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The direct nano-patterning of ZnO using

nanoimprint lithography with ZnO-sol and
thermal annealing
ARTICLE in MICROELECTRONIC ENGINEERING MARCH 2009
Impact Factor: 1.2 DOI: 10.1016/j.mee.2009.03.078

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Microelectronic Engineering 86 (2009) 22282231

Contents lists available at ScienceDirect

Microelectronic Engineering
journal homepage: www.elsevier.com/locate/mee

The direct nano-patterning of ZnO using nanoimprint lithography

with ZnO-sol and thermal annealing
Ki-Yeon Yang a, Kyung-Min Yoon a, Kyung-Woo Choi b, Heon Lee a,*
a
b

Department of Materials Science and Engineering, Korea University, 5-1 Anam-Dong, Sungbum-Ku, Seoul 136-701, South Korea
Korea Institute of Nuclear Safety, 19, Gusung-dong, Yu-sung-gu, Daejeon 305-338, South Korea

a r t i c l e

i n f o

Article history:
Received 25 November 2008
Accepted 6 March 2009
Available online 16 March 2009
Keywords:
ZnO nano-pattern
ZnO-sol
ZnO-gel
Nanoimprint lithography

a b s t r a c t
Nano-patterned ZnO layer was fabricated by ZnO-sol imprinting with a polymeric mold, followed by
annealing. Instead of polymer based imprint resin, ZnO-sol was used as an imprint resin. During the
imprinting process, the organic solvent in the ZnO-sol was absorbed into a polymeric mold and thus,
ZnO-sol was converted to ZnO-gel. These patterns were subsequently annealed at 650 C for 1 h in atmospheric ambient to form ZnO patterns. X-ray diffraction (XRD) and photoluminescence (PL) conrmed
that ZnO-gel was completely converted into ZnO by annealing. Using this ZnO-sol imprinting method,
ZnO nano-patterns, as small as 50 nm, were fabricated on Si and oxidized Si wafer substrates. The ZnO
nano-patterns were characterized using scanning electron microscopy (SEM) and Transmission electron
microscopy (TEM).
2009 Elsevier B.V. All rights reserved.

1. Introduction
Zinc oxide (ZnO) is an attractive oxide semiconductor, with a
wide band gap (3.3 eV) [1] and large exitonic binding energy
(60 mV) [2] that enable application to various elds such as thin
lm gas sensors [3], photo-detectors [4] and light emitting diodes
[5] especially for UV region. Patterning of ZnO thin lm usually requires at least three processes: deposition of ZnO layer, lithography
and etching of ZnO. To use ZnO nano-structures in various applications, an inexpensive and simple ZnO patterning technique needs
to be developed.
This paper presents the direct nano-patterning of ZnO, using
nanoimprint lithography (NIL) with ZnO-sol and thermal annealing. By thermal imprinting of ZnO-sol with polymeric imprinting
stamp such as PDMS, the organic solvent in the ZnO-sol was removed and ZnO-gel patterns were nally formed while the pattern
morphology was maintained. Then, ZnO-gel pattern was converted
to ZnO pattern by thermal annealing. Compared to photolithography, NIL can effectively fabricate nano-scale patterns with simple
process, high throughput and relatively low cost [6]. By using the
imprinting technique with the solgel process, the number of process steps can be decreased and the expensive processes such as
photolithography and reactive ion etching steps can be skipped.
Therefore, ZnO nano-patterns can be made inexpensively and various kinds of ZnO-based nano-devices can be realized using solgel
nano-imprinting.

* Corresponding author. Tel.: +82 2 3290 3284; fax: +82 2 928 3584.
E-mail address: heonlee@korea.ac.kr (H. Lee).
0167-9317/$ - see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.mee.2009.03.078

