Surface & Coatings Technology 229 (2013) 1217

Contents lists available at SciVerse ScienceDirect

Surface & Coatings Technology

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

Plasma polymerization of hexamethyldisiloxane: Investigation of the effect of carrier

gas related to the lm properties
C. Chaiwong a, b,, P. Rachtanapun c, S. Sarapirom a, D. Boonyawan a, b
a
b
c

Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai, Thailand
ThEP Centre, Commission of Higher Education, 328 Sri Ayuddhaya Road, Bangkok, Thailand
Department of Packaging Technology, Faculty of Agro-Industry, Chiang Mai University, Chiang Mai, Thailand

a r t i c l e

i n f o

Available online 31 August 2012

Keywords:
Plasma polymerization
Hexamethyldisiloxane
RF discharge
Compressive stress

a b s t r a c t
In this work we present the inuence of carrier gases in the deposition of low-pressure discharge plasma of
hexamethyldisiloxane (HMDSO). Plasma polymerized HMDSO lms were deposited with an inductively-coupled
discharge reactor using Ar and O2 as carrier gases. The lms deposited in Ar contained polymeric structure in the
form of SiOxCyHz and could signicantly improve the barrier to water vapor of poly(lactic acid) (PLA). The SiOx-like
structure of HMDSO lms was obtained when using O2 as the carrier gas. However, the lms supported some state
of residual stress leading to lm failures and a signicant loss of barrier performance of PLA. The formation of organic and inorganic contents in the lms was conrmed by X-ray photoelectron spectroscopy (XPS). The discharge
power had an effect on the topography of the lms. Rough surface with coarse texture was obtained when the process was done in Ar at high discharge powers. On the other hand, the deposition process in O2 induced smoother
surface of plasmapolymerized lms.
2012 Elsevier B.V. All rights reserved.

1. Introduction
An increasing interest in organo-silicon thin lms has been observed owing to their potential applications in, for example, protective coatings [1], gas barrier coatings [2], and chemical sensors [3].
These lms can be prepared via wet chemical processes such as hydrolysis and ring-opening polymerization of dimethyltrichlorosilane
and hexamethylcyclotrisiloxane [4]. Wet chemical processes need
solvents or catalysts and are multiple steps. The lms obtained from
these processes are unfortunately thick and non-uniform; therefore
their applications are restricted. Plasma polymerization is a singlestep process effective to deposit thin lms with high degree of
cross-linking and pinhole-free on various substrates. Chemical solvents
and catalysts are not necessary. In the process of plasma polymerization
induced by a plasma-enhanced chemical vapor deposition (PECVD),
polymer lms are deposited through reactions between reactive species
produced by the plasma discharge and the substrates. A number of
plasma sources and monomers have been employed to fabricate
organo-silicon lms. The characteristics of the lm are highly dependent
on the process conditions [57]. Hexamethyldisiloxane (HMDSO;
(CH3)3\Si\O\Si\(CH3)3) is one of the monomers being employed
to produce polymer thin lms via PECVD because it is non-toxic, commercially available, and has a high vapor pressure at room temperature.
Corresponding author at: Department of Physics and Materials Science, Faculty
of Science, Chiang Mai University, Chiang Mai, Thailand. Tel.: + 66 53 943 379;
fax: + 66 53 222776.
E-mail address: cchwng@gmail.com (C. Chaiwong).
0257-8972/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.surfcoat.2012.08.058

