0.7

0.6

0.5
EDP

0.4

0.3

0.2

0.1

0
1 2 3 4 5 6 7 8
J

Figure 12. RP-EDP generated during tin electroplating and the corresponding SEM image of deposit (Jk = 2 mA.cm−2 , c = 10 mM, t = 720 s). A–RP-EDP,
B–SEM image.

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 Journal of The Electrochemical Society, 160 (11) D530-D537 (2013) D537

(B)
0.5

0.45
(A)
0.4

0.35

0.3
EDP

0.25

0.2

0.15

0.1

0.05

0
1 2 3 4 5 6 7 8
J

Figure 13. RP-EDP generated during tin electroplating and the corresponding SEM image of deposit (Jk = 2 mA.cm−2 , c = 50 mM, t = 720 s). A–RP-EDP,
B–SEM image.

Conclusions 5. B. N. Stirrup and N. A. Hampson, J. Electroanal. Chem., 67, 45 (1976).

Electrochemical impedance was used to investigate the mechanism
of Sn electroplating process. Results revealed that charge transfer re-
sistance decreases with η exponentially at this experimental condition.
New parameters are proposed during the EEN measurements to
cultivate the relationship between the EEN feature and the structure
of tin deposits. The parameter n1 can be classified into three parts:
(a) when the current density is relatively low, n1 increases with in-
creasing the current densities and reaches the maximum value at
3 mA cm−2 . (b) when increases the current densities from 3 mA cm−2
to 4 mA cm−2 , n1 decreases to a smaller value. (c) n1 increases with
increasing the current densities from 4 mA cm−2 to 20 mA cm−2 .
Another parameter n2 which is always opposite to parameter n1 is
found to have the same variation trend with the crystallite size of Sn
deposits.
The oscillation amplitude of the potential noise generated at low
Sn2+ ions concentration is much larger than that of high concentra-
tions, which may be correlated with that tin electroplating process is
coupled with hydrogen evolution at low Sn2+ concentrations.
Acknowledgment
This work was supported by National Natural Science Foundation
of China (Grant No. 21073162 and 21273199).
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