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Biomedical Microdevices 6:4, 341–347, 2004


C 2004 Kluwer Academic Publishers. Manufactured in The Netherlands.

Electrowetting (EW)-Based Valve Combined with Hydrophilic


Teflon Microfluidic Guidance in Controlling Continuous
Fluid Flow
Ji-Yen Cheng∗ and Lo-Chang Hsiung
Research Center for Applied Sciences, Academia Sinica, Taiwan
E-mail: jycheng@gate.sinica.edu.tw

Abstract. Electrowetting (EW)-based techniques have been widely 1999). Furthermore, a selective surface modification tech-
used in manipulating discrete liquid. However, few articles discussed nique was applied to silicon microfluidic channels to cre-
the controlling of continuous fluid flow by using EW-based tech-
ate surface-tension-confined microstructures for manipu-
niques. In this paper, an EW-based valve combined with plasma-
modified Teflon surface, which serves as a microfluidic guidance, lating of biomaterials (Li et al., 2001). In addition, the
in controlling continuous fluid flow has been demonstrated. The hydrophilic/hydrophobic patterns had been deposited on
plasma-modified Teflon surface is firstly demonstrated for confining the substrates by a commercialized plotter and a modified
continuous fluid flow. The EW-based microfluidic device possesses pen to form a path for liquid flow (Lam et al., 2002). The
the functions of a valve and a microchannel without complex moving
mass printing of the hydrophilic/hydrophobic patterns on
parts and grooved microchannels. The quantitative characteristics
of the EW-based valve are also studied. Propylene carbonate (PC) is the substrates provides an inexpensive and fast method for
firstly demonstrated as the working liquid in the EW-based device production of disposable diagnostic devices. Moreover, a
because of its applications in parallel oligonucleotide synthesis. It is series of pressure-sensitive microfluidic gates to regulate
found that lower valve actuation voltage reduces the deterioration liquid flow have been successfully fabricated (Zhao et al.,
of the valve and improves the valve stability.
2003). Photolithography in combination with photocleav-
Key Words. electrowetting, microvalve, microfluidic guidance, con- able SAMs, was used to generate hydrophilic/hydrophobic
tinuous fluid flow, propylene carbonate surface patterns for fabricating microfluidic gates. Aque-
ous liquids flow only along the hydrophilic path-
ways when the pressure is maintained below a critical
value.
1. Introduction
Teflon is a highly insulating polymer well known for
its potential in electronics, optic, biomaterial and bioelec-
Electrowetting (EW)-based techniques have been widely
tronics (Makohliso et al., 1998). However, its surface is
used in manipulating discrete liquid (Lee et al., 2002;
extremely hydrophobic, which makes it unsuitable for use
Paik et al., 2003; Velev et al., 2003). However, it has
in areas involving adhesive bonding, coating and pattern-
not been used to control continuous liquid flow until the
ing. Therefore, many efforts have focused on Teflon sur-
reversible EW-based switching of two-phase flows was
face modification, primarily by chemical treatments (Rye,
demonstrated (Huh et al., 2003). The EW-based valve con-
1988; Siperko et al., 1989) and plasma treatments (Tan
trols continuous liquid without complex moving parts. It
et al., 1993; Cho et al., 1994; Winter et al., 1995), for
could be beneficial for the development of a cell/particle
transforming the extremely hydrophobic Teflon surface
sorting system.
into “relative hydrophilic”. In this work, we report the
Traditionally, grooved microchannel is the major
use of plasma-modified Teflon surface, which is relatively
choice for directing microflow. However, surface tension
hydrophilic, as the surface-tension-confined microfluidic
guided fluid motions has been demonstrated in recent
guidance.
years (Kataoka and Troian, 1999; Li et al., 2001; Lam
Propylene carbonate (PC) has been used in the
et al., 2002; Zhao et al., 2003). Comparing to conven-
light-directed parallel oligonucleotide synthesis (LeProust
tional etching processes, the manufacturing process of
et al., 2000) and the inkjet-printing oligonucleotide syn-
surface-tension-confined microfluidic guidance is sim-
thesizer (Hughes et al., 2001). In order to extend PC’s
pler. Therefore, using surface-tension-confined microflu-
application in biomedical microdevice, it is worthwhile
idic guidance may reduce the fabrication cost of
to investigate its behavior in the EW-based microfluidic
microfluidic devices. Several demonstrations of surface-
device.
tension-confined microfluidic guidance were reported.
The hydrophobic octadecyltrichlorosilane (OTS) layer
had been patterned on a hydrophilic silicon dioxide sub-
∗ Corresponding
strate to direct microscopic flow (Kataoka and Troian, author.