Usually, the deposition of HMDSO is carried out in oxygen. Other gases,

such as argon and helium, may be used to stabilize the discharge. The
properties of the lm could vary from polymeric to SiOx-like structures
depending on the process conditions [810]. In this work, we investigated the effect of different kinds of carrier gas, i.e. argon and oxygen, on the
properties of HMDSO lms. The properties of the lms were analyzed in
terms of water vapor barrier performance, surface topography, and
chemical compositions.
2. Experimental details
2.1. Experimental arrangement
Plasma polymerized HMDSO lms were prepared in a low-pressure
radio frequency (RF) plasma reactor at the frequency of 13.56 MHz. The
detail of the reactor was described in our previous work [11]. Commercially available HMDSO solution was obtained from Sigma Aldrich Inc.
(St. Louis, USA) and used as received. A ask containing HMDSO solution
was connected to the inlet port of the plasma reactor through a mass
ow controller. Ar and O2 were used to carry the vapor of HMDSO into
the plasma reactor. The ow rate of the carrier gas was kept at 1 l/min
whereas that of HMDSO was adjusted to obtain the pressure of
100 mTorr. The lm depositions were done with the RF powers of
10 W, 30 W, 40 W, 50 W, and 60 W. The deposition time was 10 min.
Si wafers and poly(lactic acid) (PLA) lm with a nominal thickness of
30 m were used as substrates. The Si substrate was used for measuring
the lm thickness. Before the lm deposition, the substrates had been
sputtered with Ar plasma for 10 s. The Ar plasma was obtained at a

C. Chaiwong et al. / Surface & Coatings Technology 229 (2013) 1217

pressure of 30 mTorr with the RF power of 30 W. The substrates were at

oating potential during the process.
Species in the plasmas were analyzed using optical emission spectroscopy (OES). The spectrometer employed in this work was a S2000
ber optics spectrometer (Ocean Optics Inc., USA) with a wavelength
range from 200 nm to 800 nm. The resolution was 0.3 nm.

13

500
Ar

450
Ar

400

3. Results and discussion

Ar

300

C2

200
150
100

CO

SiO

250

OH

50

H2

SiO

0
200

300

400

500

600

700

800

Wavelength (nm)

b
300

250

150

CO

200

CO

Water vapor transmission rates (WVTR) of the HMDSO lms on PLA

substrates were measured with a Permatran C3/31 (Modern Controls
Inc., MN, USA) according to ASTM E96-93 [12]. The testing temperature
was 25 C with 100% relative humidity. Three samples were measured
in each deposition condition.
Scanning electron microscopy (SEM) was used to examine the
surface of the samples. The SEM employed in this work was a Jeol
JSM-5910LV (Jeol, Japan).
Atomic force microscopy (AFM) was carried out to observe surface
topography of the lms on PLA substrates. The AFM used was a
NanoScope III (Digital Instrument, USA), operated in tapping mode.
The images were collected at a xed scan rate of 1 Hz. The sampling
rate was 256 samples/line.
X-ray photoelectron spectroscopy (XPS) was used to obtain chemically specic information of the lms on PLA. XPS spectra were obtained
with a Kratos Axis DLD Ultra (Kratos Analytical Ltd., UK). All peaks in the
spectra were referenced to the signature C1s peak for adventitious
carbon at 284.6 eV.
The thickness of the lms on Si wafers was measured using an
alpha-SE spectroscopic ellipsometer (J.A. Woollam Co. Inc., NE, USA)
in a spectral range of 300 nm900 nm. The spectrum was tted
using a Si with absorbing lm model.

Intensity (a.u.)

2.2. Characterization techniques

Intensity (a.u.)

350

100
OH

3.1. Optical emission spectroscopy analyses

Fig. 1 shows the emission spectra of HMDSO plasma discharged at
40 W in Ar (Ar/HMDSO) and O2 (O2/HMDSO). The emission line assignments are listed in Table 1 [7,13,14]. Methyl group abstraction
is a key step in the fragmentation of HMDSO upon electron impact
in RF discharge due to the low bond energy of Si\C. The dissociation
of methyl groups could be observed through the emission of H, H2,
and C2. The presence of SiO emission lines in the spectral range
216293 nm indicated the fragmentation of Si\O\Si. We expected
that species like SiO, C, and H played a role in the lm growth. The
emission lines of Ar were dominant in the spectrum of Ar/HMDSO
(Fig. 1(a)). The presence of weak OH and CO lines can be attributed
to the interaction between oxygen atoms in the residual water
vapor in the system and carbon or hydrogen containing species
issued from the dissociation of HMDSO. For O2/HMDSO plasma
(Fig. 1(b)), the emission lines of hydrogen were obvious. It is notable
that the emission of O could be observed at 777 nm in O2/HMDSO
whereas it could not be detected in Ar/HMDSO. The atomic hydrogen
can react with oxygen and produce OH. In O2/HMDSO, a reaction
between R1SiO and R2SiOSi can be the initiation of the long
chains Si\O\Si and produce SiOx-like structure in the lm [15].

