D428 Journal of The Electrochemical Society, 163 (8) D428-D433 (2016)

0013-4651/2016/163(8)/D428/6/$33.00 The Electrochemical Society

Voltammetric Observation of Transient Catalytic Behavior of SPS

in Copper ElectrodepositionIts Interaction with Cuprous Ion
from Comproportionation
Sung Ki Cho,a,z Hoe Chul Kim,b Myung Jun Kim,b and Jae Jeong Kimb,,z
a Departmentof Energy and Chemical Engineering, Kumoh National Institute of Technology, Gumi-si,
Gyeongsangbuk-do 39177, Korea
b School
of Chemical and Biological Engineering, Institute of Chemical Process, Seoul National University,
Gwanak-ro, Gwanak-gu, Seoul, 08826, Korea

In this study, we investigated the transient catalytic function of SPS in Cu electrodeposition via cyclic voltammetry. The addition of
SPS into the electrolyte for Cu electrodeposition caused the shift of the peak potential for the electrochemical Cu2+ reduction in the
positive direction. Its catalytic effect was manifested exclusively on Cu electrode and became stronger as Cu electrode was incubated
longer in the electrolyte prior to the measurement, which is interpreted to indicate that the catalytic function was associated with
the interaction between SPS and Cu+ generated from Cu electrode surface via comproportionation. The change in the concentration
of SPS and Cu2+ , or the change in the potential of Cu electrode affected the catalytic function, which gives an evidence of the
interaction. Cyclic voltammetry on ultramicroelectrode clearly showed the Cu+ generation and the interaction between SPS and
Cu+ .
2016 The Electrochemical Society. [DOI: 10.1149/2.1101608jes] All rights reserved.

Manuscript submitted April 26, 2016; revised manuscript received May 25, 2016. Published June 9, 2016.

