Materials Letters 81 (2012) 119122

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

Microwrinkles by deposition of aluminum onto polydimethylsiloxane

Eunbi Seo a, Seung-Hwan Lee a, Bo Sung Shin b, Won Ick Jang c, Jong Soo Ko a, b,
a
Graduate School of Mechanical Engineering, Pusan National University, Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan 609-735, Republic of Korea
b
Engineering Research Center for Net Shape and Die Manufacturing Pusan National University, Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan 609-735, Republic of Korea
c
IT Convergence Technology Research Laboratory, Electronics and Telecommunications Research Institute, 138 Gajeongno, Yuseong-gu, Daejeon 305-700, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: We observed the variation in the size of microwrinkles according to the number of unit processing cycles,
Received 19 December 2011 which consist of polydimethyl siloxane (PDMS) casting followed by the deposition of Al. As the number of
Accepted 12 April 2012 processing cycles increases, the width of the microwrinkles narrows and their height increases. After ve
Available online 28 April 2012
processing cycles were completed, the width of the microwrinkles stood at 1.73.7 m. The top surface
area of the microwrinkles became smaller upon additional processing cycles, thereby reducing the contact
Keywords:
Microwrinkle
area between the water drops and the top surface. For this reason, the contact angle increased as the number
PDMS casting of processing cycles increased. The contact angle measured after ve processing cycles was 145, implying
Al deposition that the microwrinkled surface was modied such that it became superhydrophobic.
Thermal expansion coefcient 2012 Elsevier B.V. All rights reserved.
Surface modication

1. Introduction
The development of microstructured surfaces has been a key goal
in the areas of surface science and surface engineering owing to their
broad applicability. A microstructured surface has two unique topo-
graphical characteristics: an extremely widened surface area and a
largely reduced top area. While the surface area includes the top, bot-
tom, and side faces of the microstructures, the top surface includes
only the top area of the microstructures. The wide surface area
widens the reaction area. Microstructured surfaces are thus common-
ly used in areas requiring biological/chemical reactions [1,2]. The
small top surface is utilized in elds that require low friction and sur-
face modication [3,4], as it features a small contact area. Super-
hydrophobic surface modication, in particular, is drawing keen
attention at present, as it can be used in water repellency and self-
cleaning applications, among many other practical uses [57].
Conventional methods for producing microstructured surfaces
often employ lithography and silicon etching processes or a
micromold-based polymer forming process. These techniques not
only help produce uniform and precise microstructures, but they
also involve complicated manufacturing processes and expensive
equipment. Moreover, they cannot easily be scaled up.
G. C. Martin et al. introduced a very simple process of forming
microwrinkle structures by depositing metal onto PDMS [8]. This
method incurs minimal processing costs and facilitates the construc-
tion of large-area structures; however, microwrinkles produced via
Corresponding author. Tel.: + 82 51 510 2488; fax: + 82 51 514 0685.
E-mail address: mems@pusan.ac.kr (J.S. Ko).
this route have had limited applicability, as their aspect ratios are
not sufciently large [911]. Against this backdrop, this study aims
to increase the aspect ratio of microwrinkles by using a repetitive
process of PDMS casting and Al deposition. At the same time, the con-
tact angle at the surface where the microwrinkles are created is mea-
sured to examine the potential application of the proposed method to
superhydrophobic surfaces.
2. Experimental
Fig. 1 illustrates the unit processing cycle, which consists of PDMS
casting followed by the deposition of Al. This study repeated this unit
processing cycle seven times. The manufacturing process is as fol-
lows: rst, the PDMS prepolymer was blended with a curing agent
(Sylgard 184, Dow Corning Corp., USA) at a ratio of 10:1. This PDMS
mixture was then placed into a Petri dish with a diameter of
150 mm. Bubbles were removed under a vacuum atmosphere and
the PDMS was then hardened for two hours on a hot plate at 65 C
(Fig. 1a). The thickness of the produced PDMS substrate was 5 mm.
The hardened PDMS substrate was attached to a Si wafer (Fig. 1b),
and Al was deposited to a thickness of 1000 at a deposition speed
of 10 /s at 16 C under a vacuum condition of 5 10 6 Torr. The
Al-coated PDMS substrate was separated from the wafer and put in
a Petri dish (Fig. 1d). Next, the PDMS casting process was carried
out on the Al-coated PDMS substrate to produce a PDMS substrate
with a shape opposite that of the microstructure generated on the
surface of the Al-coated PDMS substrate (Fig. 1f). The cast PDMS sub-
strate on the top was separated and attached again to the Si wafer
(Fig. 1f) to start the Al deposition process (Fig. 1g). As shown in
Fig. 1ac, no microwrinkles were created at the time the Al was

