IOP PUBLISHING JOURNAL OF MICROMECHANICS AND MICROENGINEERING

J. Micromech. Microeng. 19 (2009) 045024 (9pp) doi:10.1088/0960-1317/19/4/045024

Photodefinable PDMS thin films for

microfabrication applications
Preetha Jothimuthu1, Andrew Carroll1, Ali Asgar S Bhagat1, Gui Lin2,
James E Mark2 and Ian Papautsky1,3
1
Department of Electrical and Computer Engineering, University of Cincinnati, Cincinnati, OH 45221,
USA
2
Department of Chemistry, University of Cincinnati, Cincinnati, OH 45221, USA
E-mail: ipapauts@ececs.uc.edu

Received 18 December 2008, in final form 25 February 2009

Published 26 March 2009
Online at stacks.iop.org/JMM/19/045024

Abstract
In this work, direct patterning of polydimethylsiloxane (PDMS) is demonstrated by the
addition of a UV-sensitive photoinitiator benzophenone. As an improvement to our previous
work, patterns with both positive and negative features have been fabricated on the same
substrate. Infrared spectroscopy was used to investigate photocrosslinking behavior and
reaction chemistry of this new photodefinable PDMS (photoPDMS) material. Several
applications of the photoPDMS process have been successfully demonstrated. Multi-layer
structures and multi-level microfluidic chips can be easily fabricated using this
photopatterning process. Patterned PDMS thin films can also be removed from the underlying
substrates and used as shadow masks for defining patterns on both planar and non-planar
surfaces. The photopatternable PDMS was also found to be biocompatible once un-reacted
benzophenone is extracted from the cured film. Overall, photoPDMS offers a number of
critical advantages over conventional PDMS processing, including elimination of master
template fabrication, ability to process under ambient light processing conditions,
positive-acting tone, low cost, and rapid and easy fabrication.
(Some figures in this article are in colour only in the electronic version)

1. Introduction A number of microfabrication techniques for making

Poly(dimethylsiloxane) (PDMS) is one of the most popular
silicone elastomers used in the fabrication of microfluidic
devices in numerous lab-on-a-chip (LOC) applications [1, 2].
It offers many advantages such as good flexibility, temperature
stability from −50 ◦ C to +200 ◦ C, chemical inertness, low cost
and simple fabrication. In addition, PDMS surface properties
can be easily modified for specific applications by adsorption
of proteins or plasma processing. PDMS also has favorable
optical properties including transparency above ∼230 nm and
very low autofluorescence over a wide range of wavelengths
compared to other plastic chip materials [3]. Furthermore,
PDMS is permeable to gasses, impermeable to water and non-
toxic to cells, making it suitable for a variety of biological and
microfluidic applications [1].
3 Author to whom any correspondence should be addressed.
PDMS devices exist; these processes have been extensively
reviewed by Sia and Whitesides [4] and used by numerous
investigators for fabricating PDMS-based devices. Typically,
PDMS structures are obtained as negative replicas of a master
template fabricated using conventional micromachining
methods [1, 4]. To form PDMS replicas, uncrosslinked
prepolymer is mixed in a 10:1 ratio with curing agent and
thermally cured at 80 ◦ C for ∼2 h on the master template.
Although the process is robust and a large number of PDMS
replicas can be fabricated from a single master template, there
are limitations associated with the fabrication of a master (such
as need for clean room facilities and photoresist processing
equipment). This is problematic when the device is in
the early development stage, as master fabrication can be
time consuming and expensive, especially when only a few
prototype devices are needed or a large number of design
iterations are expected. Rapid and low-cost prototyping

