Vacuum 84 (2010) 1327e1333

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Vacuum
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Studies of radiofrequency plasma deposition of hexamethyldisiloxane lms and

their thermal stability and corrosion resistance behavior
Arup Jyoti Choudhury a, Joyanti Chutia a, *, Hemen Kakati a, Shruti A. Barve b, Arup Ratan Pal a,
Neelotpal Sen Sarma a, Devasish Chowdhury a, Dinkar S. Patil b
a
b

Material Science Division, Institute of Advanced Study in Science and Technology, Paschim Boragaon, Guwahati 781035, Assam, India
Bhabha Atomic Research Center, Trombay, Mumbai 400085, India

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 30 December 2009
Received in revised form
9 February 2010
Accepted 19 February 2010

Hexamethyldisiloxane (HMDSO) lms (thickness: 282e929 nm) are prepared by the radiofrequency
plasma assisted chemical vapour deposition (RF-PACVD) method using an Ar/HMDSO/O2 gas mixture.
The deposition process is carried out in an RF reactor at a working pressure of 1.2
101 mbar and an RF
power range of 20e100 W. From the studies on Ar/O2 and Ar/HMDSO/O2 discharge characteristics using
a self-compensated emissive probe, it is revealed that electrons play an important role in the plasma
polymerization of HMDSO monomers. Optical emission spectroscopy (OES) and Fourier transform
infrared (FT-IR) spectroscopy show that the plasma deposited HMDSO lms tend to be more inorganic in
nature at higher RF powers. A lm prepared at an RF power of 100 W exhibits more thermal stability and
corrosion resistance behavior in comparison to lms deposited at lower powers (20e80 W). A correlation
of the results obtained from OES and FT-IR analyses with the thermal stability and corrosion resistance
behavior of the lms has been attempted.
2010 Elsevier Ltd. All rights reserved.

Keywords:
Plasma assisted CVD
Hexamethyldisiloxane
Emissive probe
Thermogravimetric analysis
Corrosion test

1. Introduction
Radiofrequency plasma polymerization of organosilicon lms
has drawn considerable research interest for various technological
applications [1e10]. RF-PACVD is a well established technique for
producing highly cross-linked and adherent organosilicon lms
with a unique combination of properties, such as high hardness
[4,5,11], optical transparency [12,13], corrosion resistance [9,14]
and low gas permeability [15]. As a result, plasma polymerized
organosilicon lms have been considered as potential candidates
for applications in the eld of hard and anti-scratch coatings
[2,4,5,11], optical lters [7], corrosion resistance layers [5,12,14], gas
barriers [16,17] and humidity sensors [6]. For plasma deposition
of organosilicon lms, a silicon containing monomer such as
hexamethyldisiloxane (HMDSO) is commonly used because of its
high organic character and room temperature vapour pressure [5].
Moreover it is relatively non-toxic, non-inammable, cheap and
commercially available [17,18].
It is a well known fact that the RF-PACVD process is highly
dependent on plasma discharge parameters [19,20]. The desired
physical and chemical properties of plasma polymerized
* Corresponding author.
E-mail address: joyanti_c@sify.com (J. Chutia).
0042-207X/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.vacuum.2010.02.013

organosilicon lms can be obtained through proper control of the RF

power, monomer/gas ow rate, working pressure, deposition time
and geometry of the reactor. Besides it is also very important to
study the fundamental processes occurring in the plasma using
some useful diagnostic techniques, so that one can correlate the
plasma discharge characteristics with the lm properties. This is
essential so far as the technological applications of plasma deposited
organosilicon lms are concerned. In this regard self-compensated
emissive probe [21e23] and optical emission spectroscopy (OES)
[14,24,25] techniques are often preferred to diagnose the plasma
discharge. A self-compensated emissive probe can conveniently be
used to study the discharge characteristics of the thin insulating
polymer lm deposition process [26,27]. On the other hand OES is
a simple non-intrusive optical technique that allows easy identication of different emitted species and deduction of semiquantitative density trends of emitting species as a function of the
experimental variables [24,25].
In this work, results from the deposition of plasma polymerized
hexamethyldisiloxane (pp-HMDSO) lms on bell metal (alloy of
copper (78%) and tin (22%)) substrates using an Ar/HMDSO/O2 gas
mixture are reported. Bell metal is commonly used for making
utensils, idols and various other decorative items. But the main
disadvantage of using bell metal in such applications is that the
surface of bell metal gets oxidized upon exposure to air for a period

