Surface & Coatings Technology 200 (2006) 3035 3040

www.elsevier.com/locate/surfcoat

Preparation of plasma-polymerized SiOx -like thin films from a mixture

of hexamethyldisiloxane and oxygen to improve the corrosion behaviour
E. Vassalloa,*, A. Cremonaa, L. Laguardiaa, E. Mestob
b

a
Istituto di Fisica del Plasma-CNR, Milano, Italy
Dipartimento di Geomineralogia, Universita` degli Studi di Bari, Italy

Received 27 July 2004; accepted in revised form 1 November 2004

Available online 2 December 2004

Abstract
Chemical and electrochemical properties of plasma polymerized SiOx -like thin films have been studied to search for an alternative to the
anticorrosive coatings produced by chromate conversion treatment. The films were deposited on steel substrates by means of
hexamethydisiloxane/oxygen-fed plasmas ignited in an RF capacitive coupled parallel plates reactor. Their surface chemical characterization
was carried out by means of X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (FT-IR). The protective abilities of SiOx -like
films as a function of RF power and gas feed composition in aerated 1 M Na2SO4 solution were examined by electrochemical methods.
Alone and in combination, these techniques help us to understand the relationship between the deposition parameters and the properties of the
deposited films.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Corrosion; PECVD; Plasma polymerization

1. Introduction
Corrosion is one of the most serious problems for
metallic materials utilised for many application. From many
years, zinc particles have been used as a metal coating on
steel to reduce corrosion. However, when materials covered
with zinc are exposed to the atmosphere or aqueous
solutions a corrosion product, Zn(OH)2, is rapidly generated. Therefore, chromate chemical conversion (CCC) films
have been widely used for many engineering materials to
provide improved corrosion resistance. Chromium chemical
analysis has shown that the corrosion resistance of the CCC
films is due to the inhibiting effect resulting from the
dissolution of Cr(VI) ions [1]. Unfortunately, Cr(VI) ions
that remain in the establishment of the chromium plating are
remarkably toxic and carcinogenic for humans. According
to Appendix II of the European Directive 2000/53/CE, as

* Corresponding author. Tel.: +39 2 66173245; fax: +39 2 66173203.

E-mail address: vassallo@ifp.cnr.it (E. Vassallo).
0257-8972/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2004.11.001

from 1st July 2007 coatings containing hexavalent chromium shall no longer be used for corrosion prevention. In
the EU Directive on Waste Electrical and Electronic
Equipment, the use of hexavalent chromium is also
forbidden as from 1st January 2006. The dates quoted in
the legislation require immediate action by manufacturers of
coating materials, by coating plants, by fastener manufacturers and by vehicle manufacturers; consequently, an
alternative surface treatment is necessary [2].
Vapour phase deposition of thin films from a plasma
environment is a flexible strategy to modify the surface of
materials [3]. Several surface chemical treatments are
possible and a wide range of substrate materials can be
coated. The application of these coating includes corrosion
protection, biomaterials, vapours barrier and area where
surface modification can enhance performance. In the
plasma deposition process, a gaseous or volatile compound
is introduced into a reaction chamber, fragmented and/or
ionized in a glow discharge plasma, and reassembled on the
surface of the sample. The variables that can be readily
controlled during this ionizationdeposition process are

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E. Vassallo et al. / Surface & Coatings Technology 200 (2006) 30353040

power density, precursor gas flow rate, pressure, reactor

geometry and plasma frequency. The ionized species formed
in the process acquire energies typically in the range of 02
eV, while electrons and metastables can achieve energies up
to 20 eV [4]. The processes that simultaneously occur in the
reaction chamber are ionization, neutralisation, recombination, etching and polymerisation. For these reasons, plasmaenhanced chemical vapour deposition (PECVD) appears to
be an important technology for the surface modification of
metallic materials in order to increase their corrosion
resistance. The deposited films are usually branched, highly
crosslinked, insoluble, pinhole-free and adhere well to the
substrates. Organosilicon precursors can be utilised to
deposit SiOx thin films, which are a good candidate for
protective coating on metallic and other substrates [59].
This monomer has been chosen for the flexibility of the Si
OSi bond in the backbone [7] and also for the resistance to
water permeation characteristics of polisiloxane films [10].
In order to provide an adequate corrosion protection, the
coating must be uniform and well adhered on the substrate;
it has been demonstrated that FeOSi oxane bonds, created
at the interface between the plasma-polymer and the steel
surface, enhance the adhesion of the film [11]. In any case
preview study demonstrated that hydrogen pre-treatment
removes surface contamination layer and improves the
coating-substrate performances. In fact, hydrogen removes
carbon from the surface and creates on the surface of the
substrate catalytic active points, so that the surface reactions
between the adsorbed precursor fragments and the substrate
are facilitated [12], also at low temperatures. The goal of
this paper is to evaluate the effect of several deposition
parameters on the electrochemical behaviour of the deposited films.