0960-1317/09/045024+09$30.00 1 © 2009 IOP Publishing Ltd Printed in the UK

J. Micromech. Microeng. 19 (2009) 045024
(a )
(b )
(c )
Figure 1. Schematic diagram of photoPDMS fabrication. (a) Spin coat photoPDMS mixture and UV expose, (b) cure PDMS at 120 ◦ C,
(c) develop in toluene. Following development, photoPDMS film can be used to fabricate (d ) double-layer microfluidic chips, (e) dual-level
structures or ( f ) freestanding shadow masks.
is therefore important in developing microsystems, and
thus there is a continued interest in alternative, simpler
microfabrication methods.
One alternative rapid prototyping approach is to directly
pattern PDMS by making it sensitive to UV. Lotters et al [5]
were the first to successfully demonstrate the patterning of
PDMS by addition of 2,2-dimethoxy 2-phenylacetophenone
(DMAP) photoinitiator. The technique, however, required
special processing conditions to address the oxygen and
ambient light sensitivities of the photodefinable PDMS
mixture. Nevertheless, Almasri et al [6] used this
photodefinable PDMS formulation to fabricate a tunable
infrared filter based on PDMS springs. Dow Corning
also recently introduced photopatternable silicones (WL-5000
series) for the electronic packaging industry [7]. The product
is similar to a conventional negative photoresist in terms
of processing and high costs. This material was used by
Harkness et al [8] for microelectronic packaging applications,
and most recently by Desai et al [9] for the fabrication of
a dielectrophoresis-based device for cell patterning. In other
recent work, Tsougeni et al [10] demonstrated photopatterning
of several types of siloxane copolymers with vinyl–methyl
siloxane groups as polymerizable units by crosslinking with
three photoinitiators (4,4 -bis(diethylamino)benzophenone,
99+%, thioxathen-9-one, 98%, and Igracure 651). Huck et al
[11] described a method for fabricating buckles by patterning
gold over a PDMS substrate soaked in benzophenone, which
was observed to become stiffer upon UV irradiation. Wang
et al [12] demonstrated a photografting surface modification
method in which polyacrylic acid (PAA) in contact with a
benzophenone-treated PDMS layer was patterned by selective
exposure to UV.
In our work toward a rapid prototyping process for PDMS-
based devices, we recently introduced a simple and low-
cost method for patterning PDMS directly by the addition of
benzophenone [13]. Benzophenone is a photosensitizer often
used to initiate free-radical polymerization by UV light, and
2
P Jothimuthu et al
(d )
(e )
(f )
a number of investigators have reported its use with siloxanes
[14, 15]. We successfully demonstrated fabrication of features
on the order of 100 μm using benzophenone concentration
of 3% (w) for a standard PDMS base to curing agent ratio
of 10:1 [13]. Prototyping devices using this photodefinable
PDMS (photoPDMS) offer the advantages of a conventional
PDMS elastomer, yet simplifies fabrication by eliminating the
need for a master. The fabrication process is also low cost
and insensitive to ambient light. By using transparency masks
and a portable UV light source, devices can be prototyped
ultra rapidly in any lab, eliminating the need for clean room
processing.
In this paper, we describe improvements to the
photoPDMS process, including enhanced feature definition
and demonstration of negative freestanding patterns, as
well as increased control over feature dimensions. While
previously we only speculated on the crosslinking behavior
of the photoPDMS material, herein we report on infrared
spectroscopy measurements that permit us to elucidate this
behavior. To demonstrate the versatility of the photoPDMS
fabrication process, applications that normally involve
complex microfabrication are shown with fewer and simpler
processing steps, including a multi-level microfluidic chip and
multi-layer thin films. Another demonstrated application is the
fabrication of thin film shadow masks for patterning on both
planar and non-planar surfaces. In addition, we demonstrated
biocompatibility of the photoPDMS film using cell culture.
With these improvements, the photoPDMS process is expected
to enable rapid prototyping of low-cost PDMS devices without
clean room facilities, envisaging its numerous applications in
microfluidics and MEMS fabrication.
2. Experimental methods
The process steps for fabricating photoPDMS devices are
schematically illustrated in figure 1. Benzophenone (99%)
was purchased from Sigma Aldrich as white crystalline flakes.
J. Micromech. Microeng. 19 (2009) 045024
It is sensitive to UV in the range of 200 to 400 nm [16], and
thus can be processed in ambient light. Conventional PDMS
was mixed 10:1 ratio of base to curing agent from commercial
RTV615 (GE) or Sylgard 184 (Dow Corning) kits. To prepare