For a few decades, Cu electrodeposition has been applied to the Experimental

metallization process for the fabrication of printed circuit boards and
Materials.CuSO4 5H2 O (>98.0%, ACS reagent, Sigma-
it has been extended to the damascene process for integrated cir-
Aldrich), H2 SO4 (>95%, ACS reagent, Acros). NaCl (>99%,
cuits due to its superior ability of superfilling. During this period, Cu
ACS reagent, Acros), poly(ethylene glycol) (PEG, HO[(CH2 )2 O]n H,
electrodeposition repeatedly encountered smaller and smaller dam-
Mw 3400, Sigma-Aldrich), and SPS (Na2 [S(CH2 )3 SO3 ]2 , Raschig,
ascene feature to fill, and at present it is expected to fill the ex-
GmbH) were used as received. Cu disk (3 mm dia.), Au disk (2 mm
tremely high aspect ratio through silicon vias. In order to achieve
dia.), Ag disk (2 mm dia.), Glassy carbon (GC) disk (3 mm dia.) elec-
superfilling, the addition of organic additives, especially, the accel-
trodes, Au disk ultramicroelectrode (UME, 12.5 m dia.) were used
erating species such as SPS (bis(3-sulfopropyl) disulfide) and MPS
as a working electrode in electrochemical analyses. Deionized Milli-Q
(3-mercapto-1-propane sulfonate) into the electrolyte is absolutely
water was used as the solvent in the electrochemical experiments.
required.
The catalytic function of the accelerating species was usually
Electrochemical analysis.A CH Instruments model 631E Elec-
explained in two ways; surface adsorption-coverage and solution
trochemical Analyzer was employed for the analysis. A Pt wire (1
chemistry.1 The former is based on the enhancement of the depo-
mm dia.) counter electrode and a Ag/AgCl reference electrode in a
sition rate by the replacement of the adsorbed suppressing species
saturated KCl solution were used to set the three electrode configu-
such as PEG (polyethylene glycol) by the accelerating species where
ration. As KCl leakage (Cl leakage) through Vycor tip at the end
both species share the same adsorption site (competitive adsorp-
of the reference electrode would have a significant effect on the elec-
tion). The latter translates the catalytic function as the mediation
trochemical reduction of Cu2+ , the reference electrode was immersed
of the electron transfer from Cu2+ to Cu+ by the formation of a
in the electrolyte only in running electrochemical measurement. The
Cu(I)-thiolate complex where the actual accelerating species is a thi-
electrolyte was composed of 1 M H2 SO4 , 0 8 mM CuSO4 5H2 O,
olate (deprotonated MPS) from this point of view, and the Cu(I)-
and 1 mM additives (SPS, Cl , PEG, etc). It was purged with N2
thiolate could be either adsorbed on the electrode surface or in the
gas for at least 10 min. After N2 purging, the top surface of the elec-
solution.
trolyte was blanketed by N2 flow during CV measurement in order
The increase in the amount (surface coverage or concentration) of
to prevent O2 dissolution into the electrolyte. Before the analysis, the
the accelerating species over plating duration is a key factor for the
electrodes were pretreated as follows. All electrodes were polished
local enhancement of the deposition rate at the recess bottom accord-
with Al2 O3 polish powder (0.3 m and 0.05 m dia. in sequence). In
ing to well-developed filling mechanism.2 Accordingly, many studies
order to prevent the cross-contamination of the electrode by organic
focused on the analysis on the time-dependency of the acceleration
additives transferred from the electrolyte to the polish powder and sub-
function; hysteresis in cyclic voltammetry (CV),24 and rising transient
sequently to the electrode, and vice versa, fresh Al2 O3 polish powders
chronoamperometry,46 indicate of the transient catalytic behavior of
were used in an every polishing step. Afterwards, powder residues on
the accelerating species. According to the competitive adsorption-
the electrode surface were removed thoroughly by pouring a plenty
based explanation, the transient catalytic behavior is originated from
of deionized water. Then the polished surface was electrochemically
the gradual increase in the coverage of the accelerating species.
cleaned with the potential cycling (0 0.5 V vs. Ag/AgCl, 100
Herein, we explained the transient catalytic behavior in terms of
mV/s, 5 times) in 1 M H2 SO4 solution. In case of Cu electrode, it was
the solution chemistry. The catalytic function would be associated
kept in 1 M H2 SO4 solution until starting CV measurement since it
with the chemical reaction between SPS and Cu+ where the com-
was easily oxidized with an exposure to the air.
proporationation between Cu2+ and Cu electrode would accumulate
Cu+ near the electrode. This transient behavior was monitored via CV
measurement with varying the concentrations of SPS and Cu2+ , and Results and Discussion
the electrode potential.
CV on disk electrode.In fact, CV for Cu electrodeposition is not
very informative because Cu electrodeposition is an inner-sphere het-
erogeneous, two-electron transfer electrode reaction where the stan-
dard reduction potential for the second electron transfer (Cu+ + e
Electrochemical Society Member. = Cu, E2 0 = 0.52 V vs. NHE) is more positive than for the first step
z
E-mail: chosk@kumoh.ac.kr; jjkimm@snu.ac.kr (Cu2+ + e = Cu+ , E1 0 = 0.159 V vs. NHE) by over 100 mV, which

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 Journal of The Electrochemical Society, 163 (8) D428-D433 (2016) D429

0.4 (a) 0.4 (b)

Current (x10 A)
Current (x10 A)
0.3 0.3

4
4 0.2 0.2

0.1 0.1
Additive-free Additive-free
0.0 Cl ion
0.0 SPS 0 s
PEG-Cl SPS 30 ~ 360 s
-0.1 -0.1
0.0 -0.1 -0.2 -0.3 -0.4 0.1 0.0 -0.1 -0.2 -0.3 -0.4
Potential (V vs. Ag/AgCl) Potential (V vs. Ag/AgCl)
0.5 0.5
0.4
(c) 0.4 (d)

