Applied Surface Science 257 (2011) 8737–8741

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Surface modification of polypropylene with an atmospheric pressure plasma jet

sustained in argon and an argon/water vapour mixture
Abdollah Sarani a,∗ , Anton Yu Nikiforov a,b , Nathalie De Geyter a , Rino Morent a , Christophe Leys a
a
Ghent University, Research Unit Plasma Technology, Department of Applied Physics, Jozef Plateaustraat 22, 9000 Ghent, Belgium
b
Institute of Solution Chemistry RAS, Academicheskayastr 1, 153045, Ivanovo, Russia

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

Article history: In this paper, an atmospheric pressure plasma jet sustained in pure argon and an argon/water vapour
Received 23 March 2011 mixture has been used to modify the surface of polypropylene (PP) films. The gas temperature of the
Received in revised form 17 May 2011 plasma jet was found to be 625 K in an active zone between the electrodes and was found to increase
Accepted 17 May 2011
in the afterglow. Based on these results, the PP films are placed as close as possible to the edge of the
Available online 26 May 2011
capillary in order to avoid thermal damage to the polymer. XPS results on the untreated and modified PP
samples revealed incorporation of a significant amount of oxygen on the polymer surface, however, this
Keywords:
oxygen inclusion is more pronounced for the argon/water vapour jet due to the higher radicals density
Atmospheric pressure plasma jet
OH radicals
in the jet afterglow. One can therefore conclude that adding water vapour to an argon plasma jet can be
X-ray photoelectron spectroscopy a convenient way to increase the efficiency of plasma surface modification.
Surface modification © 2011 Elsevier B.V. All rights reserved.

1. Introduction faces will be investigated with X-ray photoelectron spectroscopy

Atmospheric pressure plasma jets have been established as suit-
able sources of low-temperature and non-equilibrium atmospheric
pressure plasmas [1–3]. The main distinctive feature of these plas-
mas is that the jet is not confined by electrodes. As a result, the
plasma jet dimensions can be adjusted in a wide range allowing
local treatment of 3D surfaces, for example the inner walls of wells,
trenches and cavities [4]. Among other applications, the treatment
of temperature-sensitive surfaces such as polymers and biomedical
tissues is of great interest [5–7]. The main effect of the plasma jet
on treated samples can be connected to UV light emission, OH and
O radicals and a high concentration of metastable particles gener-
ated in the discharge [8,9]. Accordingly, a higher radicals flux in the
afterglow plasma is of major importance from technological point
of view. A possible way to increase the radicals density can be an
addition of a small amount of oxygen or water vapour to the feed
gas [8,10]. Recently, the influence of water vapour content on the
spectral properties of an atmospheric pressure argon plasma jet
has been examined. It was revealed that a higher intensity of UV
radiation (in the range of 306–315 nm) which is related to the pro-
duction of OH radicals is observed at 0.05% of water vapour in the
mixture [8]. Based on these results, an atmospheric pressure plasma
jet sustained in pure argon and an argon/0.05% water vapour mix-
ture will be employed in this work for the surface modification of
polypropylene (PP) films. The untreated and plasma-treated PP sur-
∗ Corresponding author. Tel.: +32 9 2643836; fax: +32 9 2644198.
(XPS) to determine the effect of water vapour addition on the treat-
ment efficiency. Moreover, the gas temperature of the plasma jet
will be determined for both discharge gases, since this is an impor-
tant parameter when employing plasma jets for surface treatment
of polymers.
2. Experimental procedure
A schematic representation of the experimental set-up is shown
in Fig. 1, together with an image of the plasma jet in pure argon. The
dielectric barrier discharge (DBD) plasma jet is generated between
two electrodes, placed in a quartz capillary with inside and outside
diameters of 1.3 and 3.0 mm respectively. As previously mentioned,
besides pure argon, also an argon/0.05% water vapour mixture is
used as feed gas, which can be obtained by using a bubbler sys-
tem filled with distilled water. However, for both discharge gases,
the total gas flow is maintained at 1.5 standard litres per minute
(slm). The jet in both gases is generated by applying a sinusoidal
wave voltage with a fixed frequency of 71 kHz, while the peak-to-
peak voltage values are slightly varied in order to obtain a constant
input power of 12.8 W. Lissajous figures have been used to calcu-
late this input power, as described in detail in [11,12]. Partially
resolved spectra of OH radicals emission in the region 300–350 nm
are collected using an Avantes spectrometer with a resolution of
0.05 nm.
The surface modification efficiency of the plasma jets in argon
and argon/water vapour is also investigated in this work. For this
purpose, polypropylene (PP) films (Goodfellow-UK) are modified

