Carbon 43 (2005) 303–309

www.elsevier.com/locate/carbon

Structural investigation and gas barrier performance of

diamond-like carbon based films on polymer substrates
G.A. Abbas, S.S. Roy *, P. Papakonstantinou, J.A. McLaughlin
Nanotechnology Research Institute, School of Electrical and Mechanical Engineering, University of Ulster, Newtownabbey, BT37 0QB, UK

Received 28 June 2004; accepted 9 September 2004

Abstract

In this report, tetrahedral amorphous carbon (ta-C), hydrogenated amorphous carbon (a-C:H), silicon doped tetrahedral amor-
phous carbon (ta-C:Si:H), and silicon doped hydrogenated amorphous carbon (a-C:H:Si) films with thickness in the range 50–
370 nm have been produced by PECVD (Plasma Enhanced Chemical Vapour Deposition) and FCVA (Filtered Cathodic Vacuum
Arc) techniques on Polyethylene terepthalate (PET) and polycarbonate (PC) substrates. The paper is concerned with exploring the
links between the atomic structure, gas barrier performance in carbon based films deposited on polymer substrates. A range of tech-
niques including XRR, NEXAFS, Raman, surface profilometry, nano-indentation and water vapour permeation analysis were used
to analyze the microstructure and properties of the films. The intensity and area of p* peak at the C K (carbon) edge of the NEXAFS
spectra was lower in the FCVA films in comparison to that of PECVD ones confirming the higher sp3 content of FCVA films. The
surface of ta-C films showed a network of micro-cracks, which is detrimental for gas barrier application. However, the surfaces of
both ta-C:H:Si and a-C:H:Si silicon-incorporated films were almost free of cracks. We also found that the incorporation of Si into
both types of DLC films lead to a significant reduction of water vapour transmission rate.

2004 Elsevier Ltd. All rights reserved.

Keywords: A. Diamond-like carbon; B. Arc discharge, Chemical vapor deposition; D. Microstructure

1. Introduction resistance, and high susceptibility to either gases or

Plastics are presently widely used as cheap, transpar-
ent, light-weight, and unbreakable substitutes for glasses
in several applications, including automotive and soft
drink industries as well as for organic light emitting de-
vices (OLED) display applications. Moreover, a variety
of medical devices made of polymers are now been used
as ophthalmic lenses and as heart valves being im-
planted in human body. However, the use of polymers
is limited because of its low hardness, poor scratch
*
Corresponding author. Tel.: +44 28 80368997; fax: +44 28 903
66863.
E-mail address: s.sinha-roy@ulster.ac.uk (S.S. Roy).
chemicals.
Alternatives have been developed for modifying the
polymer surfaces to have a high gas barrier property,
good adhesion and chemical stability in different hazard
environments [1–6]. The surface modification of poly-
mer films with amorphous diamond-like carbon (DLC)
is one of these new promising methods. DLC films have
all the properties needed for excellent barrier coatings
including: high hardness, excellent chemical and thermal
stability and it is transparent in the visible spectrum. In
addition, carbon is already present in plastics, and there
is no implication with regards to recycling.
Recently, a number of techniques have been used for
coating polymer substrates with DLC films including
PECVD [7], ion implantation (II) [8–10], ion beam as-
sisted deposition (IBAD) [11], and pulsed laser deposition