0167-577X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2012.04.058
120 E. Seo et al. / Materials Letters 81 (2012) 119122
a Petridish b c
PDMS
f g
PDMS*
Si wafer
Unit
Processing
Cycle
e d
PDMS*
Fig. 1. Fabrication process of the microwrinkles: (a) PDMS casting; (b) attachment of the PDMS substrate onto the Si wafer; (c) Al deposition using a thermal evaporator; (d) at-
tachment of an Al-deposited PDMS substrate at the bottom of a Petri dish; (e) PDMS casting; (f) attachment of the PDMS substrate on the Si wafer; and (g) Al deposition using a
thermal evaporator.
deposited on the surface of the PDMS substrate after the rst PDMS
casting process. As indicated in Fig. 1dg, however, repeated process-
es were carried out starting from the second PDMS casting process,
and microwrinkles are created during iteration of the process. Against
this backdrop, the processes in Fig. 1dg are dened as a unit process-
ing cycle.
3. Results and discussion
Fig. 2a, b, c, and d shows scanning electron microscopy (SEM) im-
ages of the microwrinkles generated on the surface after the rst,
third, fth and seventh processing cycles, respectively. The enlarged
SEM image in Fig. 2a shows that cracks were created throughout
the Al layer after the rst processing cycle. The edges of the cracked
Al sections were not separated and were observed to be directed up-
ward in an overlapped condition. This suggests that the cracks on the
Al layer were generated not by tensile stress but by compressive
stress. The temperature dropped from 16 C at the time of Al deposi-
tion to 6 C after the process, leading to a temperature discrepancy of
10 C. The thermal expansion coefcient of PDMS was 310 mm/C,
roughly 13 times higher than that of Al (24 mm/C). For this reason,
the PDMS that expanded at 16 C was contracted to a greater extent
than the Al at 6 C, placing compressive stress on the Al and conse-
quently generating compressive stress-induced cracks. At cracks
where two sections meet, i.e., a crossing, one of the sections is slightly
lifted above the other, creating a micro-uplift.
In the second processing cycle, a second PDMS casting step was
conducted using the cracked-Al/PDMS substrate as a mold. The sur-
face topography of the second casted PDMS replica has the reverse
surface topography of the cracked-Al/PDMS substrate. With the sec-
ond Al deposition on the microwrinkled surface of the second casted
PDMS replica, compressive stress is again generated on the deposited
Al layer due to the difference between the thermal expansion coef-
cients of PDMS and Al. The surface topography changes by the com-
pressive stress. Compressive stress is newly generated in each
processing cycle. Therefore, as the PDMS casting and Al deposition
processes are repeated, the microwrinkles become narrower while
their height increases. This tendency can be clearly observed through
a comparison of the SEM images after the third, fth, and seventh
processing cycles, shown in Fig. 2b, c, and d.
Al
Si wafer
Petridish
The width of the microwrinkles measured after three processing
cycles stood at 3.24.6 m, while this value declined to 1.73.7 m
after ve processing cycles. On the other hand, the height of the
microwrinkles measured after three processing cycles fell in a range
of 0.91.6 m, as compared to a range of 1.02.0 m after ve process-
ing cycles. The width of the wrinkles remained virtually unchanged
after seven processing cycles but their height increased to be 1.8
3.4 m, with their aspect ratio nearing 1:1. The widths and heights
of the wrinkles were measured through magnied SEM images.
Three samples were used for the measurements, and the dimensions
of ten different wrinkles were measured for each sample. Each di-
mensional value of the wrinkles described in the paper is thus the av-
erage value from thirty measured values.
The width of the microwrinkles narrowed as the number of pro-
cessing cycles increased, causing the wrinkles to become higher
with a smaller top surface area. In this sense, this microwrinkled sub-
strate can be considered a superhydrophobic substrate. Fig. 3 shows
the contact angles measured after each processing cycle. The average
values from 10 measurements were used as the contact angles, and
the volume of the water drops used in the measurement process
was 6 l. The contact angle was determined to be 116 after the rst
processing cycle, but it increased signicantly to 145 after the fth
cycle. The contact angle remained low after the rst processing
cycle because the microwrinkles were wide and not sufciently
high, with the water drops wetting the entire area of the wrinkles.
After the fth processing cycle, on the other hand, the contact area
between the water drops and the top surface of the wrinkles
remained small when the upper width of the wrinkles was narrow;
as the height of the microwrinkles became high enough, water
drops were propped up at the top of the wrinkles without the sides
or bottom of the wrinkles becoming wet. This reduced the surface en-
ergy of the microwrinkles and thereby increased the contact angle.
After the completion of seven processing cycles, the contact angle
measured on the substrate surface was 148, thus indicating that
the microwrinkled surface was modied into a superhydrophobic
surface. The value of the contact angle measured here is similar to
that on the surface of natural lotus leaves.
The contact angle increased considerably as the number of pro-
cessing cycles increased, but the extent of this increase was reduced
greatly upon completion of the fth processing cycle. This major
gap in the extent of the contact angle increase was directly related
 E. Seo et al. / Materials Letters 81 (2012) 119122 121