341
342 Cheng and Hsiung

In this paper, the EW-based valve combined with the the microfluidic guidance beyond the valve as shown in
plasma-modified Teflon microfluidic guidance in control- Figures 2(b) and (c).
ling continuous fluid flow has been demonstrated. The
characteristics of the EW-based valve device are investi-
gated. PC is firstly demonstrated as the working liquid in 2.2. Fabrication of testing device
the EW-based device. To our knowledge, PC is the first The manufacturing process of the EW-based valve and
organic liquid used in EW study. the microfluidic guidance is schematically shown in Fig-
ure 3. The device consists of an unpatterned ITO glass
(243735X0, Merck) cover plate and a patterned ITO glass
2. Experiments substrate plate.
A photoresist layer is patterned on the ITO glass sub-
2.1. Testing system strate plate with inlet/outlet holes as shown in Figure 3(a).
The testing system is shown schematically in Figure 1. The ITO patterns of the ITO glass substrate plate are ob-
Liquid is injected into the testing device by a constant tained by wet etching as shown in Figure 3(b). The pho-
pressure pump. The constant pressure pump controls the toresist is then stripped away before 500 nm Teflon layer
hydraulic pressure in the chamber of testing device. A (AF1601S, Dupont) is spin-coated on the patterned ITO
0.01”-inner-diameter tubing (1527XL, UPCHURCH) is glass substrate plate as shown in Figure 3(c). Both the
used as the injection tube. The actuation AC voltage source cover plate and the substrate plate are dip-coated with flu-
for the EW-based valve is set at frequency of 2 KHz. The orosilane (16585, Lancaster) to improve the adhesion be-
liquid flow images are taken by a zoom lens (MLM3X-MP, tween Teflon and the glass plate before the Teflon coating.
computar) and a CCD video camera (Fire-i400, unibrain). Successively, a photoresist layer is patterned on the Teflon
The frames of interest are digitized and analyzed by a layer as Figure 3(d). The fluorosurfactant (FC4432, 3M)
computer. is blended with the photoresist to improve the wettability
Figure 2 shows the illustrations of the progress of the of the photoresist solution on the Teflon layer. An RIE
liquid motions in a microfluidic guidance during the elec- system (plasmalab 80 plus, OXFORD) is used to generate
trical actuation of the EW-based valve. After liquid is argon plasma (the chamber pressure of the RIE system
pumped into the chamber of the testing device, it flows is 100 mTorr. Argon gas flow rate is 20 sccm. Forward
along the hydrophilic plasma-modified Teflon microflu- power is 45 W. Treating time is 20 s.) to modify hydropho-
idic guidance. bic Teflon surface to be relatively hydrophilic as shown in
When liquid reaches the border of the hydrophobic EW- Figures 3(e) and (f). An unpatterned ITO glass cover plate
based valve, without applied voltage, the liquid is blocked is also spin-coated with a 500 nm-thick Teflon. Finally,
as shown in Figure 2(a). Successively, the electrical po- two plates are stacked together by a stainless fixture to
tential is applied to the EW-based valve, and then the hy- form an enclosed microfluidic guidance. A Teflon spacer
drophobic valve surface is transformed into hydrophilic. is used to define the gap size between the two ITO glass
The liquid then flows through the EW-based valve and plates, shown in Figure 3(g).

Fig. 1. System setup for the operation of the EW-based valve and microfluidic guidance.
Electrowetting (EW)-Based Valve Combined with Hydrophilic Teflon Microfluidic Guidance 343

Fig. 2. The progress of the liquid motion during the electrical actuation of the EW-based valve. Liquid flows along plasma-modified Teflon
microfluidic guidance and is blocked at the border of EW-based valve without electrical actuation (a). Liquid flows through EW-based valve after the
valve is electrically actuated (b). Liquid passes the EW-based valve with electrical actuation of the valve, and then flows along the plasma-modified
Teflon microfluidic guidance (c).

Fig. 3. Fabrication process of the EW-based valve and the hydrophilic microfluidic guidance.
344 Cheng and Hsiung

Table 1. Contact angle changes of propylene carbonate at various


actuation voltages in the parallel-plate systems

Symmetric Asymmetric
Voltage parallel-plate systema parallel-plate systemb

40 VAC ∼4◦ (top/bottom) ∼10◦ (top)


∼3◦ (bottom)
70 VAC ∼12◦ (top/bottom) ∼22◦ (top)
∼5◦ (bottom)
a Both top and bottom Teflon layers are unmodified.
b Top Teflon layer is unmodified, while bottom Teflon layer is modified.