0169-4332/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2011.05.071
8738 A. Sarani et al. / Applied Surface Science 257 (2011) 8737–8741
Fig. 1. Schematic representation of the experimental set-up and visual view of the
plasma jet.
with the plasma jets by scanning the polymer surface with a scan-
ning velocity of 1000 mm/min. The distance between the edge of
the capillary and the polymer is very small (2 mm) in order to
avoid thermal damage to the substrate, as will be discussed in
detail in Section 3. The untreated and plasma-treated PP samples
are analysed with XPS within a few hours after plasma treat-
ment to gather information on their chemical composition. XPS
measurements are performed on a Kratos Axis Ultra DLD spec-
trometer equipped with a Mg X-ray source (h = 1253.6 eV) at a
power of 225 W. The pass energy for survey spectra was 160 eV
with 1 eV step size and for high-resolution C 1s spectra 40 eV
with 0.1 eV step size. The base pressure in the main chamber
during analyses is not higher than 2 × 10−9 Pa, the analysis area
is approximately 700 ␮m × 300 ␮m and the spectra are acquired
at an emission angle of 90◦ . Elements present on the surface
are identified from survey spectra and quantified (in at%) with
CasaXPS software using a Shirley background and applying the
relative sensitivity factors supplied by the manufacturer of the
instrument. CasaXPS software is also used for the curve fitting
of the high-resolution C 1s peaks: the hydrocarbon component
of the C 1s spectrum (285.0 eV) is used to calibrate the energy
scale and a Shirley background was chosen. After this calibration
step, the C 1s peaks are deconvoluted using Gaussian–Lorentzian
peak shapes with a 30% Lorentzian component and the full-
width at half maximum (FWHM) of each line shape is constrained
below 1.6 eV.
3. Results
3.1. Plasma characterisation
Discharge properties in a wide range of water vapour concentra-
tions have been described in our previous work [10]. The electron
density in the pure argon plasma was estimated based on current
density measurements and considering the mobility of the elec-
trons in argon. The current density J is linearly proportional to the
electron density as shown in the following equation:
E
J = ne eve = ne ee E (1)
N
where e is the elementary charge in I s−1 , E the electrical field in
V m−1 and e the electron mobility in argon gas. The reduced elec-
trical field (E/N) has been estimated to be 1.1 × 10−22 V m2 allowing
us to estimate the electron mobility (9.5 × 10−9 cm2 Torr V−1 s−1 )
[13]. Using Eq. (1), the electron density in the pure argon plasma
jet is found to be 1.5 × 1013 cm−3 . The addition of water vapour
to the argon plasma jet results in a decrease in electron density
due to electron attachment and a high rate of electron collisions
with H2 O. However, quantitative estimation of the electron den-
sity in this case requires the data for electron mobility in Ar/H2 O
mixtures, which are unknown. The electron temperature in the
pure argon plasma can also be determined from emission spec-
tra, thereby applying a line ratio technique and taking into account
the self-absorption effect [10]. The line ratio technique gives the
excitation temperature, which is close to the electron tempera-
ture in this type of discharge [14–16] and thus provides us with a
rough estimation of the electron temperature. In the present work,
three transitions of Ar: 696.54 nm 2p2 → 1s5 , 763.51 nm 2p6 → 1s5 ,
and 811.53 nm 2p9 → 1s5 (in Paschen notation) were used, yield-
ing an electron temperature of 0.97 eV for the pure argon plasma.
The addition of water vapour to the feed gas leads to an unexpected
decrease in electron temperature, which is most likely due to effec-
tive collisions of H2 O with excited argon species, as described in
detail in [10]. Using the ICCD technique, it was observed that the
jet consists of “plasma bullets” and the structure and propaga-
tion of such a “plasma bullet” is already investigated by Engemann
et al. [17] using a high speed photograph technique. In addition,
the dynamic of the jet propagation is almost independent on the
water content. As the temperature of the gas phase is a critical
parameter for plasma modification of polymer surfaces, special
attention has been paid to the estimation of the temperature of
the gas. The spectral lines of OH(A2 ˙ + − X2 ˘) radicals have been
used for the determination of the gas temperature. The Boltzmann
plot method [18,19] is used to estimate the OH rotational tempera-
ture. The energy and probability data of OH transitions were taken
from [20,21]. Fig. 2(a) shows experimental spectra of the plasma
with noted transitions used for the Boltzmann plot method. In
Fig. 2(b) and (c) the value of ln(I/(2J + 1)SJ  J  ) is presented as a
function of the levels energy for pure Ar and Ar + 0.05% H2 O. Con-
sidering the overpopulation of high rotational states of OH radicals
with rotational numbers above 13, the temperature has to be esti-
mated from the slope of the first part of the presented plots (at
J < 13) [10,22]. Fig. 3 presents the space resolved temperature in
the afterglow of pure argon and the argon/0.05% water vapour mix-
ture. The rotational temperature, in case of pure argon, is around
650 K near the ground electrode and slightly increases outside the
capillary up to 770 K. For the argon/water vapour mixture, the rota-
tional temperature inside the quartz capillary has a value of 625 K
and increases to 150 K outside the capillary. 2 mechanisms of gas
heating in the afterglow can be suggested: first of all, the increase
of the gas temperature along the jet can be explained by excita-
tion of N2 to high vibrational/rotational levels. As most effective
excitation process, one can mention the charge transfer by the reac-
tion: N2 (X1 ˙) + Ar* → N2 (C3 ˘) + Ar [10]. However, also other N2
excited species can be generated in the afterglow as shown by Aki-
shevet et al. [23] which can also lead to a temperature increase.
Secondly, the increase of the temperature can be due the fact that
propagation of the jet outside the capillary results in the forma-
tion of filaments. The local current density in the filaments will
be higher as well as the temperature of radicals. Despite the high
gas temperatures, no surface defects due to heating were observed
 A. Sarani et al. / Applied Surface Science 257 (2011) 8737–8741 8739