0008-6223/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.09.016
304 G.A. Abbas et al. / Carbon 43 (2005) 303–309
(PLD) [12], techniques. To our knowledge, so far there is
no work reported on ta-C coatings on polymers synthe-
sized by the FCVA technique. The high level of compres-
sive stress in ta-C films is a major drawback of these types
of coatings. It does not only put an upper limit to the
thickness of the coatings over wide range of substrates,
but it also has a dramatic effect on the surface morpho-
logy on soft substrates such polymers [12]. This area is lar-
gely unexplored.
In this study, we demonstrate the fabrication of supe-
rior gas barrier, hard, transparent and stress free DLC
coatings on different types of polymer substrates such
as PC and PET. We propose a strategy (incorporation
of silicon) for releasing the compressive stress in these
films. Moreover, the silicon-induced-modification in sur-
face morphology, electronic structure, and the gas bar-
rier performance of different DLC films is also explored.
2. Experimental
In this study we used untreated 75-lm thick optical
grade Poly(ethylene terepthalate) (PET) (Hostaphane)
and polycarbonate (PC) coated commercial CDs as sub-
strates. The pure ta-C films were produced by FCVA
system equipped with double bend off-plane (DBOP) fil-
ter to screen the macro-and micro-particles. A scanning
waveform was used at the exit of the plasma duct to scan
the plasma beam before deposition onto the out-of-sight
substrates. The substrate holder has been also rotated to
increase the thickness uniformity of the deposited films.
Films were prepared under floating condition, i.e. with-
out any substrate bias with 80 A arc current at room
temperature and a pressure of 1 · 10
6 Torr. The pure
a-C:H films were deposited by RF (13.56 MHz) PECVD
using C2H2/Ar plasma with a ratio of 2:1 at electrode
self-bias voltage of 300 V. For silicon-incorporated sam-
ples, Tetramethylsilane (TMS) vapour was introduced
as a Si source inside the plasma deposition chambers
for both coating systems. Details of the deposition tech-
niques can be found elsewhere [13].
The XRR measurements were performed using a
Philips Analytical high resolution X-ray diffractometer
using a Cu Ka (k = 1.541 Å) for the determination of
the film density and thickness. A nano-indenter was
used to measure the hardness of the films. A water va-
pour permeation analysis system (Permatran-W 3/31)
was used for Water vapour transmission rate (WVTR)
measurements under conditions of (20 C and 70%
RH). A surface profilometer (TencorP-10) was used to
measure the residual stress of DLC films on Si substrates
by using the radius of curvature method with an average
of 6 measurements at different locations for each film.
The stress, rs, in a thin film of thickness tf is given by
stoneyÕs equation
 2  
Es ts 1 1
rs ¼
; ð1Þ
6ð1
ms Þ tf R R0
where Es, ms, and ts are the Young modulus, Poisson ra-
tio and thickness of the substrate respectively. The R0
and R are the radii of curvature of the substrate before
and after coating, respectively. An optical profilometer
[WYKO NT800] was used for surface morphology
study. Nano-indentation tests were carried out using a
Nano-indenter XP (Nanoinstruments Inc) with a high-
resolution (1 nN) dynamical contact module (DCM)
head. In addition, the indenter was fitted with the con-
tinuous stiffness mode (CSM) option. The indentations
were performed using CSM mode at a constant rate of
0.05 s
1 up to 100-nm depth. The Hardness (H) values
are averaged over eight indents.
The silicon content in DLC films was determined by
X-ray photoelectron spectroscopy (XPS) in an XSAM
800 (KRATOS) spectrometer. An ISA Labram 300 Ra-
man spectroscope equipped with Ar ion laser (514.5 nm)
was used to examine the structure of the films. In order
to precisely estimate the sp2 contents in the film, NEX-
AFS measurement was carried out at the Synchrotron
Radiation facility of CCLRC at Daresbury using the
Beam Line 1.1. Soft X-rays generated from synchrotron
source were used for scanning the films within energy
range of 275–320 eV.
3. Results and discussion
3.1. Density, stress and gas barrier properties of carbon
nano-layers on PET
X-ray reflectivity (XRR) is a widely used technique,
for determining density and thickness of thin films by
measuring the reflection coefficient as a function of the
glancing angle of incidence, R = f(h). Fig. 1 shows two
representative XRR spectra of a PECVD (100-nm thick)
and a FCVA (50-nm thick) samples. The reflectivity
sharply decreases at the critical angle from which the
density (q) value can be evaluated [14]. One can notice
the difference in the critical angle of the two films, with
a lower incidence angle shift as an indication of lower
density. The ta-C film has a higher density (3.2 g/cm3)
in comparison to the PECVD film, in which the value
of density reduced to be 2.3 g/cm3.
This is an expected result. Obviously, the energy of
the carbon ions together with the hydrogen content play
a crucial role in determining the density value. For the
FCVA system, no hydrogen was included, the carbon
ions were of relatively high energy, mono-energetic
(20–30 eV) and highly ionized. This is contrast to the
PECVD system, where the precursor gas (C2H2) in-
cluded hydrogen, the ion energies were broadly distrib-
uted around value of 5 eV leading to a lower film
 G.A. Abbas et al. / Carbon 43 (2005) 303–309 305

tent, have a high diamond-like property (sp3  70%)

with high stress values up to (8–12 GPa). On the other
10
4
hand, PECVD a-C:H films contain higher hydrogen
content (up to 30%), which resulted in less compact struc-
Reflectivity (a.u)

