Thin Solid Films 520 (2012) 2293–2300

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Thin Solid Films

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Fluoropolymers coatings on polydimethylsiloxane for retarding swelling in toluene

Valentina Arima ⁎, Monica Bianco 1, Antonella Zacheo 1, Alessandra Zizzari, Elisabetta Perrone,
Lucia Marra, Ross Rinaldi
National Nanotechnology Laboratory (CNR-Istituto di Nanoscienze), Distretto Tecnologico ISUFI, Università del Salento, via Arnesano, 73100 Lecce, Italy

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

Article history: Microfluidic architectures for lab-on-a-chip applications are often made of polydimethylsiloxane (PDMS), a
Received 20 September 2010 polymeric material easy to use, cheap and widely compatible with biomaterials but with a low stability to-
Received in revised form 23 September 2011 wards organic solvents. Its chemical resistance can be increased by covering the channel walls with relatively
Accepted 24 September 2011
stable films. In this perspective, fluoropolymers are a class of interesting materials due to their inertness
Available online 2 October 2011
properties. In this work we prepared coatings of fluoropolymers on PDMS and we characterized them by
Keywords:
Quartz Crystal Microbalance, Atomic Force Microscopy, and contact angle. The swelling tests performed
PDMS gave a proof of their application for increasing PDMS stability towards organic solvents. The incorporation
Fluoropolymers of fluoropolymers into PDMS microchannels was also demonstrated.
Teflon © 2011 Elsevier B.V. All rights reserved.
Microfluidics

1. Introduction perfluoropolyether has been already synthesized [16] and incorporated

Polydimethylsiloxane (PDMS) is a polymeric material widely used
for fabrication of a variety of microfluidic devices since it is inexpen-
sive and allows one to stamp sophisticated channel designs with high
fidelity using reusable molds. Despite these advantages, PDMS chan-
nels have several limitations due to the high permeability to liquids
and gases [1–5] and to the significant swelling into the most common
organic solvents [4,5]. The limited chemical compatibility of PDMS is,
therefore, the major problem that reduces its applications to micro-
fluidic technology for organic synthesis [5]. This drawback has moti-
vated the development of coatings able to decrease the permeability
of PDMS to liquids or gases and retard the adsorption process of che-
micals acting on the superficial wettability properties [6].
Many surface modification strategies have been employed includ-
ing sol–gel technology, [7,8] modification with borosilicate glass, [9–
11] and polymer grafting after surface activation by plasma bombard-
ment [9–11].
Oxygen or ammonia plasma treatments are usually reliable, repro-
ducible, and relatively inexpensive methods for activating PDMS
allowing the introduction of many functional groups, but their effect
is only temporary [9–11]. The immediate reactive conversion of the
functional groups formed by plasma treatment with polymers in-
duces more durable surface modifications [12–15].
Among the possible polymers that could be used to coat PDMS,
fluoropolymers seem to be very intriguing because of their properties
of inertness to most solvents and chemicals. Photocurable
⁎ Corresponding author. Tel.: + 39 0832 298218; fax: + 39 0832 298230.
E-mail address: valentina.arima@unisalento.it (V. Arima).
1
These authors contributed equally to this work.
into PDMS architectures [17], significantly improving their solvent-re-
sistance. Another approach is to coat PDMS channels with thin films
of amorphous copolymers of polytetrafluoroethylene (PTFE) and 2,2-
bis-(trifluoromethyl)-4,5-difluoro-1,3-dioxole. These polymers, generi-
cally called Teflon AF, have been already demonstrated to inhibit the
solvent adsorption making PDMS molds more manageable for imprint-
ing [18,19]. However, Teflon AF layers do not adhere well to PDMS be-
cause of their very low surface energy, which also leads to the desired
poor wetting properties. A simple method to increase Teflon adhesion
on glass and silicon relies on spin-coating deposition of perfluorooctyl-
triethoxysilane [20].
Nevertheless, before the realization of functional Teflon-shielded
PDMS microfluidic networks, it is important to fully characterize
PDMS/Teflon AF interfaces and to prevent undesired effects due to struc-
tural re-organization of the polymeric matrices. Some studies [21–24]
aimed at characterizing Teflon coated PDMS surfaces have been per-
formed but they often appear fragmentary in the perspective of produc-
ing stable materials for microfluidic applications, being more focused on
the hydrophobic properties of these layers [21,22,24] rather than on
their solvent-repellent behavior and their structural stability [23].
In this work, aiming at the incorporation of Teflon AF coatings in low
cost PDMS devices to reduce their solvent adsorption, we produced and
studied by Quartz Crystal Microbalance (QCM), Atomic Force Microsco-
py (AFM) and contact angle, a number of Teflon coatings on PDMS. After
evaluating their thicknesses, their morphological and wettability prop-
erties, their capability of retarding toluene adsorptions, their stability
over the time and the adhesion properties, we defined the thickness
needed to produce stable and reproducible coatings able to significantly
reduce solvent adsorption. Finally, a method to introduce coatings with
the desired thickness into PDMS microreactors is described.

