Development of a rapid cure

polydimethylsiloxane replication
process with near-zero shrinkage
Mohsin Ali Badshah
Hyungjun Jang
Young Kyu Kim
Tae-Hyoung Kim
Seok-min Kim

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J. Micro/Nanolith. MEMS MOEMS 13(3), 033006 (JulSep 2014)

Development of a rapid cure polydimethylsiloxane

replication process with near-zero shrinkage
Mohsin Ali Badshah, Hyungjun Jang, Young Kyu Kim, Tae-Hyoung Kim,* and Seok-min Kim*
Chung-Ang University, School of Mechanical Engineering, 84 Heukseok-Ro, Dongjak-Gu, Seoul 156-756, Republic of Korea

Abstract. Replicated polydimethylsiloxane (PDMS) micro/nanostructures are widely used in various research
fields due to their inexpensiveness, flexibility, low surface energy, good optical properties, biocompatibility,
chemical inertness, high durability, and easy fabrication process. However, the application of PDMS micro/nanostructures is limited when an accurate pattern shape or position is required because of the shrinkage that occurs
during the PDMS curing process. In this study, we analyzed the effects of processing parameters in the PDMS
replication process on the shrinkage of the final structure. Although the shrinkage can be decreased by decreasing the curing temperature, this reduction also increases the unnecessary curing time. To minimize the inherent
shrinkage in the PDMS replica without an accompanying curing time increase, we propose a PDMS replication
process on a high modulus substrate (glass and polymer films) with compression pressure, in which the adhesion force between the substrate and the PDMS, and the compression pressure prevent shrinkage during the
curing process. Using the proposed method, a PDMS replica with less than 0.1% in-plane and vertical shrinkage
was obtained at a curing temperature of 150C and a curing time of 10 min. 2014 Society of Photo-Optical Instrumentation
Engineers (SPIE) [DOI: 10.1117/1.JMM.13.3.033006]

Keywords: polydimethylsiloxane; shrinkage; polydimethylsiloxane on glass substrate; polydimethylsiloxane on polyethylene terephthalate film; shrinkage compensation.
Paper 14024 received Mar. 12, 2014; revised manuscript received Jun. 18, 2014; accepted for publication Jul. 14, 2014; published
online Aug. 5, 2014.

1 Introduction
During the last decade, optical, biomedical, and chemical
devices have been revolutionized by the many well-known
silicon and glass-based micro/nanofabrication technologies.
However, the use of silicon and glass-based micro/nanofabrication techniques is limited in some applications due to
their complexity and high process cost.13 By comparison,
polymer micro/nanoreplication techniques have many
advantages, such as a wide range of available materials, ease
of processing, biomedical compatibility, and low cost. Due to
these advantages, polymer micro/nanoreplication processes
are receiving more attention in many different fields, such
as photonic devices, high density data storage devices, electronics, plasmonics, and chemical and biological sensors.48
Since the polymer micro/nanoreplication techniques were
introduced by Whitesides in 1998 as soft lithography, polydimethylsiloxane (PDMS) began to play an important role in
micro/nanopolymer replication technologies.9,10 In polymer
replication processes, PDMS is widely used as a mold
material because of its superior properties when compared
with metal or silicon mold, such as low surface energy
(22 to 24 dyncm), high optical transparency (85%), inexpensiveness, flexibility, chemical inertness, high durability,
and an easy fabrication process.1113 The excellent optical
transparency and biocompatibility of PDMS make it attractive not only as a mold material but also as a component
material in various fields.14,15 PDMS micro/nanostructures
are fabricated by polymerization of monomer with initiator
and shrinkage typically occurs during the curing process.
Because of the shrinkage during the fabrication process,
*Address all correspondence to: Tae-Hyoung Kim, E-mail: kimth@cau.ac.kr;
Seok-min Kim, E-mail: smkim@cau.ac.kr