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A.J. Choudhury et al. / Vacuum 84 (2010) 1327e1333

of time. A paper on the deposition of alumina lm on bell metal by

RF magnetron sputtering for enhancing its corrosion resistance
behavior has recently been published [28]. However to the best of
our knowledge no work has been done on the RF plasma deposition
of HMDSO coating on bell metal for its surface protection. It has,
therefore, been a sincere effort to study the surface modication of
bell metal by depositing thermally stable and corrosion resistant
HMDSO coatings on its surface by the RF-PACVD method. Moreover
the effect of RF power on the plasma chemistry and discharge
characteristics also needs to be investigated for a fundamental
understanding of the RF plasma polymerization process for surface
modication of bell metal. In this present work, the RF plasma
discharge characteristics are studied using a self-compensated
emissive probe [23]. Actinometric optical emission spectroscopy
(OES) technique is utilized to detect and analyze the excited species
present in the glow discharge. The results obtained from OES and
Fourier transform infrared (FT-IR) spectroscopy analyses are
observed to have a correlation with the thermal stability and
corrosion resistance behavior of the pp-HMDSO lms. The
pp-HMDSO lms are characterized by step prolometry, Fourier
transform infrared (FT-IR) spectroscopy, atomic force microscopy
(AFM), thermogravimetric analysis (TGA) and copper acetic acid
salt (CASS) test.

2. Experimental
2.1. Film deposition
A schematic representation of a capacitively coupled RF plasma
polymerization system is shown in Fig. 1. The deposition process is
carried out in a vertically placed stainless steel cylindrical chamber
of 40 cm diameter and 45 cm length. The chamber is evacuated to
a base pressure of 6
106 mbar with an oil diffusion pump backed
by a rotary pump (21 m3 h1). Argon gas is designed to ow
through a at-bottom ask containing liquid hexamethyldisiloxane
(HMDSO) monomer (purity >99%, ACROS Organic), kept in
a constant temperature bath at 40  C. All the gases (argon and
oxygen) and HMDSO vapour are allowed to enter the chamber
simultaneously through a at cylindrical gas shower plate (9.25 cm
in diameter) as shown in Fig. 1. The bottom surface of the shower
plate contains 60 tiny holes each having a diameter of 5
102 cm.
The RF electrode (10 cm in diameter) is placed horizontally at the
center of the chamber with proper insulation and connected to an
RF (13.56 MHz) source (COMDEL-CPS-500AS, 0e500 W) through an
L-type matching network. Cold water is circulated through the
electrode so as to keep it cooled during the plasma pretreatment

Fig. 1. Experimental setup of the RF plasma polymerization system.

and polymerization process. The gas shower plate is placed 5 cm

above the RF electrode and the substrates are placed on the surface
of the electrode.
Before deposition, the bell metal substrate surfaces are nely
polished (grit size w2 mm) and after that they are cleaned properly
using acetone, isopropyl alcohol and distilled water. The substrates
are then pretreated with argon plasma (ow rate 5 sccm) at an RF
power of 40 W for 10 min in order to remove the native oxide
present on the surfaces. Afterwards, the deposition process is
carried out for 30 min at a working pressure of 1.2
101 mbar and
an RF power range of 20e100 W. Both argon and oxygen gas ow
rates are set at 5 sccm while the HMDSO monomer ow rate is
maintained at 35 sccm (MFC) (Aalborg, USA). Finally after deposition, the RF power is turned off and the substrates are allowed to
cool in an oxygen ow (35 sccm) for 15 min. The substrates are
collected from the RF chamber after 6 h and immediately transferred to a vacuum desiccator.
The plasma phase diagnostics are carried out using selfcompensated emissive probe and optical emission spectroscopy
(OES) techniques. The reason behind using a self-compensated
probe is to minimize the perturbation effects of the RF voltage
across the probe sheath [29e31]. The emissive probe is constructed using a 0.7 cm long, 0.01 cm diameter thoriated tungsten
lament [23]. For all measurements, the probe tip is placed 2.5 cm
above the RF electrode. The probe is operated under warm
conditions, below the temperature threshold for emission [26].
Prior to each measurement, a DC voltage of 4 V and then 4 V is
applied to the emissive probe so as to clean it by electron and ion
impact in argon plasma. The probe bias is varied from 55 to
55 V to record the IeV characteristics in an XeY recorder. For
optical emission spectroscopy (OES), a 300 mm focal length
monochromator (BENTHAM M300) having a resolution of 0.1 nm
equipped with a 1200 lines/mm grating is used. The emission lines
from different excited species in the discharge are studied in the
wavelength range of 300e900 nm. A ber optic probe is put
approximately 15 cm away from the plasma discharge. Proper care
is taken to detect maximum light emission and avoid background
radiation. The output signal is fed into a photomultiplier tube and
then transferred to a personal computer through a data acquisition
(DAQ) card. The emission spectra are recorded using LabVIEW
software.