2. Experimental
Plasma polymerization has been carried out in a stainless
steel reactor with a parallel plate configuration and a 5 cm
inter-electrode gap. The upper electrode (diameter=15 cm)
is RF driven, the lower ground steel electrode (diameter 20
cm) holds the substrate to be processed. The reactor was
pumped by a turbomolecular and a rotary pump. The flow
rates of the feed gases and of the HMDSO vapour were
controlled by means of MKS mass flow meters, and the
pressure was monitored by an MKS capacitive gauge. SiOx
films were deposited on iron dishes. The experiments were
performed varying the HMDSOO2 flow rate ratio and the
input power, keeping constant the pressure at 100 mTorr.
After cleaning the sample using acetone, the substrates were
in situ pre-treated with hydrogen plasma at 50 W and 500
mTorr to give an oxygen-free surface and a buffer layer to
enhance the film adhesion.
SiOx films were also deposited onto polished Si
substrates for ex situ FTIR chemical characterization
performed by means of a Perkin Elmer Spectrum One IR

Fourier spectrometer under N2 purging and in the presence

of a desiccant reducing water adsorption on the samples. In
order to gather information about the chemical composition
of deposited SiOx films, X-ray photoelectron spectroscopy
(XPS) analysis was performed by a Leybold LHS10
spectrometer using an unmonochromatised Al Ka source.
Base vacuum was 10 9 mbar or better. The energy scale of
the spectrometer was calibrated using Cu and Au by the
binding energies Cu2p3/2=932.6 eV and Au4f7/2=84.0 eV.
Survey spectra were acquired in fixed retarding ratio mode
(retarding ratio=3) and high resolution spectra were
recorded in fixed analyser transmission mode, with a pass
energy of 30 eV. Calibration of binding energy scales was
performed by taking the alkyl component of the C1s
photoelectron peak (BE=284.8 eV). Hardware and software
for spectra acquisition and processing are described in
Desimoni and Malitesta (1986) and Malitesta et al. (1989).
In particular background subtraction is performed by the
Shirleys method (Shirley, 1972). As far as the fitting
procedure is concerned, a non-linear least squares fitting
program was employed to fit as many peaks as the guessed
chemical species to experimental spectrum. In this process,
peak parameters (position, height, width, etc.) are optimised
starting from initial estimates. Quantitative analysis was
performed by using high-resolution spectra. Atomic ratios
were obtained by dividing each peak area by empirically
derived sensitivity factor. Polarization measurements of the
electrodes, both bare and covered with SiOx film, were
carried out potentiodynamically in aerated 1 M Na2SO4
solution at pH 5.3 and at the laboratory temperature of
25F1 8C. After the immersion of the electrode in the
solution for the time necessary to achieve the stability of the
open-circuit potential (generally 3 h), the potential of the
electrode was swept at a rate of 0.166 mV/s from the initial
potential of 250 mV vs. E corr to the final potential of 1000
mV vs. E corr. A three-electrode electrochemical configuration was used with a clamp on electrolyte cell attached by
a rubber O-ring. The exposure area of the samples was 1
cm2. A SilverSilver chlorine (AgAgCl) electrode as
reference and a titanium counter electrode were employed.

3. Results and discussion

3.1. SiOx film characterization
3.1.1. Infrared spectroscopy
In Fig. 1, the infrared spectra of the deposited films
(about 1200 nm thick) are shown as a function of the O2/
monomer ratio in the plasma feed gas. The characteristic
features of the SiOSi group [1320] are evident:
asymmetric stretching and bending mode at around 1070
and 800 cm 1, respectively. The adsorption bands at 2970
and 1260 cm 1, relative to the stretching of CHx and the
bending modes of methyl groups in Si(CH3)x , mark the
presence of organic components in the film.

E. Vassallo et al. / Surface & Coatings Technology 200 (2006) 30353040

Fig. 1. Effect of feed gas composition on FTIR spectra obtained at 100 W

and 100 mTorr (the O2/HMDSO ratios are marked on the spectra).

