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Fabrication and characterization of multilayered nanoporous platinum films

deposited by electroplating and nonionic surfactant molds

Article  in  Applied Surface Science · July 2013

DOI: 10.1016/j.apsusc.2013.04.009

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 Applied Surface Science 277 (2013) 100–104

Contents lists available at SciVerse ScienceDirect

Applied Surface Science

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

Fabrication and characterization of multilayered nanoporous

platinum films deposited by electroplating and nonionic
surfactant molds
Yi-Jae Lee, Jae-Yeong Park ∗
Department of Electronic Engineering, Kwangwoon University, 447-1, Wolgye-Dong, Nowon Gu, Seoul, 139-701, Republic of Korea

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

Article history: Multilayered nanoporous Pt (NPt) thin film on silicon substrate was newly fabricated and characterized
Received 12 November 2012 for highly sensitive electrochemical sensor applications. The multi-layered NPt films were fabricated by
Received in revised form 24 March 2013 using nonionic surfactant and electroplating technique. The surface morphologies of the fabricated mul-
Accepted 3 April 2013
tilayered NPt films (single, double, and triple layer) were then characterized using field emission scanning
Available online 18 April 2013
electron microscopy (FESEM). The fabricated NPts films exhibited highly dense nanopores with irregu-
larly arranged grain boundaries. Their thicknesses were 0.7, 0.77, and 1 ␮m, which were highly affected
Keywords:
by the structural geometries of the bottom layer. The electrochemical properties of the as-synthesized
Nanoporous Pt
Multilayer
multilayered NPt films were tested in 1 M sulfuric acid and phosphate buffered saline (PBS, pH 7.4) with
Electroplating different concentrations of hydrogen peroxide (H2 O2 ). The fabricated NPt films on silicon substrate exhib-
Nonionc surfactant ited highly improved electrochemical roughness factors (RF) of 151.45, 901.35, and 1277.7 (mean values),
Roughness factor respectively. As expected, they exhibited high sensitivities of 279.6, 337.5, and 517.8 ␮A mM−1 cm−2 in
H2 O2 concentrations up to 7 mM, respectively, due to extremely enlarged specific surface activation area.

© 2013 Elsevier B.V. All rights reserved.

1. Introduction the controlling of multilayer films and porous nanostructures has

Over the past few years, extensive research has been performed
to develop micro/nano structured materials with high real surface
area, because of their many applications in electrochemical sensors
and catalysis. 2D or 3D porous metal films for optical applications
have also recently been of interest, since they permit easy fabrica-
tion of devices or electrodes [1–3].
For improving their operating performances, the porous struc-
ture should be well distributed and miniaturized. In the most
practical applications, the electrodes with macropore or nanopore
were strongly demanded and used according to their particular
pore sizes. When these electrodes are used for the electrochemical
sensors, there are some advantages of the fast, easy, and effective
transfer of reactants by the macropores, while the electrode with
nanopores will increase its real surface activation area resulting in
high catalytic properties. The nanoporous gold or platinum with
high surface area by prepared alloying/dealloying or electroplating
method is particularly used as electrochemical catalyst, electrode
of battery or fuel cells [4–6]. Since their unique chemical and
physical properties are different from those of bulk metals [7–9],
∗ Corresponding author. Tel.: +82 2 940 5113; fax: +82 2 942 1502.
E-mail address: jaepark@kw.ac.kr (J.-Y. Park).
received intense interest in recent years for their uses in analytical
and material chemistries. Development of new techniques for 2D
or 3D nanostructures of the metal nanoparticles is a critical process
and an important goal in the chemistries for practical application
in nanotechnology and biotechnology [10–12].
Most metallic multilayers have been produced by molecular
beam epitaxy (MBE) growth [13], sputtering [14] or vacuum deposi-
tion methods [15]. Electroplating method is widely used as a surface
finishing process for avoiding corrosion of metal surface, because
this method is very simple and cost effective for production in com-
parison with the other methods. Furthermore, it is easy to fabricate
the multilayered macro-nano porous metal, alloy, and composite
materials with large surface activation area by controlling of the
electroplating conditions [6,16,17].
In this study, highly rough and catalytic multilayered
nanoporous Pt (NPt) films on silicon substrate were newly fabri-
cated and characterized for electrochemical sensor applications.
The multilayer NPt films on Si substrate were fabricated via non-
ionic surfactant and multi-electroplating technique. Subsequently,
the morphologies and electrochemical properties of the respec-
tive NPt films (single, double, and triple layer) were characterized
using field-emission SEM (FESEM), cyclic voltammetry, and amper-
ometric method. The electrochemical roughness factors (RF) and
electro-catalytic properties of the as-synthesized NPt films were

