Treatment of SU-8 surfaces using atmospheric pressure dielectric barrier discharge

plasma
Juliana de Novais Schianti, Fellype do Nascimento, Jhonattan Cordoba Ramirez, Munemasa Machida, Lucas
Heitzmann Gabrielli, Hugo Enrique Hernandez-Figueroa, and Stanislav Moshkalev

Citation: Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 36, 021403 (2018); doi:
10.1116/1.4999045
View online: https://doi.org/10.1116/1.4999045
View Table of Contents: http://avs.scitation.org/toc/jva/36/2
Published by the American Vacuum Society
Treatment of SU-8 surfaces using atmospheric pressure dielectric barrier
discharge plasma
Juliana de Novais Schiantia)
Communications Department, School of Electrical and Computer Engineering, University of Campinas,
Campinas, SP 13083-852, Brazil
Fellype do Nascimentob)
Center for Semiconductor Components and Nanotechnologies, University of Campinas, Campinas, SP
13083-570, Brazil
Jhonattan Cordoba Ramirez
Communications Department, School of Electrical and Computer Engineering, University of Campinas,
Campinas, SP 13083-852, Brazil
Munemasa Machida
Institute of Physics Gleb Wataghin, University of Campinas, Campinas, SP 13083-859, Brazil
Lucas Heitzmann Gabrielli and Hugo Enrique Hernandez-Figueroa
Communications Department, School of Electrical and Computer Engineering, University of Campinas,
Campinas, SP 13083-852, Brazil
Stanislav Moshkalev
Center for Semiconductor Components and Nanotechnologies, University of Campinas, Campinas, SP
13083-870, Brazil
(Received 4 August 2017; accepted 6 February 2018; published 21 February 2018)
Dielectric barrier discharge (DBD) plasma was used to change the wettability of a SU-8 photore-
sist, reducing the contact angle and improving the surface smoothness. As most polymers, SU-8
has hydrophobic surfaces which prevents the adhesion of biological samples when used to fabri-
cate biochemical sensors. Here, DBD Plasma treatment was conducted over the SU-8 surface,
reducing the contact angle from 78 to 12 . The advantage of this treatment is that the SU-8 sur-
face maintains the hydrophilic surface behavior over 24 h time period. DBD plasma modified the
SU-8 surface wettability under low temperature variation and does not cause great irregularities
on the surface. The highest value of root mean square surface roughness after 10 min exposure
was 2.9 6 0.3 nm. Published by the AVS. https://doi.org/10.1116/1.4999045

I. INTRODUCTION losses and offers a relatively high optical refractive index.

Polymers offer various advantages over silicon technol-
ogy in order to produce biosensors, not only considering the
economic factors, but also the bioavailability, flexibility in
microfabrication, and low toxicity. Some biosensor devices
are capable to execute multiple functions commonly per-
formed by many technicians in a laboratory, everything in a
small substrate. These kinds of biosensors are called lab-on-
a-chip devices, and offer portability, high sensibility, fast,
and label free analysis.1 The last advances in this area
involve the production of photonics biosensors in lab-on-a-
chip devices, with the ability to detect samples in a range of
some nanograms or even picograms per milliliters.2
The SU-8 has been widely used as a structural material
for lab-on-chip devices.3,4 SU-8 is an epoxy-based polymer
used as a negative tone resist in a liquid phase state, which
allows a great number of applications considering its simple
manipulation. SU-8 has excellent characteristics such as
thermal and chemical stability, biocompatibility, and trans-
parency to visible light. It is also suitable for building high-
aspect-ratio structures with high mechanical robustness.5,6
Besides, SU-8 presents high optical performance with low
a)
Electronic mail: jschianti@gmail.com
b)
Electronic mail: fellypen@ifi.unicamp.br
With these characteristics combined with low cost, SU-
8 presents a good strategy to produce photonics biosensors.7
Regardless of those advantages, a serious issue for use of SU-
8 in bioanalytical applications is related to its hydrophobic
surface and the tendency to absorb specific bioanalytes.8–11
Different types of processes for SU-8 surface modifica-
tions have been explored to control its hydrophobicity char-
acteristics (surface contact angle of approximately 80 ) using
wet chemicals, ultraviolet (UV) light and ozone, and plasma
treatment.12–15 All of these methods aim at creating func-
tional groups on the polymer surface, promoting the reduc-
tion of the contact angle, and consequently increasing its
wettability and surface energy.16–20
A successful wet chemical process used to change the
hydrophobicity of SU-8 is the immersion in ceric ammonium
nitrate (CAN) etchant, a solution used to etch chromium films
in MEMS applications. The samples with SU-8 are immersed
in a diluted CAN solution under temperature control followed
by an ethanolamine immersion to modify the surface. This
procedure results in a reduction of the SU-8 contact angle
down to 10 , stable for a few days. Despite being a simple
procedure with great results, CAN solution leaves a cerium
monolayer film on the SU-8 surface.8,14 This presence could
be toxic for many biological applications.