FCVA ( =3.1 g cm-3 )
10
2
PECVD (ρ =2.3 g cm-3 )
0
10
500 1000 1500 2000 2500
Incident angle (arcsecond)
Fig. 1. Two representative XRR spectra of a-C:H film (100-nm thick)
and ta-C (50-nm thick) deposited on silicon substrates using PECVD
and a FCVA, respectively.
density. According to the subplantation model, the high-
est densities occur for ion energies just above a critical
value, which is necessary to penetrate the surface layers
inducing stress, transforming sp2 states into sp3 states
[15,16].
The measurements of water vapour transmission rate,
WVTR, for a-C:H, ta-C and Si doped DLC coatings on
PET substrates are listed in Table 1. The results show
that, undoped DLC coatings did not show a significant
reduction in the water vapour transmission rate. More-
over, lower density PECVD film had a superior gas
barrier property (WVTR = 0.56 g/m2 day) than the high-
er-density ta-C film (WVTR = 1.4 g/m2 day). Silicon-
incorporation into both the hydrogenated amorphous
carbon and tetrahedral amorphous carbon films reduced
the water vapour transmission rate over two orders of
magnitude.
It appears that the Si-incorporation succeeded in
relaxing the stressed-structures for both types of DLC
films. However, different amount of silicon was neces-
sary to release the different level of stress in both films.
While a silicon content of 7.8 at.% was enough for relax-
ing a stress level of 3.5 Gpa in a-C:H, a 21.5 at.% of sil-
icon was necessary for releasing a compressive stress of
12 GPa in ta-C films (see Table 1).
Both density and stress measurements are in agree-
ment. Usually, ta-C films, with very low hydrogen con-
ture, containing high percentage of voids, with lower
stress values.
There are two factors could be responsible on the
relaxation of the DLC structure. Firstly, the formation
of weaker Si–H bonds, which caused the relaxation of
a three-dimensional rigid network and reduced the com-
pressive stress in the films [17]. Secondly, the substitu-
tion of carbon atoms of the sp3 bonds by Si atoms
and the formation of Si–C bonds can play a role in
3000 releasing bond distortion of the nearby strong sp3 C–C
bonds (3.7 eV; 411 kJ mol
1) with large strain in the
weaker Si–C bonds (3.21 eV; 320 kJ mol
1) and decreas-
ing the residual stress of the DLC structure [18,19]. We
have to emphasize that using TMS precursor gas as a sil-
icon source inside the FCVA deposition chamber has
been resulted in incorporation of hydrogen as well as sil-
icon in the ta-C films. Therefore, the Si incorporation in
both ta-C and a-C:H films seems to relax the stressed
structure but with development of more polymer-like
structure in these films.
3.2. Structural characterization of carbon nano-layers
on PC
3.2.1. Raman spectroscopy
Depending on the sp3/sp2 ratio of carbon bonds, the
visible Raman spectra of DLC films always show a sin-
gle G peak or two peaks (G peak and D peak) in the
1100–1800 cm
1 region [20,21]. The G peak is connected
to the presence of all sp2 structures, both olefinic
(chains) and aromatic (rings) while the D peak is related
to the presence of aromatic rings only [20]. Two repre-
sentative Raman spectra are demonstrated in Fig. 2.
One can clearly observe the difference between the ta-
C and a-C:H spectra. Significant changes occurred near
the D peak position. The D peak was prominent in a-
C:H film indicating a higher sp2 content. This shoulder
has disappeared and the spectrum becomes more sym-
metric for ta-C film. The spikes appear in the spectra
due to the polymer substrate.
The spectra were fitted with two Gaussian peaks for
G and D bands. Raman parameters calculated from