ZnO nano-patterns were fabricated by direct imprinting of

N,N-dimethylformamide (DMF)-based ZnO-sol and subsequent
annealing process. The ZnO patterns were characterized by scanning electron microscopy (SEM), Transmission electron microscopy
(TEM), X-ray diffraction (XRD) and photoluminescence (PL).
2. Experimental section
For the experiment, 0.5 M ZnO-sol was prepared by dissolving
0.05 mol of zinc acetate 2-hydrate (Zn(CH3COO)2
2H2O) in 0.1 l
of DMF and dropping diethanolamine (DEA) into the solution as
a sol stabilizer while maintaining the molar ratio of DEA/Zn2+ at
1:1 [7]. Due to the high wettability of the DMF solvent, this ZnOsol can be spin-coated on the various substrates, including Si wafer. As the organic solvent in the ZnO-sol must be removed during
the imprinting process in order to form the ZnO-gel patterns from
ZnO-sol, a poly-dimethylsiloxane (PDMS)-based polymer mold
was chosen due to its capability to absorb the solvent without
deformation [8]. The PDMS mold was fabricated by spin-coating
a 10:1 ratio mixture of Sylgard 184 (from Dow Corning) A and B
on the anti-adhesion-treated Si master mold, which has nano-dot
array patterns with a diameter of 250 nm and a height of 250 nm
[9], at 500 rpm for 10 s and then curing process was followed at
80 C for 1 h. The h-PDMS mold was fabricated with two steps. In
the rst step, h-PDMS layer is formed by spin-coating of mixture
vinyl PDMS prepolymer from Gelest, platinum divinyltetramethyldisiloxane from Gelest as a catalyst, 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane from SigmaAldrich as a modulator and hydrosilane prepolymer from Gelest and toluene. The spin-coating of the

K.-Y. Yang et al. / Microelectronic Engineering 86 (2009) 22282231

mixture was done at 3000 rpm for 30 s and baking process was followed at 60 C for 1 h. In the second step, a 10:1 ratio mixture of

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Sylgard 184 A and B from Dow corning was spin-coated on the

h-PDMS coated mold at 500 rpm for 10 s and baked at 80 C for

Fig. 1. (a) Schematic procedure of direct ZnO patterning process using NIL and ZnO-sol and (b) diagram of imprinting process ow.

Fig. 2. SEM, TEM micrographs of (a) ZnO-gel patterns on Si wafer after imprinting process and (b) ZnO patterns on Si wafer after annealing process at 650 C.

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K.-Y. Yang et al. / Microelectronic Engineering 86 (2009) 22282231

1 h. After curing of the PDMS, the h-PDMS/PDMS mold was demolded from the Si master mold [10]. The thickness of both PDMS
and h-PDMS/PDMS molds was about 1.2 mm.
Fig. 1 shows (a) a schematic of the overall procedure of direct
ZnO nano-patterning method and (b) a diagram of imprinting process ow. The ZnO-sol was spin-coated on the pre-cleaned substrate at 20004000 rpm for 60 s. Then, the PDMS-based
polymeric mold was placed on the substrate and imprinting process was done using a pressure vessel type imprint system, described elsewhere [11]. This process can be divided into two
stages. In the rst stage, spin-coated ZnO-sol was pressed with
the polymeric mold at a pressure of 500 kPa in order to ll the
nano-sized cavities of PDMS stamp with ZnO-sol. In the second
stage, the temperature was raised to 200 C while maintaining
the pressure. During this second stage, organic solvent in the
ZnO-sol solution was removed by diffusion through PDMS polymeric mold. As a result, ZnO-sol was converted to ZnO-gel. The
nano-sized patterns of ZnO-gel were stable. After imprinting process, the ZnO-gel patterns were annealed at 650 C for 1 h in atmospheric ambient using Rapid Thermal Annealing (RTA) instrument
in order to be converted into ZnO.

gel patterns with a diameter of 240 nm and a height of 145 nm

were fabricated by thermal imprinting of ZnO-sol. These ZnO-gel
patterns were then converted into ZnO patterns by annealing at
650 C for 1 h. After annealing, the dimensions of ZnO were re-

3. Results and discussion

SEM and TEM micrographs of the ZnO-gel patterns and ZnO patterns on the Si wafer are shown in Fig. 2. As shown in Fig. 2a, ZnO-

Fig. 4. X-ray diffraction spectra of patterned and un-patterned ZnO layer on quartz
substrate.

Fig. 3. SEM micrographs of ZnO patterns using h-PDMS mold on Si wafer substrate. (a) ZnO patterns using h-PDMS mold, derived from the same master mold of Fig. 2, (b)
50 nm sized ZnO nano-patterns on Si wafer and (c) residual thickness of ZnO patterns as a function of spin-coating rpm.