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the application of PDMS molds is limited; micro/nanocontact printing or imprinting processes require very precise
alignment. Also, PDMS micro/nanostructures cannot be
applied to devices that require either high dimensional accuracy or further assembly processes with other devices.16,17
The shrinkage of PDMS during its fabrication process is
influenced by the processing conditions, and several
approaches have been employed to minimize the shrinkage
of PDMS micro/nanostructures. One well-known method to
minimize the shrinkage is to use a low curing temperature.
However, a low curing temperature requires long curing
times because the polymerization time of PDMS is inversely
proportional to the curing temperature (more than 24 h is
required to polymerize PDMS at room temperature).18
Furthermore, the use of a low-temperature curing process
also decreases the mechanical properties of the final-polymerized PDMS,19,20 which negatively affects the durability of
PDMS molds and devices. A simple and straightforward
shrinkage compensation method, in which the initial template pattern was enlarged considering the shrinkage ratio
of PDMS, was widely used.21 However, a strict PDMS curing condition should be maintained to obtain accurate pattern
dimensions after shrinkage because the shrinkage ratio of
PDMS is sensitive to the curing conditions. Since the
PDMS curing is manually conducted in most laboratory
experiments, it is almost impossible to perfectly compensate
the shrinkage using the redesigning method of template pattern. Therefore, a method to eliminate the shrinkage of
PDMS is required. In this research, a method to fabricate
rapid-cure PDMS microstructures with near-zero in-plane
shrinkage was proposed using a PDMS replication process
0091-3286/2014/$25.00 2014 SPIE

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Badshah et al.: Development of a rapid cure polydimethylsiloxane replication process with near-zero shrinkage

on a high modulus substrate. The basic shrinkage characteristics of the PDMS replica at various curing conditions were
investigated using the UV replicated template; the feasibility
of the proposed rapid-cure PDMS replication method with
near-zero shrinkage was examined by comparing the shrinkage amounts of replicated PDMS microstructures on a polyethylene terephthalate (PET) film and glass substrates to
those of the conventional PDMS replica.
2 Experimental Method to Examine the Shrinkage
of a PDMS Replica
To examine the effects of processing conditions on the
induced shrinkage, the experimental conditions were
selected to minimize the influences of other processing
parameters. Various materials and fabrication processes
can be used to prepare the template for the PDMS replication
process, and a single template can be reused many times. In
this study, UV-replicated polymer templates using a UVcurable polyurethane-acrylate (UP088, SKC, Ulsan,
Republic of Korea) from a single micro-patterned silicon
master were used for experiments.22,23 The polymer template
was used only once in the PDMS replication process to avoid
the influences of shape changes in the template during the
repeated PDMS replication processes. Figure 1 shows a
schematic of the fabrication process of the polymer template
and the PDMS replica. A silicon master pattern was prepared
by conventional photolithography and a reactive ion etching
process, and a self-assembled monolayer was coated onto the
silicon master as an anti-adhesion layer by dipping the silicon master in 2% dimethyldichlorosilane dissolved in octamethylcyclooctasilane.22,23 The replicated PDMS master was
obtained from the silicon master, and the cloned polymer
templates were replicated from the PDMS master using a

UV replication process. Although the photolithographed

photoresist patterns and the etched silicon patterns from a
single mask showed good reproducibility and can be used
as templates for PDMS replicas, the fabrication cost of a silicon-based template is relatively expensive for the one-timeuse template in this study. Furthermore, a slight difference in
pattern height between samples could be caused by unstable
spin coating or reactive etching processes, respectively. The
UV replication process from a single PDMS master pattern is
an appropriate fabrication method for the one-time-use template in this study, because it showed high reproducibility
and also provided a fast and low-cost fabrication method
for multiple templates. After preparation of the template, a
mixture of Sylgard 184 A and B (Dow Corning, Midland,
Michigan) with a 101 weight ratio was poured onto the template and cured in a convection oven. Finally, the replicated
PDMS was released from the template and the shrinkage was
measured using a microscope equipped with a motorized
stage synchronized with a microscope image (STM 6,
Olympus, Tokyo, Japan).
Figure 2(a) shows the fabricated 4-inch silicon master pattern with a 50 50 mm2 micro-pattern area. The patterned
area was divided into 25 10 10 mm2 unit cells with various
microstructures including lines, rectangular arrays, and dot
arrays with pattern widths of 30 to 200 m, as shown in
Fig. 2(b). To determine the shrinkage of the PDMS replica,
a long distance measurement method was used instead of
pattern width or pattern pitch measurement using a single
scanning electron microscope (SEM) or a microscope image,
because the long distance measurement method can provide
better accuracy in terms of a measurement error ratio to the
measured value. In the short distance measurement process
using single SEM image, the pixel selection error due to the

Fig. 1 A schematic diagram of the polydimethylsiloxane (PDMS) replication process used in this study.