Current (x10 A)
Current (x10 A)

0.3 0.3

4
4

0.2
0.2
0.1
0.1
0.0
0.0 -0.1
Additive-free Additive-free
-0.1 SPS-Cl 0 s -0.2 PEG-Cl-SPS 0 s
SPS-Cl 30 ~ 360 s PEG-Cl-SPS 30 ~ 360 s
-0.2 -0.3
0.1 0.0 -0.1 -0.2 -0.3 -0.4 0.1 0.0 -0.1 -0.2 -0.3 -0.4
Potential (V vs. Ag/AgCl) Potential (V vs. Ag/AgCl)

0.10 (e)
0.05
0.00
Ep (V)

-0.05 Additive-free
Cl ion
-0.10 PEG-Cl
SPS
-0.15 SPS-Cl
PEG-Cl-SPS
-0.20
0 50 100 150 200 250 300 350
Incubation time (s)

Figure 1. (a-d) Cyclic voltammograms (scan rate: 50 mV/s) for electrochemical reduction of Cu2+ (2 mM) on Cu disk electrode in 1.0 M H2 SO4 electrolyte with
the addition of various additives (1 mM each). (e) The plot of the change in peak shift (Ep = Ep Ep in additive-free condition) according to the incubation time.

exhibits indistinguishable single wave in CV. In the electrochemical
reduction of Cu2+ , the reaction product can be considered as unit
activity (when the deposit is more than monolayer) because it is insol-
uble, so that the onset potential (emerging potential) of CV is equal to
the equilibrium potential and the slope of i-V curve is steeper than the
case of soluble product.7 However, the actual CV slope of the elec-
trochemical reduction of Cu2+ is sluggish because it is non-reversible
reaction with the slow kinetics, as well as mass transfer overpotential
and IR drop. In addition, after the first electron transfer, the product
Cu+ ions have a chance to be disproportionated while most of them
would be reduced to Cu0 . The disproporationation, therefore, would
change the concentrations of Cu2+ and Cu+ slightly. These tell us that
general quantitative analysis on CV for Cu electrodeposition would be
very difficult. Nevertheless, CV is one of the most suitable methods
for investigation on the change in the reaction kinetics of Cu elec-
trodeposition by organic additives. Herein, CV change in association
with SPS was monitored with the change in the time period (noted as
an incubation time) for the electrode being immersed in the electrolyte
prior to starting the potential scan.
Fig. 1 shows CVs for the electrochemical reduction of Cu2+ on Cu
electrode in the electrolyte containing various organic additive combi-
nations. Low Cu2+ concentration in the electrolyte compared to that in
the electrolyte for the conventional Cu electrodeposition (0.2 1.0 M)
was intended for small iRs (Rs 20 ohm)8 drop. The addition of
1 mM Cl and PEG-Cl (1 mM each) resulted in a well-known accel-
erating and suppressing effect, respectively (Fig. 1a), and any mean-
ingful changes on CV after experiencing the electrode incubation were
not observed in both cases (The data were not shown here). On the
other hands, the incubation in all electrolytes containing SPS (1 mM)
caused the gradual shift in CV as it became steeper and its peak (Ep )
was shifted to more positive direction (Figs. 1b1d). This transient
behavior of CV was not observed after a few minutes (5 min), and
it seemed to being stagnated. Similar change in the response of elec-
trochemical analysis such as LSV, chronoamperometry, according to
the pre-immersion of Cu electrode in the electrolyte has been reported
previously.5,6,9
In CV for quasi-reversible or irreversible reaction, its peak poten-
tial (Ep ) and slope (or Ep - Ep/2 ) are the function of the standard rate
constant (k0 ). Although an accurate quantitative analyses might not
be applied herein, the positive shift in Ep would show the improve-
ment in the reaction kinetics by the catalytic function of SPS, and the
extent of the peak shift (Ep = Ep Ep in additive-free condition)
would represent the degree of acceleration. Fig. 1e exhibits the plot
of Ep against incubation time in the various additives condition.
The positive Ep value indicates of the accelerating function whereas
negative value indicates of the suppressing function. Almost constant