2.2. Film analyses

The compositional characterizations of the pp-HMDSO lms are
carried out by means of Fourier transform infrared spectroscopy
(FT-IR) (BRUKER VECTOR 22) using a 30 specular reectance
accessory. The spectra of the lms are obtained in the transmittance
mode, within the spectral range of 4000e400 cm1 (spectral resolution: 4 cm1), by averaging 30 scans and then subtracting the
spectrum obtained from the substrate before deposition of the lm.
The thickness of each lm is measured with a stylus proler
(Veeco, Dektak-150, USA) having a vertical resolution of 1 
A
(maximum).
Atomic force microscopy (AFM) images are obtained in
ambient conditions with a digital multimode scanning probe
microscope (SPM) (Veeco, USA) equipped with a nanoscope IVA
controller (resolution: horizontal, 0.2 nm and vertical, 0.01 nm).
The images are taken in tapping mode at a scanning rate of 1 Hz
(scan size 2.4 mm
2.4 mm). The rms distribution proles of the
pp-HMDSO lms are measured by scanning probe microscopy
software (WSxM).
The thermal stabilities of the lms are investigated using
thermogravimetric analyses (TGA/SDTA851e, Mettler Toledo, USA),

A.J. Choudhury et al. / Vacuum 84 (2010) 1327e1333

within the temperature range of 27e1200  C (temperature accuracy, 0.25%, weighing precision 0.01%).
The corrosion test on the lms is done in a closed testing
chamber (internal volume, 0.1 m3) by the standard copper acetic
acid salt (CASS) test according to the ASTM-B-368 module. The
CASS test is performed at room temperature and the lms are kept
under observation for 72 h.

1329

Table 1
Variation of Ar/HMDSO/O2 plasma discharge characteristics with RF power.
RF power (W)

Plasma potential (V)

Electron density (
109 cm3)

20
40
60
80
100

24
20
18
15
13

3.1
3.5
4.0
4.3
4.6

3. Results and discussion

3.2. Optical emission spectroscopy (OES) analyses
3.1. Plasma discharge characteristics
In this work, the electron temperature is evaluated for Ar/O2
and Ar/HMDSO/O2 discharges keeping both argon and oxygen
ow rates xed (5 sccm) and maintaining the same variation of
RF power. From the analyses of IeV characteristics obtained from
the self-compensated emissive probe, electron temperature (Te)
and electron density are evaluated considering the emissive
probe as a cylindrical Langmuir probe [26]. Electron temperatures
are estimated from the slope of the IeV characteristics in the
region between the ion and electron saturation currents while
electron densities are estimated from electron saturation
currents. The plasma potential for each deposition condition in
Ar/HMDSO/O2 discharge is also determined with the help of the
oating potential method [32]. The variation of electron
temperature in Ar/O2 and Ar/HMDSO/O2 discharges as a function
of RF power is shown in Fig. 2. It may be seen from the plots
contained in Fig. 2 that electron temperature in Ar/O2 discharge
increases (from 5.25 to 5.85 eV) while in case of Ar/HMDSO/O2
discharge, it decreases (from 5 to 3.5 eV) with the rise in RF
power. Moreover from the plots presented in Fig. 2, it may be
observed that in plasma polymerization of HMDSO monomer,
electrons increasingly lose their energy from 0.25 to 2.35 eV with
the RF power rising from 20 to 100 W. This possibly indicates
that electrons utilize their energy mainly in ionization and
dissociation of HMDSO monomer through inelastic collisions and
thus play an important role in the plasma polymerization process.
The effect of RF power on Ar/HMDSO/O2 discharge characteristics
at a constant working pressure of 1.2
101 mbar is depicted in
Table 1. From the data presented in Table 1, it is observed that
electron density increases from 3.1
109 to 4.6
109 cm3 while
plasma potential decreases from 24 to 13 V with the increase in
RF power.