50
H2

SiO

0
200

300

500

600

700

800

Wavelength (nm)
Fig. 1. Optical emission spectra of (a) Ar/HMDSO, and (b) O2/HMDSO obtained at RF
power of 40 W.

in O2 (O2/HMDSO) deteriorated the barrier to water vapor of PLA. The

transmission rates were higher than that of uncoated PLA.
In plasma polymer deposition process, lm deposition is achieved
by the interactions between the generated active species on the surface of substrates. Process parameters, monomers, and methods of
discharge have a great inuence on the lm properties. In the case
of inductively-coupled discharge, the degree of ionization and dissociation of the plasma becomes higher and leads to higher frequency

Table 1
Emission lines of HMDSO plasma.
Species

Wavelength (nm)

SiO

216293 (main system)

424 (weak system)
414.0
586670
427.1
656.3, 486.1, 434.0
512.9516.5
575800
281309
777

3.2. Water vapor transmission rate measurements

The results of water vapor transmission rate (WVTR) measurements
of HMDSO lms on PLA substrates are shown in Fig. 2. HMDSO lms deposited in Ar (Ar/HMDSO) at the discharge powers of 10 W, 30 W, and
40 W could substantially decrease the WVTR of PLA. When the discharge power was further increased to 50 W and 60 W, the transmission rates of the composite lms became higher. The lms deposited

400

SiH
H2
H, H, H
C2
CO
OH
O

14

C. Chaiwong et al. / Surface & Coatings Technology 229 (2013) 1217

30

argon+HMDSO

oxygen+HMDSO

WVTR (g/m2.day)

25
20
15
10
5
0

10W

30W

40W

50W

60W

uncoated

RF powers (W)
Fig. 2. Water vapor transmission rates (WVTR) of Ar/HMDSO and O2/HMDSO lms on
PLA. The lms were deposited at varied RF powers with a xed deposition time of
10 min. WVTR of uncoated PLA is also shown in the gure.

of electron-neutral collisions when the RF power increased. The plasma density is generally proportional to the power absorbed by the
plasma. For a high supplied RF power, a high plasma density is responsible for a strong skin effect i.e. most of the RF energy is deposited within a certain skin depth of the plasma and reduces the absorbed
power. Some electrons undergo thermal motion and traverse the skin
layer quickly thus the electric eld has short time to interact with
them. The electrons gain less energy from the electric eld. However,
they acquire some energy which can be transferred to the heavy particles outside the skin layer producing more excited species and radicals due to their shortened mean free path inside the discharge. As
the plasma density is raised, the plasma potential decreases to maintain the quasineutrality. This induces an increasing DC-sheath voltage
on the substrate resulting in a greater ion bombarding energy. Therefore, a competition between sputtering and deposition in the process occurs. Sputtering of the surface may cause a coarse texture with voids in
between which in turn contributes to the higher WVTR in the Ar/
HMDSO lms prepared with the RF of 50 W and 60 W. Addition of oxygen in O2/HMDSO is expected to promote lms with dense SiOx-like
structure that can decrease the gas transmission of the substrates. However, our results are inconsistent with the expectations. In the next section, we report the observation of the lm topography to clarify the
factors that affect the WVTR of the lms.