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 D430 Journal of The Electrochemical Society, 163 (8) D428-D433 (2016)

0.2 c2 0.5
(a) c1 (b)
0.0 Additive-free
0.0 Additive-free

Current (x10 A)

Current (x10 A)
SPS 0 s
SPS 0 s -0.5 SPS 30 s
SPS 30 s
4

4
a1 SPS 60 s
-0.2 SPS 60 s -1.0 SPS 120 s
SPS 120 s

-0.4 0.10 -1.5

0.2

0.05 -2.0
-0.6 a2
0.00
-2.5 0.0

0.3 0.0 -0.3 0.0 -0.2 -0.4

-0.8 -3.0
0.4 0.3 0.2 0.1 0.0 -0.1 -0.2 -0.3 0.4 0.2 0.0 -0.2 -0.4
Potential (V vs. Ag/AgCl) Potential (V vs. Ag/AgCl)

0.2
(c)
0.0 Additive-free
Current (x10 A)

SPS 0 s
-0.2 SPS 30 s
4

-0.4 SPS 60 s
SPS 120 s
-0.6
0.12
-0.8
-1.0 0.06

-1.2 0.00
0.0 -0.1 -0.2 -0.3
-1.4
0.2 0.1 0.0 -0.1 -0.2 -0.3 -0.4
Potential (V vs. Ag/AgCl)
Figure 2. Cyclic voltammograms (scan rate: 50 mV/s) on (a) Au disk, (b) GC disk, and (c) Ag disk electrodes, respectively, in 1.0 M H2 SO4 electrolyte containing
2 mM Cu2+ and 1 mM SPS.

positive or negative Ep values of Cl and PEG-Cl represent con-
sistent accelerating or suppressing effect. At short incubation time
(<50 s), a slight change in Ep (<10 mV) was observed, and it would
be associated with the approach to saturation of the additive cover-
age where it is expected to take less than 1 min in this concentration
range.10,11 The above-mentioned transient catalytic function of SPS
in all additive combinations resulted in the gradual increase in Ep .
Although it was difficult to define absolute 0 s incubation experi-
mentally, repeated experiments confirmed that in case of SPS alone,
Ep started with negative value. It indicated that SPS on un-incubated
Cu electrode weakly inhibited the electrochemical reduction of Cu2+ ,
which accorded with a study which mentioned the suppression effect
of SPS alone.12,13 Note that changes in Ep from all electrolytes with
SPS had similar time period, and it was also similar with that of rising
transient in chronoamperometries which have been reported in the
many researches.46
Interestingly, the transient catalytic effect of SPS was not observed
on Au, GC, and Ag electrodes in the equivalent condition (Fig. 2).
Rather, SPS slightly inhibited the Cu2+ reduction on Au and GC
surface. On Au surface, Cu underpotential deposition (peak c1 ) as well
as Cu overpotential deposition (peak c2 ) was kinetically perturbed by
SPS (Fig. 2a). As the catalytic function of the thiolate on Au surface
has been reported elsewhere,14 these results would imply that the
catalytic function of SPS is related to its time-evolving chemical
interaction of SPS with Cu electrode for the formation of the thiolate.
The electrochemical reduction of SPS was not reported
elsewhere,10,13 and any peak from SPS itself was not evolved in the
potential region of CV (Data were not shown here) whereby it can be
ruled out in this condition. Many studies mentioned the interaction of
SPS with Cu+ as follows.13,15,16
1
4Cu+ + 2SPS 4Cu2+ + 4(thiolate)
2
2Cu2+ + 2Cu (I) thiolate + SPS
Initially, Cu+ was not in the electrolyte and it would be generated
only on Cu electrode surface via the first electron transfer of Cu2+
or comproportionation reaction. The transient catalytic function of
SPS with the incubation would be strongly related to its interaction
with Cu+ . As a reducing agent for the reductive bond cleavage of
disulfide, Cu+ would convert SPS to two thiolates (Reaction 1 in
Eq. 1).17,18 It was followed by the re-formation of disulfide bond by
the catalytic oxidation of thiol accompanying the reduction of Cu2+
with the transition metal thiolate complex formation (Reaction 2 in
Eq. 2),19 which might be fundamentals of the catalytic function of
SPS and MPS for Cu electrodeposition. Eq. 1 also represents the
interconversion between SPS and MPS in associated with the thiol-
disulfide exchange.
As the incubation was initiated, Cu+ would start to be generated
from Cu electrode via following comproportionation reaction.
k1 k1 [Cu+ ]2
Cu2+ + Cu +
2Cu where K = = [2]
k1 k1 [Cu2+ ]
Herein, the equilibrium constant for a disproportionation-
comproportionation can be derived from following equation.7
RT
ln K = E 10 E 20 = 0.36(V) [3]
F
Therefore, K is about e14 which means the amount of Cu+ is small
(40 M) compared to that of Cu2+ (2 mM). Low concentration of
Cu+ would be the reason why the separate Cu+ reduction peak was
not detected in CV on disk electrode. Comproportionation would
be followed by the reaction of Eq. 1, resulting in the increase in
the thiolate amount near the electrode. At the same time, Cu+ and
thiolate would also diffuse out to the bulk electrolyte whereby the
concentration of thiolate would reach to a certain steady-state level.
Assuming that Ep is roughly proportional to the concentration of
thiolate, the catalytic function would gradually increase and maxi-
mized, which is consistent with the observation in the shift of CV
[1] (Fig. 1).
The rate of the formation of Cu+ (Eq. 2) and thiolate (Eq. 1) would
be so slow that the transition spans the incubation time period (a few
minutes) though it is not clear how total reaction rate is determined,