Fig. 2. Variation of electron temperature in Ar/O2 and Ar/HMDSO/O2 discharges as

a function of RF power.

The emission spectrum from the glow region of Ar/HMDSO/O2

discharge at an RF power of 100 W is shown in Fig. 3. The main
transitions that are observed in the spectrum are reported in
Table 2 [33,34]. As seen from the plots contained in Fig. 3, the main
emitted species in Ar/HMDSO/O2 plasma are N2, SiH, CH, SiO, CO, H2
and O. The presence of emission peaks/bands due to CH, SiO, H2 and
O species in the spectrum (Fig. 3) gives the evidence of fragmentation of eCH3 and SieOeSi functional groups upon energetic
electron impact due to RF power. The presence of N2 in the OES can
be attributed to the trace amount of air present in the deposition
system [35] which is assumed to get injected into the chamber
during the ow of gases (Ar/O2) and HMDSO monomer at the
working pressure of 1.2
101 mbar, possibly contributed by either
the gas cylinders (Ar/O2) or the monomer bath (or both). However,
the high peaks of N2 do not necessarily mean there is a large
amount of N2 inside the deposition system, because a very little
amount of N2 can result in the signicant appearance of the spectral
bands in the glow discharge [35].
The emission spectra obtained at various RF powers
(20e100 W) are analyzed using the actinometric technique
[14,24,25]. Species like SiH (414 nm), CH (431.8 nm), SiO
(427.1 nm), CO (451.1 nm) and O (744 nm) are selected for analysis
as they are expected to play an important role in the lm deposition process. We use the relative intensity of argon line at
750.2 nm to normalize the peak heights of the above species of
interest [36]. The variation of relative concentrations of SiH, CH,
SiO, CO and O species as a function of RF power is shown in Fig. 4.
It may be seen from the plots included in Fig. 4 that the relative
concentration of each species is dependent on the variation of RF
power. The relative concentrations of SiO, CO and O species are
found to be increased with RF power which may be accredited to
the increase in degree of ionization and dissociation of HMDSO/O2
molecules due to dissipation of RF power in the plasma. However
the relative concentrations of CH and SiH species may be observed

Fig. 3. Optical emission spectrum of Ar/HMDSO/O2 discharge obtained at an RF power

of 100 W.

1330

A.J. Choudhury et al. / Vacuum 84 (2010) 1327e1333

Table 2
Species detected in Ar/HMDSO/O2 plasma discharge carried out at an RF power of
100 W.
Species

Wavelength (nm)

Transition

N2

357.7 (0,0)
380.5 (0,1)
386e394
431.8 (0,0)
427.1
420.1
414
451.1
483.5
519.8
561.0
586e670
750.2
811.3
774
844

C3 Pu eB3 Pg
-id-a
X2 PeB2 S
A2 DeX2 P
A2 PeX1 S
3s23p4(1S)4se3s23p4(1S)4p
A2 DeX2 P
B1 SeA1 P (0,0)
-id- (0,1)
-id- (0,2)
-id- (0,3)
X1 Sg eG1 Pu
3s2 3p5 2p01=2 4se3s2 3p5 2p01=2 4p
3s2 3p5 2p03=2 4se3s2 3p5 2p03=2 4p
5 Pe5 S
0
3 Pe3 S
0

CH
SiO
Ar II
SiH
CO

H2
Ar I
O
a

Identical.