3.3. SEM results

In order to elucidate the lm properties that have an inuence on
the WVTR, SEM was carried out. The results are shown in Fig. 3. All
the samples coated with Ar/HMDSO lms were relatively smooth.
On the contrary, the O2/HMDSO lms were covered with cracks.
Film delamination was also observed. It is obvious that cracking of
HMDSO lm had a profound impact on the WVTR as previously observed. Deformation of the substrate was also found. The fracture
and deformation of the lm and the substrate lead to signicant loss
in the barrier of the composite lms [16].
It is known that cracking and delamination of thin lms are the consequences of residual stress. In general, the residual stress results from
the contribution of intrinsic and thermal stresses. In our work, the contribution of thermal stress can be ruled out since the deposition temperature was relatively at room temperature. Intrinsic stress is caused by
the deposition conditions during the growth and typically involves the
microstructure of a lm. Moreover, the mismatch between mechanical
properties of the lm and the substrate can contribute to the intrinsic
stress [17]. The cracking of the O2/HMDSO lms on PLA indicates that
high level of intrinsic stress was generated. According to Krner et al.
[18] a high compressive stress of 487 MPa could be generated in the
HMDSO lm deposited in oxygen onto polyethylene terephthalate

Fig. 3. SEM micrographs of (a) smooth Ar/HMDSO lm on PLA, (b) cracking and delamination of O2/HMDSO lm on PLA, and (c) delamination of O2/HMDSO lm and deformation of PLA substrate. The lms were deposited at 40 W.

(PET). It can be implied that SiOx-like structure with high bond energy
was formed and induced an increase in the elastic modulus of the deposited lm. Therefore, a mismatch between mechanical properties was induced leading to the fracture of the lms.
3.4. XPS analyses
The elemental composition of the HMDSO lms on PLA substrates
were obtained using XPS. The samples prepared at 10 W and 30 W
were chosen to present the effect of the carrier gases. The atomic

C. Chaiwong et al. / Surface & Coatings Technology 229 (2013) 1217

15

Table 2
XPS composition analysis of HMDSO lms on PLA substrates.
Carrier gases

RF powers (W)

Ar
Ar
O2
O2

% Atomic concentration

10
30
10
30

Atomic concentration ratio

Si

Si/C

Si/O

19.69
16.54
27.94
27.49

48.58
61.41
6.50
3.15

31.72
22.32
65.96
69.36

0.41
0.27
4.30
8.72

0.62
0.74
0.42
0.40

concentrations of Si, O, and C in the lms gained from the survey

scans are shown in Table 2. The Ar/HMDSO lms contained high
level of carbon. For the O2/HMDSO lms, the carbon content was
decreased signicantly while the oxygen and silicon contents were
increased. The increase in oxygen and silicon can lead to the formation
of the lms with a high degree of cross-linking. The O/Si and C/Si ratios
presented in Table 2 indicated that lms with chemical composition
close to SiOx were produced when O2 was used as the carrier gas. The
substantial loss of carbon in the lms through the addition of O2 could
result from the preferential etching of the carbon content in the lm
by the excessive oxygen in the plasma and the enhanced oxidation reaction in the bulk plasma [6,15]. Progressive removal of organic composition from the lm occurred when the discharge power increased.
Oxygen atoms in the plasma could also oxidize the carbon fragments
of HMDSO forming CO or CO2 which did not involve in the lm
formation.

To obtain the insight information on the chemical bonding in the

HMDSO lms, the Si2p and C1s peaks of the lms deposited at
30 W were deconvoluted and shown in Fig. 4. The Si2p peak of the
lm deposited in Ar could be tted with 3 peaks corresponding to
SiO2(CH3)2, SiO(CH3)3, and SiO4. The SiO2(CH3)2 peak was distinctive.
The high portion of SiO2(CH3)2 suggested that the lm possessed a
structure that is similar to polydimethylsiloxane (PDMS). The presence of SiO(CH3)3 was the product of oxidized PDMS. The C1s could
be deconvoluted to a large peak corresponding to C\C/C\H and a
small peak corresponding to C\O. For the lm deposited in O2, the
deconvolution of Si2p revealed only 2 peaks corresponding to SiO4
and to SiO(CH3)3 with the absence of SiO2(CH3)2. The inorganic structure SiO4 which represents Si in a fully oxidized state was dominant
in the deconvoluted peak. The C1s contained 3 peaks i.e. a large
peak of C\C/C\H and 2 small peaks corresponding to C\O and
COOH/COOR. The latter is induced by the oxidation scheme of methyl

b
C-C/C-H
SiO2(CH3)2

SiO4

SiO(CH3)3

C-O

106

105

104

103

102

101

100

99

289

288

287

286

285

284

283

282

281

Binding energy (eV)