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 Journal of The Electrochemical Society, 163 (8) D428-D433 (2016) D431

1.0 (a) 1.0 (b)

0.8 0.8

Ep / Ep,t=360
Ep / Ep, t=360
0.6 0.6
0.4 0.4
0.2 0.5 mM SPS 0.2 1 mM Cu2+
1 mM SPS 2 mM Cu2+
4 mM Cu2+
0.0 4 mM SPS 0.0
8 mM Cu2+

-0.2 -0.2
0 60 120 180 240 300 360 0 60 120 180 240 300 360
Incubation time (s) Incubation time (s)
SPS conc. (mM)
0 1 2 3 4 5 6 7
0.12
(c)
0.10
Ep, t=360s (V)

0.08

0.06

0.04
0 1 2 3 4 5 6 7 8 9
2+
Cu concentration (mM)
Figure 3. (a, b) The plot of the change in peak shift (Ep = Ep Ep in additive-free condition) with respect to the peak shift at 360 s against the incubation time
with varying (a) SPS (at 2 mM Cu2+ ) and (b) Cu2+ concentration (at 1 mM SPS). The standard deviation of measured Ep /Ep,t = 360s was less than 0.02.
(c) The plot of the change in peak shift (Ep = Ep Ep in additive-free condition) at 360 s incubation against SPS and Cu2+ concentration.