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Badshah et al.: Development of a rapid cure polydimethylsiloxane replication process with near-zero shrinkage

Fig. 2 (a) Image of a 4-inch silicon master pattern prepared by photolithography and the reactive ion
etching process, (b) microscope image of replicated patterns on PDMS replica.

(a)

2.5

Temperature/Curing time
25 0C/48 h
50 0C/15 h
75 0C/6 h
100 0C/60 min
125 0C/30 min

2.0

Shrinkage %

unsharp edge image of pattern is one of the major measurement errors. The pixel selection error shows a great impact
on the shrinkage ratio for short distance measurement, but its
impact minimizes in long distance measurement to calculate
the shrinkage ratio. In this study, the distances between the
specific microstructures with lengths of 14, 42, and
70 mm across the full 4-inch polymer template and replicated PDMS were measured using an optical microscope
with a synchronized stage. Comparing 12 diagonal distances
between the polymer template and the PDMS replica, 12
shrinkage values were calculated for a single-PDMS replica.
To allow analysis of variance (ANOVA), more than three
samples were prepared at each processing condition.

1.5

1.0

0.5

0.0
0

Thickness (mm)

3 Effects of Processing Parameters on the Induced

Shrinkage of the PDMS Replica
Among the various processing parameters affecting the
shrinkage of a PDMS replica, the curing temperature and
the PDMS replica thickness were selected as the design
factors in this research. To examine the effects of curing
temperature and thickness of the PDMS replica on the
shrinkage, the polymer template was attached to the bottom
of a Petri dish and covered with different amounts of
uncured PDMS mixtures. The PDMS samples of different
thicknesses on the templates were then polymerized in a
convection oven at various temperatures. Figures 3(a)
and 3(b) show the changes in PDMS shrinkage by curing
temperature and thickness. Since the required curing time
for PDMS is inversely proportional to the curing temperature, we allowed sufficient curing time for each experiment
according to the PDMS manufacturers guide. According to
the ANOVA results, the curing temperature was the dominant factor affecting the PDMS shrinkage; the effect of
PDMS thickness was negligible. It was also found that
the amount of shrinkage was proportional to the curing temperature as shown in Fig. 3(b). Approximately 2.52%
shrinkage (mean value) was obtained from the PDMS replica cured at a temperature of 150C for 20 min, and the
shrinkage was dramatically decreased to 0.37% at a temperature of 25C for 48 h.
4 Development of a Rapid Cure and Near-Zero
Shrinkage PDMS Replication Process
Although <0.5% shrinkage occurred in the fabricated PDMS
at a room temperature condition, it was deemed to be too
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(b)

Fig. 3 (a) Effects of the initial thickness of PDMS on the shrinkage

ratio at various temperatures, (b) the effect of curing temperature
on the shrinkage ratio.

time-consuming (more than 24 h of curing time was

required). Furthermore, the PDMS cured at a relatively low
temperature showed poor mechanical properties, which
would deteriorate the durability of a PDMS mold or
PDMS devices.18,19 To overcome these disadvantages of
the room temperature curing process, we proposed a method
to replicate PDMS with near-zero shrinkage and rapid curing
time by replicating PDMS on a high-modulus substrate.
Figure 4 shows the schematics of the PDMS replication process on a substrate. The uncured PDMS mixture was poured
onto the polymer template, and a substrate was placed on top,
using care to avoid trapping bubbles. Then, the PDMS on the

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Badshah et al.: Development of a rapid cure polydimethylsiloxane replication process with near-zero shrinkage

Fig. 4 Schematic of the PDMS molding process with high modulus materials.