0040-6090/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2011.09.063
2294 V. Arima et al. / Thin Solid Films 520 (2012) 2293–2300
2. Experimental details
2.1. Fabrication of PDMS molds
Sylgard-184, a two-part poly(dimethylsiloxane) (PDMS) elasto-
mer, was purchased from Dow Corning (USA). PDMS substrates
were fabricated by mixing base and curing agent in 10:1 weight
ratio. The base and curing agent were mixed and degassed until all
air was removed in a sonicator. Defined amounts of prepolymer
were poured onto Petri dishes and polymerized at 140 °C for
15 min. Many samples of dimensions 1 × 1 cm 2 and 0.3 mm thick
were cut for performing AFM and contact angle experiments.
2.2. Fabrication of Teflon coated PDMS molds
A number of PDMS samples were produced and different functionali-
zation procedures were developed in order to prepare Teflon coated sam-
ples and explain the origin of their main morphologic features (see Fig. 1).
2.2.1. PDMSpl samples
After their preparation, PDMS molds were introduced into a com-
mercial atmospheric plasma generator (Diener, Pico, low pressure
plasma system) to induce oxygen plasma (at 50 W for 80 s), therefore
modifying the PDMS surface properties.
2.2.2. PDMSfs samples
Soon after plasma activation, some PDMSpl substrates were treated
with pure 1H,1H,2H,2H-Perfluorooctyltriethoxysilane (Aldrich, 98%).
The silane was deposited by spin coating and annealed at 90 °C for
10 min.
2.2.3. PDMStf samples
Soon after silane treatment, 0.2 wt.%, 1% or 2 wt.% solutions of an
amorphous fluoropolymer, Poly[4,5-difluoro-2,2-bis(trifluoromethyl)-
1,3-dioxole-co-tetrafluoroethylene] (PTFE AF 1600, dioxole 65 mol%, Al-
drich) in Fluorinert FC 70 (Sigma-Aldrich) were spun-coated at 1000,
1500, 2000 and 4000 RPM for 60 s thus generating coatings of different
thicknesses on the PDMSfs surfaces. The samples produced are named
PDMS0.2tf2000, PDMS1tf1000, PDMS1tf2000, PDMS1tf4000, PDMS2tf1000,
PDMS2tf1500, PDMS2tf2000, and PDMS2tf4000.
Finally Teflon coatings were processed using the following proce-
dure: 1) bake at 100 °C for 10 min, 2) bake at 150 °C for 10 min and 3)
bake at 300 °C for 15 min.
2.2.4. PDMSan samples
In order to understand the origin of the morphology of PDMStf
samples observed by AFM (Section 3.4), PDMSan samples were pro-
duced by annealing of PDMSpl samples at a) 90 °C for 10 min, b)
100 °C for 10 min, c) 150 °C for 10 min and d) 300 °C for 15 min.
Fig. 1. Functionalization scheme of PDMS samples. Some PDMS samples were treated sequentially with: (a) oxygen plasma producing PDMSpl samples; (b) 1H,1H,2H,2H-Perfluor-
ooctyltriethoxysilane resulting in PDMSfs samples; (c) with Poly[4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole-co-tetrafluoroethylene] producing PDMStf samples.
2.3. QCM measurements for thickness estimation
A sensor crystal with Au surface (Q-sense E1, Q-Sense, Göteborg,
Sweden) was coated with a thin layer of PDMS polymer. The crystal
was initially cleaned by oxygen plasma treatment, then Sylgard-184 di-
luted in toluene (0.5 wt.%) was spun-coated on the crystal and allowed
to polymerize at 140 °C for 15 min. After determining PDMS thickness
in air, silane and Teflon were deposited according to the procedure
reported above for samples PDMSfs and PDMStf. Their thicknesses
were evaluated by a comparison between bare PDMS, PDMSfs and
PDMStf samples by QCM in air. The reported thickness values are an av-
erage over three (3, 5, 7) overtones of each measurement and the errors
are calculated as standard deviation.
2.4. Atomic Force Microscopy measurements
Morphological features of PDMS samples were characterized by
AFM in tapping mode (Nanoscope IIIa, Veeco, USA) using silicon can-
tilevers (model RFESPA) with a tip radius of 8 nm and a resonance
frequency of 70–85 kHz. The reported values of crack height, width,
peak-to-peak distance as well as wave amplitude, height and distance
between adjacent waves are an average over tens of measurements
acquired on different areas of the samples. The errors were calculated
as standard deviations from the medium value.
2.5. Contact angle measurements
Static water contact angles were measured using the sessile drop
method and a CAM 200 (KSV Instruments Ltd., Finland) instrument.
