Journal of Materials Processing Technology 153–154 (2004) 804–810

Characterization of DLC coatings deposited by rf magnetron sputtering

S. Chowdhury, M.T. Laugier∗ , I.Z. Rahman
Department of Physics, Materials and Surface Science Institute (MSSI), University of Limerick, National Technological Park, Limerick, Ireland

Abstract

In this work diamond-like carbon (DLC) thin films have been deposited by rf magnetron sputtering in an argon gas filled chamber using
graphite target under different substrate temperatures. The bonding property was characterized by micro Raman and estimated sp3 /sp2 in
DLC films. Raman spectra showed that sp3 -bonded carbon fraction increases from 50 to 80 ◦ C temperatures and an increase in the substrate
temperature above 80 ◦ C results in an increase in the sp2 -bonded carbon atoms in DLC thin films. Mechanical properties namely, hardness
and Young’s modulus were determined by CSMTM nanohardness tester. The hardness (H) and Young’s modulus (E) were found in the
range of 11–22 and 110–160 GPa, respectively, at different substrate temperatures and increased with increase of substrate temperature up
to 125 ◦ C and decreased thereafter. These results indicate that substrate temperature has a strong influence on the bonding properties of
the deposited films and the changes in bonding ratio (sp3 /sp2 ) were correlated with changes in the mechanical properties.
© 2004 Elsevier B.V. All rights reserved.

Keywords: DLC; rf magnetron sputtering; Micro Raman; Nanoindentation

1. Introduction bility of the depositing particles at the substrate [3]. Accord-

Carbon usually exists in several forms: graphite, diamond,
and the new form of fullerenes. All three of these forms
are crystalline in structure but have varying properties based
on the bonding order of carbon atoms. Diamond-like car-
bon (DLC) on the other hand, is amorphous in structure,
containing both sp2 (dominating bond in graphite) and sp3
(dominating bond in diamond) bonded carbon. Robertson
and O’Reilly [1] have suggested an attractive bonding model
for amorphous carbon that consists of sp2 -bonded clusters
interconnected by a random network of sp3 -bonded atomic
sites (Fig. 1). There is a significant interest in DLC coatings
because of their unique combination of desirable properties
like high hardness, low friction coefficient, good wear resis-
tance, smoothness of surface and lack of magnetic response.
These films are being developed for a wide range of applica-
tions including tribological, optical, electronic and biomed-
ical applications [2]. However, the properties of DLC have
been characterized by the volume fraction of sp3 bonds,
which can be controlled by the film deposition mechanism.
Therefore, the investigation of the bonding and mechanical
properties of DLC grown by various deposition condition
are of great interest. Substrate temperature is an important
parameter in rf magnetron sputtering and influences the mo-
∗ Corresponding author. Tel.: +353-61-202257; fax: +353-61-202423.
E-mail address: michael.laugier@ul.ie (M.T. Laugier).
ing to the sub-plantation model [4], a low energy ion will
not have enough energy to penetrate the surface, so it will
just stick to the surface and remain in its lowest energy state,
which for carbon is sp2 . If the ion energy is higher than the
penetration threshold, Ep , it has a probability to penetrate the
surface and enter a surface interstitial site. This will increase
the local density. The local bonding will then reform around
that atom according to this new density. The film is amor-
phous, so the incident atom and the target atoms are equiva-
lent. In the highly energetic conditions of ion bombardment
existing during film growth, atomic hybridizations will ad-
just easily to changes in the local density, and become more
sp2 if the density is low and more sp3 if the density is high.
The aim of this article is to characterize the mechani-
cal and bonding properties of DLC thin films deposited at
different substrate temperatures. The mechanical properties
namely hardness and Young’s modulus were investigated by
nanoindentation technique and bonding properties by micro
Raman spectroscopy.
2. Experimental
DLC films were deposited by rf magnetron sputtering
(Leybold Lab 500) system with a high-purity (99.99%) py-
rolytic graphite disk target 75 mm in diameter, mounted on
the cathode at a distance of ∼10 cm from a rotatable sub-
strate table. Base pressure of the deposition chamber was