0169-4332/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2013.04.009
 Y.-J. Lee, J.-Y. Park / Applied Surface Science 277 (2013) 100–104
tested in 1 M sulfuric acid and phosphate buffered saline (PBS, pH
7.4) with different concentrations of hydrogen peroxide (H2 O2 ),
since it is a very important intermediate or product in biochemical
reactions.
2. Experimental method
2.1. Chemicals and apparatus
All the chemicals used were of analytical reagent grade. All
the solutions were prepared with deionized water (resistivity
≥18 M-cm). The prepared electroplating mixture for the NPt
was comprised of 42% (w/w) C16 EO8 (octaethylene glycol mono-
hexadecyl ether, 98% purity, Fluka), 29% (w/w) deionized water
(18 M-cm) and 29% (w/w) HCPA (hexachloroplatinic acid hydrate,
99.9% purity, Aldrich) [18,19].
The detailed surface morphologies of the fabricated multilay-
ered NPt films were characterized using field emission scanning
electron microscopy (Hitachi S-4300, Japan) at an acceleration volt-
age of 15 kV. The NPt films were also measured to check their
surface RF in 1 M sulfuric acid (H2 SO4 , 95–98%, ACS, Sigma–Aldrich)
solution using cyclic voltammetry. 0.5 M H2 O2 (30–32%, Dong-Woo
Fine Chem., Korea) solution was prepared to test their electrochem-
ical behaviors by diluting them in 0.1 M PBS (pH 7.4) solution.
All electrochemical experiments were carried out using an elec-
trochemical analyzer (Model 660D series, CH Instruments Inc., USA)
at room temperature. A traditional three-electrode system, which
comprised a flat platinum bar as a counter electrode, respective
NPt films (single, double, and triple layer) as a working electrode,
and an Ag/AgCl reference electrode with 3 M NaCl, was used for
the electroplating of these NPt films and for their electrochemical
characterization.
Amperometric measurements of H2 O2 were carried out in 0.1 M
PBS (pH 7.4) under the desired potentials. The responsive currents
corresponding to each H2 O2 concentration were recorded after the
transient being reached the steady state [19]. Before each measure-
ment, the NPt films were electrochemically cleaned in the potential
regions of the onset of oxygen and hydrogen evolution in a solu-
tion of 1 M H2 SO4 at a scan rate of 200 mV s−1 . The amperometric
curves, which were treated as the specific response to the H2 O2
Fig. 1. (a) Electroplating method for NPt film and (b) fabrication sequence of the multilayered NPt thin film by using C16 EO8 surfactants and HCPA-based electroplating
technique.
101
concentrations in PBS, were obtained after the consecutive addition
of 1 mM H2 O2 .
2.2. Fabrication of the multilayered NPt films
Fig. 1 shows the fabrication sequences of the multilayered NPt
thin films made by using nonionic surfactants (C16 EO8 ) and HCPA-
based electroplating technique. As shown in Fig. 1(a), the NPt film
was electroplated on top of sputtered Pt formed on silicon oxide
substrate. Liquid crystal templates of C16 EO8 were formed on top
of the Pt layer by lowering the temperature down from 85 ◦ C
to room temperature after dipping the sample into the prepared
electroplating mixture. The temperature was controlled by water-
jacketed vial. At this step, a liquid crystalline hexagonal structure
was formed on top of the sputtered Pt surface. After that, Pt ions
were electroplated into the formed nano-mold by applying a con-
stant potential of −0.12 V vs. Ag/AgCl (35 mC charge condition) [18].
The NPt film was finally formed by removing the surfactant mold
with distilled water for several hours. Although the color of the
fabricated NPt film was black at first, it became shiny after several
segments of cyclic voltammetry in 1 M H2 SO4 .
As shown in Fig. 1(b), the double and triple layered NPt films
were fabricated on the top of single and double layered NPts films
by repeating the electroplating sequences shown in Fig. 1(a). The
thickness and surface roughness of each layer is different due to
the change of plating current caused by the resistance change and
surface morphologies of each bottom layer at the fixed potential
and charge conditions. Unlike the formation of single layered NPt
film, the surface structures of the double and triple layered NPt
films can be more complex due to the irregular formation of the
surfactant mold on the electroplated NPt film.
3. Experimental results and discussions
3.1. Morphological study of multilayered NPt films
Fig. 2 shows the top views of FESEM images of the fabricated