The presented results correspond to an average of measurements
performed onto many areas of the samples. The errors are calculated
as standard deviations from the medium value.
2.6. Swelling behavior in toluene
To obtain the swelling ratio in terms of weight, PDMS thick molds
were put in contact for 10 min with a silicon substrate where some
drops of toluene were dispensed. The samples were subsequently
dried at room temperature for 40 min and then their weights measured.
This experimental set up allows only the PDMS surface to get in contact
with the solvent. The reported swelling ratios are an average over 5
samples and the errors are calculated as standard deviations.
2.7. Adhesion/erosion tests with QCM
QCM was also used to study the adhesion of Teflon on PDMS. A
layer of PDMS2tf2000 was deposited onto a QCM crystal covered
with a thin layer of PDMS and inserted into the QCM flow chamber.
The thickness of the layer was initially evaluated in air. Then water
 V. Arima et al. / Thin Solid Films 520 (2012) 2293–2300
was injected at 400 μl/min for 2 h. After drying the samples, the thick-
ness measurement in air was repeated. The same procedure was per-
formed washing the crystal at 800 μl/min and at 1200 μl/min for 2 h.
Other experiments were carried out to verify if the treatment with
toluene weakens the interaction between PDMS and Teflon. After
evaluating mass weight in air, the QCM crystal covered with a layer
of PDMS2tf2000 was put in contact with toluene as described in Sec-
tion 2.6. After the swelling treatment, it was inserted into the QCM
cell and sample mass evaluated in air. Then water was injected at
400 μl/min for 2 h. After drying the samples, the mass measurement
in air was repeated. The same procedure was performed washing
the crystal at 800 μl/min and at 1200 μl/min for 2 h.
2.8. Device fabrication and characterization
PDMS devices consist of two moieties: a relatively thin one con-
taining microchannels and another one, thicker than the previous
one, with punched holes. The microchannels have a serpentine geom-
etry and are 300 μm wide and 50 μm deep. The PDMS chips were fab-
ricated using an elastomer PDMS kit (Sylgard-184, Dow Corning,
USA). The Sylgard-184 mixtures were prepared at a mass ratio of
10:1 and poured on a SU-8 mold fabricated by optical lithography. A
layer of 50 μm was deposited on a silicon substrate and cured at
65 °C for 3 min and 95 °C for 6 min. After the PDMS pouring on the
mold, the PDMS mixture was subsequently cured at 140 °C for
15 min to cross-link the polymers. Another flat PDMS mold of 5 mm
thickness was produced with the same procedure and 2 holes were
punched with biopsy punchers of 2 mm diameter to be used as inlets
and outlet.
A commercial atmospheric plasma generator was employed to in-
duce oxygen plasma and consequently modify the PDMS surface
properties.
The PDMS microchannels and the flat cover were then sealed by
sticking the two plasma-treated substrates together.
After preparation of the PDMS device, silane/Teflon coatings were
introduced by injection via syringe pumps. In more detail, soon after
oxygen plasma treatment and sealing, holes were glued to PEEK/
fused silica tubings (PEEKsil tubings from IDEX 1/32 in. O.D., 25 μm
I.D.) and connected to a syringe pump (Kd Scientific, Model 200
Series).
Pure perfluorooctyltriethoxysilane was injected into the PDMS
microchannels at 10 μl/min flow rate. The surface chemical modifica-
tion was achieved after removing the residual silane solution from
the microchannels with the syringe pumps. This injection was fol-
lowed by a bake at 90 °C for 10 min. Subsequently a solution com-
posed of Teflon AF (0.2 wt.%) and fluorinert FC70 (99.8 wt.%) was
introduced into the silane functionalized microchannels (as described
above) and three consecutive bakes at a) 100 °C for 10 min, b) 150 °C
for 10 min and c) 250 °C for 15 min were carried out. The presence of
the coating inside the microchannels was verified by Scanning Elec-
tron Microscopy (SEM) (Raith 150) after cutting the device in cross
and evaporating a Au layer of 5 nm.
3. Results and discussion
The functionalization process used for the preparation of PDMStf
samples is summarized in Fig. 1. PDMS coatings were prepared after
