Microelectronic Engineering 83 (2006) 12771279

www.elsevier.com/locate/mee

Formation of more stable hydrophilic surfaces of PDMS

by plasma and chemical treatments
Dhananjay Bodas, Chantal Khan-Malek

FEMTO-ST, Dept LPMO CNRS UMR 6174, 32 Avenue de lObservatoire, Besancon Cedex 25044, France
Available online 23 February 2006

Abstract
In the present work hydrophilic stability of Sylgard 184 poly(dimethyl siloxane) (PDMS) was studied with the objective to create more
stable hydrophilic surfaces. The surface modication of PDMS was carried out by conventional (oxygen plasma) and unconventional
plasma modication (2-step modication using oxygen and C2F6) processes and also by chemical grafting using oxygen plasma polymerization of 2-hydroxyethyl methacrylate (HEMA). The hydrophilic stability of the modied surfaces was monitored as a function of time
elapsed after treatment and quantied. The surfaces were characterized using static contact angle measurements and Attenuated Total
Reection Fourier Transform Infrared Spectroscopy (ATR-FTIR).
2006 Elsevier B.V. All rights reserved.
Keywords: PDMS; Oxygen plasma treatment; 2-Step modication; HEMA grafting; Hydrophilic stability

1. Introduction
Poly(dimethyl siloxane) (PDMS) elastomer is the most
widely and one of the most versatile material used in the
construction of microuidic devices, in particular for rapid
prototyping. One of the reasons for the popularity of PDMS
is the particularly straightforward manufacturing methods.
PDMS has as essential characteristics that it is elastomeric,
can be optically transparent, chemically inert, permeable to
gases and amenable to fabrication via rapid prototyping.
However, in spite of the many advantages of PDMS, the
surface of PDMS is naturally hydrophobic and cannot be
used as it is for a variety of applications. A number of eorts
have been made to modify the surface of PDMS micro channels, in order to enhance hydrophilicity and EOF which
limit its applicability for analytical devices [1].
It has long been recognized that in order to modify the
surface properties of PDMS, various techniques can be utilized that involve, physical or chemical treatments or a combination of both [24]. Particularly oxygen plasma has been
widely used to modify the surfaces of PDMS (e.g., [5]).
*

Corresponding author. Tel.: +33 381 853 999; fax: +33 381 853 998.
E-mail address: chantal.khan-malek@lpmo.edu (C. Khan-Malek).

0167-9317/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.mee.2006.01.195

However, the characteristics of oxygen-plasma-modied

PDMS surfaces gradually change during aging and the surface recovers its hydrophobicity after a short time as has
been observed by some groups [6]. The quick hydrophobic
recovery of PDMS surfaces associated with most of the currently employed treatments is one of the current issues limiting the use of PDMS for microuidic devices.
To overcome the problem of quick hydrophobic recovery, work on use of 2-step modication has been carried
out by Gilmor et al., [7] using various gases, e.g., SiCl4,
CCl4, etc., after the oxygen plasma treatment. Also deposition of 2-hydroxyethyl methacrylate (HEMA) lm instead
of gases has been employed after the oxygen plasma treatment to stabilize the hydrophilicity by Choi and Yang [8].
In the present work, three methods were investigated to
carry out the surface modication of PDMS: (1) an oxygen
plasma treatment; (2) a novel 2-step plasma modication
using O2 and C2F6; and (3) surface grafting using HEMA
and oxygen plasma [8].
2. Experimental section
A 2-component PDMS from Dow Corning (SYLGARD
184) with a 10:1 base to curing agent mixing ratio was used.