Fig. 3. OH(A2 ˙ + − X2 ˘) rotational temperature as a function of the distance from

the ground electrode for plasma jets in pure Ar and Ar/0.05% water vapour mixture.
Error of the method is ±50 K.

to evaluate the chemical composition of the plasma-treated PP

surfaces and is a highly surface-sensitive technique, analysing
approximately the uppermost 8.5 nm of a surface [24]. The sur-
vey scans lend information on the ratios of the different elements
present at the surface, while the high-resolution peaks can ren-
der information on the molecular environment of each element.
Fig. 4 shows the survey scan of the polymer surface while the
atomic composition of the PP films before and after plasma treat-
ment in pure argon and argon/water vapour is presented in Table 1.
As can be seen in Table 1, the untreated PP film already contains
a significant amount of oxygen (5.3%) which is most likely due
to surface contamination or more probably low-level surface oxi-
dation. Table 1 also shows that after plasma treatments in pure
argon, the oxygen content strongly increases to 13.7%, while the
argon/water vapour plasma treatment can add even more oxygen
to the PP surface (15.1%). Table 1 also shows that both plasma treat-

Fig. 2. (a) Emission band of OH radical in Ar and Ar/H2 O 0.05% mixture and Boltz-
mann plots of the OH(A2 ˙ + − X2 ˘),  = 0 transition in plasma jets sustained in (b)
pure argon and (c) argon/water vapour mixture.

on PP films plasma-treated with extended exposure times (2 min).

Another indirect confirmation of negligible sample heating induced
by the DBD plasma jet has been obtained by placing a thermocouple
inside the quartz capillary and switching on the plasma for 2 min. In
this case, only a small increase in capillary temperature (t ≈ 20 ◦ C)
has been observed. As a summary, from practical point of view, the
distance between the edge of the capillary and the polymer sur-
face to be treated should be as low as possible in order to minimize
thermal damage.