activation of the surface by oxygen plasma (PDMSpl samples). This
process allows the introduction of hydroxyl groups on the PDMS sur-
face to be used for anchoring the perfluorinated silanes (PDMSfs sam-
ples). In PDMStf samples, among the perfluorinated side chain of the
silane and the fluoropolymer, fluorophilic interactions take place.
They are believed to be strong enough to increase the adhesion of
the Teflon layer on PDMS given that fluorophilic interactions have
been demonstrated to drive the self-assembly of block copolymer as
well as phase segregation phenomena [25–27]. Because of its
2295
chemical inertness, Teflon AF has a limited solubility also in fluorinat-
ed solvents; therefore the most concentrated solution obtained by
dissolving under stirring Teflon AF beads in fluorinert was 2 wt.%
and the whole procedure lasted some days at 50 °C. Two more diluted
solutions were also prepared (0.2 wt.% and 1 wt.%) and depositions of
the three solutions were performed at different spinning rates (1000,
1500, 2000, 4000 RPM) with the aim of producing thick, reproducible
and stable coatings.
3.1. Surface wettability modifications during functionalization
We initially follow the modifications that occurred at macroscale
on such materials after steps a, b and c of Fig. 1 (Table 1) using contact
angle measurements. As expected, the contact angle value, typical of
hydrophobic no-treated PDMS, is promptly decreased by plasma
treatment and then gradually increased after perfluorooctyltriethoxy-
silane and Teflon AF deposition. On PDMSfs samples, perfluorosilanes
assemble in the form of multilayers in which Si–O groups and fluori-
nated chains are randomly oriented. The alternation of domains of
different hydrophobicity originates on average a limited hydrophobic
surface. The arrangement in the form of multilayers justifies the dis-
crepancy between the contact angle values reported in previous
works for fluorinated surfaces [28] (related to monolayers of fluori-
nated silanes) and the one reported in Table 1 for PDMSfs samples.
Teflon AF definitively modifies the wettability properties, strongly in-
creasing the water repellent behavior [29]. For the prepared samples
we measured values between 100 and 125° (Table 1).
3.2. Thickness evaluation: QCM measurements
The coating thicknesses were calculated using a Quartz Crystal Mi-
crobalance with a dissipation (QCM-D) instrument from Q-Sense. The
dissipation signal provides insights about the viscoelastic properties of
the absorbed layers [30–32]. Meaningful fluctuation of dissipation sig-
nal means that the material is soft and that Sauerbrey equation under-
estimates the mass [33]. Therefore, after checking that there were no
relevant dissipation variations for PDMS, PDMSfs, and PDMStf samples,
Sauerbrey equation was used to fit the data, setting PDMS and silane
densities at 1023 kg/m 3 [34] and Teflon density at 2160 kg/m3. The
thicknesses of the PDMS and of the silane deposited on the gold quartz
crystals were evaluated to be 21± 1 nm and 5 ± 1 nm respectively. In
the case of homogenous coatings, the results obtained from different
overtones are expected to be roughly comparable. This effect was ob-
served in the case of samples 3–7 reported in Table 2 in bold. For sam-
ples 1, 2 and 8 error values higher than 10% were found (Table 2);
this strange behavior would suggest that a not so homogenous and
compact layer was deposited in such conditions.
The hypotheses of the different superficial arrangement of the Tef-
lon films were verified by optical inspection, AFM and contact angle
studies.
3.3. Morphology and wettability of PDMStf samples: optical inspection,
AFM and contact angle measurements
Optical images and typical AFM morphologies of the investigated
samples are shown in Fig. 2. The presence of a thick film on the PDMS
surface is clearly visible for samples 4–8, (Teflon thickness≥ 100 nm),
being characterized by waves at macroscale (Fig. 2a). In the case of thin-
ner Teflon layers (samples 1–3), the morphology seems to be more sim-
ilar to bare plasma-PDMS samples (Figs. 2b and 4).
Table 1
Contact angles of PDMS, PDMSpl, PDMSfs and PDMStf samples.
PDMS PDMSpl PDMSfs PDMStf
115 ± 7 25 ± 3 61 ± 7 100–125
2296 V. Arima et al. / Thin Solid Films 520 (2012) 2293–2300