the photoPDMS, benzophenone was dissolved in xylene in a
3:5 ratio and added to the conventional PDMS mixture to yield
a concentration of 3% (w). A degassing step was performed to
remove air bubbles trapped during mixing. The photoPDMS
mixture was spin coated at 2000 rpm to obtain a 20 μm thick
film on a glass wafer. The thickness of the photoPDMS layer
can be controlled by varying the spin speed to achieve a layer
thickness ranging from 10 μm to 80 μm [13]. The spin-coated
layer was selectively exposed to UV radiation at wavelengths
<365 nm with an exposure energy of 12 mW cm−2 through
a chrome mask for 10 min. Either a conventional aligner
(without an I-line filter) or a portable UV lamp can be used for
exposures. A proximity exposure at a distance of ∼80 μm was
used. This was followed by a soft bake step in a convection
oven at 120 ◦ C for approximately 50 s for a 20 μm thick film,
and a 3–5 s development in toluene or 30 s in methyl isobutyl
ketone (MIBK) to wash off the exposed regions.
Figure 1 also demonstrates how the process can be
repeated to form dual-layer or dual-level devices. In dual-
layer fabrication (figure 1(d )), a single layer of microchannels
is initially patterned on a glass substrate by the aforementioned
process. The process is repeated on top of a PDMS slab to form
a second layer, which is then bonded to the first layer by plasma
bonding. Enclosing the upper level microchannels with
another PDMS (or glass) substrate results in a completed dual-
layer chip. Additional layers can be achieved by repeating
the process. Dual-level structures can be fabricated by spin
coating a second layer directly on the previously patterned
first layer, as shown in figure 1(e). Patterned thin films (single
or multi-level) can also be peeled off the glass substrate by
immersion in toluene for ∼2 min (figure 1( f )) and can be used
for shadow masking applications.
Fourier transform infrared spectroscopy (FTIR) measure-
ments were performed to investigate interaction among the
three components of photoPDMS, namely the PDMS base,
the curing agent and benzophenone. The measurements were
recorded in the absorption intensity mode in the mid-IR range
400–4000 cm−1 at a resolution of 4 cm−1 and 16 scans per
sample. The characterized mixtures included (a) base and
benzophenone; (b) crosslinker and benzophenone; (c) base,
crosslinker and benzophenone. FTIR measurements of each
mixture were performed in the liquid phase made immediately
before and after UV exposure. The collected spectra were
corrected for atmospheric water and carbon dioxide from the
reference scan using standard methods [20].
Biocompatibility of photoPDMS was evaluated by
culturing NIH 3T3 fibroblasts and examining their
proliferation. Three PDMS formulations, two samples each,
were prepared and cured in a standard six-well culture plate.
One formulation was the photoPDMS material prepared as
described above. Two additional samples of photoPDMS were
prepared using the extraction procedure described by Lee et al
[17] which swells PDMS in a strong solvent to remove any
un-reacted polymer components. The RTV615 PDMS was
3
P Jothimuthu et al
used as control surfaces. NIH 3T3 fibroblasts were plated
directly on the six PDMS substrates (∼104 cells per 2 mL of
serum per well). Prior to seeding cells, PDMS was incubated
with IMDM (10% serum) at 37 ◦ C for 4 days [18]. Two days
after plating the cells, cell viability on each of the substrates
was examined using MTT (3-(4,5-dimethylthianzol-2-yl)-2,5-
diphenyltetrazolium bromide) assay [19], which stains live
cells and is used to measure their relative quantity. Absorbance
measurements were made with a spectrophotometer at 545 nm
and used to calculate relative cell viability of photoPDMS
substrates by normalizing to the absorbance of the commercial
PDMS.
3. Results and discussion
3.1. PhotoPDMS fabrication
A variety of features fabricated with photodefinable PDMS are
illustrated in figure 2. Feature sizes ranging from 100 μm to
2 mm were successfully fabricated. Figure 2(a) shows an SEM
image of 250 μm wide patterns with 250 μm line spacing
in a 20 μm thick film. Figure 2(b) demonstrates large area
patterning; the line width of these features is 400 μm with
a height of 20 μm. PhotoPDMS is only sensitive to light
<365 nm due to the absorption spectrum of benzophenone
that peaks at 260 nm, with a tail at 365 nm [16]. Thus,
the photoPDMS is processed under the normal ambient light
conditions in a conventional laboratory. Indeed, dust particles
seen on the surface of the device in figure 2 are due to
processing outside the clean room. Unlike the traditional
fabrication method in which PDMS channels are the negative
replicas of a master, the PDMS features of figure 2 are
the direct replications of the mask pattern. These positive