021403-1 J. Vac. Sci. Technol. A 36(2), Mar/Apr 2018 0734-2101/2018/36(2)/021403/6/$30.00 Published by the AVS. 021403-1
021403-2 de Novais Schianti et al.: Treatment of SU-8 surfaces
Another example of surface treatment employs an UV
source in an ozone-rich environment to generate a hydro-
philic surface. The contact angle can be reduced from 78 to
12 through proper control of the UV power source, ozone
concentration, and processing time. Ultraviolet sources with
different wavelengths can be used and good results in terms
of roughness have been reported with this technique.13,21
Plasma procedures are also commonly used to modify SU-
8 surface. Argon and oxygen plasmas have been applied to
change SU-8 wettability.14,22–25 Walther et al. compared the
results of SU-8 processing using two kinds of plasmas: a low
temperature atmospheric pressure argon plasma produced by
microwaves and an oxygen plasma produced by a low fre-
quency RF source.14 After the argon plasma treatment, the
SU-8 surface presented a contact angle of 30 and lower sta-
bility when compared to the oxygen plasma, with the contact
angle changing to 52 after 5 days of storage. On the other
hand, oxygen plasma treatment presented the contact angle
below 10 after just 8 min of processing. After 5 days, the
samples treated by oxygen plasma presented some variation
in the contact angle, but the surfaces were still hydrophilic,
with the contact angle lower than 20 .14,23
Alternatively, other types of plasma that are used to modify
hydrophobic polymer surfaces could also offer a solution to
SU-8. Atmospheric pressure plasma jets (APPJ) produced in
open environments have been used to treat a wide variety of
materials, organic and inorganic, like wood, metals, and
polymers.16,26–28 These kinds of plasma have some advantages
over the vacuum ones, such as lower implementation costs,
higher versatility, and no need of vacuum systems.26,29,30 There
is a work reporting the use of microwave atmospheric pressure
plasma, operated with argon gas, to treat SU-8 samples.14
Another important parameter to be considered in many
applications, especially bioanalytical, is the surface rough-
ness. SU-8 has a very smooth surface after spin coating, usu-
ally below 0.50 nm root mean square (RMS). Roughness is a
critical parameter for nanophotonic biosensors because very
small damages in nanometric structures such as waveguides
cause increased loses for the propagating light. Among the
procedures presented earlier, oxygen plasma treatment shows
more roughness than the others, even though hydrophilicity
is also more stable, which means that the SU-8 surface
remains hydrophilic for five days after storage, maintaining a
low contact angle of 20 .14
Considering this scenario, we proposed the use of a dielec-
tric barrier discharge (DBD) atmospheric pressure plasma as
an option for SU-8 surface treatment. Our focus is the use of
SU-8 photoresist for optical applications, such as nanopho-
tonic waveguides for bioanalytical detections. Our plasma
treatments were performed using an APPJ obtained from a
DBD device operated with helium gas. We note that the use
of a DBD plasma jet for treatment of SU-8 surfaces has some
advantages over the RF plasma treatment because it reduces
the SU-8 surface roughness if the process duration is ade-
quately chosen.25,31 The DBD plasma treatment does not
introduce bubbles-like irregularities (buckling) on the SU-
8 surface for short-time exposure due to its low temperature.
J. Vac. Sci. Technol. A, Vol. 36, No. 2, Mar/Apr 2018
021403-2
We show the contact angle evolution under different plasma
treatment durations and measure for how long the surface
remains hydrophilic. Using atomic force microscopy (AFM),
the SU-8 surface roughness was characterized, showing that
we were able to reach around 0.21 nm RMS with 2 min plasma
treatment, actually decreasing the original value of 0.44 nm
surface roughness. X-ray photoelectron spectrometer (XPS)
was used to characterize the chemical changes over the SU-8
surface, before and after DBD plasma treatment. The tempera-
ture variation over SU-8 surface was also estimated (see
supplementary material),37 showing that DBD plasma offer a
low thermal load and do not cause any damage to the SU-8
sample due to heating.
II. EXPERIMENT
A. SU-8 sample preparation
Silicon wafer substrates were first cleaned using standard
Piranha (H2SO4 þ H2O2, 4:1) bath, followed by an hydro-
fluoric acid dip for 30 s to remove native oxides. After that,
an RCA cleaning process (NH4OH þ H2O2 þ H2O and
HCl þ H2O2 þ H2O) cleaning was performed. Finally, the
wafers were rinsed in deionized water, blown dried with N2,
and heated in an oven at 200  C for 2 h. The silicon samples
were coated with a solution of 10 ml of SU-8 2100 (composed
by 75% solid) diluted in 27.5 ml of cyclopentanone. The
reduced viscosity of the resist allowed us to obtain a 1 lm
thick film by spin coating at 3000 RPM for 30 s. They were
then prebaked for 1 min at 65  C and 3 min at 95  C. After a
slow cooling to environmental temperature (21  C), the 1 cm2
samples were exposed to UV using a Tamarack Contact
Printer with a 365 nm wavelength sources and energy of 150
mJ. The samples were postbaked at 65 and 95  C for 1 min
each, and finally developed for 60 s in SU-8 Developer, rinsed
with isopropyl alcohol for 10 s, and blown dried with N2.
B. DBD plasma
SU-8 samples were then processed with the DBD plasma
under different conditions as described on sequence. The
experimental setup used to treat SU-8 samples with the DBD
plasma is shown in Fig. 1. The basic operation of the device
is as follows: a continuous gas flow is injected inside the
poly(vinyl chloride) (PVC) tube and high-voltage pulses are
applied to the electrode inside the glass tube. Due to the size
of the PVC opening (10 mm), the working gas interacts with
the surrounding ambient air and when the high voltage (HV)
is turned on, an initial plasma discharge is formed in the
region between the glass tube and the PVC tube producing a
plasma jet that leaves the tube through opening. The result-
ing plasma is composed by excited and ionized species—
atoms and molecules—and can be used for surface treat-
ment. One of the features of the DBD plasma device used in
this work is that it does not require a second electrode
around the PVC tube to produce the plasma jet. Even if we
remove the ground electrode, we still have a plasma jet leav-
ing the PVC tube opening.
An initial plasma discharge is formed in the region
between the glass tube and the PVC tube producing a plasma
021403-3 de Novais Schianti et al.: Treatment of SU-8 surfaces 021403-3