Table 2 3.4. Understanding the origin of morphology

Thicknesses of the produced PDMStf samples evaluated by QCM.

Sample number Sample name
1 PDMS0.2tf2000
2 PDMS1tf4000
3 PDMS1tf2000
4 PDMS1tf1000
5 PDMS2tf4000
6 PDMS2tf2000
7 PDMS2tf1500
8 PDMS2tf1000
AFM image of Fig. 2c shows a homogenous layer of Teflon that
covers PDMS surface. This image was acquired on PDMS2tf2000 sam-
ples but we observed similar morphologies for samples thicker than
100 nm. A more detailed study on the morphology of these layers is
reported in Section 3.4. Samples 1–2 show the morphology reported
in Fig. 2d. Since we observed Teflon islands on the background tex-
ture due to the thermal treatment of PDMSpl samples (full explana-
tion in the next paragraph), and we acquired a very unstable QCM
signal, we believe that such samples are not compact enough to effi-
ciently shield PDMS from toluene adsorption. On the contrary, no Tef-
lon islands were observed in AFM images of sample 3 (morphology
similar to bare annealed PDMSpl samples of Fig. 4c), thus suggesting
the presence of a thin Teflon layer on PDMS.
The theory of a less compact layer for samples 1–2 and of a ho-
mogenous thin layer for sample 3 was also supported by contact
angle measurements. Observing the results listed in Table 3 and the
low surface coverage of teflon particles (Fig. 2d), it is clear that the
wettability is strongly influenced by the properties of the underlying
silane layer. The contact angle values of samples 1–2, hence, derive
from an average of silane and Teflon wettability properties. Sample
3 has a contact angle value equal to samples 5–7 that confirms the
presence of a homogenous Teflon coverage. The higher error values
reported for samples 1 (Table 3) once again suggest that samples 1–
2 are less homogenous than sample 3–7 as documented by the AFM
images of Fig. 2.
Thickness (nm) In order to explain the two different morphologies of Teflon on
PDMS (shown in Fig. 2c–d), we first compared the AFM images (see
…
49 ± 14 Fig. 3) of the produced samples (PDMS, PDMSpl, PDMSfs, PDMS0.2tf2000
34 ± 1 and PDMS2tf2000).
107 ± 4 PDMS is a very interesting material for microdevices, but its sur-
107 ± 3
face is easily modified by common fabrication processes such as plas-
204 ± 2
234 ± 6 ma and annealing treatments [21]. Untreated PDMS (Fig. 3a) doesn't
713 ± 80 exhibit particular structures resulting in a rms of 0.2 ± 0.1 nm. After
the oxygen plasma treatment (PDMSpl sample, see Fig. 3b) repeated
cracks of 58 ± 21 nm height, 700 ± 100 nm width and tens of micro-
meters length, appear on the surface. The same morphology seems
to characterize PDMSfs samples (Fig. 3c) being the silane layer only
a thin homogenous coating on PDMS (as also QCM studies suggest).
On PDMS0.2tf2000 samples (Fig. 3d) Teflon AF assembles in the form
of circular nanostructures with average height and diameter of respec-
tively 48 ± 12 nm and 120 ± 30 nm. The structures seem to decorate
the PDMSfs samples with an average density of 10 particles/μm2 but ad-
ditional features are also generated in the form of periodic waves. The
peak-to-peak distance between two waves and the amplitude of these
waves are respectively of 590 ± 30 nm and 44 ± 7 nm.
Waves disappear if a thick and homogenous layer of Teflon AF
(PDMS2tf2000) is spun coated on PDMSfs. As Fig. 3e shows, Teflon AF
seems to be, in this case, uniformly deposited on PDMSfs and only repeat-
ed cracks, attributed to the plasma treatments (see Fig. 1b), are still
visible.
Therefore, Teflon islands, formed at low concentration, are
replaced by a uniform layer. The film of Fig. 3e shows more pro-
nounced cracks probably because defects act as nucleation sites
from which the film starts growing.
In order to explain the origin of the features (essentially cracks and
waves) shown in Fig. 3b–e, we prepared some PDMS samples to observe
the effect induced by only plasma (PDMSpl) and both plasma/annealing
processes (PDMSan), necessary to prepare PDMStf surfaces. Images and
line profile of such samples are shown in Fig. 4. From a comparison be-
tween PDMSpl, PDMSan and PDMStf samples, it clearly appears that