features clearly demonstrate the robustness and feasibility of
the photoPDMS process.
In addition, freestanding features (via exposure through
a dark-field mask) have been demonstrated in this work by
using a MIBK developer and modifying the soft bake process.
Figure 2(c) shows 250 μm wide line features with 250 μm
spacing in a 20 μm thick film. Large area patterning is shown
in figure 2(d ). In our previous work [13], freestanding features
were washed off the glass substrate during the development
process. However, by curing the wafer for longer times
(∼80 s) these features could be retained, though their
dimensions were larger than that of the mask.
The difficulty in achieving freestanding features is most
likely due to two factors. First, poor adhesion between the
PDMS and glass substrate prevents small patterns from staying
on the glass after being submerged in the developer. Also,
toluene quickly swells PDMS and may cause features to peel
off the substrate after expanding. In order to correct these
complications, an intermediate layer of cured PDMS and a
milder developer can be used. Curing a thin layer (20–
80 μm) of PDMS on top of the glass substrate before the
normal patterning process provides a strong bond between the
substrate and the photoPDMS layer. The use of MIBK, a
milder solvent than toluene, prevents the sudden expansion of
features due to swelling. Together, these adjustments allow
for consistent and well-defined freestanding features.
J. Micromech. Microeng. 19 (2009) 045024
Figure 2. SEM images of (a) conventional and (c) freestanding photoPDMS features 250 μm wide at 250 μm spacing, and (b) conventional
and (d ) freestanding large area photoPDMS patterns with feature sizes varying from 200 μm to 2 mm.
Figure 3. Sidewall profile of a single-layer microchannel patterned
on a glass substrate.
Two difficulties in using the photoPDMS process exist,
namely sloped sidewalls and sensitivity of feature dimensions
and definition to curing time. The definition of the sidewalls
shows a slope of approximately 40◦ –60◦ . This can be seen
clearly in the cross-sectional microscope images of a positive
line feature in figure 3. The slope can be attributed to the
combination of several factors. One factor is the higher
thermal conductivity of the substrate (1.13 W mK−1 for glass
versus 0.17 W mK−1 for PDMS), which causes photoPDMS to
preferentially cure from the bottom by conduction rather than
convection inside a convection oven. Also, it was observed that
the sidewall angle and the feature widening were influenced
by the duration of curing and the material substrate. Another
factor that attributes to the sidewall angle is likely the diffusion
of the photoinitiator radicals in the exposed regions during the
long exposure time of 10 min [21]. Nevertheless, the observed
sidewall angles are comparable to those reported by Desai et al
[9] for the Dow Corning product and are acceptable for many
packaging and microfluidic applications.
4
P Jothimuthu et al
Dimensions of features created with the photoPDMS
process can vary significantly from those of the mask. The
most influential factor for this behavior was found to be the
soft bake processing step, where under-curing causes pattern
widening and over-curing reduces feature dimensions. Due
to the short (50 s) duration of the curing process, this feature
variation is difficult to control. Thus, to achieve a better control
over the photoPDMS soft bake step, several insulating layers
between the glass wafer and the metal base of the oven were
used to reduce film curing by conduction. Using a stack of
three 1 mm thick plastic (e.g., cyclo olefin copolymer) wafers
as a spacer between the glass substrate and the convention
oven rack, or using an 80 μm thick cured intermediate layer
of PDMS as insulation, the curing time was increased to
approximately 6 min for a 20 μm film. This additional time
permits the photoPDMS film to be cured accurately, giving
more consistent feature dimensions.
3.2. PhotoPDMS chemistry
In traditional PDMS fabrication, structures are formed
as negative replicas by curing a two-component silicone
elastomer mixture (base monomer and curing agent) over a
master template. In terms of chemical structure, the base pre-
polymer is composed of ∼60 repeating units of −OSi(CH3)2−
terminating with a vinyl−CH=CH2 group (Sylgard 184, Dow
Corning). The curing agent is similar, but is much smaller with
only about ten repeating units and has periodic silicon hydride
−OSiHCH3− units. During the curing step, the hydrosilation
of olefins takes place, i.e. the base and the curing agent
crosslink forming −Si−CH2−CH2−Si− complexes. This is
illustrated in equation (1). The resulting structure is insoluble
and is completely cured [1, 2, 22–24]:
J. Micromech. Microeng. 19 (2009) 045024 P Jothimuthu et al