0924-0136/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2004.04.265
 S. Chowdhury et al. / Journal of Materials Processing Technology 153–154 (2004) 804–810 805

trometer. Green laser (argon ion laser 514.52 nm) was used
3
----Sp C atom for all the measurements. Spectra were recorded from 400
----Sp2 C atom to 1900 cm−1 and fitted by two Gaussian peaks. Peak posi-
----H atom tions, amplitudes, widths at half maxima and surface areas
for each peak were measured. Integral intensity Id /Ig ratios
were calculated from the ratio of the area of D peak and
G peak, which signifies the sp3 /sp2 ratio in the films. To
facilitate measurement of film thickness, a step was made
during deposition. Thickness values were determined from
atomic force microscope (AFM) line analysis. Nanoindenta-
tion testing on the samples was carried out using a CSMTM
Fig. 1. In DLC sp2 -bonded carbon interconnected by a random network nanohardness tester (NHT) to measure the mechanical prop-
of sp3 -bonded atomic sites. erties namely hardness and Young’s modulus. The nanohard-
ness tester was calibrated by using glass and fused silica
4 samples for a range of operating conditions. Maximum load
of 0.5 and 1 mN were used in order to avoid substrate effects
3.5
for all deposited samples and the loading and unloading rate
Deposition rate (nm min -1)

3 were maintained at 1 and 2 mN min−1 , respectively. In order

2.5 to ensure the absence of thermal drift a 10 s pause time was
given between loading and unloading cycles. The hardness
2
and Young’s modulus were then determined by the Oliver
1.5 and Pharr method [5].
1

0.5
3. Result and discussion
0
30 50 70 90 110 130 150 170 190
Deposition Temperature ( oC)
3.1. Film deposition

Fig. 2. Variation of deposition rate of DLC films on different substrate
temperatures during deposition.
around 1.0 × 10−3 Pa. Pure argon (99.999% purity) was
used as inert gas in the chamber. The sputtering target was
pre-sputtered for about 5 min before deposition to remove
any surface impurities that may have been present on the tar-
get. The films were deposited at temperatures of 50, 80, 125
and 180 ◦ C using a resistance heater located behind the sub-
strate holder. The process pressure was 0.2 Pa with rf power
of 200 W. Silicon (1 0 0) wafers were used as substrate ma-
terial and standard chemical cleaning procedure was main-
tained before deposition. Raman spectra of the deposited
films were obtained using a LabSpec Micro Raman spec-
During sputtering, the deposition rate of DLC films in-
creases with increase of substrate temperature up to 80 ◦ C
and then gradually decreases as the temperature increases.
Fig. 2 shows the deposition rate of DLC films at differ-
ent substrate temperatures. The deposition rate is generally
given by the dynamic equilibrium between the flux of incom-
ing species and the flux of the re-sputtering particles. Atomic
mobility increases with temperature initially resulting in an
increased deposition rate. At higher temperatures, increased
atomic mobility can lead to reflection of atoms from the
substrate and the deposition rate eventually decreases [3].
Thickness of the deposited films measured by AFM line
analysis in non-contact imaging mode, were around 300 nm
as shown in Fig. 3.

Fig. 3. AFM line analysis for measuring thickness of the deposited film: (a) step in the deposited films and (b) step measurement by AFM line analysis.
806 S. Chowdhury et al. / Journal of Materials Processing Technology 153–154 (2004) 804–810

Fig. 4. Raman spectra of the DLC films deposited at different substrate temperatures.