Fig. 2. Top-view and cross-sectional SEM images captured after the rst (a), third (b), fth (c) and seventh (d) processing cycles.

with the width and depth of the microwrinkles measured at each pro-
cessing cycle. The decline in the microwrinkle width and the increase
in the microwrinkle height remained signicant until the fth pro-
cessing cycle, whereas little change was found in subsequent cycles.
The PDMS casting- and Al deposition-based surface microstructuring
technology used in this study is a very simple process that involves
exploiting the thermal expansion coefcients of the two materials. The
proposed approach can generate microwrinkled surfaces that are as
wide as the deposition area of the metal deposition equipment. In this
work we did not raise the deposition temperature signicantly so as to
identify the change in the shape and size of the microwrinkles according
to the processing cycle; however, better results can be expected with
fewer processing cycles if the deposition temperature is set to a level
much higher than 16 C during the Al deposition process. In this vein,
this technology is a very feasible method for creating large, low-cost
microstructures.
4. Conclusion
Microwrinkles were created by exploiting the gap between the
thermal expansion coefcients of the cast PDMS and the Al. The
width of the microwrinkles was reduced according to the number of
processing cycles consisting of PDMS casting and Al deposition
while the height of the wrinkles increased. After the completion of
122 E. Seo et al. / Materials Letters 81 (2012) 119122
Fig. 3. Contact angle measured after each processing cycle; the inset photos are water
drop images on the microwrinkled surfaces that were used to measure the contact
angles.
ve processing cycles, the width of the microwrinkles ranged from
1.7 m to 3.7 m, with little change in the wrinkle width observed
after additional processing cycles. The top surface area of the wrinkles
decreased upon additional processing cycles, reducing the contact
area between water drops and the top surface of the wrinkles. There-
fore, the surface energy of the microwrinkled surface decreased as the
number of processing cycles increased, thus increasing the contact
angle. After the completion of ve processing cycles, the contact
angle measured on the microwrinkled surface was 145, indicating
that the produced surface was superhydrophobic. The microwrinkle
generation technology employed in this study can be applied to a
wide array of areas, including surface modication applications, as it
ensures relatively easy production of large microstructures at a low
cost.
Acknowledgment
This research was supported by the Pioneer Research Center Pro-
gram through the National Research Foundation of Korea funded by
the Ministry of Education, Science and Technology (2010-0019313).
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