Fig. 2. Optical images of (a) sample 6 and (b) sample 1 of Table 2. AFM images of (c) sample 6 of Table 2 over an area of 30 × 30 μm2 and (d) of sample 2 of Table 2 over an area of
10 × 10 μm2.
 V. Arima et al. / Thin Solid Films 520 (2012) 2293–2300
Table 3
Thickness, contact angles and swelling ratio of PDMS and PDMStf samples in toluene.
Sample number Sample name Thickness Contact angle Swelling ratio
– PDMS – 115 ± 7 2.6% ± 0.4%
1 PDMS0.2tf2000 Teflon islands 111 ± 11 1.7% ± 0.3%
3 PDMS1tf2000 34 ± 1 122 ± 4 1.7% ± 0.3%
5 PDMS2tf4000 107 ± 3 122 ± 2 1.6% ± 0.3%
6 PDMS2tf2000 204 ± 2 122 ± 1 0.8% ± 0.1%
7 PDMS2tf1500 234 ± 6 124 ± 1 1.8 ± 0.1%
plasma treatment generates regular patterns on PDMS (as it can be seen
in the optical image of Fig. 4a) creating cracks with repeatable height
and width (Table 4). Each crack usually exhibits double peak features
(see Fig. 4d) whose depth seems to be in the hundreds of nm range.
The entire PDMS surface is visibly damaged by these cracks. Although
this treatment generates discontinuities in the usually so homogeneous
PDMS surface, it is necessary to introduce the desired functionalities.
Occasionally, higher resolution images (Fig. 4b) show some waves
perpendicularly oriented with respect to the cracks whose distance be-
tween adjacent waves and amplitude are respectively 1070±30 nm
and 0.3±0.1 nm. The annealing treatment up to 300 °C, used after 0.2%
Teflon AF deposition, determines clearly visible waves, perpendicular to
the cracks, characterized by a distance (between the peaks of adjacent
waves) of 820±60 nm and a height of 57±4 nm (Fig. 4c). The appear-
ance of both these features is explained by Whitesides's theory on ther-
mal stress [35]. It seems that oxygen plasma treatment produces a
hydrophilic silica-like layer on PDMS surface, harder than the bulk one.
It was demonstrated that waves perpendicularly oriented to defects are
formed when PDMS is heated at temperatures between 50° and 250 °C
for more than 45 min. Actually, while PDMS is thermally expanded, plas-
ma oxidation forms a relatively incompressible layer that has a lower co-
efficient of thermal expansion than the unoxidized, bulk PDMS. Therefore
the surface oxide layer is placed under compressive stress when PDMS
cools down at room temperature and contracts. As a consequence, the
surface buckles into a pattern of waves to relieve the stress. In proximity
of cracks, the stress perpendicular to the step is relieved by expansion.
It is also known that the presence and the density of the waves are
a function of the top layer thickness and therefore proportional to the
applied plasma dose [21].
In PDMSpl samples the plasma treatment generates the hard
silica-like layer and partially damages it (generating patterns of
Fig. 3. AFM images over an area of 10 × 10 μm2 of PDMS samples (a) untreated, (b) plasma treated (PDMSpl), (c) silane functionalized (PDMSfs), (d) treated with a 0.2 wt.% Teflon
AF solution at 2000 RPM (PDMS0.2tf2000) and (e) treated with a 2 wt.% Teflon AF solution at 2000 RPM (PDMS2tf2000).
2297
fractures) because of etching and local heating effects. The weak ther-
mal expansion due to the temperature increase is supposed not to be
so powerful to form high amplitude waves. The following annealing
treatments are, however, strong enough to generate waves orientated
perpendicularly to defects, the plasma-induced cracks, in this case
[35]. It is also known that more a bigger thickness of the top silica
layer (due to stronger plasma dose) determines closer waves [34].
Teflon AF on PDMS increases the thickness of the hard layer on the
top of bulk PDMS and therefore it is expected to affect the wave for-
mation after annealing. From the comparison (Table 4) between the
structures (cracks and waves) of PDMSpl, PDMSan and PDMS0.2tf2000
samples it comes up that the Teflon addition has the effect of produc-
ing smaller and higher density waves (see Table 4).
In the case of a thick Teflon layer (PDMS2tf2000 samples) the film
deposition increases the crack dimensions but nothing can be con-
cluded about its influence on the wave formation process probably
being the silica-like layer of very low thickness (considering the ap-
plied plasma dose it is expected to be in the range of tens of nm
[35]) compared with the 200 nm Teflon multilayer. We believe that
the 2% Teflon solution which is more viscous than the 0.2% one, is eas-
ily trapped during the spin coating process in the crack areas. In the
area of the sample far from the cracks, less solution is deposited. As
consequence, the film appears thicker in proximity of the cracks in
PDMS2tf2000 samples.
3.5. Swelling behavior
To give a proof of the PDMS swelling reduction due to the depos-
ited Teflon coatings, a measure of swelling ratio [4,5] was experimen-
tally obtained using toluene, a very aggressive solvent for PDMS. As
detailed in the Section 2, only the PDMS surface was in contact with
the solvent. The swelling ratio S was determined by the formula: S
(%) = {(W − W0)/W0} ∗ 100, where W is the sample weight after dry-
ing and W0 is the weight prior to exposure to the solvent. The S values
are given in Table 3 for samples with Teflon islands and covered with
films of thickness between 34 and 234 nm.
The results show an appreciable reduction of the PDMS swelling
ratio for samples 1–2 functionalized with Teflon islands and thin
films up to 100 nm (sample 5). A 3-fold reduction was found for sam-
ple 6.
2298 V. Arima et al. / Thin Solid Films 520 (2012) 2293–2300

Fig. 4. (a) Optical image of PDMSpl samples; (b) AFM image of a PDMSpl sample over an area of 10 × 10 μm2; (c) AFM image of a PDMSan sample over an area of 30 × 30 μm2; (d)
line profile along the line shown in (c) and labeling of waves and cracks.