and it would be related to the time required for reaching maximum due to the decrease in the relative amount of accelerating species
degree of acceleration. Fig. 3 showed the change in the Ep with compared to the reactant (Cu2+ ).
respect to the saturated one (Ep at 360 s incubation) according to Nernst relation between Cu+ concentration and the electrode po-
the incubation time and the effect of SPS and Cu2+ concentrations. tential predicts that Cu+ concentration thermodynamically decreases
As the concentration of SPS (Fig. 3a) and Cu2+ (Fig. 3b) increased, as the electrode potential was polarized negatively. Although the
the rate of peak shift became faster. It implies of the increase in actual concentration of Cu+ would be different from one from Nernst
the rate of the formation of Cu+ (Eq. 2) and thiolate (Eq. 1), which relation due to non-reversibility of Cu2+ reduction, the tendency ac-
would be reasonable. The change in SPS and Cu2+ concentrations cording to the potential would be similar and it has been already
also accompanied the change in the absolute value of Ep at 360 experimentally proved by rotating ring disk electrode,13,20 and scan-
which is an indication of the degree of acceleration. Increase in SPS ning electrochemical microscopy.21 Accordingly, it can be expected
concentration would also increase the amount of thiolate as well as that the incubation under applying the negative potential would not
its formation rate whereby Ep increased with SPS concentration. raise catalytic function as the catalytic function of SPS is initiated
On the other hands, the increase in Cu2+ concentration reduced the by Cu+ . Fig. 4a shows cyclic voltammograms of the electrochemical
degree of acceleration. Actually, it increased in the current for the reduction of Cu2+ on Cu electrode incubated in the electrolyte for
electrochemical reduction of Cu2+ , followed by increase in IR drop, 360 s under different applied potential. The imposing of the negative
which would perturb CV in the negative direction. It also might be potential during the incubation would cause the Cu deposit followed

(a) 0.4
OCP (b) 0.09
Cu concentration (M)

-0.05 V 30
-0.15 V
+
Current (x10 A)

0.3 -0.25 V 0.06 20

4

Ep (V)

0.2 0.03 10
0.1 0.00 0
Nernst condition
0.0
-0.03
0.0 -0.2 -0.4
-0.1
0.1 0.0 -0.1 -0.2 -0.3 -0.4 0.08 0.00 -0.08 -0.16 -0.24
Potential (V vs. Ag/AgCl) Potential (V vs. Ag/AgCl)

Figure 4. (a) Cyclic voltammograms (scan rate: 50 mV/s) for electrochemical reduction of Cu2+ (2 mM) on Cu disk electrode in 1.0 M H2 SO4 electrolyte in the
presence of 1 mM SPS. Before scanning potential, Cu electrode was incubated in the electrolyte for 360 s under imposing various potentials. (b) The plot of the
change in peak shift (Ep = Ep Ep in additive-free condition) and nernstian Cu+ concentration according to the incubation potential (incubation time: 360 s).

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 D432 Journal of The Electrochemical Society, 163 (8) D428-D433 (2016)

(a)
0

Current (x10 A)
8
-2

-4
Additive-free
SPS
-6

0.4 0.2 0.0 -0.2 -0.4

Potential (V vs. Ag/AgCl)
(b) 5
(c) 0.6 iL = 4nFCCu2+DCu2+r0
2x10-11 A

Current (x10 A)
E = Eeq + RT/nF ln(1-i/iL)
ip, Cu upd (x10 A)

8
0.4
10

3 0.4 0.3 0.2

2 0.2

1 Additive-free Additive-free
SPS SPS
0.0
0
0.00 0.03 0.06 0.09 0.1 0.0 -0.1 -0.2 -0.3 -0.4
Scan rate (V/s) Potential (V vs. Ag/AgCl)
Figure 5. (a) Cyclic voltammograms (scan rate: 20 mV/s) on Au disk ultramicroelectrode (UME, 12.5 m dia.) in 1.0 M H2 SO4 electrolyte containing 2 mM
Cu2+ and 1 mM SPS. (b) The plot of peak current for Cu underpotential deposition on Au against the scan rate in the presence of SPS in the electrolyte. (c) Cyclic
voltammograms (scan rate: 20 mV/s) for the electrochemical reduction of Cu2+ on Au disk UME (12.5 m dia.) in 1.0 M H2 SO4 electrolyte containing 2 mM
Cu2+ and 1 mM SPS.