3.2. Polymer surface modification

XPS measurements have been carried out on untreated and

plasma-treated PP films to estimate the influence of water vapour Fig. 4. XPS spectra of untreated PP films and PP films plasma-treated in pure argon
on the modification efficiency of the plasma jet. XPS can be used and argon/water vapour mixture.
8740 A. Sarani et al. / Applied Surface Science 257 (2011) 8737–8741
Table 1
Atomic composition and concentration of the different chemical bonds on untreated and plasma-treated PP films.
Plasma C (at%) O (at%) N (at%)
No 94.3 5.3 0.4
Argon 84.5 13.7 1.8
Argon/water vapour 83.1 15.1 1.8
Fig. 5. High resolution C 1s peaks of untreated PP films and PP films plasma-treated in pure argon and argon/water vapour mixture.
ments introduce a small amount of nitrogen on the polymer surface,
however, this nitrogen incorporation is much less pronounced
compared to the oxygen inclusion. To obtain further insight into
the chemical bonds present on the surface of the plasma-treated
PP films, curve fitting of the high-resolution C 1s peak can be per-
formed. Fig. 5 shows the C 1s peaks of the PP films before and after
plasma treatment in argon and argon/water vapour respectively.
The C 1s envelope of the untreated PP film can be decomposed
into 3 distinct peaks: a peak at 285.0 ± 0.1 eV corresponding to
C–C and C–H bonds, a peak at 286.5 ± 0.1 eV due to C–O or C–N
functional groups and a peak at 287.70 ± 0.1 eV due to C O bonds
[25–27]. As shown in Fig. 5, following plasma jet treatments, large
changes in the C1 s peak can be seen: the peak at 285.0 eV tend to
decrease, while the peaks at 286.8 and 287.7 eV strongly increase.
Moreover, a new peak at 289.1 ± 0.1 eV, which can be attributed
to O–C O groups occurs after plasma treatment [25–27]. Based on
these deconvoluted C 1s peaks, the concentrations of the differ-
ent chemical bonds on the PP films can be obtained and Table 1
presents the concentration of the chemical groups for the differ-
ent PP samples. This table clearly shows that the concentration
of the C–C and/or C–H bonds decreases after plasma treatments,
while the concentration of the oxygen-containing groups (C–O,
C O and O–C O) strongly increases. Most likely, also a few C–N
bonds are incorporated on the plasma-treated PP samples, how-
ever, from the XPS results, it is nearly impossible to make a clear
distinction between C–O and C–N functional groups. However, one
can conclude that the plasma jets attack the C–C and C–H bonds in
the PP polymer chains to form C–O, C O, O–C O and a few C–N
bonds. Table 1 also shows that after argon/water vapour treat-
ment the amount of oxygen- and nitrogen-containing groups is
slightly higher, showing the positive influence of water vapour on
the treatment efficiency. The plasma jet sustained in argon/water
vapour probably contains a higher amount of O and OH radicals,
which can explain the more effective oxygen incorporation. From
practical point of view, it is thus very important to optimize the
radicals concentration in the plasma jets to obtain the highest poly-
C–C/C–H 285.0 eV C–O/C–N 286.5 eV C O 287.7 eV O–C O 289.1 eV
94.5 3.4 2.1 0.0
88.3 4.8 3.5 3.4
85.2 5.9 4.2 4.7
mer modification efficiency but to prove this statement, additional
experiments on radicals density measurements will be required.
4. Conclusion
In this study, pure argon and argon/water vapour atmospheric
pressure plasma jets have been used to modify the surface of PP
films. To minimize thermal damage of the heat-sensitive polymer,
the gas temperature of the two plasma jets is calculated in order to
determine the best location of the polymer substrate. It is shown
that the distance between the edge of the capillary and the poly-
mer surface should be as low as possible in order to minimize
thermal damage. PP films have been plasma-treated with argon
and argon/water vapour jet to determine the influence of water
vapour addition on the modification efficiency. It was found that
adding water vapour to the argon feeding gas results in a more
pronounced oxygen incorporation on the PP surface, which can be
attributed to a higher radical concentration. One can therefore con-
clude that adding the correct concentration of water vapour to an
argon plasma jet can be a convenient way to increase the efficiency
of plasma surface modification.
Acknowledgments
This work is financially supported by the Belgian Program on
Interuniversity Attraction Pole IAP-VI/08 (Project in Plasma Sur-
face Interaction “PSI”-P6/08). The authors would also like to thank
Prof. E. Payen and A. Beaurain from the Unité de Catalyse et Chimie
du Solide (Université des Sciences et Technologies de Lille) for per-
forming the XPS measurements.
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