III. RESULTS AND DISCUSSION

A. Contact angle and recovery time
The first test was conducted with the intent to observe the
surface modifications in SU-8 after DBD plasma treatment
over different exposure times. In Fig. 2, we show that the
contact angle decreases as the exposure time increases.
Maximal angle reduction was observed with an exposure of
8 min, driving the angle from 78 down to 12 .
The results of all tested exposures are plotted in Fig. 3(a),
where it can be seen that the contact angle with the SU-8 sur-
face decreases to 20 in less than 1 min of exposure and the
minimum angle achieved is slightly above 10 . Figure 3(b)
shows the recovery curve for the contact angle as a function
of aging time; the contact angle recovery is fast in the first
5 min but slows down after about 20 min and the surface
remains hydrophilic (angle below 45 ) for the full 72 h of
testing.

FIG. 1. (Color online) Scheme of the DBD device and setup used for plasma
treatment of SU-8 samples. Ue and Ui refer to external and internal diame-
ters, respectively. Elements are out of scale.
B. Surface roughness
Scans from the AFM surface analysis of three samples
are presented in Figs. 4(a)–4(c): SU-8 sample before plasma
treatment, after 2 min treatment, and after 10 min treatment,
respectively.

jet that exits the tube through a 10 mm opening and can be

used for surface treatment. For the treatment of SU-8 surfaces,
we used helium as the working gas at a flow rate of 3.2 l/min.
The gas temperature was estimated to be Tg ¼ (375 6 25) K,
and the vibrational temperature Tv ¼ (2800 6 50) K. These
temperatures were determined using a well-known method
based on optical emission spectroscopy, using light emissions
from the second positive system of N2 molecules—C 3Pu
! B 3Pg transitions of N2 I—in the wavelength range from
365 to 385 nm.32,33 A pulsed HV signal with 15 kV of
amplitude and 1 ls width operated at 60 Hz repetition rate
produces a plasma with approximately 80 mW of power. The
distance between the PVC tube exit and the SU-8 sample was
3 mm, and the dimensions of samples were approximately
10  10 mm2. We used a dielectric material plate (PVC) as
the sample holder, and since it is an electrical insulating
material between the active electrode and the ground one, the
sample formed by the SU-8 film deposited over the Si sub-
strate (Si is an electrical conducting) acts as a floating elec-
trode in this configuration.

C. Characterization
The contact angles were measured before and after the
DBD plasma treatment using a CCD camera and deionized
water droplets with volume controlled by syringe. The images
were processed using the ImageJ software. The surface rough-
ness was evaluated by AFM microscope NT-MDT, Ntegra-
Spectra UV solid-state laser (473 nm) 50 mW, resolution of FIG. 2. (Color online) Water droplets on SU-8 samples for characterization
of contact angles. (a) Before DBD plasma exposure the contact angle is 78 .
300–450 nm. The chemical elements over surface were ana- (b) The angle decreases to 26 after 15 s of exposure and (c) to 12 after
lyzed by a K-alpha x-ray spectrometer (Thermo Scientific). 8 min.

