Thin Solid Films 475 (2005) 303 – 307

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Structures and mechanical properties of diamond like carbon films

prepared by closed-field unbalanced magnetron sputtering
Hyun S. Myunga,*, Yong S. Parka, Jae W. Leeb, B. Honga, Jeon G. Hana
a
Center for Advanced Plasma Surface Technology (CAPST), Sungkyunkwan University, 300 Chunchun-dong, Jangan-gu, Suwon 440-746, Korea
b
Korea–Germany Industrial Technology Cooperation Center, 4th floor, Dongil Bldg., 1719-4, Seocho 3-dong, Seocho-gu, Seoul, Korea

Available online 24 August 2004

Abstract

Diamond like carbon (DLC) films were synthesized by closed-field unbalanced magnetron sputtering (CFUBM) using carbon targets in
Ar and Ar/C2H2 atmosphere. The deposition rate, structure and mechanical properties of these films were studied as a function of applied bias
voltage on the substrate during deposition. The film structures were investigated using Raman spectroscopy. The hardness and elastic
modulus were measured by nano-indentation tests and the friction coefficient of DLC films was measured by a ball-on-disc type wear tester.
Raman analysis showed that sp3/sp2 ratio in DLC films changed with increasing substrate bias voltage. Hydrogenated DLC films deposited at
the bias of 200 V exhibited a maximum hardness of 28 GPa and a relatively low friction coefficient of about 0.1.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Diamond like carbon (DLC); High rate sputtering; CFUBM

1. Introduction properties of DLC coatings were investigated as a function of

Diamond like carbon (DLC) films have several applica-
tions in different industrial areas due to high hardness, high
elastic modulus, low friction coefficient, high electrical
resistivity, good chemical inertness and low surface rough-
ness, etc. [1] These films can be synthesized by various
techniques such as chemical vapor deposition (CVD) [2,3],
ion beam deposition [4,5], arc ion plating [6,7], laser ablation
[8] and sputtering [9–12]. Among these techniques, sputter-
ing has many advantages such as process simplicity and
control, film homogeneity for deposition of DLC. However,
low deposition rate has been a major weak point in the
deposition of DLC films by magnetron sputtering owing to
the low sputtering yield of carbon [12].
In this study, therefore, hydrogen-free and hydrogenated
DLC films were synthesized by closed field unbalanced
magnetron sputtering (CFUBM) to increase the deposition
rate and physical properties. Film structures and mechanical
* Corresponding author. Tel.: +82 31 299 6646; fax: +82 31 290 5669.
E-mail address: mhs0106@hanmail.net (H.S. Myung).
0040-6090/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2004.07.017
dc substrate bias.
2. Experimental details
Hydrogen-free and hydrogenated amorphous DLC films
were deposited by CFUBM in Ar and Ar/C2H2 atmosphere.
The schematic diagram of this system is shown in Fig. 1.
Unbalanced magnetron sources are installed on both sides of
the chamber symmetrically. The target power density for each
graphite (99.999% purity) target was constant value of 30 W/
cm2. The substrates were heated to 1508C and rotated during
the process. The detailed experimental conditions are listed in
Table 1.
The deposition rate of DLC films synthesized with
various bias voltages was calculated by measuring film
thickness using an alpha-step profilometer. The coating
thickness was kept at a constant value of 1.0 Am. Silicon
(100) wafers and D2 steel were used as substrates to
characterize the microstructure and mechanical properties.
Raman spectra were measured with a Jobin Yvon T64000
spectrometer using the 514.4-nm line of an Ar laser as the
304 H.S. Myung et al. / Thin Solid Films 475 (2005) 303–307

ball at normal load of 3 N. The sample rotation velocity was

0.3 m/s and the sliding distance was 100 m.