single layered NPt film (a-b), the double layered NPt film (c-d), and
the triple layered NPt film (e-f). As shown in Fig. 2(a–b), the single
layered NPt film shows very dense grains which have high porosity.
102 Y.-J. Lee, J.-Y. Park / Applied Surface Science 277 (2013) 100–104
Fig. 2. FESEM top-view images of the fabricated single layered NPt film (a-b), double layered NPt film (c-d), and triple layered NPt film (e-f) by multiple electroplating.
The detailed morphological analysis for single layered NPt films was
reported in our previous works [18]. Meanwhile, the doubled lay-
ered and triple layered NPts films clearly show densely formed NPt
films, which have grain (100–200 nm) boundary. The nanopores of
2–3 nm are continuously formed along the grain boundary. The Pt
grains were irregularly shaped, inhomogeneous in size, and closely
stacked on each other.
Fig. 3 shows the FESEM cross-sectional images of the fabricated
single layered NPt (a-b), double layered NPt (c-d), and triple lay-
ered NPt (e-f) films. As shown in Fig. 3(a), (c), and (e), the NPts
films were very dense and flat. The thickness of single layered NPt
film electroplated on sputtered Pt film was about 0.7 ␮m, and the
Pt grains were located with irregular grain boundaries as shown
in Fig. 3(a-b). However, the thickness of double layered NPt film
was approximately 0.77 ␮m, since the surface morphologies of the
electroplated NPt film was different with the sputtered Pt film. The
secondly formed surfactant mold on the single layered NPt film
would be more complex and irregular. However, the thickness of
triple layered NPt film (1–1.2 ␮m) was increased, since the dou-
ble layered NPt film would be more dense and aggregated than the
single layered NPt film as shown in Fig. 3(e–f). These results demon-
strate our assumption for the effects of surfactant mold formation
on the bottom layers (sputtered Pt, single layered and double lay-
ered NPt films) as described in Fig. 1(b).
3.2. Electrochemical analysis of the multilayered NPt films
Cyclic voltammetry of the fabricated NPt films (single, double,
and triple layer) were performed to study their electrochemical
RF and catalytic properties. The effect of the redox behavior on
the electroplated NPt films was investigated, as shown in Fig. 4.
The cyclic voltammograms were obtained in 0.1 M PBS (pH 7.4) at
scan rates of 50 mV s−1 . The measured results of the fabricated NPt
films clearly showed redox peaks caused by adsorption/desorption
of oxygen and hydrogen during the anodic and cathodic scanning.
However, it was hardly to see redox peaks in the curve of plane
Pt. With increasing number of NPt film layer, there is a corre-
sponding increase in the anodic and cathodic current peaks in the
cyclic voltammogram as shown in Fig. 4. This result indicates that
the electrochemical catalytic property can be improved by elec-
troplating multiple layers of NPt films. Particularly, the increased
hydrogen reduction region (0.2 ∼ −0.3 V) by the adsorption of
hydrogen atoms demonstrates that the real surface activation area
of the fabricated multi-layer electroplated NPt film was extremely
enlarged.
We can also calculate and compare the RF of respective fab-
ricated NPt films at the hydrogen adsorption region (see Fig. 4a)
through cathodic scanning as shown in Fig. 5. The RF was calculated
using the inset equation shown in Fig. 5. Ar and Ag represent the
real surface (interface) area and geometric surface (interface) area,
respectively. The response currents shown in Fig. 4 at the applied
potentials ranging from −0.3 to 0.2 V were caused by the adsorp-
tion/desorption of hydrogen atoms. The oxidation and reduction
peak couples a /a and b /b in Fig. 4 correspond to the formation
and oxidation of hydrogen atoms and the formation and reduction
of platinum oxide, respectively. The formation of hydrogen atoms
takes place at about 0.2 V in the cathodic scan, and hydrogen evo-
lution takes place at about −0.2 V in the anodic scan. The formation
of platinum oxide takes place at about 0.6 V in the anodic scan, and
its reduction peak potential is about 0.5–0.6 V in the cathodic scan.
Since the charge is necessary to form a monolayer of adsorbed
hydrogen and the electrode area is covered by each hydrogen atom,
the electrochemical RF is easily calculated. The RFs of the NPt films
are determined as the calculation of the adsorption charge divided
 Y.-J. Lee, J.-Y. Park / Applied Surface Science 277 (2013) 100–104 103