(a)

PDMS replica without substrate

PDMS replica with PET film
PDMS replica with glass

3.0

2.5

Shrinkage %

2.0

1.5

1.0

0.5

0.0

-0.5
75

100

125

150

Temperature C

(b)

(c)

(d)

(e)

Fig. 5 (a) Comparison of shrinkage ratio between PDMS replicas without substrate, with glass and with
polyethylene terephthalate (PET) film at various curing temperatures, and SEM images of (b) polymer
master obtained from a PDMS master using the UV-replication method, (c) PDMS replica without substrate cured at 150C, (d) PDMS replica with a PET film cured at 150C, and (e) PDMS replica with glass
substrate cured at 150C.

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Badshah et al.: Development of a rapid cure polydimethylsiloxane replication process with near-zero shrinkage

substrate was polymerized in a convection oven with compression pressure of 0.12 kPa. The compression pressure was
applied to minimize the thickness of the PDMS layer, which
can help shrinkage compensation effects due to the substrate.
Furthermore, the applied compression pressure can also
improve the replication quality of a PDMS replica.20 As
the high modulus substrates, a soda-lime glass (Tensile
strength: 19 to 77 Kgmm2 ), with a thickness of 1 mm,
and a PET film (SH34, SKC, Korea, Tensile strength: 18
to 21 Kgmm2 ), with a thickness of 188 m, were used.
To increase the adhesion properties between the substrate
and PDMS, an O2 plasma treatment was applied to the
glass substrate, and a primer-coated PET film was used.
The shrinkage characteristics of PDMS on the different substrates were compared with the PDMS replica prepared by
the conventional method, as shown in Fig. 5(a). As shown
in Sec. 3, the shrinkage of the PDMS replica prepared by
the conventional method was increased by increasing the
curing temperature. However, the PDMS replicas on a substrate showed less than 0.1% shrinkage throughout the entire
curing temperature range. The slight increase of shrinkage in
PDMS on a substrate cured at a high temperature could be

explained by the thermal expansion of the substrate at high

curing temperatures; the relatively greater shrinkage of
PDMS on PET substrates compared with those on glass
substrates could also be explained by the difference in the
thermal expansion coefficient of the substrates. The mean
measured shrinkages of PDMS cured at 150C were
2.52%, 0.09%, and 0.04% for materials without substrate, on PET substrate and on glass substrate, respectively.
Figures 5(b)5(e) show a comparison of the SEM images of
the line pattern microstructures on (b) UV replicated polymer
template, (c) PDMS without substrate cured at 150C,
(d) PDMS on PET substrate cured at 150C, and (e) PDMS
on glass substrate cured at 150C. The designed line width of
the micro line array was 30 m and the pitch was 60 m.
The measured eight-pitch distances were (b) 478.3 m,
(c) 466.2 m (2.52% shrinkage), (d) 477.8 m (0.105%
shrinkage), and (e) 478.1 m (0.042% shrinkage), respectively, which are comparable to the shrinkage values
measured using the long distance measurement method.
The main reason for this large difference between the
PDMS replica with and without substrate may be the adhesion force between the PDMS and the availability of the

Fig. 6 Cross-sectional surface profile of (a) polymer template, and PDMS replicas (b) without substrate,
(c) on a PET film, and (d) on a glass substrate cured at 150C.

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Badshah et al.: Development of a rapid cure polydimethylsiloxane replication process with near-zero shrinkage