3.2. Bonding properties
The Raman spectra of the DLC films deposited under
different substrate temperature are shown in Fig. 4. Ob-
vious difference between the spectra of the DLC films as
a function of substrate temperatures of 50, 80, 125 and
180 ◦ C can be observed. The spectra consist of a main G
band at 1553–1565 cm−1 and a broad shoulder D band at
1345–1386 cm−1 .
Raman measurements are presented in Table 1 for differ-
ent substrate temperatures. The Raman main band is due to
the lattice vibration of sp2 -bonded carbon atoms (graphite
or G band) at 1580–1590 cm−1 . If the size of the graphite
domains decreases, a low frequency modulation correspond-
ing to the disordered zone of graphite that correspond to D
peak at 1350 cm−1 becomes Raman-active. This results in
the lack of long-range order in the graphite sheets that is
referred as disordered-peak [6]. Disorder may be induced
by grain boundaries or imperfections such as sp3 -bonded
carbon, substitutional nitrogen atom and other impurities. It
was found that G peak position moves at higher frequencies
at high and low deposition temperatures and a shoulder at
low frequency (D band) became a noticeable peak. A sig-
nificant change in the peak shape occurs at about 80 ◦ C. At
that temperature, the Raman spectra exhibit an asymmetric
broad single peak. The G band position for 50, 80, 125 and
180 ◦ C samples are 1565, 1553, 1556 and 1556 cm−1 and
the integral intensity ratios (Id /Ig ) are 3.64, 1.02, 1.20, and
1.13, respectively. So the following observation can be noted
from Raman analysis:
1. G band position moves downwards at the temperature
from 50 to 80 ◦ C and then shifted upward with increase
in substrate temperature shown in Fig. 5.
2. Id /Ig ratio decreases from 50 to 80 ◦ C and then increases
with increase in substrate temperature as shown in Fig. 6.
In a theoretical study of the Raman spectroscopy for amor-
phous carbon, Beeman et al. [7] found that increasing the
amount of sp3 -bonded atomic sites in amorphous carbon re-
sult in a shift of the G band position to lower frequencies.
Richter et al. [8] reported on the calculation of the frequency
of G band using a simple valance force model, suggested
that frequency shifts in the G band are caused by changes in
the force constant associated with change in the sp3 -bonded

Table 1
Experimental results for DLC films with different substrate temperatures using Raman spectroscopy and Nanoindentation technique
Sample Power (W) Ar gas (Pa) Temperature (◦ C) Bonding properties Mechanical properties