3. Result and discussion

3.1. Deposition rate of DLC coatings

The influence of the bias voltage on the deposition rate

Fig. 1. Schematic diagram of the CFUBM system.
excitation wavelength. The hardness and elastic modulus of
the sample were measured using a commercial nano-
indentation instrument (Nano-indenter XP) and were deter-
mined by continuous stiffness method (CSM) technique.
Continuous loading–unloading indentations up to a max-
imum load of 30 mN were applied. Wear tests were
performed by a ball-on-disc tester using an AISI52100 steel
is shown in Fig. 2. The maximum deposition rate of
hydrogen-free amorphous DLC (a-C) coatings was
obtained at no bias approximately 1000 2/min. This value
is about 3–4 times higher than that of a-C films deposited
at the same experimental condition using same coating
device with conventional magnetron sputtering source. It
is due to the realization of a high density plasma by
electron confinement in the closed field configuration. In
case of hydrogenated amorphous DLC (a-C:H) deposited
in an Ar/C2H2 atmosphere, the maximum deposition rate
was measured about 2000 2/min owing to addition of
carbon species. The deposition rate decreased with
increasing substrate bias voltage. This behavior is mainly
due to a resputtering effect of the growing layer by
energetic ions.

3.2. Structures of DLC films

Table 1
Deposition conditions for DLC coatings
Raman spectroscopy was performed to identify the
Conditions Substrate Ar partial Graphite target Treatment structure and property of the deposited a-C films. Usually, a
bias (V) pressure power density time (min)
(Pa) (W/cm2)
crystalline diamond peak is observed at 1332 cm 1 and a
crystalline graphite peak is found at 1580 cm 1. In general,
Ar plasma 700 2.0 0 30
precleaning
the Raman spectrum of DLC films is derived from
DLC a-C and 0 to 200 0.4 30 10 corresponding features in the spectrum of graphite. The
a-C:H) spectrum comprises two broad features centered at 1550
coatings cm 1 (corresponding to the G line associated with the
Base pressure: optically allowed zone center mode of crystalline graphite)
0.003 Pa
Substrate
and at 1350 cm 1 (roughly corresponding to the D line
temperature: associated with disordered allowed zone edge modes of
150 8C
Jig rotation
speed:
10 rpm
Ar gas purity:
99.999%
(5 N)
Resistivity of
silicon
substrate:
1 V cm
Target to
substrate
distance:
60 mm
Ar: C2H2 gas
ratio was
maintained
constant
value
of 80:20 Fig. 2. Variation of deposition rates with substrate bias voltage.
 H.S. Myung et al. / Thin Solid Films 475 (2005) 303–307 305

graphite [1–12]. Fig. 3 illustrates the visible Raman spectra

and G peak position changes of the deposited a-C films with
the variation of substrate bias voltage. G peak position of a-C
films was changed toward lower wavenumber with increas-
ing the bias voltage up to 100 V. However, out of this range,
upshift of the G peak position occurred with increasing the
bias voltage up to 200 V.
The Raman spectrum is considered to depend on
clustering of the sp2 phase, bon disorder, presence of sp2
rings or chains and the sp2/sp3 ratio. These factors act as
competing forces on the shape of the Raman spectra. In a
recent Raman study of DLC a three-stage model has been
proposed for the interpretation of Raman spectra. Ferri and
Robertson define an amorphization trajectory ranging from
graphite to a-C (or diamond) consisting of three stages, as
shown Fig. 4 [13]. In stage 2 of this model, upshift of the G Fig. 4. Amorphization trajectory, showing a schematic variation of the G
peak position has been associated with an increase in the position [13].
number and clustering of sp2 sites into ordered rings.
According to this interpretation, the results shown in Fig. 3 mechanisms induced by increasing bias voltage, namely,
suggest that the increase of bias voltage first leads to a the enhancement of carbon ion bombardment in the low bias
reduction and then to an increase of ordered sp2 clusters. voltage region that favors the formation of diamond like
This behavior could be ascribed to two competitive films (higher sp3 content), and the increase in the growing