Table 3
Effect of RF power on the thickness and deposition rate of pp-HMDSO lms.
RF power
(W)
20
40
60
80
100

Deposition time
(min)

Film thickness
(nm)

Deposition rate
(nm/min)

30

282
334
551
662
929

9.4
11.1
18.3
22.0
31.0

of the lms deposited at an RF power range of 20e100 W are shown

in Fig. 5(a). The assignments of the peaks are listed in Table 4
[37e40]. As seen from the spectra contained in Fig. 5(a), the characteristic features of SieOeSi groups are evident from the bands at
1053, 800 and 450 cm1 which signify the asymmetric stretching,
bending and rocking mode respectively [37e39]. The absorption
band at 1260 cm1 relative to the bending mode of methyl group in
Si(CH3)x indicates the presence of organic content in the lms
[38,39]. However, the spectra show the presence of no band corresponding to the eCH3 mode, which is one of the main functional
groups of HMDSO monomer [37,38]. A weak peak at 1620 cm1
signifying the eC]O mode is observed to appear in the spectra
above an RF power of 20 W, contained in Fig. 5(a) [39,40]. The band
corresponding to the broad signal in the region of about
3700e3000 cm1 can be attributed to the eOH stretching mode in H
bonded silanol [2,37,39,40]. For convenience, the FT-IR spectra of the
pp-HMDSO lms in the spectral range (1500e400 cm1) of interest

Fig. 4. Variation of relative concentrations of various emitted species as a function of

RF power.

to be decreased (Fig. 4) above RF powers of 40 and 60 W respectively.

It possibly occurs due to extensive dissociation of these species
caused by energetic electron impact above an RF power of 40 W. It is
important to mention here that dissociation of SiO (8.3 eV) and CO
(8.24 eV) species is less likely to take place in the plasma discharge
in comparison to SiH (4.26 eV) and CH (3.5 eV) species because of
their relatively high bond dissociation energies. The above ndings
can be considered to be well supported by the results drawn from
emissive probe studies which show a signicant loss of electron
energy in Ar/HMDSO/O2 plasma with the increase in RF power.
3.3. Film growth
In the present plasma polymerization process, the negative DC
self-bias voltage is found to be increased from 25 to 125 V with RF
power. The thickness and deposition rate of pp-HMDSO lms
prepared at an RF power range of 20e100 W are summarized in Table
3. From the data presented in Table 3, it is apparent that the deposition
rate of the pp-HMDSO lm increases with RF power. This is attributed
to the increase in electron density with enough available energy
which can be used for plasma polymerization of HMDSO monomer.
3.4. FT-IR spectroscopy analyses
FT-IR absorption spectroscopy is performed to study the internal
chemical structures of the pp-HMDSO lms. Typical infrared spectra

Fig. 5. (a) FT-IR spectra of pp-HMDSO lms prepared at RF powers of (a) 20, (b) 40, (c)
60, (d) 80 and (e) 100 W and (b) FT-IR spectra of pp-HMDSO lms prepared at RF
powers of (a) 20, (b) 40, (c) 60, (d) 80 and (e) 100 W in the spectral range of interest
(1500e400 cm1).

A.J. Choudhury et al. / Vacuum 84 (2010) 1327e1333

1331

Table 4
Assignments of peaks detected in FT-IR spectra of pp-HMDSO lms prepared in the
RF power range of 20e100 W.
Wavenumber (cm1)

Assignments

3700e3000
1620
1253
1052
930
800
450

eOH stretching mode

eC]O mode
Si(CH3)x symmetrical bending mode
SieOeSi asymmetric stretching mode
SieOH bending mode
SieOeSi bending mode
SieOeSi rocking mode

are shown in Fig. 5(b). As observed from the spectra contained in

Fig. 5(b), an increase in RF power leads to the following observations:
(a) The intensity of bands relative to SieOeSi (1053 and 800 cm1)
increases
(b) SieOeSi stretching peak shifts to a lower wave number region
(1053e1040 cm1)
(c) SieOH (930 cm1) band intensity increases in the RF power
range of 20e80 W and at 100 W, the intensity of the band
signicantly decreases
(d) The intensity of band due to the Si(CH3)x mode decreases and
(e) A new band assigned to the SieOeSi (450 cm1) mode appears
in the spectra above an RF power of 40 W and subsequently the
intensity of the band increases.

