Applied Surface Science 253 (2007) 4512–4514

www.elsevier.com/locate/apsusc

Surface modification of silicate glasses by nanoimprint using

nanostriped NiO thin film molds
Shusaku Akiba, Wakana Hara, Takahiro Watanabe, Akifumi Matsuda,
Masayasu Kasahara, Mamoru Yoshimoto *
Materials and Structures Laboratory, Tokyo Institute of Technology, 4259-R3-6 Nagatsuta-cho,
Midori-ku, Yokohama 226-8503, Japan
Received 30 March 2006; received in revised form 2 October 2006; accepted 3 October 2006
Available online 13 November 2006

Abstract
Nanoscale surface modification of silicate glasses was examined by applying nanoimprint technique using a nanostriped NiO thin film mold.
The mold had the pattern composed of regularly arranged straight nanogrooves, which was formed by high-temperature annealing of the Li-doped
NiO epitaxial thin film deposited on the atomically stepped sapphire (a-Al2O3 single crystal) substrate. The glass imprint was proceeded through
the simple steps of heating (600 8C), pressing (1 kPa) and then cooling in air. The nanoimprinted glass surface transferred reversely from the
mold exhibited the multi nanowire array having an interval of 80 nm, wire width of 70 nm, and wire height of 20 nm.
# 2006 Elsevier B.V. All rights reserved.

PACS : 61.43.Fs; 61.46. w; 61.66.Fn; 81.65.Cf

Keywords: Oxide glass nanopattern; Nanogroove; Imprint; Oxide glass; Oxide thin film mold

1. Introduction been mostly fabricated by electron-beam lithography and dry

Patterning of oxide glass surface at the micro- or nanoscale
has been conducted to fabricate optically functional devices
such as micro-lens, photonic crystal and optical diffractive
elements [1–3]. Furthermore, addition of physically or
chemically versatile functions to these glasses are expected
if surface nanopatterning could be attained easily and mass-
productively for the silicate glasses widely used as windows of
automotive or architectural, displays, glass container, decora-
tion glass, etc.
Nanoimprint lithography has been attracting much atten-
tion as one of the most useful fabrication techniques for simple
and low-cost nanopatterning [4]. Nanoimprint replication of
nanopatterns with a resolution down to a few nanometers can
be obtained in a single step of pressing the nanopatterned mold
onto the surface of glassy materials such as polymers and
oxide glasses at the temperatures around their glass transition
temperatures (Tg) [5–8]. Nanoscale-patterned molds have
* Corresponding author. Tel.: +81 45 924 5388; fax: +81 45 924 5365.
E-mail address: m.yoshimoto@msl.titech.ac.jp (M. Yoshimoto).
0169-4332/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2006.10.002
etching of Si, SiO2, SiC, Ni, etc. [9–11]. However, the
electron-beam technique needs a complicated equipment and
machinery operation for scanning artificial patterns, and
therefore not so suitable for making large area molds. On the
other hand, aluminum oxide with self-organized nanoholes,
which was formed through anodic oxidation of aluminum have
been also used as a template in the nanoimprint mold
fabrication [12,13].
Recently, we have succeeded in fabrication of Li-doped
NiO thin films with a straight nanogroove array pattern. These
films could be obtained by high-temperature annealing of the
epitaxial Li-doped NiO thin films deposited on the sapphire
(a-Al2O3 single crystal) substrates with straight steps and flat
terraces [14]. The striped nanopattern was appeared all over
the thin film surface after annealing. This NiO thin film with
self-organized pattern is thought to be suitable as the
nanoimprint mold for oxide glasses, partly because of its
thermal expansion coefficient relatively similar to oxide
glasses, high mechanical strength and oxidation durability. In
this work, nanoscale surface processing of oxide glasses was
examined by applying nanoimprint using the nanostriped NiO
thin film as a mold.
 S. Akiba et al. / Applied Surface Science 253 (2007) 4512–4514 4513