Table 1
Summary of the study of DLC nano-nalyes on PET
DLC type Deposition method Thickness (nm) Si% WVTR (g/m2 day) Density (g/cm3) Stress (GPa)
a-C:H PECVD 148 0 0.5611 2.27 3.5
a-C:H:Si PECVD 237 7.8 0.0316 1.94 0.5
ta-C FCVA 127 0 1.407 3.2 8–13
ta-C:Si:H FCVA 370 21.5 0.0892 2.2 0
Uncoated-PET – – – 1.614 – –
306 G.A. Abbas et al. / Carbon 43 (2005) 303–309
Fig. 2. (a) Typical Raman spectra of a-C:H films synthesized by PECVD. (b) Raman spectra of a ta-C films synthesized by FCVA.
Table 2
Summary of the studies of ta-C and a-C:H nano-layer coated PC substrates
DLC Type Thickness (nm) ID/IG ratio
a-C:H by PECVD 100 0.83
ta-C by FCVA 100 0.25
the fittings are listed in Table 2. The ID/IG ratio in-
creased and the G linewidth and G position decreased
in a-C:H films compared to those of ta-C films. In amor-
phous carbon films the ID/IG intensity ratio, G line
width and G peak position are the most commonly used
indicators of any structural changes. The high ID/IG ra-
tio and narrow G line width in a-C:H films indicates
higher sp2 content. This prediction was further sup-
ported by NEXAFS measurements reported later. It is
well established that the G peak dispersion of any car-
bon films depend on various factors such as film thick-
ness, deposition condition, substrate, laser wavelength,
film stress and to some extent on instrumental precision.
So the above factors should be taken into consideration
when comparing results from the literature. We found
(Table 2) the ta-C film has a higher G peak position than
that of a-C:H film. Recently, Shin et al. [22] found the G
peak of the Raman spectrum shifts to higher wave num-
bers with the increase of compressive stress. The higher
stress in ta-C films may be one of the reasons for the
higher G wave number in ta-C films.
The intensity of the D band is quite sensitive to the
size of crystalline nano-domains. The relation for esti-
mating the size of ordered regions from the ID/IG ratio
in the Raman spectra of carbon is as follows [20]:
ID
¼ CðkÞL2a ;
IG
where C is a constant having a value of approxi-
mately 0.0055 at 514.5 nm and La (620 Å) is a linear
dimension of the ordered region. The sp2 cluster size
estimated from Eq. (2) was much higher for a-C:H films
(12.28 Å) than ta-C films (6.7 Å). The increase of
cluster size at a-C:H films leads to the formation of
structures with reduced three-dimensional cross-linking.
G position G width sp2 content Hardness (GPa)
1554 150 60% 2
1565 220 35% 8
The increase in sp2 cluster size in a-C:H films is in agree-
ment with a reduction in hardness as evaluated by nano-
indentation studies shown in Table 2.
The measurement of the mechanical properties on
thin films is problematic due to the effect of the underly-
ing substrate. The common approach for dealing with
this problem and to get the substrate-independent meas-
urements is to restrain the indentation depth to less than
10% of the film thickness [23]. However, for films 100-
nm thick as in our case, 1/10 of film thickness corre-
sponds to 10 nm. Accurate measurements at this scale
are difficult to obtain due to vibration, tip rounding ef-
fects and difficulties in precise determination of the loca-
tion of the specimen surface. Since the main purpose in
our study is to obtain a ranking in the mechanical prop-
erties between ta-C and a-C:H films, we considered data
obtained at a contact depth of 50% (around 50 nm in our
case) of the coating thickness as representative of the
composite film/substrate.
3.2.2. NEXAFS spectroscopy
The sp2 content was quantitatively determined for ta-
C and a-C:H films by near edge X-ray absorption fine
structure (NEXAFS) spectroscopy and is listed in Table
2. The details of the sp2 content determination are pro-
vided in the literature [24]. Fig. 3a shows a C K-edge
ð2Þ NEXAFS spectra of ta-C and a-C:H films on PC sub-
strate along with HOPC graphite. All spectra were nor-
malized to the maximum peak at about 290 eV and
shifted upward for ease of comparison.
A pre-edge resonance at 285.5 eV is due to transitions
from the C 1s orbital to the unoccupied p* orbitals ide-
ally originating from sp2 (C=C) sites, and also from sp