Fig. 6. TGA and DTGA curves of a pp-HMDSO lm prepared at an RF power of 60 W.

curve exhibits a three-step weight loss of the lm. The rst step
(40e185  C) is assigned to the weight loss due to moisture. The
second step (185e394  C) may arise due to the removal of organic
contents while the third step (394e610  C) can be attributed to the
loss of inorganic contents present in the lm. The degradation
temperatures of the lms prepared in the RF power range of
20e100 W, their percentage of weight loss in each step and the
corresponding temperature ranges are summarized in Table 5. It is
observed from the data depicted in Table 5 that the weight loss of
the inorganic contents in the lm deposited at 100 W is quite small
as compared to the lms obtained at lower powers (20e80 W). The
percentages of total weight loss of the lms are observed to be
increased (from 73 to 25%) with RF power. It is further seen that the
degradation temperatures (Ton) of the lms prepared at higher RF
powers (80e100 W) are more than those of lms prepared in the
power range of 20e60 W. The improvement in thermal stabilities of
the pp-HMDSO lms at higher RF powers is associated with the
increase in relative concentrations of SiO species generated in the
RF discharge as observed from actinometric OES analyses. Moreover it can be assumed that at higher RF powers, more organic
contents (carbon and hydrogen) present in the lms are removed
through oxidation reactions and increased incorporation of
inorganic SieOeSi groups into the lms takes place which have
stronger bond enthalpy (SiO, 799 kJ mol1) than CH (299 kJ mol1)
and SiH (338 kJ mol1) groups. This is well supported by FT-IR
analyses which show an increase in the content of SieOeSi
groups in the pp-HMDSO lms with increasing RF power.

The shifting of band for the SieOeSi mode has previously been
reported [17,41,42]. It is now well accepted that shifts in the SieOeSi
stretching wave number towards lower values indicate an increase
in the lm density [43,44]. The decrease in the intensity of band
relative to the Si(CH3)x mode may indicate the enhanced character
of cross-linked structure of the lms [37]. Another important point
to be noticed is that no functional group containing nitrogen is
detected in the FT-IR spectra. This gives the evidence that nitrogen
does not participate in the lm formation process although it shows
its presence in the OES spectra (Fig. 3). It is assumed that dissociation of N2 (10 eV) is less favorable as compared to SiH (4.26 eV) and
CH (3.5 eV) species because of its strong bond dissociation energy,
which is also supported by the fact that no nitrogen containing
species is detected in the OES spectra (Fig. 3) [45]. The above
discussions suggest that pp-HMDSO lm chemistry tends to be
more inorganic in nature with increasing RF power.
3.5. Thermogravimetric analyses (TGA)
The thermal degradations of the pp-HMDSO lms are studied by
using thermogravimetry. Polymer samples (pp-HMDSO lms) of
2e3 mg are heated in N2 atmosphere, at the rate of 20  C/min, over
a temperature range of 30e750  C. Fig. 6 shows the TGA and
differential-TGA (DTGA) curves of a pp-HMDSO lm prepared at an
RF power of 60 W. As seen from the plots contained in Fig. 6, the
degradation temperature (Ton) of the lm starts near 185  C and
about 58% of its total weight is lost near 610  C. Besides, the TGA

3.6. CASS test

The standard copper acetic acid salt (CASS) test (ASTM-B-368)
[28,46] is performed on pp-HMDSO lms to study their chemical
properties. Here a homogeneous solution is prepared from 5% NaCl
and 0.026% CuCl2 solutions and the pH of the solution is maintained

Table 5
Thermal behaviors of pp-HMDSO lms deposited in the RF power range of 20e100 W.
RF power
(W)

Degradation temperature,
Ton ( C)

First step (moisture)

Weight loss (%)

Temperature range ( C)

Weight loss (%)

Temperature range ( C)

Weight loss (%)

Temperature range ( C)

20
40
60
80
100

188
181
185
221
239

4.7
4.3
3.4
1.75
1.13

43e188
46e181
40e185
56e221
45e239

13.2
14.1
12.5
24.4
21.3

188e381
181e399
185e394
221e379
239e378

55.2
51.6
42.5
20.8
2.57

381e596
399e633
394e610
379e582
378e691

Second step (organic contents)

Third step (inorganic contents)

