Materials Letters 115 (2014) 187–189

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Facile fabrication of transparent and conductive nanowire networks

by wet chemical etching with an electrospun nanofiber mask template
Keisuke Azuma, Koichi Sakajiri, Hidetoshi Matsumoto n, Sungmin Kang, Junji Watanabe,
Masatoshi Tokita n
Department of Organic and Polymeric Materials,Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8552, Japan

art ic l e i nf o a b s t r a c t

Article history: Two-dimensional aluminum (Al) nanowire (NW) networks offering transparent conductors were
Received 12 August 2013 fabricated by simple wet etching of Al metalized polymer film using a polystyrene (PS) nanofiber (NF)
Accepted 15 October 2013 mask template. NW networks—500 nm in width, 50 nm in thickness, and with an area fraction of 22.0%—
Available online 23 October 2013
was prepared by electrospinning PS with 283 nm in diameter on a metalized film, bonding the NF to the
Keywords: film by annealing at 200 1C, etching unmasked Al and then dissolving the PS mask. The NW width and
Electrospinning the area fraction of Al NW network can be controlled readily by the NF diameter and the deposition time
Nanofiber of PS NF mask, respectively. The NW networks thus prepared are flexible and exhibit 80% optical
Wet etching transmittance and sheet resistance of 45 Ω sq
1, indicating that they can be an indium-tin oxide (ITO)
Transparent conductor
replacement.
Aluminum metalized film
& 2013 Elsevier B.V. All rights reserved.

1. Introduction 2. Material and methods

Transparent conductors are required as electrodes in opto-
electric devices, such as touch panels, liquid crystal displays, and
solar cells. Standard transparent conductors are made of indium
tin oxide (ITO). Because indium is rare and expensive, nanocarbons
(e.g., carbon nanotubes (CNTs) [1,2] and exfoliated graphene flakes
[3–7]) and metal nanowires [8–11] have attracted much attention
as promising alternative materials to ITO. The important perfor-
mance factors of transparent conductors are sheet resistance (Rs)
and transmittance (T). The required performance is dependent on
the application, e.g., electrodes in solar cells and large area
displays require a low Rs of 20 Ω sq
1, [12,13] whereas those
in touch screens require T 495%, and Rs is allowed to be as high as
400–600 Ω sq
1 [14].
In the present study, we demonstrate that two-dimensional
(2D) aluminum nanowire (Al NW) networks work as a transparent
conductor with T ¼80% at an Rs ¼45 Ω sq
1. The Al NW network
was prepared by the wet chemical etching of an Al thin layer, on a
poly(ethylene terephthalate) (PET) film, using an electrospun
polymer nanofiber as a sacrificial mask template. Al NW transpar-
ent conductors have practical advantages owing to the character-
istics of Al, such as good electrical conductivity, stability at
ambient conditions, and relative low cost.
n
Corresponding authors. Tel.: þ 81 35 734 2834.
E-mail addresses: matsumoto.h.ac@m.titech.ac.jp (H. Matsumoto),
mtokita@polymer.titech.ac.jp (M. Tokita).
Fig. 1 shows a schematic diagram of the Al NW network
fabrication procedure. Initially, polystyrene nanofibers (PS NFs)
are deposited on the target electrode of an Al thin film with an
area of 70  70 mm2 by the electrospinning of a PS solution
(Fig. 1a) [15–17]. The Al thin film of 50 nm in thickness was
deposited on a PET film and exhibited an Rs ¼1.5 Ω sq
1.
PS solutions were prepared by dissolving PS (Mw ¼23,000,000,
Polysciences. Inc.) in a 1:1 (w/w) mixture of tetrahydrofran and N,
N-dimethylformamide. The PS solution was placed in a syringe,
equipped with a needle (0.2 mm internal diameter) and pumped
at a flow rate of 5 μL min
1. The needle was placed 150 mm away
from the film and had a potential difference of 4.5 kV against the
film. All spinnings were carried out at a temperature of 207 5 1C
and at relative humidity of less than 35%. The deposition time
ranged from 0.5 to 5 min. Two types of smooth (bead-free) NFs
with average diameters (D) of 283 7 43 nm and 723 794 nm were
successfully deposited on the Al metalized PET film by using PS
solutions at concentrations of 0.25 and 0.98 wt%, respectively. The
electrospinning was followed by annealing of the as-deposited
fiber film at 200 1C for 30 min; the PS-NF mask was adherent to
the Al surface.
After annealing, the film was immersed in 1 M potassium
hydroxide aqueous solution for 1 min to remove the bare Al areas
(Fig. 1b). Finally, the PS NF mask was removed by dissolving in
chloroform (Fig. 1c). The prepared Al NW network is transparent,
highly flexible, and strongly adhesive to the polymer substrate
(Fig. 1d).