by the change in the electrode surface condition, or the change in
the surface concentration of Cu2+ and SPS. However, it would not
alter significantly as even at 0.25 V (vs. Ag/AgCl) incubation for
360 s, the total charge was about 0.071 C/cm2 which corresponds to
26 nm of Cu deposit or 7.3 106 mole of chemical species. After
the incubation, the electrode was stirred shortly in order to replenish
Cu2+ and SPS near Cu electrode surface. The incubation at the open
circuit shifted CV considerably as shown previously whereas the shift
became smaller as Cu electrode was incubated at more negative poten-
tial. Fig. 4b is a plot of Ep versus the incubation potential, overlaid
with the curve of Nernst relation between Cu+ concentration and po-
tential. Both of Ep and Cu+ concentration decreased as the potential
applied negatively. The incubation at very negative potential (0.25 V
vs. Ag/AgCl) exhibited the suppression effect (negative Ep ) as sim-
ilar as the un-incubation on Cu electrode. These support our explana-
tion on the acceleration function associated with the reaction between
SPS and Cu+ from the comproportionation. Meanwhile, this might
be interpreted in terms of the potential-dependent adsorption of SPS
along with surface coverage-based acceleration explanation. How-
ever, Walker et al. reported that the adsorption of SPS was rather
enhanced at more negative potential whereby more catalytic func-
tion of SPS was expected at more negative potential.22 Usually, Cu
electrodeposition for superfilling is carried out at low overpotential
(<0.25 V) in order to prevent the thick deposit on trench top.23
Above results suggests that the low overpotential requirement for su-
perfilling is also associated with Cu+ being present near the surface
and initiating the catalytic function of SPS.
CV on UME.The electrochemical character of UME is the small
current (<108 A) which leads to the rapid approach to a steady-state,
and therefore, CV on UME manifests virtually steady-state voltam-
metry with the negligible perturbation of IR drop and transient mass
transfer effect. Accordingly, the transient behaviors associated with
the formation of Cu+ and thiolate can be separated from the steady-
state electrochemical Cu2+ reduction in CV on UME.
Fig. 5a is CV for the electrochemical reduction of Cu2+ on Au
UME in the absence and presence of SPS in the electrolyte, which
shows the current for Cu electrodeposition and its stripping. The
incubation did not affect CV in either case, which is consistent with
CV on Au disk electrode (Fig. 2a). The suppressing effect of SPS
was obviously observed on Au UME as all current responses were
decreased with the addition of SPS. The decrease in the peak current
of the underpotential deposition (Fig. 5b) implies that the suppressing
effect of SPS arises from the surface adsorption. Fig. 5c exhibits
CVs in the potential region for the overpotenital deposition of Cu
after Cu underpotential deposition. The product of the electrochemical
reduction of Cu2+ is insoluble Cu metal which can be considered to
be at essentially unit activity. If the kinetics of the reduction is rapid
(Nernstian multistep process, n = 2), i-E curve is then,7
 
RT il i
E = E eq + ln [4]
nF il
where Eeq is the equilibrium potential (0.063 V vs. Ag/AgCl in 2 mM
Cu2+ on Cu electrode), R is ideal gas contant, T is temperature, F is
Faraday constant, and il is limiting current. For disk UME, il is,
il = 4n FCCu 2+ DCu 2+ r0 [5]
where CCu2+ is the bulk concentration of Cu2+ in the electrolyte
(2 mM), DCu2+ is the diffusion coefficient of Cu2+ (5.8 106
cm2 /s.24,25 ), and r0 is the radius of the disk electrode (6.25 m). Actual
i-E curve for the electrochemical reduction of Cu2+ was displaced to
more negative potential and broadened, compared to the theoretical
curve (dash line) for the facile kinetics, though it eventually reach
to il . It indicates that the electrochemical reduction of Cu2+ is not
electrochemically reversible and the addition of SPS made k0 smaller.
For the addition of SPS, CV curve was crossed at the reverse scan,
which would be associated with the gradual evolution of the catalytic
function of SPS during CV, which is similar to the hysteresis on CV.24
Cu-electrodeposited (0.4 V vs. Ag/AgCl for 100 s, 7.0 107
C) Au UME can serve as Cu UME with slight increase in the