Another important feature is the absorption of the

characteristic bands of SiOH bonds [1323], OH stretching
in H-bonded silanol at around 3500 cm 1 and the bending
mode at 930 cm 1. It can be observed that, in low dilution
conditions, the film infrared spectra show the characteristic
features of carbon-containing moieties (in particular, SiC
bonds). This is in agreement with the kinetics described by
Lamendola et al. [24], which states that under low dilution
conditions the deposition precursors are mainly SiCx Hy and
CHx radicals, and the film stoichiometry can be expressed as
SiC x H y O z . As the O 2 /monomer ratio increases, the
enhanced oxidation efficiency produces more SiO radicals
and CO2volatile molecules than Si and CH, leading to a
marked inorganic character of the film (SiOSi functional
groups prevail over Si(CH3)x ), thus the film chemistry
approaches the SiO2 one. Unfortunately, this can result in a
contemporaneous increase of the silanol concentration [25
27], reducing the chemical stability of the coating and
therefore its corrosion resistance. This inconvenience can be
solved rising the input power, in order to reduce the SiOH
concentration as well as the residual organic groups. The
effect of the power has been investigated at a constant O2/
HMDSO ratio of 6,6. In Fig. 2, the infrared adsorption

Fig. 2. Effect of RF power on the FTIR spectra obtained at 100 mTorr and
O2/HMDSO ratio 6.6.

3037

Fig. 3. XPS spectra of films deposited from HMDSO and 58.8% O2, at 200
W and 510 1 mbar.

spectra of the plasma-deposited films are shown at different

power conditions.
It is interesting to observe that the presence of carbon
within the film is detected only for a power value of 50 W.
The SiOH-related bands decrease when power increases.
This trend can be explained with a higher input energy,
leading to a higher ion bombardment of the growing film,
which can enhance the condensation of vicinal silanol
groups to form SiOSi bridges.
3.1.2. X-ray photoelectron spectroscopy
The chemical composition of the deposited SiOx films
has been investigated by XPS. In particular, it was studied
the intensity of the peaks Si2p, Si2s, C1s, and O1s. This
analysis, as well as infrared, permits to follow the evolution
of the concentration of diverse elements as a function of
preparation conditions. Fig. 3 shows the XPS spectrum of a
film obtained by an RF plasma of HMDSO mixed with
oxygen (oxygen percentage 58.8%).
X-ray photoelectron spectroscopy has shown that oxygen content rises from 43% to 65%, while the silicon
atomic concentration remains almost constant at 29%, when
the O2/HMDSO ratio varies in the range from 1.4 to 13.3
(see Fig. 4).

Fig. 4. Surface composition as a function of the O2/HMDSO ratio for

samples obtained at 100 W and 510 2 mbar.

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E. Vassallo et al. / Surface & Coatings Technology 200 (2006) 30353040

Moreover, the carbon content drops to a nearly negligible

value, indicating the decay of the organic moieties as the
oxygen concentration in the plasma increases. The carbon/
silicon (C/Si) and oxygen/silicon (O/Si) atomic ratio trends
are plotted in Fig. 5a against the discharge power.
Considering that the C/Si and O/Si ratio are respectively 3
and 0.5 for the monomer and 2 and 1 for PDMS [28], the C/
Si trend indicates that when power increases an abstraction
of the methyl groups, substantial loss of carbon on deposited
film occurs, while as SiO bonds did not seem to undergo
scission to an appreciable extent. On the other hand, the O/
Si trend suggests that slight oxidation process takes place
when the power rises.
The experimental determined O1s binding energy of
532.2 eV is consistent with the O1s signal in siloxane (Si
OSi) by comparison with earlier studies (Gengenbach and
Griesser, 1999 and references therein). The carbon peaks
have been decomposed in two component, a high contribution, attributed to carbon bound to hydrogen (CH) and to
carbon bound to silicium (CSi), both considered at a
binding energy of 284.8 eV, and a minor component at
higher binding energy, consistent with carbon singly bound
to oxygen such as ether, hydroxyl or epoxy carbon
functionary at a binding energy of 286.3 eV. The inves-

tigation of the Si2p signal results in a peak shift towards

higher binding energy when power increases. The high
value of its FWHM indicates several environments of
silicon atoms. We assumed that this signal is a compound
line with unresolved contributions from chemically different
species and assuming that all the silicon atoms in the deposit
have a valence of four. The major factor in determining the
Si2p binding energy is the number of oxygen atom. On the
other hand, the secondary effect upon the position of Si2p
signal due to various combination of carbon and hydrogen
atoms fulfilling the remaining bonding requirements of the
silicon has been assumed negligible in comparison to the
shift caused by an oxygen. The spectra data has been fitted
by four component peak within the Si2p envelope: SiOC3
(BE=101.5 eV), SiO2C2 (BE=102.1 eV), SiO3C (BE=102.8
eV) and SiO4 (BE=103.4 eV). Each component has been
fitted as symmetrical peak. The Gaussian to Lorentzian ratio
is kept constant at 85%. The fitting of Si2p spectra from
HDMSO/O2 deposits is illustrated in Fig. 5b.
The effect of power in glow discharges on the
distribution of the four silicon environments is reported in
Fig. 5c. When power increases, the proportions of SiOC3
and SiO2C2 decrease in favour of the more highly oxidized
SiO3C and SiO4 species. This is indicative of the role of the