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.10.054
188 K. Azuma et al. / Materials Letters 115 (2014) 187–189

Fig. 1. Schematic of the fabrication method of the Al NW networks on a polymer film: (a) deposition of polymer nanofiber mask by electrospinning on Al metalized
substrate, (b) wet chemical etching, (c) removal of nanofiber mask, and (d) the obtained Al NW network metalized polymer film (photograph: Sample Al-2 in Table S1).

Fig. 2. (a) Laser microscope images of Al NW networks on PET films with W of

(a) 500 nm and (b) 1500 nm, fabricated using PS NF masks with D of 283 and
723 nm, respectively.

3. Results and discussion

The formation of the Al NW networks was confirmed by

confocal laser scanning microscopy (CLSM, KEYENCE VK-9710). Fig. 3. Effect of deposition time of the PS NF mask on (a) optical properties
2D networks of Al NWs with widths (W) of 500 and 1500 nm were (transmittance at λ¼ 550 nm) and (b) electrical properties of Al NW networks. φ is
prepared by using the PS NF masks with a D of 283 and 723 nm, the area fraction of the NW networks.
 K. Azuma et al. / Materials Letters 115 (2014) 187–189
Fig. 4. Performance comparison of Al NW networks with W of 500 and 1500 nm to
the values reported for conventional transparent conductors.
respectively (Fig. 2a and b). Thus, the W is approximately twice the
size of D. The PS-NF masks become fluid and spread over the Al
surface during annealing at 200 1C, which is much higher than the
glass transition temperature of PS (100 1C). If fibers are skewed to
each other, they can make junction points, thereby reducing the
number disconnections in the final NW network. The area fraction
of the Al NW network, which was estimated from the CLSM
images, increases with deposition time.
All the Al NW networks exhibit constant transmittances over
the whole visible wavelength range of 400–700 nm (Fig. S3). T at
550 nm (JASCO V-570 spectrometer) and Rs of the prepared Al NW
networks (four-point probe method, Mitsubishi Chemical Loresta-
EP MCP-360 resistivity meter) are plotted as a function of the
PS-NF deposition in Fig. 3a and b, respectively. T and Rs decrease
with an increase in the area fraction (φ). Al NWs with a smaller
W¼500 nm (Al-1–Al-3) show a higher T than those of the Al NWs
with a larger W¼1500 nm (Al-4–Al-6). Al-1–Al-3 with a smaller W
exhibit a T greater than 71% and Rs higher than 20 Ω sq
1. Al-4–
Al-6 with the larger W have an Rs lower than 80 Ω sq
1 and a T
less than 66%. By looking at the effect of different widths on T and
Rs, the smaller-width NW network is more effective for transpar-
ent conductor use.
In Fig. 4, the T and Rs of these Al NW networks are compared to
those of conventional transparent conductors, such as Ag NW,
single-walled CNT (SWCNT), copper nanofiber (Cu NF), and gra-
phene [2,3,6,18,19]. T and Rs of the Al NW networks with
W¼500 nm and φ ¼22% (Al-2) are comparable to those of ITO
and Cu NF. Thus, the Al NW network with a W less than 500 nm is
a promising material for transparent conductors.
4. Conclusions
We have demonstrated that transparent and conductive Al NW
networks can be fabricated by the wet chemical etching of a 50 nm
189
thick Al thin film with an electrospun polymer NF mask. W and φ
of the NWs, which are crucial factors in determining the optoelec-
trical properties of transparent conductors, can be easily con-
trolled by the D of the NF mask and the electrospinning deposition
time, respectively. Al nanowire networks with a W ¼500 nm and
φ ¼22.0% exhibited T ¼80% and Rs ¼ 45 Ω sq
1, which are compar-
able to conventional transparent conductors. This method can be
applied to the fabrication of nanowire networks of highly con-
ductive metals, such as Ag and Cu, and it allows the wire width
and the area fraction to be controlled. Further studies are now in
progress and the results will be reported in the future.
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.matlet.2013.10.054.
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