Binding energy (eV)

d
C-C/C-H

SiO4

SiO(CH3)3

C-O
O-C=O

108

107

106

105

104

103

Binding energy (eV)

102

101

100

292

290

288

286

284

282

280

Binding energy (eV)

Fig. 4. Deconvoluted peaks obtained from XPS measurements of lms deposited on PLA at 30 W. (a) Si2p of Ar/HMDSO, (b) C1s of Ar/HMDSO, (c) Si2p of O2/HMDSO, and (d) C1s of
O2/HMDSO.

16

C. Chaiwong et al. / Surface & Coatings Technology 229 (2013) 1217

groups [15]. These ndings support that the lms with organic structure SiOxCyHz was formed when Ar was used as a carrier gas meanwhile inorganic structure was induced in the lms deposited in O2.

3.5. AFM measurements

AFM measurements were carried out for uncoated PLA and selected samples of HMDSO lms on PLA. The results are shown in Fig. 5.
The uncoated PLA has a smooth surface with the root mean square
(rms) roughness of 2.99 nm. The Ar/HMDSO of 10 W shows a rather
smooth surface with some protrusion annular structures. A considerable change in the surface topography occurred in the lm deposited
at 50 W. The surface was rather rough with a coarse texture. The rms
roughness increased to 37.70 nm. This feature can be attributed
to the impinging of high energy ions caused by the increased
DC-sheath voltage on the substrate at high plasma density. It is
likely that the coarse surface deteriorates the barrier to water
vapor of the lms. The bombardment of plasma ions during the
lm growth could contribute to the high surface roughness resulting

in more defect sites; such as pinholes, voids and microcracks. Moreover

the deformation of the PLA substrate caused by the failure of the lms
increased the surface of the composite lm exposing to the water
vapor. These defects enhance diffusion of the water vapor through the
lms. For the O2/HMDSO lm of 10 W, the surface was covered with
random protrusions. When the RF power was increased to 50 W, a
smoother surface was observed. This can be explained by the etching
of the surface of the lm due to the presence of oxygen, as seen in the
emission spectrum.

3.6. Film thickness measurements

The thickness of the lms on Si substrates was shown in Table 3.
The thickness of O2/HMDSO lms was less than that of Ar/HMDSO
lms. This can be described by the etching of the lm during the deposition process caused by oxygen in the plasma. The thickness of the
lms was not proportion to the RF powers. Cracking occurred in the
O2/HMDSO lms although the thickness was half of the Ar/HMDSO
lms indicating that the lms were under stress.

Fig. 5. Surface topography obtained from AFM measurements of (a) uncoated PLA, (b) Ar/HMDSO lm at 10 W, (c) Ar/HMDSO lm at 50 W, (d) O2/HMDSO lm at 10 W, and (e) O2/HMDSO at
50 W. Films were deposited on PLA for 10 min. Note the difference in z-axis scales.

C. Chaiwong et al. / Surface & Coatings Technology 229 (2013) 1217

Acknowledgments

Table 3
Thickness of the lms on Si substrates.
RF powers (W)

