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Electrochemistry Communications 10 (2008) 514518

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Electroplating of metal nanotubes and nanowires in a

high aspect-ratio nanotemplate
Jie Fu, Serhiy Cherevko, Chan-Hwa Chung*
Department of Chemical Engineering, Sungkyunkwan University, Suwon 440-746, Republic of Korea
Received 9 December 2007; received in revised form 29 December 2007; accepted 15 January 2008
Available online 26 January 2008

Abstract
Ordered metal (Co, Pt, and CoPt alloy) nanotube and nanowire structures were fabricated by a simple electroplating method in high aspectratio anodic aluminum oxide (AAO) membrane. The growth rate in pulse mode is always larger than that in constant-current mode, which
represents that diffusion limitation exists in this electroplating condition. It is also found that the sputtered Au layer structure could influence the
electroplating. Traditional nanowires could be fabricated in the template with a uniform Au layer as conducting contact. In case of unblocked
AAO membrane, metal electroplating begins from the Au particles which were attached inside the holes during the sputtering step and produces
metal nanotubes. Pt and CoPt nanotubes could be easily prepared by this method and might be applied as catalyst and magnetic material. 2008
Elsevier B.V. All rights reserved.
Keywords: Electroplating; AAO; Nanotemplate; Nanowire; Nanotube; CoPt

1. Introduction
Recently, one-dimensional (1D) nanostructures of metals
and semiconductor materials have attracted considerable
interest due to their charming performances in several fields,
especially the magnetic or catalytic Co, Fe, and Pt nanowires
[15]. Compared to the traditional chemical vapor deposition
(CVD) or other growth techniques for nanostructures,
electroplating has lots of advantages, such as low cost, easy
implementation, and absence of high vacuum. Besides,
accompanying with nanotemplate method makes it easier to
confine and control the profile of nanomaterials. Anodic
aluminum oxide (AAO) membrane is the most widely used
nanotemplate due to its self-assembled regular hexagonal
array. By fabricating the smaller pore-diameter AAO and
treating with chemical ornament, various 1D nanostructures
are to be obtained, down to tens of nanometer in diameter.
*

Corresponding author. Tel.: +82 31 290 7260; fax: +82 31 290 7272.
E-mail address: chchung@skku.edu (C.-H. Chung).

However, most of those works were concerned about

nanowires. To fabricate metal nanotubes, people need to
functionalize the pore walls first, such as silane treatment
[6,7], or seek to the electroless deposition which requires a
series activation steps [7,8]. During our research about
electroplating Co, Pt, and CoPt alloy nanowire, we found that
metal nanotubes could be fabricated directly by electroplating
method, which is a mediate state in nanowire growth process.
In this paper, we will present our experimental details and
explain this nanotube and nanowire growth process.
2. Experimental
Commercial AAO membrane (200 nm pore-diameters, and
60 lm thickness, Whatman International Ltd.) was firstly
sputtered with gold by ion coater (HOYEON Tech. Co. Ltd.,
sputtering current: 15 mA, sputtering time: 10 20 min) to
provide conductive contact. The sequent electroplating was
carried in traditional three-electrode system.
Here we used the Ag/AgCl electrode (0.222 V vs. SHE) as the
reference electrode, Pt plate as the counter electrode,

-2481/$ - see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2008.01.015

J. Fu et al./Electrochemistry Communications
(2008) 514518 515
and the10 Au-sputtered
AAO membrane was the working
Fig. 1. SEM images of the backside of AAO membranes with Au sputtering for: (a) 0 min, (b) 10 min, (c) 15 min, and (d) 20 min. 516 J. Fu et
al./Electrochemistry Communications 10 (2008) 514518

Fig. 2. Schematic illustration of electroplating process in: (a) blocked, and (b)
unblocked AAO membrane.

growth rate is calculated by both nanowire length per time (left ordinate)
and nanowire volume per time (right ordinate).