CH3 CH3 CH3 CH3 CH3 CH3 CH3

Pt
H 2C CH Si O Si O Si CH CH2 + H 3C Si O Si O Si O CH3
CH3 m CH3 n CH catalyst
CH3 CH3 H CH3 3

m = ~60 n = ~10

CH3
H 3C Si CH3

O CH3
H 3C Si CH3 H 3C Si CH3
(1)
n O CH3 CH3 CH3 O
H 3C Si CH2 CH2 Si O Si O Si CH 2 CH2 Si CH3
O CH3 CH3 m CH3 O
H 3C Si CH3 H 3C Si CH3
CH3 O
n
H 3C Si CH3
CH3

The crosslinking mechanism of the photoPDMS mixture, Alternatively, benzophenone radicals react with the base
however, is different. Although there are several monomer forming short complexes (equation (4)), preventing
possible reaction mechanisms that could account for the them from crosslinking with the curing agent. This can be
benzophenone’s inhibition of crosslinking, the most likely observed from the post-exposure bake where the unexposed
mechanism is based on the reduction of carbonyl groups by PDMS is cured and crosslinked, while the exposed PDMS is
hydrosilanes. When benzophenone (also known as diphenyl washed away in toluene:
OH
ketone) is mixed with PDMS and irradiated using UV H 3C CH3 CH 3
C
<365 nm, a benzophenone radical is formed (equation (2)):
+ H 2C CH Si O Si O Si CH CH2
n
H 3C CH3 CH3
*
O O OH
CH3 CH3 CH3
h RH C .
+ R HC Si O Si O Si CH
n
CH3 CH2
n CH 2 CH3 CH3

(2) C (4)

HO
The benzophenone radicals react with the silicon hydride
groups present in the PDMS crosslinker (equation (3))
FTIR analysis was performed to confirm the proposed reaction
[25–29]. This hydrogen abstraction of benzophenone prevents
mechanism. Table 1 summarizes the expected and measured
the crosslinker from undergoing traditional organometallic
positions of IR absorption bands of the chemical groups from
crosslinking with the PDMS oligomer and creates a crosslinker the samples taken before and after UV exposure. Figure 4(a)
radical. The radical can then undergo either disproportionation compares the FTIR spectra for the sample containing base
to form a stable soluble complex with a Si=C bond or radical
coupling to form with a Si−Si bond:

OH
C CH3 CH3 CH 3 CH3

+ H3C Si O Si O Si O Si CH3
n
CH 3 H CH3 CH3
OH (3a)
CH CH 3 CH 3 CH 3 CH 3

+ H 3C Si O Si O Si O Si CH 3
n
CH 3 CH 3 CH 3
CH3 CH3 CH3 CH3
H3C Si O Si O Si O Si CH3
CH3 CH3 nCH
O 3
O
CH3 CH3 CH3 CH3 (3b)
C C
+ H 3C Si O Si O Si O Si CH3
n
CH3 CH3 CH3

5
J. Micromech. Microeng. 19 (2009) 045024 P Jothimuthu et al

Table 1. Expected and measured characteristic frequencies of the functional groups in photoPDMS.
Functional Chemical Expected peak Measured
group bond (cm−1) [23] peak (cm−1)
PDMS base monomer −Si−CH3 Si−C 1260 1260
800 800
−Si−O−Si Si−O 1130–1000 1011
−CH=CH2 C=C 1600 1600
−CH=CH2 C−H 960 960
Crosslinker −Si−O−Si Si−O 1130–1000 1011
−Si−H Si−H 2280–2080 2169
−Si−CH3 Si−C 1260 1260
Benzophenone −C=O C=O 1750–1680 1664

exposure, indicating the formation of benzophenone radicals

Figure 4. FTIR spectra of the photoPDMS mixture illustrating
(a) the reaction between benzophenone and PDMS monomer and
(b) the reaction between benzophenone and crosslinker taken before
(solid red) and after (dotted blue) UV exposure. Insets show
close-ups of the relevant regions.
and benzophenone, which indicates that the carbonyl group
(C=O) peak at 1664 cm−1 reduced in intensity after UV
(equation (2)). The vinyl C=C peak at 1600 cm−1 that
corresponds to the CH=CH2 stretch decreased in intensity,
while the other vinyl functionality at 960 cm−1 corresponding
to the C−H deformation remained unchanged, indicating
reaction between benzophenone radicals and the PDMS base
(equation (4)).
The FTIR spectra of the samples containing the
crosslinker and benzophenone (figure 4(b)) also exhibited a
decrease in the C=O carbonyl group peak at 1664 cm−1,
indicating benzophenone radical formation. In addition, the
Si−H silicon hydride group peak at 2169 cm−1 also decreased,
confirming that hydrosilanes reduce carbonyl groups by acting
as hydrogen donors. This confirms interaction between the
benzophenone radicals and the crosslinker (equation (3)).
The proposed possible reactions for the interaction of
benzophenone and the crosslinker involve the silicon hydride
group donating hydrogen to the benzophenone in its triplet
state which forms benzopinacol. However, the peak that
denotes the hydroxyl group (OH) from the benzopinacol
formation in the region 3400–3500 cm−1 was not observed.
The crosslinker unit which donated hydrogen can undergo two
formations, namely disproportionation and radical coupling
where it forms either Si=C or Si–Si bonds, respectively. In this
case, however, the Si=C peak that occurs at ∼1000 cm−1 may
be masked by the broad band of Si−O−Si, and the changes that
may have occurred for the Si=C bond could not be observed.
The FTIR spectra for the three-component sample mixture
of base, crosslinker and benzophenone are shown in figure 5
and support the proposed reactions. From the analysis,
it can be concluded that benzophenone free radicals form
during the UV irradiation of the photoPDMS mixture and
react with both the vinyl groups of the base and the silicon
hydride groups of the crosslinker. Thus, benzophenone
prevents the traditional polymerization of the base and the
crosslinker through hydrosilation of olefins and instead forms
a weakly crosslinked region which gets washed off during
the development stage. The unexposed regions, where
benzophenone did not form radicals, undergo normal curing,
making the photoPDMS mixture behave as a positive tone
resist.