Surprisingly, sample 7 was less efficient than sample 6 in shielding
from toluene adsorption. We suspect that Teflon adhesion could de-
crease with thickness increase after a certain threshold value.
Considering these results, we focused on 200 nm coatings
(PDMS2tf2000) to demonstrate their time stability, their resistance to me-
chanical stress induced by liquid injection at moderate flow and finally to
develop a procedure to incorporate them in PDMS microfluidic devices.
3.6. Stability over the time: AFM, contact angle and swelling measurements
Considering the swelling tests, 200 nm Teflon coatings appear satis-
fying enough to be chosen to be implemented into a real functional de-
vice. One point to be investigated before developing a deposition
method to introduce Teflon coatings inside PDMS microchannels is the
stability of the morphological, wettability and swelling properties dur-
ing the time, being well known the dynamic nature of PDMS [36–39].
The evolution over the time of 200 nm Teflon coated PDMS was
monthly monitored by AFM.
For comparison we also followed aging effects of samples PDMSan
and PDMS0.2tf2000.
From AFM images of PDMSan samples (not reported) at different
time points, it seems that crack shape is essentially the same but
waves appear smaller and their density unchanged. The wave
amplitude and, consequently, the rms of the surface decrease, the en-
tire structure of the waves collapses.
The same behavior is also visible in the case of PDMS0.2tf2000 sam-
ples: wave height decreases and Teflon nanostructures become larger
and flatter, not easily differentiable from the waves. Crack shape and
dimensions appear rather unmodified.
In the case of PDMS2tf2000 samples we observed that the crack
height decreases, but no considerations related to wave evolution can
be done being the PDMS surface completely covered by a thick Teflon
AF layer.
In order to compare the observed phenomena for the three samples,
we analyzed the line profiles extrapolated from AFM images of cracks
and waves. The parameters chosen to quantify the structural variations
are essentially wave height for samples PDMSan and PDMS0.2tf2000
(being crack height less influenced by aging effects) and crack height
for PDMS2tf2000 (being waves not visible in this case). We reported
the time scale corresponding to a height reduction of 30% for each sam-
ple. These results are summarized in Table 4. Wave height decreases of
30% after 6 months in the case of PDMSan and after 4 months for
PDMS0.2tf2000. PDMS2tf2000 shows a reduction of 30% of crack height
but, unluckily, a direct comparison with PDMSan was not possible.
Compared with PDMSan samples, PDMS0.2tf2000 surfaces become
“flatter” earlier or at least the process appears more visible on them,

Table 4
Characteristics of the main features observed in AFM images of Figs. 2–4, along the line profiles shown in Fig. 4c of PDMSpl, PDMSan, PDMS0.2tf2000 and PDMS2tf2000 samples.