1332

A.J. Choudhury et al. / Vacuum 84 (2010) 1327e1333

at 3.1 by adding the required amount of glacial acetic acid. Onethird (1/3rd) of each lm is dipped inside the solution over a total
observation time of 72 h. A virgin bell metal sample dipped inside
the solution serves as reference. The virgin bell metal sample and
the lms are observed visually as well as with an optical microscope (Metzer, MBE e 9995, resolution 15
) every 12 h. At an
observation time of 24 h, the portion of virgin bell metal surface
dipped inside the solution is found to change its colour from bright
golden to blackish thereby showing corrosion of the surface. The
visual image as given in Fig. 7(a) shows the corrosion of virgin bell

metal. The inset of Fig. 7(a) is the microscopic image of the corroded
part of the virgin bell metal. During the same observation time
(24 h) the pp-HMDSO lms show no sign of cracks or spots on their
surfaces. At an observation time of 48 h, the portions of the lms
prepared at RF powers of 20 and 40 W respectively and dipped
inside the solution are observed to be peeled off due to permeation
of salt solution into the lm surfaces. The other lms show no
change in their surface morphologies as observed visually as well as
with the optical microscope. Regarding the lm prepared at an RF
power of 60 W, it is found that at an observation time of 60 h, the
portion of its surface dipped inside the solution is peeled off while
minute cracks are observed on the lm surface prepared at an RF
power of 80 W. Fig. 7(b) shows the lm surface prepared at an RF
power of 80 W while the inset shows the microscopic image of the
corroded lm surface. The lm prepared at an RF power of 100 W
shows no sign of cracks (Fig. 7(c)) even after the total observation
time of 72 h. The inset of Fig. 7(c) shows the microscopic image of
the lm surface dipped inside the salt solution. The better corrosion
resistance behavior of the lm deposited at an RF power of 100 W
in comparison to the lms prepared at lower powers (20e80 W)
may be attributed to the relatively high contents of inorganic
complexes such as SieOeSi groups present in the lm, as revealed
by FT-IR analyses. Moreover the highest relative concentration of
SiO species in the plasma discharge at an RF power of 100 W, as
observed from actinometric OES analyses may be another signicant factor contributing to such enhanced corrosion resistance
behavior of the lm.

3.7. Atomic force microscopy (AFM)

Fig. 8(a) shows the three-dimensional AFM image of a pp-HMDSO
lm prepared at an RF power of 100 W while the rms roughness
distribution prole of the lm is shown in Fig. 8(b). As observed
from the AFM images, all the lms show quite smooth and crack free
surfaces. The rms roughnesses of the lms are found to be increased
from 0.32 to 0.85 nm with increasing RF power. The increasing
roughness is most likely due to the etching of the lm surfaces by
oxygen atoms present in the discharge [3].

4. Conclusion

Fig. 7. Images showing visually observed corrosion tested surfaces of a virgin bell
metal sample (a) and pp-HMDSO lms prepared at RF powers of (b) 80 and (c) 100 W
respectively. The insets show the microscopic images of the virgin bell metal and lm
surfaces kept under the salt solution.

Self-compensated emissive probe studies on radiofrequency

Ar/HMDSO/O2 discharge characteristics reveal that dissipation of
RF power in the plasma enhances dissociation and ionization of
parent gases and monomer leading to an increase in electron
density. This results in an increase in inelastic collisions between
electrons and ions and neutrals and thus causes a decrease in
electron temperature and plasma potential. From Ar/O2 and
Ar/HMDSO/O2 plasma characteristics studies, it can be surmised
that electrons play an important role in plasma polymerization of
HMDSO monomer. From in situ investigation of the plasma
discharge using optical emission spectroscopy (OES) and also
FT-IR analyses of the lm chemistry, it is observed that the
pp-HMDSO lms tend to be more inorganic in nature with
increasing RF power. The lm prepared at an RF power of 100 W
shows the maximum degradation temperature (Ton 239  C) and
lowest percentage of weight loss (25%). Moreover the lm
(prepared at 100 W) exhibits better chemical stability in
comparison to the lms deposited at lower powers (20e80 W).
These results suggest the possibility of using pp-HMDSO lms
deposited at an RF power of 100 W as a protective coating on
metallic surfaces against a severe and corrosive environment
with good thermal stability.

A.J. Choudhury et al. / Vacuum 84 (2010) 1327e1333

1333

Fig. 8. (a) AFM image and (b) rms roughness distribution prole of a pp-HMDSO lm prepared at an RF power of 100 W.

Acknowledgement
This work was supported by a grant from the Board of Research
in Nuclear Sciences, Department of Atomic Energy; Government of
India.
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