Fig. 3. FESEM cross sectional images of the fabricated single layered NPt film (a-b), double layered NPt film (c-d), and triple layered NPt film (e-f) by multiple electroplating.

by 0.21 mC cm−2 [20]. The accumulated charge density (0.21, 31.8,
189.28, and 268.31 mC cm−2 ) in a region of Fig. 4 was divided by the
aforementioned charge density of the adsorbed hydrogen mono-
layer (0.21 mC cm−2 ). The corresponding RF (fr ) of the plane Pt and
fabricated NPt films were calculated to be 1, 151.45, 901.35, and
1277.7 (mean values), respectively (see Fig. 5). Although the incre-
ment of thickness was small, the RF increment from the single to
double layers was much larger than that of the double to triple
layers. This result indicates that the real surface area involved for
electrochemical reaction was densely formed with many nano-
structured edges at the inside of the NPt films. Meanwhile, the
relatively small increment from the double to triple layers would be
caused by the aggregation effect of electroplated Pt grains. The NPt
films exhibited relative standard deviation (RSD) values of 28.7%,
13%, and 10.7%, for single, double, and triple layered NPt films,
respectively.
The voltammetric behavior of NPt films was obtained in a 0.1 M
PBS (pH 7.4) solution containing fixed concentrations of 4 mM
H2 O2 . The H2 O2 has a direct relationship with numerous biolog-
ical processes, since it is a very important intermediate or product
in biochemical reactions [19,21]. The cyclic voltammogram of NPt
films in PBS (pH 7.4) with the 4 mM H2 O2 concentration is shown in
Fig. 6 (scan rate; 50 mV s−1 ). In Fig. 6, it is clear that well-defined and
resolved voltammetric peaks are observed for the direct oxidation
of H2 O2 on the surface of the NPt films. With increasing number of

Fig. 4. Cyclic voltammetry of the electroplated NPt films (single, double, and triple Fig. 5. Comparison of the calculated RFs of the fabricated NPt films (plane Pt, single,
layer) in 1 M sulfuric acid solution (scan rate: 50 mV s−1 ). double, and triple layer).
104 Y.-J. Lee, J.-Y. Park / Applied Surface Science 277 (2013) 100–104
Fig. 6. Cyclic voltammograms of the fabricated NPt films in 0.1 M PBS (pH 7.4)
solution with 4 mM H2 O2 concentrations.
Fig. 7. Amperometric responses of the fabricated NPt films for successive additions
of H2 O2 at the applied potential 0.4 V vs. Ag/AgCl. The supporting electrolyte is 0.1 M
PBS (pH 7.4).
NPt film layers, there is a corresponding increase in the oxidation
peak current of the cyclic voltammogram. Particularly, the anodic
scan area at 0.4 V illustrates that the H2 O2 (4 mM) resulted in a clear
increase of the peak oxidation current due to the enlarged surface
activation area of the double and triple layered NPt films.
Fig. 7 shows the amperometric response of the fabricated NPt
films at 0.4 V as a result of successive addition of H2 O2 (1–7 mM),
with time intervals of 100 sec, in continuously stirred PBS (pH 7.4).
This measurement was performed after stabilizing the background
current at a nearly constant value [19]. As shown in Fig. 7, dis-
tinct signals in response to the changes of H2 O2 concentration
were observed. With larger number of layers of electroplated NPt
films, higher current response was obtained, since the improved
electro-catalytic property to the H2 O2 is caused by enlarged surface
activation area. Also, the fabricated NPt films exhibited high sensi-
tivities of 279.6, 337.5, and 517.8 ␮A mM−1 cm−2 in concentrations
up to 7 mM. The electro-catalytic activity toward the oxidation of
H2 O2 could be most likely caused by the enlarged surface activa-
tion area or surface roughness factor, which might provide many
favorable sites for electron transfer [22].
4. Conclusions
We have fabricated and characterized multi-layered NPt thin
films with extremely expanded surface activation area and high
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H2 O2 sensitivity for electrochemical sensor applications. The mul-
tilayered NPt films were fabricated by using nonionic surfactant
and repetitive electroplating technique. They were characterized
using FESEM and an electrochemical analyzer in 0.1 M PBS (pH
7.4) solution containing various H2 O2 concentrations (cyclic vol-
tammetry and amperometry). Surface morphological analysis by
FESEM clearly showed their porosities along the grain bound-
ary on the top surface. The RF of the triple layered NPt film was
improved 8 times compared to the single layered NPt thin film.
Also, the electrochemical analysis revealed the excellent electro-
catalytic properties of the H2 O2 . These results indicate that the
fabricated NPt films are useful as catalytic electrodes for fuel cell
and electrochemical sensor applications. Furthermore, the devel-
oped fabrication method is adaptable to fully integrated chemical
and bio-medical sensors and chips through batch fabrication.
Acknowledgements
This research was partially supported by the International
Collaborative R&D Program of KIAT/MKE, Industrial strategic tech-
nology development program (10041876) funded by the Ministry
of Knowledge Economy, and the research grant program of Kwang-
woon University in 2012. The authors are grateful to MiNDaP
(Micro/Nano Device & Packaging Lab.) group members at the
Department of Electronic Engineering, Kwangwoon University, for
their technical discussion and support.
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