in the inset of Figure 4. The top plate is a raw ITO glass


plate while the bottom plate is coated with an unmodified
or modified Teflon layer. The thickness of the unmodified
Teflon layer is 500 nm. The modified Teflon layer is ob-
Fig. 4. Electrowetting characteristics of the Teflon layer revealed by tained by plasma-etching of the unmodified Teflon layer.
PC contact angle change. Voltage is applied to both top and bottom
According to the data in Figure 4, the hydrophobicity dif-
ITO layers.
ference between the unmodified Teflon surface and the
modified Teflon surface are observed at various applied
2.3. Contact angle measurements voltages.
Contact angles are measured by images taken by the zoom The hydrophobicity difference between the unmodi-
lens and the CCD video camera. The uncertainty of the fied and the modified Teflon layer is caused by a new C1s
contact angle measurement system is about 3◦ . The aver- species (at 289.3 eV) presenting at the modified Teflon
age of three measurements is used for analysis. surface (Clark and Dilks, 1979; Kaplan and Dilk, 1984;
Occhiello et al., 1989; Herrera-Fierro et al., 1993; Tan
et al., 1993; Cho et al., 1994). The possible surface groups
3. Results and Discussions of the new C1s species are O C O, O C O, C O and
CF-CF2 .
The hydrophobicity differences between the unmodified Figure 5 and Table 1 show the contact angle of propy-
Teflon surface and the modified Teflon surface is shown lene carbonate (PC) in the parallel-plate systems, where
in Figure 4. The contact angles are observed from the two Teflon-coated ITO glass plates are stacked together
side of two ITO glass plates that has 250 µm gap, shown with a thin gap.

Fig. 5. Contact angle changes of PC in the symmetric parallel-plate system (a) and asymmetric parallel-plate system (b). The images are taken from
the side of the system. Voltage is applied to both top and bottom ITO layers.
Electrowetting (EW)-Based Valve Combined with Hydrophilic Teflon Microfluidic Guidance 345

In the symmetric parallel-plate system (Figure 5(a)), bottom plate and that across the dielectric layer on the
PC is introduced into the 250 µm gap between the two top plate, if the electric resistance of the testing droplet is
ITO glass plates that have same Teflon surface properties. negligible comparing to that of the dielectric layers (Cho
Both the top and the bottom ITO plates are coated with et al., 2003). Furthermore, the contact angle variation on
500 nm unmodified Teflon layer. The contact angles on the dielectrics surface is directly related to the actual volt-
both surfaces change into ∼4◦ (from ∼86◦ to ∼82◦ ) when age drop across the dielectric layer, when the contact angle
40 VAC is applied. The contact angle variation increases is not in the saturation state (Cho et al., 2003).
to ∼12◦ (from ∼86◦ to ∼74◦ ) when 70 VAC is applied. The resistivity of PC and of Teflon are 2.4 M-cm and
In the asymmetric parallel-plate system (Figure 5(b)), >1012 M-cm (Janting et al., 2000), respectively. The
both the top and the bottom ITO plates are coated with resistance of PC is much smaller than that of Teflon layer
500 nm Teflon layer. The Teflon layer at the bottom is in the parallel-plate systems (Figure 5). Therefore, the
plasma-modified after Teflon coating, while the Teflon resistance of PC can be neglected. Furthermore, according
layer on the top plate is not modified. Without applied to the data in Figure 4, the PC contact angles in Figure 5
voltage, the contact angle difference between the modified are not in the saturation state.
Teflon surface (bottom) and the unmodified Teflon surface In the parallel-plate systems (Figure 5), when 70 VAC
(top) is ∼22◦ (∼69◦ vs. ∼91◦ ). Moreover, the contact an- is applied, the contact angle variation on the unmodified
gle on the unmodified Teflon surface in the asymmetric Teflon surface in the asymmetric parallel-plate system
parallel-plate system (∼91◦ ) is larger than that in the sym- is ∼10◦ larger than that in symmetric parallel-plate sys-
metric parallel-plate system (∼86◦ ). Considering that the tem (∼22◦ vs. ∼12◦ ). This suggests that the voltage drop
uncertainty of the measurement system is about 3◦ , the across the unmodified Teflon in the asymmetric parallel-
contact angle difference can not be over-emphasized at plate system is larger than that across the unmodified
this stage. Teflon in the symmetric parallel-plate system. It is pos-
When 40 VAC is applied to the asymmetric parallel- sible that the argon plasma modification thins the thick-
plate system, the contact angle variation on the modified ness of the modified Teflon layer, so that the resistance
Teflon surface is only ∼3◦ (from ∼69◦ to ∼66◦ ). How- of modified Teflon layer decreases. This in turn decreases
ever, the contact angle on the unmodified Teflon surface the voltage drop across the modified Teflon layer. In the
changes into ∼10◦ (from ∼91◦ to ∼81◦ ). The contact an- meanwhile, the voltage drop across the unmodified Teflon
gle variation on the modified Teflon surface and that on the layer increases and results in larger contact angle change.
unmodified Teflon surface are asymmetric. Successively, For the purpose of microfluidic application, the results
when 70 VAC is applied, it is found that the asymmet- from Figure 5 are helpful in understanding the operation
ric contact angle variation is more prominent (∼5◦ for mechanism of the EW-based valve. Figure 6 shows an
the modified Teflon surface and ∼22◦ for the unmodified EW-based valve combined with a plasma-modified Teflon
Teflon surface). guidance for controlling continuous liquid flow.
The total voltage drop in the parallel-plate system con- In Figure 6, the gap size between the substrate and
sists of the voltage drop across the dielectric layer on the cover plates is 20 µm. The injection pressure of the