D peak (cm−1 ) G peak (cm−1 ) Id /Ig H (GPa) E (GPa) %R H/E

Silicon (1 0 0) – – – – – – 13 151 57 0.08
C-38 50 1386 1565 3.64 11 110 63 0.10
C-33 200 0.2 80 1350 1553 1.02 15 135 80 0.11
C-34 125 1345 1556 1.20 22 160 82 0.14
C-53 180 1347 1556 1.13 20 150 81 0.13
 S. Chowdhury et al. / Journal of Materials Processing Technology 153–154 (2004) 804–810
1566
1564
G-band wave number(cm-1)
1562
1560
1558
1556
1554
1552
40
Fig. 5. Variation of G-position and D-position with substrate temperature for DLC films.
fraction. Using these information, the down shift in the
G-position from 1565 to 1553 cm−1 with the increase of sub-
strate temperature from 50 to 80 ◦ C indicates the increase
of sp3 -bonded carbon in the deposited DLC films. Again at
80 ◦ C silicon second order peak is prominent in the Raman
spectra as shown in Fig. 4. This peak is generally strongest
for the film with the highest sp3 -bonded fraction due to
its optical transparency [9]. On the other hand, the upward
shift of G-position from 1553 to 1556 cm−1 with increas-
ing substrate temperature indicates that the sp2 -bonded frac-
tion increases as the substrate temperature increases from
80 to 180 ◦ C. High values of Id /Ig ratio at substrate tem-
perature of 50 ◦ C indicate that there is a low percentage of
sp3 -bonded carbon in the deposited films. With increase of
substrate temperature up to 80 ◦ C the Id /Ig ratio decrease
with increasing amount of sp3 fraction [10]. A slight in-
crease of Id /Ig was observed above 80 ◦ C substrate temper-
ature, that signifies the continuous decrease of sp3 fraction
and the formation of small well-ordered graphite region and
also increase of cluster size of the graphite region [11]. At
low temperature around 50 ◦ C, the substrate temperature de-
termines the mobility of the adatoms. Around this tempera-
4 rough films.
3.5
3
2.5
Id /Ig
1.5
1 deposited at different substrate temperatures using maximum
0.5
0
40 90 140
Substrate temperature (oC)
Fig. 6. Variation of Id /Ig ratio with substrate temperature for DLC films.
807
1390
1385
D-band wave number (cm-1)
1380
G-band
1375
D-band
1370
1365
1360
1355
1350
1345
1340
60 80 100 120 140 160 180 200
Substrate temperature (oC)
ture range, the diffusion rate is low and the atoms directly
come to rest. Consequently, an amorphous microstructure
with more sp2 -bonded carbon atom will form.
At higher temperature (∼80 ◦ C) substrate temperature
enhances the mobility of C atom trapped in subsurface
position and helps the relaxation of the sub-planted C
atoms. According to the sub-plantation model [4], the num-
ber of C atoms in the subsurface region increased due to
more energetic atom penetration in the surface. However,
the lattice strain energy tends to build up and destabilize
the film structure. The film density increase is metastable
and forming sp3 hybridization bonding that stabilizes the
metastable phase by releasing the strain energy. Here sub-
strate temperature plays a vital role during releasing the
strain energy. The denser the film becomes, and the more
sp3 hybridization is formed. The DLC growth is achieved
when the two processes (strain buildup versus hybridization)
balance.
For much higher substrate temperature (∼180 ◦ C), the
higher mobility provides the more energetically favourable
graphite structure to form [12]. As the deposition tempera-
ture is very high, the mobility is high enough for the carbon
atoms to migrate to the surface where they follow surface
growth processes, which results in the formation of graphitic,
Similar work by Cho et al. [13] showed that with increase
of substrate temperature beyond 180 ◦ C, the sp2 -bonded
fraction increased.
3.3. Mechanical properties
The load–displacement curves of amorphous carbon films
load of 0.5 mN are shown in Fig. 7. From these curves we
observed higher maximum and residual penetration depths
190
in the sample deposited at low substrate temperatures. Fig. 8
shows a series of AFM images of residual imprint done
by nanoindenter on 300 nm DLC sample for applied loads
from 20 to 150 mN in different cross section areas. All
808 S. Chowdhury et al. / Journal of Materials Processing Technology 153–154 (2004) 804–810
0.6
0.5
0.4
Load (mN)
0.3
0.2
0.1
0
0 5 10
Fig. 7. Typical loading–displacement behaviour of DLC films with different substrate temperatures (50 and 125 ◦ C) during indentation at maximum
applied load of 0.5 mN.
nanohardness measurements were done at a maximum load
of 0.5 mN with residual depth of 7–15 nm and thus hardness
and Young’s modulus values measured by nanoindenter on
DLC samples were free from any substrate effect. In Table 1
the nanoindentation results for DLC films deposited at dif-
ferent substrate temperatures are shown. Fig. 9 shows the
hardness (H) and Young’s modulus (E) values of DLC films
as a function of deposition temperature. It was found that
H and E values increase with increasing substrate tempera-
tures from 50 to 125 ◦ C and then decrease when temperature
reaches 180 ◦ C. Hardness and elastic modulus have been
known to vary over a wide range with sp3 /sp2 bonding ratio.
The high hardness value of DLC is due to the sp3 -bonded
tetrahedral carbon. The H and E values show almost same
agreement with the Raman analysis. There is a high fraction
of sp2 -bonded carbon in DLC sample deposited at low sub-
strate temperature around 50 ◦ C and then the sp3 fraction of
carbon increases with increase of temperature up to 80 ◦ C
Fig. 8. Series of AFM images of residual Berkovich imprint on 300 nm DLC sample for applied loads from 20 to 150 mN in different cross sectional area.
125°C
50oC
15 20 25 30 35 40 45
Depth (nm)
and thus hardness increases (Fig. 10). At higher temperature
around 125 ◦ C, the well-ordered graphite domain may be
responsible for increase in hardness (although Id /Ig ratio in-
creased). Well-ordered structure may restrict the movement
of the atoms. At a temperature 180 ◦ C higher mobility pro-
vides the more energetically favourable graphite structure
and thus the H values decreases.
Elastic recovery R = (hmax −hres )/ hmax where, hmax and
hres are the displacement at peak load and residual displace-
ment after load removal, respectively [14]. According to the
definition of R, higher R means higher elasticity of the tested
materials. Lower R-values around 60% were found for sili-
con and the DLC film deposited at low temperature around
50 ◦ C but we observed very high R-values around 82% for
those samples deposited at much higher deposition temper-
atures from 80 to 180 ◦ C as shown in Fig. 10.
Generally hardness has been regarded as a primary ma-
terial property, which defines wear resistance. There is a
 S. Chowdhury et al. / Journal of Materials Processing Technology 153–154 (2004) 804–810 809