6
J. Micromech. Microeng. 19 (2009) 045024 P Jothimuthu et al

Figure 6. (a) Photograph of a dual-layer microfluidic chip. Color

dyes were added for visualization. (b) Cross-section of the
dual-layer microchannel. (c) Photograph and (d ) cross-section of a
dual-level photoPDMS structure.

(a) (b)
Figure 5. FTIR spectra of the photoPDMS mixture showing the
reaction between benzophenone, PDMS monomer and crosslinker
taken before (solid red) and after (dotted blue) UV exposure. Insets
illustrate close-ups of the relevant regions.

3.3. Multi-layer and multi-level structures

To demonstrate feasibility and advantages of the photoPDMS

(c)
process for microfluidic devices, multi-layer channels were
fabricated (figure 6(a)). The double-layer microchannel
device was fabricated in separate layers and then sandwiched
together by plasma bonding. The first layer was patterned on
a glass wafer and the second layer was patterned on a thin
PDMS slab. This proves to be a much simpler fabrication
method with fewer processing steps when compared with the
conventional PDMS processing, which requires the fabrication
of two separate masters [30]. The cost was therefore lowered, Figure 7. (a) Planar patterning of UV adhesive bumps; (b) planar
and the method could be employed for rapid prototyping of and (c) non-planar patterning of gold with a photoPDMS shadow
biosensor microchips. Figure 6(b) shows a cross-sectional mask.
view of one of the channels. Both channels were ∼1 mm
in width and ∼70 μm in height. Characterization of this After curing and development, a second photoPDMS layer
double-layered microchannel device was performed by was spin coated on top of the first, and a larger feature was
flowing different colored dyes on each of the two levels. The aligned with the previous pattern. Figure 6(c) illustrates
overlapping reservoirs show blending of colors of the two dyes, a dual-level pattern made by overlapping square features,
demonstrating excellent channel definition as depicted in the which may be used in microscale cell culture applications.
photograph. Figure 6(d ) shows the cross-sectional view of these structures,
Dual-level devices have also been created using this with the width of the larger square being 1.5 mm and the
process. These structures were made by first patterning an smaller square being 700 μm. The film thickness of each
initial photoPDMS layer using the normal processing steps. layer was ∼20 μm.