Fig. 3. Variation of Raman spectra and G-band wavenumber position with Fig. 5. Variation of Raman spectra and G-band wavenumber position with
the variation of substrate bias voltage (a-C coatings). (a) Raman spectra. (b) the variation of substrate bias voltage (a-C:H coatings). (a) Raman spectra.
G peak position. (b) G peak position.
306 H.S. Myung et al. / Thin Solid Films 475 (2005) 303–307
Fig. 6. Hardness and elastic modulus of a-C films with the variation of
substrate bias voltage.
surface temperature at high bias voltage resulting in a
graphitization of the sp2 domains.
However, in case of a-C:H films, G peak position shifted
to a lower wavenumber as the bias voltage increased (Fig.
5). It can be said that the G peak position shifts to lower
wavenumber either when the polymeric component
decreased or when the diamond like component increased.
3.3. Mechanical properties of DLC films
The film hardness and elastic modulus of a-C films as a
function of bias voltage are illustrated in Fig. 6. The
hardness of a-C films increases gradually with increasing
bias voltage and then increases rapidly to a maximum value
of approximately 25 GPa when the bias voltage reaches
100 V. However, further increase of bias voltage results in
a rapid decrease of hardness. The elastic modulus of a-C
films was measured to be in the range of 80–210 GPa.
Consequently, the highest value of film hardness and elastic
modulus was obtained from the a-C film deposited at 100
V. However, the hardness and elastic modulus of a-C:H
Fig. 7. Hardness and elastic modulus of a-C:H films with the variation of
substrate bias voltage.
Fig. 8. Variation of friction coefficient with the variation of substrate bias
voltage; normal load: 3 N, counterpart: AISI52100 steel ball, sliding
velocity: 0.3 m/s, sliding distance: 100 m.
films were increased with increasing bias voltage and the
maximum hardness and elastic modulus were obtained
approximately 28 and 200 GPa at 200 V (Fig. 7). These
behaviors can be explained by the observed peak shift in our
previous Raman spectra. It should be considered as apparent
hardness enhancement owing to an increase of sp3 bonding
fraction.
3.4. Coefficient of friction
The friction coefficient of DLC film was evaluated from
the wear test using the tribotester of a ball-on-disc type
against an AISI52100 steel ball without lubricant (Fig. 8).
Friction coefficient was decreased with increasing substrate
bias voltage.
At low bias voltage, DLC films have a low hardness
value owing to low ion energy. Therefore, friction coef-
ficient of all coatings synthesized at low bias voltage is very
high. As the increase of bias voltage, sp3 fraction is
increased. Thus, coefficient of friction is decreased with
increasing bias voltage due to enhancement of hardness.
Therefore, minimum friction coefficient of about 0.1 was
observed at a-C deposited at 100 V and a-C:H films
deposited at 200 V.
4. Conclusions
Diamond like carbon (DLC) films were deposited by
closed field unbalanced magnetron sputtering (CFUBM)
with various bias voltages. The following results have been
obtained;
(1) The maximum deposition rate of DLC films by
CFUBM method was approximately 2000 2/min.
and the G peak position was shifted with changing
bias voltage in Raman spectra. This should be
considered as apparent structure change of DLC films
owing to a change of sp3 bonding fraction.
 H.S. Myung et al. / Thin Solid Films 475 (2005) 303–307
(2) The hardness of a-C films increases gradually with
increasing bias voltage and then increases rapidly to a
maximum value of approximately 25 GPa when the
bias voltage reaches 100 V. The further increasing of
bias voltage results in a rapid decrease of hardness and
elastic modulus. However, in case of a-C:H coatings,
the highest value of film hardness was obtained from
the a-C:H film deposited at 200 V.
(3) Friction coefficient was decreased with increasing
substrate bias voltage and minimum friction coefficient
of about 0.1 was observed at a-C films deposited at
100 V and a-C:H deposited at 200 V.
Acknowledgement
The authors are grateful for the financial support
provided by MOST and KOSEF through the Center for
Advanced Plasma Surface Technology (CAPST) at Sung-
KyunKwan University.
307
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