Fig. 5. (a) C/Si and O/Si trend as function of the power from O2/HDMSO=1.4 plasma deposits. (b) Curve fit of the Si2p peak of a deposit formed from O2/
HDMSO=1.4 plasma at 100 mTorr 50 W (a) and 100 W (b). (c) Functional composition of the deposited films determined by fitting of Si2p peak plotted
against the glow discharge power.

E. Vassallo et al. / Surface & Coatings Technology 200 (2006) 30353040

3039

Fig. 6. Potentiodynamic curve of uncoated iron.

discharge power in the process. An increase of power results

in the formation of COx gaseous species and the formation
of siliconoxygen moieties in the deposit.

Fig. 8. Effect of the RF power on the corrosion properties of iron coated

with SiOx films.

3.2. Corrosion properties of iron with SiOx -deposited films

The potentiodynamic polarization behaviour of the
coated and uncoated iron after 1 h exposure in a 1 M
Na2SO4 solution is shown in Fig. 6. The corrosion current
measured of the uncoated iron is 2.0102 AA.
In the potential range examined, the polarization curve
generally has three distinct regions: the active dissolution
region (Tafel region), the activepassive transition region
and the limiting current region. Especially, a linear E/log i
relation with a Tafel slope of approximately 60 mV/decade
was obtained. This slope value indicates that the dissolution
process is determined by the rate of diffusion of soluble
species for the electrode surface into the bulk solution.
Fig. 7 shows the variation of the corrosion properties of
an iron disk covered with a 1150 nm thick SiOx -like films
deposited by plasma with different O2/HMDSO ratios, after
1 h of immersion in 1 M Na2SO4 solution. The process was
performed at 100 W of input power after hydrogen plasma
pre-treatment.

Fig. 7. Variation of the corrosion behaviour of the iron disks covered with
SiOx -like films.

In comparison with the bare metal, a significant decrease

of the current of corrosion is observed, especially for film
deposited by an oxygen-rich plasma. In these conditions,
inorganic SiOx -like coatings are obtained, as infrared
spectroscopy reveals. The best approach to obtain inorganic
deposits from organosilicon precursors is to increase the
oxygen content of the feed gas and the power (Fig. 8).

4. Conclusions
XPS, IR and electrochemical methods have been used to
characterize the plasma deposition of SiOx films for iron
coatings with corrosive resistance capabilities. Increasing of
power or oxygen flow has an appreciable effect on the film
composition and on its properties. In particular, the
increasing of power in the glow discharge results in the
formation of COx gaseous species and of higher oxidised
silicon species in the film. On the other hand, a major
oxygen content in plasma phase produces more inorganic,
compact and cross-linked films, with good anticorrosive
properties. Nevertheless, our results have demonstrated that
this is true only when the O2/HMDSO ratio is lower than
13.3, while for values greater than 13.3, when power
increases the current corrosion increases. Probably in these
conditions the coating-metal adhesion is worse, the coating
is stressed and the film defectiveness increases. As a matter
of fact, samples coated with SiOx films obtained in plasma
fed with 5 O2/HMDSO ratio at 200 W show a significant
improvement of corrosion resistance.
In conclusion, our corrosion measurements, in 1 M
Na2SO4 with pH 5.3, showed that PECVD appears to be a
promising technique in enhancing the corrosion properties of
materials. Oxygen and power play an important role in
determining the electrochemical behaviour of deposited film.
However, other experiments at pH 10 and pH 2 revealed that
SiOx thin films, obtained by means of the PECVD
technology, exhibit also considerable corrosion protection

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E. Vassallo et al. / Surface & Coatings Technology 200 (2006) 30353040

in mild basic and acid media [29]. To make an in-depth study

of the effect of SiOx films on corrosion behaviour,
impedance measurements for the coated and uncoated iron
are in progress. Moreover, electrochemical measurements
will be supported by scanning electron microscopy (SEM),
FTIR and XPS before and after corrosion test.

Acknowledgements
The authors of this work would like to thank Prof. C.
Malitesta for XPS measurements and for technical assistance.

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