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 Journal of The Electrochemical Society, 163 (8) D428-D433 (2016) D433

(a) 0.8
Additive-free
(b ) 0.8
Incubation
0s

Current (x10 A)

Current (x10 A)
0.6 150 s 0.6
8

8
300 s
450 s
0.4 600 s
0.4
Additive-free
0.2 1st 0.2 SPS 0 s
2nd SPS 60 s
SPS 120 s
0.0 0.0 SPS 180 s
0
0.0 -0.1 -0.2 -0.3 -0.4 0.0 -0.1 -0.2 -0.3 -0.4
Potential (V vs. Ag/AgCl) Potential (V vs. Ag/AgCl)

Figure 6. Cyclic voltammograms (scan rate: 20 mV/s) for the electrochemical reduction of Cu2+ on Cu ultramicroelectrode (UME) in 1.0 M H2 SO4 electrolyte
containing (a) 2 mM Cu2+ , and (b) 2 mM Cu2+ and 1 mM SPS, with various incubation time. Cu UME was prepared via Cu electrodeposition (0.4 V vs.
Ag/AgCl for 100 s, 7.0 107 C) on Au UME (12.5 m dia.).

electrode area. Contrary to Au UME, Cu UME exhibited the tran- Acknowledgments

sient behavior of CV (Fig. 6). In the absence of SPS in the electrolyte,
a small peak which is distinguished from wave corresponding to the
electrochemical reduction of Cu2+ was observed at the beginning of
the forward scan for CV (Fig. 6a), though it was not detected on big
Cu electrode (Fig. 1a). It became bigger with the incubation time and
it did not appear at the consecutive scan. Same peak was also observed
elsewhere,13 and it is associated with Cu+ from the comproportiona-
tion reaction. In general, disproportionation-comproportionation does
not change the current response though it can affect the concentra-
tion profiles of relevant species near the electrode.26,27 In this situ-
ation, however, the initial presence of final reduced species (Cu0 as
an electrode) induced the comproportionation reaction with Cu2+ at
the open circuit, and subsequently produced Cu+ whose reduction
current would be added to Cu2+ reduction current. The small peak
disappeared with the addition of SPS, which would be an evidence
for the interaction between Cu+ and SPS (Fig. 6b). The suppress-
ing effect of SPS on un-incubated Cu electrode was also observed
on UME, but the reaction kinetics was improved gradually with the
incubation. Hysteresis in CV indicates the transient enhancement of
the reaction kinetics during the scan. During the forward scan, the
interaction between SPS and Cu would continue, and accordingly the
catalytic function would be maximized soon whereby the current at
the backward scan showed a saturated level compared to the forward
scan, regardless of the incubation time. Hysteresis disappeared grad-
ually with the longer incubation. It indicates the maximized catalytic
function which is consistent with reaching maximum Ep .
Conclusions
The transient catalytic function of SPS on Cu electrodeposition
was observed through CV. The facts that its catalytic effect emerged
only on Cu electrode and increased with the incubation time, indi-
cates that Cu+ was essential component for catalysis. The change in
the concentration of SPS and Cu2+ or in the electrode potential had
implications for the degree of acceleration, indicating that the tran-
sient catalytic function was based on the chemical reaction between
Cu+ and SPS. The formation of Cu+ and its interaction with SPS
was also confirmed through the steady-state voltammetry of UME.
These results imply that transient catalytic function can be explained
by the chemical reaction of SPS as well as the competitive adsorption
mechanism.
This paper was supported by Research Fund, Kumoh National
Institute of Technology (2015-104-006).
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