PDMS Wavesa(nm) Cracks (nm) 30% collapse

samples (months)
Distanceb Amplitude Height Peak to peak Height Width

PDMSpl 1070 ± 30 0.3 ± 0.1 1.3 ± 0.3 400 ± 100 58 ± 21 700 ± 100 –
PDMSan 820 ± 60 57 ± 4 61 ± 1 700 ± 200 78 ± 6 1400 ± 200 6
PDMS0.2tf2000 590 ± 30 44 ± 7 43 ± 4 200 ± 100 50 ± 12 800 ± 100 4
PDMS2tf2000 – – – 400 ± 200 620 ± 85 1500 ± 100 6
a
Estrapolated from a line profile perpendicular to the cracks and in the middle of the flat areas of the samples.
b
Calculated as a peak-to-peak distance between two adjacent waves.
 V. Arima et al. / Thin Solid Films 520 (2012) 2293–2300
Fig. 5. Contact angle evolution over the time for PDMS, PDMSpl, PDMS0.2tf2000 and
PDMS2tf2000 samples.
being PDMS0.2tf2000 samples characterized by smaller wave compared
with PDMSan samples (see Table 4). Teflon nanoparticles appear, dur-
ing the time, larger and flatter probably because, being polymeric struc-
tures, they are flexible enough to follow the relaxation of the PDMS
itself.
The dynamic process, due to re-orientation of bulk/superficial
polymeric chains and to the diffusion of low molecular weight spe-
cies, [36–39] that explains the well-known phenomenon of “hydro-
phobic recovery” [40], is associated to a change in the PDMS
superficial and bulk properties and probably becomes visible on the
surface in the form of a structural collapse.
PDMS2tf2000 samples appear more stable to aging effects due to
the uniform deposition of a thick layer that simply “masks” the dy-
namic process occurring in the layers below.
Additionally, changes in the wettability properties as a function of
time of the produced materials were investigated by contact angle
measurements (Fig. 5). PDMSan samples showed a very high variabil-
ity during the time. Soon after plasma treatments, their contact angles
start increasing and they reach a plateau value approximately 3 days
after the preparation. This behavior is a consequence of the hydro-
phobic recovery. These wettability changes are not detectable for
untreated PDMS, PDMStf samples that appear very stable in the peri-
od of 1 week from their production as well as after many months
(data not reported). This clearly means that the morphological
changes don't influence the wettability properties of PDMStf samples.
The observed structural collapse has to be considered only as a long-
term effect of the polymeric matrix re-organization processes (start-
ing soon after the preparation) that doesn't affect the interfacial prop-
erties of Teflon coatings.
Measurements of the swelling ratios after one month from the prep-
aration of a 200 nm layer resulted in 1.0%± 0.2% reduction. This number
is very close to the value of freshly prepared samples (Table 3) and al-
lows one to conclude that Teflon layer of 200 nm is a good choice in
terms of morphological, wettability and swelling reduction properties.
3.7. Adhesion and erosion tests with QCM
The last point to be clarified before developing a method for
inserting Teflon coatings into PDMS microchannels is the resistance
of the 200 nm thick Teflon layer to moderate flow conditions.
Table 5
Experimental results for the QCM tests at different speed of MQ flow.
Flow rate Weight gain (%) Swelling ratio (%)
f2 −f1 f3 −f1
(μl/min) ∗100
f1
∗100
f1
400 7.4 ± 1.9 1.2 ± 0.5
1200 2.3 ± 1.9 1.1 ± 0.2
2299
To evaluate the tendency of the Teflon layer to erosion or/and de-
tachment, a quartz crystal covered with PDMStf2000 layer (prepared
as described in Section 2.7) was inserted in the QCM chamber. The
Teflon weight was measured in air (f1). Subsequently, the QCM cell
was filled with MQ water flowing in continuous for 2 h and frequency
and dissipation shifts measured in real-time during the flow and after
water injection in air (f2). Six experiments were performed at 25 °C
using different flow rates: 400 μl/min, 800 μl/min and 1.2 ml/min
(each experiment was repeated twice). After drying, the quartz crys-
tals were removed from the QCM chamber and treated with toluene
to evaluate (following the protocol described in Section 2.6 for swell-
ing tests) if such treatment could affect the adhesion of Teflon to
PDMS. Then, quartz crystals were immediately reassembled into the
QCM chamber ready to measure the oscillating frequency for all over-
tone of the quartz crystals (f3). The experiments with MQ water flow
were repeated on toluene treated quartz crystals and frequency shifts
detected in real-time (f4).
In the six experiments performed, we usually noticed a weight in-
crease after the water and toluene treatments and only in the case of
two experiments (reported in Table 5) we observed a decrease in
weight.
Weight increases after water treatments can be ascribed to resid-
ual humidity, being QCM very sensitive even to water monolayer ad-
sorption (one monolayer causes an increase of ~ 0.25 mg/m 2
corresponding to 1.4 Hz) and being the QCM crystal not thermally
treated to favor water evaporation.
An interesting result concerns with the swelling test data (“swell-
ing ratio” of Table 5) whose results are comparable, within the exper-
imental errors, with the values reported in Table 3 for the
PDMS2tf2000 sample.
In the cases reported in Table 5 (2 of the 6 examined samples), it
seems that toluene treatment encourages Teflon erosion. Luckily
even in the worse case, this corresponds to a removal of less than
20 nm of Teflon which means a 10% (maximum) reduction of the
original thickness.
3.8. Microchannels fabrication and SEM studies
The experiments performed on PDMS slides, the studies of surface
morphology, wettability and the swellings tests allowed one to define
that a Teflon layer of about 200 nm is able to reduce toluene adsorp-
tion. In order to verify the applicability of the developed method to
fabricate PDMS microreactors for organic chemistry, we have pro-
duced a PDMS microreactor using standard soft lithography/plasma
sealing techniques and introduced a coating of the desired thickness
using a microfluidic injection, optimizing parameters such as injec-
tion speed and concentration of the solution. Details of the fabrication
are reported in the experimental section. The device was cut in many
points and the cross sections analyzed by SEM. PDMS and Teflon
show a different contrast that allowed the definition of an average
thickness of the coating of 198 ± 20 nm. SEM images of the cross sec-
tion of the microchannels are shown in Fig. 6a. Fig. 6b–d is zoomed at
the PDMS/Teflon interfaces and show that the layer formed by the
fluoropolymer covers the two vertical (Fig. 6c) as well as the two pla-
nar walls (Fig. 6b and d) of the microchannels. Therefore, it can be
reasonably concluded that the optimized procedure via micropump-
ing injection allows the production of uniform coatings inside PDMS
Weight loss (%) Estimated Teflon loss
f4 −f2
∗100
f2
(nm)
7.4 ± 0.6 18 ± 1
1.1 ± 0.4 3±1
2300 V. Arima et al. / Thin Solid Films 520 (2012) 2293–2300

Fig. 6. SEM images of (a) cross section of the microchannels. Zoom on the (b) and (d) planar interfaces, (c) lateral wall of the microchannels.

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