K.-Y. Yang et al. / Microelectronic Engineering 86 (2009) 22282231

2231

Fig. 5. Photoluminescence spectra of un-patterned and patterned ZnO layer on quartz substrate. Patterned ZnO layer consists of array of 200 nm diameter ZnO islands.

duced to a diameter of 210 nm and a height of 130 nm. Compared

to the size of master mold, the dimensions of ZnO patterns were
decreased by 16% and 48% in the x- and z-directions, respectively.
Fig. 2c is the cross-sectional TEM micrograph of directly patterned
ZnO using PDMS mold. According to Fig. 2c, ZnO nano-patterns was
formed by direct patterning method and the directly patterned
ZnO layer has very slight residual layer. Fig. 2b and c also show a
slightly tapered ZnO pattern prole due to the slight deformation
of the PDMS mold during imprinting.
In order to form the ZnO patterns with a vertical prole, the
high rigidity h-PDMS/PDMS mold was used, instead of conventional soft PDMS mold. Fig. 3 presents SEM micrographs of the
ZnO patterns, fabricated by imprinting with h-PDMS/PDMS mold
and annealing. As shown in Fig. 3, these ZnO patterns also shrank
by about 20% and 40% in the x- and z-directions, respectively, compared to the dimension of master mold. The prole of the ZnO pattern, derived by imprinting with the h-PDMS/PDMS mold, was
more vertical than that of ZnO patterns, imprinted with the PDMS
mold. As shown in Fig. 3b, ZnO pattern, with 50 nm of width and
75 nm of height, was successfully fabricated using direct patterning with the h-PDMS/PDMS mold.
The thickness of the residual layer of the imprinted patterns
strongly depends on the initial thickness of the spin-coated
imprinting resist and the density and height of the pattern. The
surface area of hole array on the polymeric mold, used in this
study, is about 42%. Fig. 3c shows that the residual thickness of
the ZnO patterns after imprinting and annealing as a function of
the spin-coating speed. According to Fig. 3c, the residual thickness
of the ZnO patterns was decreased with increasing the spin-coating
speed. Thus, the thinner residual layer was obtained with faster
spin speed since initial thickness of spin-coated ZnO-sol layer becomes thinner at higher spin speed. In case that low viscosity metal
oxide sol resin is used, the thickness of residual layer can be adjusted by imprinting pressure. However, in this study, only
500 kPa of imprinting pressure was applied to prevent the deformation of the polymeric mold and thus, reow of the excessive
ZnO-sol toward the outside of the mold by pressing force is limited.
In this research, a residual layer thinner than 10 nm was obtained
after imprinting and post-imprinting annealing. Such a thin residual layer can be easily removed by plasma etching process and
each ZnO-dot patterns can be isolated [12].
ZnO nano-patterns, formed by ZnO-sol imprinting, were characterized by XRD and PL analysis. Blanket ZnO layer was prepared as
a reference sample using ZnO-sol imprinting to compare with patterned ZnO layer. The identical conditions of spin-coating, baking
and annealing processes were applied to make blanket ZnO layer.
XRD patterns of the patterned and un-patterned ZnO layer on
quartz wafer are shown in Fig. 4. For both layers, diffraction peaks
of (1 0 0), (0 0 2) and (1 0 1) planes of ZnO were appeared at 31.8,
34.5 and 36.2, respectively. The diffraction peaks from the
nano-patterned ZnO were weaker and broader due to the nanoscale pattern size. The XRD patterns conrmed the nano-patterned

ZnO material was obtained by imprinting and annealing processes

and the phase of ZnO is polycrystalline.
Fig. 5 shows the PL spectra of the patterned and un-patterned
ZnO layers on the quartz wafer. The patterned ZnO layer exhibited
a dot pattern with a diameter of 200 nm and a height of 110 nm.
Luminescence emissions at 376 nm and 378 nm were observed
from the un-patterned and patterned ZnO layers, respectively, both
of which corresponded to the band gap energy of ZnO (3.3 eV).
The emission intensity from the patterned ZnO layer was about
ve times stronger than that from the non-patterned ZnO layer,
which was attributed to the inuence of the periodical dot patterns
that suppress the total internal reection at the interface between
ZnO and air ambient.
4. Summary
In this study, ZnO nano-patterns were fabricated by ZnO-sol
imprinting and annealing. The ZnO-gel patterns were fabricated
by imprinting of ZnO-sol with PDMS-based polymeric mold and
subsequently converted to ZnO by annealing at 650 C. By optimizing the spin-coating speed of ZnO-sol, ZnO-gel patterns with near
zero residual layer (thinner than 10 nm) was obtained. According
to the XRD and PL characterization, the patterned ZnO layer, fabricated by imprinting of ZnO-sol and subsequent annealing, was
polycrystalline with a band gap of 3.3 eV.
Acknowledgments
This work was supported by Korea Health 21 R&D Project
(Grant No. A050750) from Ministry of Health and Welfare, basic research program from Korea Science and Nano R&D program
through the Korea Science and Engineering Foundation funded by
the Ministry of Education, Science and Technology (2008-04501).
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