D. Bodas, C. Khan-Malek / Microelectronic Engineering 83 (2006) 12771279

3. Results and discussion

Fig. 1 shows the ATR-FTIR spectra of pristine PDMS
and PDMS modied with oxygen, O2 + C2F6 and HEMA.
The spectra for all treated samples were obtained within
5 min of the modication process. Comparison of the pristine and modied PDMS samples with their spectral values
and corresponding group assignments are shown in Table
1. The ATR-FTIR data show characteristic peaks depending on the treatment used which conrms the surface mod-

(d)

1710

1163

3363

1841

(c)

(b)
3413

(a)
692

1404

2958

The 2-components were thoroughly mixed and degassed in

vacuo to remove bubbles. The mixture was cured at a
100 C temperature for 1 h. Three dierent processes were
explored. All plasma treatments were conducted in a Plassys reactive ion etching (RIE) system using an RF power
supply of 13.56 MHz frequency for the plasma excitation.
For oxygen plasma modication, pressure of the system
and oxygen ow rate was kept constant at 100 lbar and
20 sccm, respectively. RF plasma power was varied from
50 to 150 W and also the time of plasma exposure (treatment time) was varied from 1 to 15 min.
The second process corresponds to a novel 2-step modication carried out using a combination of O2 and C2F6.
The rst step consisted in the formation of functionalized
silanol groups on the PDMS surface using pure oxygen
plasma with a constant system pressure and oxygen ow
rate of 100 lbar and 20 sccm, respectively. RF power of
100 W was used for 30 s for the modication. In the next
step, a 3:1 mixture of C2F6 and oxygen was used at a constant pressure of 60 lbar. RF power was varied from 100
to150 W with a time variation of 515 min.
The third process involved a monomer HEMA, commercially available from Aldrich Chemicals. The modication was conducted in several steps. Firstly, oxygen
modication was carried out at a system pressure of
100 lbar and ow rate 20 sccm, and an RF power of
100 W was used for 30 s for the modication. HEMA
was then spin coated onto the oxygen modied PDMS surface at a spin speed of 1500 rpm for 15 s (thickness
600 nm). The HEMA-coated PDMS was nally treated
with oxygen plasma at a constant pressure of 100 lbar at
an oxygen ow rate of 20 sccm. RF power was varied from
50 to 100 W with a time variation of 15 min.
ATR-FTIR spectra were recorded on a Nicolet 5-PC
FTIR spectrometer to assess the changes on the surface
after dierent modications. The FTIR spectra were
recorded within 5 min of surface modication. All the samples were also characterized for hydrophilic stability using
contact angle measurements. In our experiments, a manual
contact angle measurement setup was used having a error
of 2. Deionized water and diiodomethane (Aldrich
Chemicals) droplets (2 lL) were delivered on the PDMS
surface by a calibrated syringe. The static contact angles
were measured before and after modication, as well as a
function of time in the time interval of 012 h, every
5 min at the beginning and every hour thereafter.

Transmission (%)

1278

1256
1 015
4000

3500

3000

2500

2000

1500

1000

7 90
500

Wave Number (cm-1)

Fig. 1. ATR-FTIR spectra for: (a) pristine PDMS, (b) O2 plasma

modied, (c) 2-step O2 + C2F6 plasma modied, and (d) HEMA modied
PDMS.

Table 1
Comparison of ATR-FTIR spectral values of PDMS with their group
assignments before and after modication
Assignments

Pristine
PDMS

Oxygen
modication

2-Step
modication

HEMA
modication

H2O
OH
Methyl CH
CF
C@O
CH3 asymmetric
deform
CH3 symmetric
deform
Primary alcohol
SiOSi
asymmetric
deform
SiC
Si(CH3)2
Surface

3413

2964

1408

2959

1408

2959
1841

1408

3363
2959

1710
1408

1259

1259

1259

1259

1015

1015

1015

1163
1015

851
790
691

851
785
691

851
790
691

851
790
691

ication in addition to the regular peaks of PDMS [710].