10
20
30
40
50
60

17

Thickness (nm)
Ar/HMDSO

O2/HMDSO

95.6 0.5
164.7 0.7
188.7 0.9
131.3 0.3
172.1 0.9
167.4 0.4

51.6 0.2
43.5 0.8
54.5 0.2
51.9 0.3
88.6 0.9
66.0 0.3

4. Conclusions
We report the effect of carrier gases; Ar and O2; on the properties of
plasma polymerized HMDSO lms. In the process of plasma polymerization, HMDSO monomer was broken into smaller fragments as seen in the
emission spectra of the plasmas. The complexity of chemical structure
and the dissociation process of HMDSO in the plasma state as well as
the interactions between the plasma and the substrate result in a variety
of structures. The structure of the lm can be either organic or inorganic.
The organic structure is similar to polymethylsiloxane whereas the inorganic one is similar to silicon oxide.
The lms deposited in Ar contain organic structure in the form of
SiOxCyHz. The lms could signicantly enhance the barrier to water
vapor of PLA. The inorganic structure was obtained when O2 was used
as the carrier gas. However, the mechanical mismatch between the
lm and the PLA substrate led to lm cracking and delamination. The
failures of the lm resulted in a complete destruction of the barrier to
water of PLA. The discharge power contributed to the plasma species
and the energy of the ions traversing through the plasma sheath leading
to etching and diverse surface topography of the lms.

C. Chaiwong would like to acknowledge the nancial support

from the Thailand Research Fund (TRF) under the contract number MRG5380224 and the Thailand Center of Excellence in Physics
(ThEP).

References
[1] Y.S. Lin, C.H. Hu, C.A. Hsiao, Compos. Sci. Technol. 71 (2011) 1579.
[2] K. Li, J. Meichsner, Surf. Coat. Technol. 116119 (1999) 841.
[3] M.L.P. da Silva, I.H. Tan, A.P. Nascimento Filho, E. Galeazzo, D.P. Jesus, Sens. Actuators
B Chem. 91 (2003) 362.
[4] J. Chojnowski, S. Rubinsztajn, L. Wilczek, Macromolecules 20 (1987) 2345.
[5] R. Morent, N. De Geyter, S. Van Vlierberghe, P. Dubruel, E. Schacht, Surf. Coat.
Technol. 203 (2009) 1366.
[6] A. Walkiewicz-Pietrzykowska, J.P. Espins, A.R. Gonzlez-Elipe, J. Vac. Sci. Technol.
A 24 (2006) 988.
[7] Y. Wang, J. Zhang, X. Shen, Mater. Chem. Phys. 96 (2006) 498.
[8] S. Saloum, M. Naddaf, B. Alkhaled, Vacuum 82 (2008) 742.
[9] A.J. Choudhury, J. Chutia, H. Katati, S.A. Barve, A.R. Pal, N.S. Sarma, D. Chowdhury,
D.S. Patil, Vacuum 84 (2010) 1327.
[10] A.J. Choudhury, S.A. Barve, J. Chutia, A.R. Pal, R. Kishore, Jagannth, M. Pande, D.S.
Patil, Appl. Surf. Sci. 257 (2011) 8469.
[11] C. Chaiwong, P. Rachtanapun, P. Wongchaiya, R. Auras, D. Boonyawan, Surf. Coat.
Technol. 204 (2010) 2933.
[12] American Society for Testing and Materials, Annual Book of ASTM Standards,
E96-93, Vol. 04.06, Philadelphia, 1996.
[13] M. Goujon, T. Belmonte, G. Henrion, Surf. Coat. Technol. 188189 (2004) 756.
[14] A. Granier, M. Vervloet, K. Aumaille, C. Valle, Plasma Sources Sci. Technol. 12
(2003) 89.
[15] G.F. Leu, A. Brockhaus, J. Engemann, Surf. Coat. Technol. 174175 (2003) 928.
[16] D. Tsubone, H. Kodama, T. Hasebe, A. Hotta, Surf. Coat. Technol. 201 (2007) 6431.
[17] C. Chaiwong, D.R. McKenzie, M.M.M. Bilek, Surf. Coat. Technol. 201 (2007) 5596.
[18] L. Krner, A. Sonnenfeld, R. Heuberger, J.H. Waller, Y. Leterrier, J.A.E. Mnson,
Ph. R. von Rohr, J. Phys. D: Appl. Phys. 43 (2010) 115301.