25 180 increasing substrate temperature up to 80 ◦ C and then

160 gradually decreases with further rise in substrate temper-
20 140
ature. Micro Raman analysis shows that G band position
moves downwards at temperature from 50 to 80 ◦ C and
Hardness (GPa)

120
15
then shifted upward with increase of substrate temperature.
E (GPa)

100 substrate temperature enhances the mobility of C atom

80 trapped in subsurface position and helps the relaxation of
10 H( GPa)
E(GPa) 60 the sub-planted C atoms. The Id /Ig ratio decreases from 50
to 80 ◦ C and then increases slightly with increasing sub-
5 40
strate temperature. Therefore, sp3 -bonded carbon fraction
20
increases from 50 to 80 ◦ C temperatures and an increase in
0 0 the substrate temperature after 80 ◦ C results in an increase
40 90 140 190
Substrate tem perature ( oC)
in the sp2 -bonded fraction of carbon atoms in DLC thin
films. The hardness (H) and Young’s modulus (E) values
Fig. 9. Hardness (H) and Young’s modulus (E) values of different DLC show good agreement with the micro Raman analysis. Due
films deposited at different substrate temperature.
to the higher amount of sp2 -bonded carbon structure in the
DLC samples at low substrate temperatures, both H and
90 0.16 E values were low at low temperatures. With increasing
80 0.14
substrate temperature the fraction of sp3 -bonded carbon in
70 the DLC film increases and thus both H and E values in-
0.12
60 creased up to 80 ◦ C. At higher temperature around 125 ◦ C
0.1
50
well-ordered graphite domains may be responsible for hard-
%R

H/E

0.08 ness increase, although Id /Ig ratio increased. At temperature

40
30 %R 0.06 about 180 ◦ C higher mobility provides the more energet-
20
H/E 0.04 ically favourable graphite structure and thus the hardness
10 0.02 values decreases. So, the hardness of DLC thin films not
0 0
only depends on the sp3 content which may increase with
40 60 80 100 120 140 160 180 200 temperature but may found to depend also on the level of
Substrate tem perature ( oC) well-ordered sp2 -bonded carbon. The effect of temperature
on the H and E values was more complex than previously
Fig. 10. Variation of elastic recovery (%R) and plastic resistance parameter reported.
(H/E) with different substrate temperatures for DLC films.

strong evidence to suggest that the elastic modulus can also
have an important influence on wear behaviour, in particu-
lar, the elastic strain to failure, which is related to the ratio of
hardness (H) and elastic modulus (E). It has been shown by
a number of authors [15,16] that the elastic strain to failure
could be a more suitable parameter for predicting wear re-
sistance than hardness alone. It is also significant that the ra-
tio between H and E described in terms of ‘plasticity index’
or ‘elastic strain to failure’ are widely quoted as a valuable
parameter in determining the limit of elastic behaviour in
a surface contact, which is clearly important for the avoid-
ance of wear [17]. We have found that the parameter H/E of
the DLC films increases with increase of substrate tempera-
ture up to 125 ◦ C and then decreases slightly when tempera-
ture reaches 180 ◦ C as shown in Fig. 10. Further studies are
planned to investigate the effect of H/E on wear.
4. Conclusion
Diamond-like carbon films were prepared at different
substrate temperatures from 50 to 180 ◦ C. During sput-
tering, the deposition rate of DLC films increases with
Acknowledgements
This work is financially supported by Higher Education
Authority (HEA), Ireland through the program for research
in Third Level Institutions.
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