7
J. Micromech. Microeng. 19 (2009) 045024
Figure 8. Microscope images of cell culture on (a) a conventional PDMS control surface, (b) an extracted photoPDMS surface and (c) a
photoPDMS surface. (d ) Absorbance measurement and cell viability for the three surfaces.
3.4. Thin-film applications
Patterned freestanding thin films for shadow masking
applications were also fabricated using the photoPDMS
process. To fabricate thin films, RTV615 formulation of
PDMS was used since it is more elastic than Sylgard 184.
Following patterning, the films were peeled from the substrate
by immersing in toluene for 2 min. The resulting flexible thin
films were used as shadow masks for patterning both planar
and non-planar surfaces.
Figure 7(a) illustrates a pattern of UV adhesive bumps
made using a thin film photoPDMS shadow mask ∼20 μm
thick, with through square pattern features ranging from
500 μm to 2 mm in size. A photoPDMS thin film was
also used as a shadow mask for patterning gold on a planar
(figure 8(b)) and a non-planar (figure 8(c)) surface. The
patterned gold squares had slightly rounded edges (figure 8(b),
inset) and approximately 5% reduction in the pattern size of
the 1.2 mm features was shown. This is most likely due
to poor contact between the shadow mask and the substrate
during the deposition process. Patterning on planar surfaces
is traditionally done by metal masking or by other well-
established methods such as physical vapor deposition of the
metal layer followed by patterning by photolithography and
chemical etching techniques. However, patterning on a non-
planar surface is not trivial and requires special processing
such as stereolithography, which is complex, time consuming
and requires specialized equipment. Using this simple process
8
P Jothimuthu et al
of directly patterning PDMS, the above-mentioned limitations
can be easily overcome. Also, this method can be potentially
used for patterning proteins and cells on a non-planar 3D
structure.
3.5. PhotoPDMS biocompatibility
PDMS is commonly used in a wide variety of biological
applications. It is thus important for an alternative
material to be tested for biocompatibility before it can
be considered a reasonable substitute. In this work,
biocompatibility of photoPDMS was assessed by culturing
NIH 3T3 fibroblast cells on the photoPDMS and comparing
with the conventional PDMS substrates used as controls. In
addition, two photoPDMS samples were prepared using the
extraction process to remove any un-reacted crosslinker and
photoinitiator.
Figure 8 illustrates bright field microscope images of the
three types of substrates following cell culture. It was found
that cells proliferated readily on both the conventional PDMS
(control) and the extracted photoPDMS surfaces. However,
little to no cells grew on the plain photoPDMS substrate.
Cell viability was calculated to be 76.1% for the extracted
photoPDMS and ∼0% for the plain photoPDMS (figure 8(d )).
This result suggests that benzophenone, even in very small
concentrations, is toxic to cells. Nevertheless, using the simple
extraction procedure following device fabrication, cytotoxicity
J. Micromech. Microeng. 19 (2009) 045024
due to benzophenone can be addressed, allowing photoPDMS
to be used for biological applications.
4. Conclusions
Photopatterning of PDMS using benzophenone
photosensitizer by UV irradiation was demonstrated in
this work. Thin films 20–80 μm in thickness with features
ranging from 100 μm to a few millimeters in size were
successfully demonstrated. This innovative photosensitive
polymer material can be used for rapid prototyping of
multi-layered microfluidic chips, thus introducing a simplified
fabrication process for complex microstructures. The
application of thin films as shadow masks for patterning
metal on planar and non-planar surfaces was also successfully
demonstrated. FTIR spectroscopy was used to elucidate
the photocrosslinking behavior of photoPDMS, and bio-
compatibility of photoPDMS was confirmed by cell culture,
although an extraction process is needed to remove any
un-reacted benzophenone. Overall, the photoPDMS process
eliminates the need for a master, permits processing under
ambient light conditions and is expected to enable rapid
prototyping of low-cost devices without clean room facilities,
envisaging its numerous applications in microfluidics and
MEMS fabrication.
Acknowledgments
The authors would like to thank Vidhyasagar Jayaseelan for
help with FTIR analysis and Girish Kumar for help with cell
cultures and biocompatibility testing (Department of Chemical
and Materials Engineering, University of Cincinnati). This