JVST A - Vacuum, Surfaces, and Films

021403-4 de Novais Schianti et al.: Treatment of SU-8 surfaces
FIG. 3. (Color online) Quantitative contact angle characterization. (a) Measured
contact angle for different exposure intervals of DBD plasma treatment. (b)
Recovery curve for the contact angle after 2 min exposure.
We notice that with 2 min of treatment the process seems
to reduce the scale of large variations on the surface while
possibly introducing new smaller scale features. That leads
to an overall reduction in RMS surface roughness from
0.44 nm before treatment to 0.212 nm after 2 min exposure,
as indicated in Table I.
This roughness reduction has not been observed in other
experiments with RF plasma treatments23,25 and, together
with the contact angle results, represents a definite advantage
for the proposed DBD plasma process. Nonetheless, an exces-
sive exposure (10 min) causes the appearance of large ampli-
tude irregularities (bubbles-like irregularities) on the SU-
8 surface, in a way similar to that observed in other works.23
C. XPS analysis
In Fig. 5, the XPS spectra for SU-8 before processing (a)
and after DBD plasma processing (b) are shown. The XPS
spectrum without plasma presents oxygen and carbon as the
most representative peaks on SU-8 surface composition.
After DBD plasma treatment, the changes in survey spectra
J. Vac. Sci. Technol. A, Vol. 36, No. 2, Mar/Apr 2018
021403-4
FIG. 4. (Color online) AFM images of SU-8. (a) Sample not treated; (b) sam-
ple treated for 2 min; and (c) sample treated for 10 min.
are visible: a reduction of the peak of carbon, with a respec-
tive increase of the oxygen.
More detailed XPS spectra of samples before and after
plasma treatment, in regions near C 1s and O 1s peaks, are
shown in Fig. 6, together with their respective deconvolution
results. For the C 1s region, the ratio between intensities of
C-C and C-H bindings at 284.7 eV and C-O bindings at
286.1 eV does not practically change (variation within 5%)
after plasma processing although in some other works some
increase of C-O peaks was reported.14,34,35
For the O1s region, for the untreated SU-8 sample the
main peak observed is C-O peak at 532.7 eV. After treat-
ment, additional peaks can be seen at 540.9 and 531.1 eV.
Both peaks can be assigned to antimony oxide that is a com-
ponent related to a photoacid activator in a SU-8 photoresist
TABLE I. RMS surface roughness (Rq) of the SU-8 samples.
Exposure time (min) Rq (nm)
0 0.44 6 0.04
2 0.212 6 0.012
10 2.9 6 0.3
021403-5 de Novais Schianti et al.: Treatment of SU-8 surfaces
FIG. 5. (Color online) XPS survey spectra of SU-8: (a) sample not treated
and (b) sample treated with DBD plasma over 10 min.
FIG. 6. (Color online) Analysis on the high-resolution XPS spectra: (a) and (b) show the C1s peaks for untreated and treated SU-8 surface, respectively, and (c)
and (d) show the O1s peaks for untreated and treated SU-8 surface with DBD plasma.
JVST A - Vacuum, Surfaces, and Films
021403-5
and the appearance of these peaks was reported in various
works where SU-8 was treated by different plasmas.14,32,36
The peak near 531.1 eV can also be partially assigned to
C¼O bindings appeared due to treatment; however, the spec-
tral resolution does not allow to separate the contributions
from antimony oxide and C¼O group.14,23,31
IV. SUMMARY AND CONCLUSIONS
In conclusion, we have shown that atmospheric pressure
plasma jet produced by DBD can be used for the treatment of
SU-8 surfaces with successful promotion of wettability as
well as an overall reduction in the surface roughness depend-
ing on the exposure time. The XPS spectra indicate some
changes in the composition of the surface layers of the SU-
8 resist, in particular, appearance of a peak related to anti-
mony oxide as was also observed in other studies with differ-
ent plasma sources used for the SU-8 treatment. The DBD
plasma treatment reduces the large irregularities on the sur-
face and, due to its low temperature; it does not introduce
bubbles-like irregularities on the SU-8 surface for short-time
exposure. It is also important to note that the DBD plasma
produces long-lived surface changes that were verified
observing the contact angle recovery as a function of aging
time.
021403-6 de Novais Schianti et al.: Treatment of SU-8 surfaces 021403-6

19
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J. Vac. Sci. Technol. A, Vol. 36, No. 2, Mar/Apr 2018