than that in CC mode, which represents that diffusion

limitation exists in this electroplating process and mainly
attributes to the high aspect-ratio of nanotemplates.
In case of the unblocked AAO membrane, as shown in
scheme (Fig. 2b), a nanotube fabrication was observed at

Fig. 5. SEM images of electroplated Pt nanotubes (a) before and (b) after
removing AAO templates.

the initial state of electroplating. Fig. 5a and b show the typical

SEM images of Pt nanotube structures before and after removal
of AAO membrane, respectively. Pt nanotubes with a few
micrometers length were electroplated using this unblocked
AAO nanotemplate, where the coverage of sputtered Au was
about 50% of pore opening. Firstly, during the Au sputtering
step some Au particles attached on the inner walls inevitably. It
is possibly assumed that Pt ions firstly deposited on those Au
particles, and as-deposited Pt particles became the next reactive
cites for further electroplating. At last, they connected with
each other as nanotubes inside the holes and grew thicker and
longer to nanowires eventually. Secondly, Pt electrolyte had a
relatively smaller diffusion rate due to the big size of complex
molecules (Pt-p-salt) and the low concentration (only 0.01 M).
Compared with Co electrolyte in which nanotubes grew to
nanowires within a short period, this diffusion limitation
decelerated the electroplating reaction and made it possible to
obtain these nanotube structures. Furthermore, AAO membrane
with 80% coverage of Au
Fig. 3. SEM images of Co nanowire with length of: (a) 3 lm, and ( b ) 60 lm.

current density for both CC mode and pulse mode. At first, it

sputtering layer in Fig. 1c was soon blocked during the

electroplating and followed the wire-growth mechanism. Thus,
only 50% coverage in Fig. 1b was the suitable condition for

J. Fu et al./Electrochemistry Communications 10 (2008) 514518 517

seems that surface reaction mainly controls the process.

However, the growth rate in pulse mode is always larger

Fig. 4. The growth rate of Co nanowire vs. current density in constantcurrent

mode (square symbol) and current-controlled pulse mode ( dot symbol). The

nanotube fabrication in our experiment.

Similar growth pattern observed in CoPt alloy electroplating
process was in confirmation of our previous explanation. Fig.
6a and b show SEM images of CoPt nanotube and nanowire,
respectively, which were prepared on the AAO membrane in
Fig. 1b. In CoPt electrolyte, both Co and Pt ions had relatively
bigger size and lower concentration. The additives that used to
maintain the solution pH value stable also aggravated the
diffusion limitation. After 1 h electroplating with 5 mA/cm 2 in
CC mode, we got CoPt nanotubes (Fig. 6a). In succession, CoPt
nanowires (Fig. 6b) were produced after further electroplating
on the same sample with same current density for 5 h. These
results are consistent with our explanation about the nanotubes
and nanowires growth mechanism as presented in Fig. 2.
This Pt nanotube template might be used in several

Fig. 6. SEM images of: (a) 2 lm CoPt nanotube, and (b) 5 lm CoPt nanowire.

applications due to its large surface area, such as catalyst layer for various electro-oxidation reactions of methanol and hydrogen.
CoPt is also applicable as magnetic materials. We are currently investigating the catalytic performance of Pt nanotubes and the
magnetic property of
CoPt nanostructures.

4. Conclusions
In conclusion, we have studied the mechanism of metal electroplating in high aspect-ratio AAO membrane with different Au
sputtering structures. Diffusion limitation exists in this electroplating process. When use the unblocked AAO membrane, metal
electroplating begins from the Au particles attached on the AAO inner walls and forms a nanotube structure at the initial state. After
a further electroplating, the metal deposition could fully fill the template as nanowires. By controlling the Au sputtering structure
and other experimental conditions, such as current density, operating mode, and electrolyte compositions, we were able to
manipulate this electroplating process and fabricate particular nanotube or nanowire structures.
Acknowledgements
This work was supported by the Korea Science and Engineering Foundation (KOSEF) grant funded by the Korea government
(MOST) (No. R01-2007-000-10322-0).
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