applied pressure to the high modulus substrate, which functioned to create a permanent bond and prevented the polymerization shrinkage of PDMS that typically occurs during the
process. The slight difference between the design and measured pattern shapes of the UV-replicated templates was
caused by the conventionally cured PDMS master which
was used as a master in the UV-replication process.
To examine the vertical shrinkage characteristics of the
replicated PDMS microstructures, we measured the threedimensional (3-D) surface profiles using the confocal microscope (LEXT OLS4100, Olympus, Tokyo, Japan). Figure 6
shows the measured cross-sectional surface profiles of
(a) UV replicated polymer template, and replicated PDMS
(b) without substrate, (c) on PET substrate, and (d) on
glass substrate cured at 150C. The measured pattern heights
(mean value) were (a) 3.444 m, (b) 3.350 m (2.73% vertical shrinkage), and (c) 3.411 m (0.09% vertical shrinkage), and (d) 3.417 m (0.07% vertical shrinkage),
respectively. It was noted that the measured vertical shrinkage of PDMS cured by conventional method (2.73%) was
almost the same as the lateral shrinkage value (2.52%); the
vertical shrinkage of PDMS could also be suppressed by a
proposed rapid-cure PDMS replication method. Although
the adhesion force between PDMS and the substrates cannot
suppress the vertical shrinkage of PDMS, the compression
force, which is applied to minimize the thickness of a
PDMS layer on the substrates, can minimize the vertical
shrinkage of PDMS.24 This result clearly shows that the proposed rapid cure PDMS replication approach can minimize
not only the lateral shrinkage but also the vertical shrinkage.
5 Conclusion
A precisely controlled PDMS replication process was developed to analyze the effects of curing temperature and the
thickness of PDMS on the shrinkage of the final mold.
We confirmed that the curing temperature was the dominant
factor for the shrinkage in the PDMS replication process, and
the shrinkage increased proportionally to the curing temperature. To realize the near-zero shrinkage PDMS replica without increasing curing time, a PDMS replication process on a
substrate with a compression pressure was proposed, and
0.04% and 0.1% in plain shrinkage values and 0.07%
and 0.09% in vertical shrinkage values were obtained from the
PDMS replicas on glass and PET substrates, respectively.
Although the higher dimensional accuracy was obtained
from the replicated PDMS microstructure on a glass substrate,
PDMS on glass substrates loses the flexibility, which is one of
the advantages of PDMS microstructures. The PDMS on PET
film substrate, however, still provided this flexibility. Based on
these advantages and disadvantages of the two proposed rapid
cure near-zero shrinkage PDMS replication methods, PDMS
on glass substrates for applications requiring precise alignment and PDMS on PET film substrates for applications
requiring flexibility seem to be the best options.
Acknowledgments
This work was supported by the Human Resources
Program in Energy Technology of the Korea Institute of
Energy Technology Evaluation and Planning (KETEP)
and was granted financial resources from the Ministry
of Trade, Industry and Energy, Republic of Korea
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(No. 20134030200350) and the Chung-Ang University

Research Scholarship Grants in 2012.
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Mohsin Ali Badshah received his BSc mechanical engineering from
the University of Engineering and Technology (UET) Lahore,
Pakistan, in 2010. He is now pursuing his MS degree from ChungAng University (CAU), Republic of Korea, and is a member of the
Nano
Manufacturing
Technology
Laboratory,
Chung-Ang
University. His research interests include fabrication of nanostructure
devices, nanotechnology, and biosensors.
Hyungjun Jang is pursuing his BSc in mechanical engineering from
Chung-Ang University (CAU), Republic of Korea, and he is a member
of the Nano Manufacturing Technology Laboratory, Chung-Ang
University. His research interests include fabrication of micro-

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Badshah et al.: Development of a rapid cure polydimethylsiloxane replication process with near-zero shrinkage
nanostructure devices, glass microfluidics channel using vitreous carbon mold and optical devices.
Young Kyu Kim received his BS degree in mechanical engineering
from Chung-Ang University in 2013. He is now pursuing his MS and
PhD degrees in Chung-Ang University and is a member of the Nano
Manufacturing Technology Laboratory, Chung-Ang University. His
research is fabrication of all-glass micro Fresnel lens using vitreous
carbon mold for optical lens of concentrator photovoltaic.
Tae-Hyoung Kim received his PhD degree in informatics from Kyoto
University, Japan, in 2006. He is currently an associate professor at
the School of Mechanical Engineering, Chung-Ang University. His

J. Micro/Nanolith. MEMS MOEMS

current research interests include robust control, multiagent system,

particle swarm optimization, system identification, model predictive
control, iterative learning control, and systems biology.
Seok-min Kim received his PhD degree from the School of Mechanical Engineering at Yonsei University, Seoul, Republic of Korea. He is
currently an associate professor in the School of Mechanical Engineering at Chung-Ang University, Seoul. His current research interests include design and fabrication of micro/nanostructures for
optical biosensors, micro fluidic chips, concentrator photovoltaic system, digital display, LED lighting, and enhanced boiling heat transfer
surface.

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