work was supported by the National Science Foundation (BES-
0428600 and DMR-0314760) and the University of Cincinnati
Institute for Nanoscale Science and Technology.
References
[1] Sia S K and Whitesides G M 2003 Microfluidic devices
fabricated in poly(dimethylsiloxane) for biological studies
Electrophoresis 243 563–76
[2] Duffy D C, McDonald J C, Schueller O J A and
Whitesides G M 1998 Rapid prototyping of microfluidic
systems in poly(dimethylsiloxane) Anal. Chem.
70 4974–84
[3] Piruska A, Nikcevic I, Lee S H, Ahn C, Heineman W R,
Limbach P A and Seliskar C J 2005 The autofluorescence of
plastic materials and chips measured under laser irradiation
Lab Chip 5 1348–54
[4] McDonald J C and Whitesides G M 2002
Poly(dimethylsiloxane) for fabricating microfluidic devices
Acc. Chem. Res. 35 491–9
[5] Lötters J C, Olthuis W, Veltink P H and Bergveld P 1997 The
mechanical properties of the rubber elastic polymer
polydimethylsiloxane for sensor applications J. Micromech.
Microeng. 7 145–7
[6] Almasri M, Zhang W, Kine A, Chan Y, LaRue J C and
Nelson R 2005 Tunable infrared filter based on elastic
polymer springs Proc. SPIE 5770 190–8
[7] Dow Corning R
WL-5000 series Datasheet, Dow Corning,
available at www.dowcorning.com
P Jothimuthu et al
[8] Harkness B R et al 2004 Photopatternable silicone
compositions for electronic packaging applications Proc.
SPIE 5376 517–24
[9] Desai P S, Taff M B and Voldman J 2008 A photopatternable
silicone for biological applications Langmuir 24 575–81
[10] Tsougeni K, Tserepi A and Gogolides E 2007 Photosensitive
poly(dimethylsiloxane) materials for microfluidic
applications Microelectron. Eng. 84 1104–8
[11] Huck W T S, Bowden N, Onck P, Pardoen T, Hutchinson J W
and Whitesides G M 2000 Ordering of spontaneously
formed buckles on planar surfaces Langmuir 16 3497–501
[12] Wang Y, Lai H H, Bachman M, Sims C E, Li G P and
Allbritton N L 2005 Covalent micropatterning of
poly(dimethylsiloxane) by photografting through a mask
Anal. Chem. 77 7539–46
[13] Bhagat A A S, Jothimuthu P and Papautsky I 2007
Photodefinable polydimethylsiloxane (PDMS) for rapid
lab-on-a-chip prototyping Lab Chip 7 1–7
[14] Muller U, Tempet H J and Neuegufeld N 1991
Photocrosslinking of silicones-5. Photo-induced
polymerization of silicone with pendant acrylate groups in
the presence of oxygen Eur. Polym. J. 27 621–5
[15] Muller U, Jockusch S and Timpe H J 1992 Photocrosslinking
of silicones: VI. Photocrosslinking kinetics of silicone
acrylates and methacrylates J. Polym. Sci. A 30 2755–64
[16] https://www.sigmaaldrich.com/catalog/search/ProductDetail/
SIAL/239852
[17] Lee J N, Park C and Whitesides G M 2003 Solvent
compatibility of poly(dimethylsiloxane)-based microfluidic
devices Anal. Chem. 75 6544–54
[18] Kumar G, Wang Y C, Co C and Ho C 2003 Spatially
controlled cell engineering on biomaterials using
polyelectrolytes Langmuir 19 10550–6
[19] Ciapetti G, Granchi D, Verri E, Savarino L, Cavedagna D and
Pizzoferrata A 1996 Application of a combination of neutral
red and amido black staining for rapid, reliable cytotoxicity
testing of biomaterials Biomaterials 17 1259–64
[20] Hsu C P 1997 Infrared spectroscopy Handbook of
Instrumental Techniques for Analytical Chemistry
(Englewood Cliffs, NJ: Prentice-Hall)
[21] Iojoiu C, Ropot M, Abadie M J M, Harabagiu V, Pinteala M
and Simionescu B C 2000 Synthesis and photocrosslinking
of benzyl acrylate substituted polydimethylsiloxanes Eur.
Polym. J. 36 2115–23
[22] Campbell D J, Beckman K J, Calderon C E, Doolan P W,
Moore R H, Ellis A B and Lisensky G C 1999 Replication
and compression of bulk and surface structures with
polydimethylsiloxane elastomer J. Chem. Educ. 75 537–41
[23] http://www.gelest.com/Library/
[24] http://www.dowcorning.com
[25] Weizmann C, Bergmann E and Hirshberg Y 1938
Photochemical interaction between ketones and alcohols
J. Am. Chem. Soc. 60 1530–3
[26] Hammond G S, Baker W P and Moore W M 1961 Mechanisms
of photoreactions in solution: I. Reduction of benzophenone
by toluene and cumene J. Am. Chem. Soc. 83 2795–9
[27] Hammond G S and Moore W M 1959 The role of a triplet state
in the photoreduction of benzophenone J. Am. Chem. Soc.
81 6334
[28] Moore W M, Hammond G S and Foss R P 1961 Mechanisms
of photoreactions in solutions: I. Reduction of
benzophenone by benzhydrol J. Am. Chem. Soc.
83 2789–94
[29] Chatgilialoglu C, Scaiano J C and Ingold K U 1982 Absolute
rate constants for the reactions of tert-butoxyl radicals and
some ketone triplets with silanes Organometallics 1 466–9
[30] Unger M A, Chou H, Thorsen T, Scherer A and Quake S R
2000 Monolithic microfabricated valves and pumps by
multilayer soft lithography Science 288 113–6