2. Experimental procedures

The nanopatterned molds for glass nanoimprint were

prepared by annealing the epitaxial Li-doped NiO thin films
deposited on atomically stepped sapphire (0 0 0 1) substrates.
The stepped sapphire substrates were obtained by annealing the
mirror-polished commercial substrates of 0.3 mm thickness
with the nominal miscut angle of 0.158 at 1000 8C for 3 h in air
as reported previously [14]. The epitaxial NiO thin films were
fabricated by pulsed laser deposition using KrF excimer laser
(wavelength: 248 nm, pulse duration: 20 ns, repetition: 5 Hz,
energy fluence: 3.0 J/cm2) and the sintered target of 10 mol%
Li-doped NiO (99.9% purity) in the ultrahigh vacuum (UHV)
chamber (base pressure of 5  10 9 Torr). The ablated film
precursors were deposited on the sapphire (0 0 0 1) substrate at
room temperature (not heated, 20 8C) under 1.0  10 5 Torr
O2 gas. Post-annealing of the NiO thin films for forming the
nanopattern on the film surface was conducted at 700 8C for 3 h
in air.
Next, by using the nanogroove-striped NiO thin films as the
molds, nanoimprinting was carried out onto the silicate glass
plate having the glass transition temperature (Tg) of 521 8C.
The nominal composition (wt.%) of the silicate glass was Fig. 2. AFM surface image (1 mm  1 mm) and height profile of the Li-doped
68.9SiO2–8.8Na2O–8.4K2O–10.1B2O3–2.8BaO–1.0MgO. The NiO thin film mold.
process of the glass nanoimprint is schematically depicted in
Fig. 1. The nanopatterned mold was contacted to the surface of
the glass plate and then heated them at 600 8C and pressed at the sapphire substrate used for film growth. A cross-sectional
1 kPa for a few minutes in air. When the sample was cooled height profile of the striped nanogrooves is also shown in Fig. 2.
down to below 40 8C, the mold was separated from the glass The resultant grooves on the Li-doped NiO thin film exhibited
plate. The surface morphology of the specimens was observed the upper width of 60 nm and the depth of 15 nm. In
by atomic force microscopy (AFM, SII SPI-3700). addition, it was confirmed that the straight nanogrooves were

3. Results and discussion

Fig. 2 shows an AFM image of the nanogroove-striped

surface of the Li-doped NiO thin film mold, which had
thickness of about 25 nm. The straight nanogroove array can be
seen in Fig. 2. The interval between grooves is 80 nm, which
corresponds well to the distance of the straight atomic steps on