(C„C) sites, if present. This peak is not visible in the
spectrum of diamond, because diamond does not have
 G.A. Abbas et al. / Carbon 43 (2005) 303–309
Fig. 3. (a) C K-edge NEXAFS spectra of ta-C and a-C:H films on PC
substrate along with graphite reference. (b) Angular dependence of the
C K-edge NEXAFS of a ta-C film on PC substrate.
any sp2 (C=C) sites. Therefore, the peak intensity of this
resonance can be considered as an index of sp2 content.
It is clear from Fig. 3a that the intensity and area of p*
peak (which indicates the sp2 content in the film) at the
C K (carbon) edge decreased significantly in ta-C films in
comparison to that of a-C:H films.
It is important to note that, the NEXAFS spectrum
solely shows information on the surface of the film and
it is not influenced by film thickness. The peak near
289 eV corresponds to the r* C–H transition of the C–
H bonds that would originate from the inherent C–H
bonds in films and/or from the absorption of hydrocar-
bon to the surface dangling bonds [25,26]. The broad
band between 290 and 310 eV results from overlapping
C 1s ! r* transition at sp2 or/and sp3 sites. Finally the
sp2 content in a-C:H films deposited on PC is 25% higher
than that of ta-C films, and is consistent with other spect-
roscopic measurements.
The presence of local order in the DLC nano-layer is
observed (Fig. 3b) in the angular dependence of the
NEXAFS. As the synchrotron light is linearly polarized
horizontally, the resonance intensity of the p* transition
307
is very sensitive to the orientation of the p* orbital with
respect to the polarization vector. Thus, if the p* orbit-
als in the DLC specimen are partially oriented with re-
spect to the incident photon beam, a rotation of the
film plane with respect to the incoming photon will show
a recognisable angular dependence. Only a C–C or C–H
r* orbital orthogonal to the p* orbital will show an
opposite trend.
Fig. 3b illustrates that the p* resonance intensity de-
creases from normal to 30 incidence while the C–H r*
exhibits an opposite trend. Our results clearly reflect that
the (C=C) p* and C–H r* bonding configurations are
orthogonal to each other. The intense C–H r* reso-
nance observed at lower angle indicates the presence
of a C–H bond in the graphitic-like basal plane. This ef-
fect is being very interesting since in general amorphous
films do not show any partial orientation. Our result
indicates that the sp2 clusters are not randomly oriented
in the ta-C films on PC substrate. Intensity of the C–H
(r*) peak as depicted in Fig. 3b showed an opposite
trend to that of C=C (p*) peak. Recently Lee et al.
[26] found by a combination of NEXAFS and electron
spin resonance spectroscopies that the surface defects
or dangling bonds in ta-C films are proportional to the
content of the sp3 hybridized bond. This means that a
higher sp3 content will be accompanied by higher defect
density. This is in agreement with our NEXAFS data of
Fig. 3 which show a high rC–H contribution in ta-C
films. The rC–H contribution in a-C:H films mainly from
the intrinsic C–H bonds of the films. The defect density
in a-C:H films might be lower, as the number of sp2 site
increases in the a-C:H films most unpaired sp2 sites do
not act as the defects but form carbon carbon double
bonds [26].
3.3. Surface morphology
The Fig. 4a shows clearly a network of cracks spread
out over the whole membrane surface with crack depths
reaching down to the film-polymer interface. By using
silicon incorporation in the a-C:H films, the cracks com-
pletely disappeared (as in Fig. 4b) [13]. Surface rough-
ness of all films was smaller than 10 nm. Fig. 5
displays optical microscopy images of various carbon-
based films coated on the PET membrane. Both pure
ta-C and a-C:H films on polymer substrate had surfaces
covered by network of micro-cracks. However, ta-C
films were characterised with deeper and wider micro-
cracks in comparison to those of a-C:H, (Fig. 5) which
is most probable due to the high stress values of ta-C
films (8–13 GPa) with respect to those of a-C:H films
(3.5 GPa).
Due to the high intrinsic stress in DLC films and lower