The presence of a 3413 cm 1 peak corresponding to the
broad absorption band of OH bond of water molecules
indicates changes in the surface characteristics of PDMS
after oxygen plasma treatment. These H2O molecules are
adsorbed by the silanol interface of the surface of PDMS
as a thin layer as a consequence of plasma treatment.
The sharp peak corresponding to OH group of silanol
moeties expected at around 3750 cm 1 [11] has not been
observed in the present study because its intensity is order
of magnitudes lower. A peak at 1841 cm 1 corresponding
to CF is observed for the 2-step modied surface using
C2F6 indicative of modication. Similarly a peak at 3363,

D. Bodas, C. Khan-Malek / Microelectronic Engineering 83 (2006) 12771279

4. Conclusion

Water Contact angle ()

O2
90

O2+C2F6

80

HEMA

70
60
50
40
30
20
10
0
0

10

11

1279

12 13

Aging time (hour)

Fig. 2. Graph of water contact angle vs. aging time for PDMS modied
with oxygen plasma, O2 + C2F6 plasma and HEMA.

1710, and 1163 cm 1 observed in case of HEMA, corresponds to OH, C@O, and primary alcohol group respectively, which are characteristic peaks of HEMA.
The pristine PDMS shows its hydrophobic behavior and
poor wettability with a 100112 water drop contact angle.
After O2 modication, the contact angle decreases with
plasma power and treatment time. Maximum hydrophilic
stability without cracking the PDMS surface was achieved
at 150 W RF power for 15 min. For the 100 W power contact angle increased rapidly within 60 min and recovered
within 2 days. Similar trend is observed for the
O2 + C2F6 modication. There is negligible decrease in
contact angle with increase in power. At powers beyond
150 W and longer time intervals the lm showed change
in color and decrease in transparency as a silica-like layer
was formed. Best results in terms of hydrophilic stability
were obtained for 150 W plasma power for 1 min. The
HEMA modied samples showed increase in hydrophilic
stability with increase in RF power. Increasing power
beyond 100 W had little eect on the hydrophilic stability.
Fig. 2 shows the best results in terms hydrophilic stability for the three PDMS treatments. PDMS treated with
oxygen plasma recovers from hydrophilicity to hydrophobicity faster compared to the O2 + C2F6 and HEMA modied PDMS. Recovery in case of oxygen plasma modied
sample might be due to the migration of low molecular
weight species from the surface to the bulk of PDMS.
The PDMS modied with HEMA showed the lowest contact angle and kept the hydrophilicity over 10 days. The
wettability in case of HEMA may be attributed to carbonyl
groups also seen in the ATR-FTIR spectrum. The
O2 + C2F6-modied PDMS did not show much lower contact angle but its hydrophilic stability, of over a week, was
much higher compared to the O2 plasma treated sample.
This high stability can be attributed to stable hydrophilic
CF groups on the surface.

The surface modication of Sylgard 184 PDMS was

studied in terms of hydrophilic stability using three dierent modication processes. Oxygen modication shows
hydrophilic stability in the range of 2 days at the power
of 150 W and exposure time of 15 min. A novel 2-step
modication using O2 + C2F6 shows a good hydrophilic
stability in the range of a week (increase in contact angle
from 64 to 85). The chemical modication using HEMA
proved to be the most ecient in terms of hydrophilic
stability with surfaces stable over 10 days (increase in contact angle from 7 to 44). The study shows in particular
the possibility of grafting long-term stable hydrophilic
functional groups onto PDMS using oxygen plasma treatment of HEMA. These results may nd use in the construction of microuidic devices with PDMS as it
increases the time available for sealing, confers superior
wetting properties to the microchannels that facilitate
channel lling, and may prevent bio-fouling. The sealing
of channels using HEMA/O2 plasma treated PDMS is
underway.
Acknowledgments
Dr. M. Fromm (LMN, Besancon) and Dr. J. Takadoum
(ENSMM, Besancon) are respectively thanked for the help
with recording FTIR spectra and for lending the contact
angle measurement apparatus.The work was performed
within the framework of the 4M Network of Excellence
Multi Material Micro Manufacture: Technology and
Applications (4M) (EC funding FP6-500274-1; www.4mnet.org).
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