Fig. 1. Schematic diagram of patterning of silicate glass surface by nanoim- Fig. 3. AFM surface image (1 mm  1 mm) and height profile of the imprinted
print. silicate glass plate.
4514 S. Akiba et al. / Applied Surface Science 253 (2007) 4512–4514
Fig. 4. AFM surface image (5 mm  5 mm) of the imprinted silicate glass plate.
formed over the entire surface of the Li-doped NiO thin film as
well as the straight atomic steps were observed on the entire
sapphire substrate.
Using the Li-doped NiO thin film mold with the pattern of
the regular nanogroove array, nanoimprinting of the silicate
glass surface was carried out in air. It is notable that demolding
had carried out quite easily after nanoimprint and cooling down
to room temperature, that low chemical reactivity between NiO
and certain glass below and around the Tg was implied.
Furthermore, the mold nanopattern was not deteriorated even
after several tens of imprinting. The AFM surface image of the
imprinted silicate glass is shown in Fig. 3. Straight nanowire
pattern transferred from the nanogroove-striped mold can be
clearly seen in Fig. 3. The interval between the lines is 80 nm,
which corresponds well to the distance of the nanogrooves on
the used mold.
Nanowires on the glass surface have the width of 70 nm
and the height of 20 nm. Even when the imprint temperatures
were higher than 600 8C, imprint patterning could be achieved.
However, the imprinted glass plate tended to be cracked due to
thermal stress with increasing temperatures.
Fig. 4 shows an AFM surface image for the enlarged area of
the imprinted glass nanopattern. The regular stripe pattern is
observed at the 5 mm  5 mm AFM scan. The nanopattern as
shown in Fig. 4 could be seen over the entire surface of the
imprinted glass plate (10 mm  10 mm). Further optimization
of imprint conditions including temperature, pressure and
heating-to-cooling cycle is necessary to achieve mass-
productive nanopatterning of glasses. In addition, shape control
of the mold pattern is important to develop functionally
modified surfaces on the glass plate. The spacing and the depth
of our mold could be modified by miscut angle of the substrate
and rate of the Li-ion dopant in NiO, however, self-assembled
oxide mold restricts the imprinted pattern to periodic and
parallel regular lines instead of permitting unlimited desirable
patterning. In future, fabrication of the nanopatterned glass
windows might be possible by applying the present nanoim-
print technique using numbers of NiO thin film molds at the
same time.
4. Conclusions
We have investigated the nanoscale surface modification of
silicate glasses by applying the nanoimprint technique using the
nanostriped Li-doped NiO thin film molds. The Li-doped NiO
thin films with straight nanogroove array could be obtained by
high-temperature annealing of the film deposited on the
atomically stepped sapphire (0 0 0 1) substrate. Nanoimprint
was conducted on the silicate glass plate heated at 600 8C under
pressing of 1 kPa for a few minutes in air. The nanowire array
pattern was obtained on the glass surface through reversely
transferring of the mold. The nanowires had an interval of
80 nm, wire width of 70 nm, and wire height of 20 nm.
Acknowledgments
This work was supported in part by Yazaki Memorial
Foundation for Science and Technology, and Grant-in-Aid for
Scientific Research and also the program of The 21st Century
Center-of-Excellence (COE) from Ministry of Education,
Culture, Sports, Science & Technology of Japanese govern-
ment.
References
[1] H. Herzing, Micro-optics, Taylor and Francis, Philadelphia, 1997.
[2] V. Fischer, T. Matsuura, S. Hirota, Laser Focus World 31 (1995) 167.
[3] M. Hock, E. Schäffer, W. Döll, G. Kleer, Surf. Coat. Technol. 163–164
(2003) 689.
[4] S.Y. Chou, P.R. Krauss, P.J. Renstrom, Appl. Phys. Lett. 67 (1995) 3114.
[5] S.Y. Chou, P.R. Krauss, P.J. Renstrom, Science 272 (1996) 85.
[6] B. Heidari, I. Maximov, E.-L. Sarwe, L. Montelius, J. Vac. Sci. Technol. B
17 (1999) 2961.
[7] T. Morita, K. Watanabe, R. Kometani, K. Kanda, Y. Haruyama, T. Kaito, J.
Fujita, M. Ishida, Y. Ochiai, T. Tajima, S. Matsui, Jpn. J. Appl. Phys. 42
(2003) 3874.
[8] Y. Hirai, K. Hanakugi, T. Yamaguchi, K. Yao, S. Kitagawa, Y. Tanaka,
Microelectron. Eng. 67–68 (2003) 237.
[9] S.Y. Chou, P.R. Krauss, W. Zhang, L. Guo, L. Zhuang, J. Vac. Sci.
Technol. B 15 (1997) 2897.
[10] S.W. Pang, T. Tamamura, M. Nakao, A. Ozawa, H. Masuda, J. Vac. Sci.
Technol. B 16 (1998) 1145.
[11] J. Taniguchi, Y. Tokano, I. Miyamoto, M. Komuro, H. Hiroshima,
Nanotechnology 13 (2002) 592.
[12] P.S. Lee, O.J. Lee, S.K. Hwang, S.-H. Jung, S.E. Jee, K.H. Lee, Chem.
Mater. 17 (2005) 6181.
[13] Y. Piao, H. Lim, J.Y. Chang, W.Y. Lee, H. Kim, Electrochim. Acta 50
(2005) 2997.
[14] M. Yoshimoto, T. Maeda, T. Ohnishi, H. Koinuma, O. Ishiyama, M.
Shinohara, M. Kubo, R. Miura, A. Miyamoto, Appl. Phys. Lett. 67 (1995)
2615.