surface tension of polymer substrates, surface crack-
ing has been previously observed for a-C:H [27,28] and
ta-C films [12,26] on different polymeric substrates.
308 G.A. Abbas et al. / Carbon 43 (2005) 303–309
Fig. 4. The optical profilometer images of (a) ta-C and (b) a-C:H:Si films on PC substrates.
Fig. 5. Optical microscopy images with a magnification · 10 of carbon based films on PET substrate (a) a 130-nm thick a-C:H layer, (b) a 150-nm
thick hard ta-C layer and (c) 300-nm thick ta-C:Si:H layer.
Earlier, Ong et al. [29] observed a similar surface mor-
phology for ta-C films on polycarbonate (PC) substrate.
They showed that oxygen plasma pretreatment for 1 h
was efficient in releasing the stress and improving both
the surface morphology and the adhesion. They sug-
gested that plasma treatment caused an introduction of
polar groups onto the surface of the polymer, which en-
hanced the adhesion. Moreover, Bonelli et al. [12] per-
formed residual stress measurements for similar PLD
ta-C films on the same PC substrates. Their films exhib-
ited a residual stress value of 4.5 GPa. They showed that
incorporation of nitrogen resulted in reduction of the
high residual stress accompanied by a crack free surface.
We have to emphasize that, the stress value on PC
substrate is expected to be lower than the corresponding
value on silicon substrate due to release of stress
through surface cracking and deformation of polymer
substrate. In this study, plastic deformation of the
PET substrates was obvious with various ta-C thick-
nesses, which is an indication of the relaxation process
of the high residual stress status in these films. Also,
the improvement in surface morphology in both a-C:H
and ta-C films can explain the enhancement in gas bar-
rier property by silicon addition. Moreover, it shows the
important role of the surface morphology of the differ-
ent DLC films on their gas barrier performance.
All the above-mentioned results are in agreement
with each other and can also be explained in terms of
deposition mechanism. The hardness was found to de-
crease in a-C:H films in comparison to that of ta-C films
(Table 2). The increase of sp2 fraction in a-C:H films is
responsible for reduction in hardness for these types of
films. PECVD deposition mechanism in which, neutral
particles with low energy stick to the growing surface
are responsible for the higher inclusion of sp2 sites.
The mechanical properties are determined by the sp3
content as well as hydrogen content in the films. The
dense and compact structure of the ta-C film with very
low hydrogen content (<2%) is responsible for the higher
hardness value.
Therefore, we may conclude that both incorporation
of hydrogen and silicon in ta-C and a-C:H films have re-
sulted in relaxing the DLC structure accompanied by a
complete reduction in the compressive stress with con-
verting the structure to more-polymer-like structure
with reduced hardness values but with superior gas bar-
rier properties.
4. Conclusions
The present study of various carbon-based nano-lay-
ers on polymer substrates can be summarised as follows:
(i) Soft a-C:H (2.3 g/cm3) and hard ta-C (3.1 g/cm3)
coatings were deposited by PECVD and FCVA
techniques, respectively on PET and PC substrates.
(ii) A network of micro-cracks was found on all the
coatings surfaces with deeper and wider spacing
for ta-C films, which was suggested to be an intrin-
sic property, correlated to the intrinsic stress (8–
12 GPa).
(iii) Si-incorporated a-C:H and ta-C films have superior
gas barrier properties and can be used as an alterna-
tive barrier coating to the metallised barrier
coatings.
 G.A. Abbas et al. / Carbon 43 (2005) 303–309
(iv) NEXAFS result confirm that the DLC films on pol-
ymer creates a locally ordered sp2 bonded network
on the film surface and the sp2 content in a-C:H
films are higher than that of ta-C films.
(v) Thin ta-C-films have improved the hardness values
of PC substrate by two orders of magnitude.
Acknowledgment
The NEXAFS measurements were performed at
CCRLC facility at Daresbury and the XRR measure-
ments at Seagate Technologies, N. Ireland.
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