Fig. 6. The observed liquid motion during the actuation of the EW-based valve. Liquid flows through the modified Teflon guidance and stops at the
border of EW-based valve without electrical actuation (a). Liquid flows through the EW-based valve (b), and then passes it after 40 V AC is applied to
actuate the valve (c). Liquid flow fills both the valve and the guidance (d).
346 Cheng and Hsiung

PC is about 46 pa. PC flows through the 750 µm-wide flow rate in the 40 VAC actuation is smaller while the flow
plasma-modified Teflon guidance and stops at the bor- rate reduces to ∼2,000 µm/sec. Moreover, the valve is ca-
der of EW-based valve as shown in Figure 6(a). The sur- pable of blocking the PC flow after the valve is repeatedly
face hydrophobicity difference between the guidance and actuated for 1000 times. These results reveal that the lower
the valve is large enough to block the PC flow. Succes- actuation voltage can decrease the valve deterioration and
sively, 40 VAC is applied to the electrode, which is be- improve the valve stability.
neath the valve and the guidance, to actuate the valve. A wider valve (500 µm-wide, 150 µm-long) is then
The hydrophobic valve surface is thus transformed into tested to study the effect of the valve size on the flow
hydrophilic. The PC then flows through the 150 µm-long rate. The 750 µm-wide guidance is used to confine the
EW-based valve as shown in Figures 6(b) and (c). Finally, flow ahead of the valve. The actuation voltage is 40 VAC .
the PC flow fills both the valve and the guidance as shown As shown in Figure 7, no obvious flow rate differences
in Figure 6(d). From the result in Figure 6, the capability are found comparing to the flow rate in 250 µm-wide
of the EW-based valve in controlling continuous liquid valve (actuated in 40 VAC ). Nevertheless, the valve is still
without moving parts is verified. Concerning the long- operational after 1000 time actuations. In summary, no
term stability of the flow guidance, the hydrophobicity obvious effect of the valve size on the flow rate is observed.
difference between the valve and the flow guidance is still The response time of the EW valve can be estimated by
prominent after the devices were fabricated for 6 months. the PC flow rate acrossing the valve length. The response
After qualitative descriptions of the working mecha- time is ∼30 ms in 70 VAC actuation and ∼60 ms in 40 VAC
nism of the device, the quantitative characteristics of the actuation.
EW-based valve have also been studied by observing the
PC flow rates across the valve as shown in Figure 7. The
liquid flow rate through a 250 µm-wide and 150 µm-long 4. Conclusions
valve is measured. A 500 µm-wide microfluidic guid-
ance is used for flow guiding ahead of the valve. When The EW-based valve combined with the plasma-modified
70 VAC is applied to actuate the valve, the flow rate is Teflon surface, which serves as the microfluidic guidance,
about 5,000 µm/sec although the deviations of the flow in controlling continuous fluid flow is demonstrated. This
rate are quite large during valve actuations. Furthermore, paper is the first demonstration on the use of plasma-
after the valve is actuated for 125 times, the un-activated modified Teflon surface for confining continuous fluid
valve can no longer block the PC flow. This indicates that flow. The EW-based microfluidic device possesses the
the hydrophobic valve surface has been transformed into functions of a valve and a microchannel without com-
hydrophilic permanently. This also reveals that the valve plex moving parts and grooved microchannels. Propylene
functionality is deteriorated after repeated actuations in carbonate (PC) is firstly used as the working liquid in
70 VAC . It is speculated that surface damage occurs in the the EW-based device because of its capability in oligonu-
valve area. cleotide synthesis. This work is the first example of EW
To prolong the functionality of the valve, lower actua- effect of organic liquid. It is found that the argon plasma
tion voltage (40 VAC ) is tested. Comparing to the devia- modification thins the plasma-modified Teflon layer, so
tions of flow rate in the 70 VAC actuation, the deviations of that the resistance of plasma-modified Teflon layer de-
creases. Moreover, lower valve actuation voltage reduces
the deterioration of the valve and improves the valve sta-
bility. The valve response time is estimated to be ∼ 30 ms
when 70 VAC actuation voltage is used. This work may
provide an alternative approach for the development of
microfluidic systems.

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