Diamond & Related Materials 18 (2009) 10231027

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Diamond & Related Materials

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d i a m o n d

Deposition of DLC lm with adhesive W-DLC layer on stainless steel

and its tribological properties
Takanori Takeno a, Toshifumi Sugawara b, Hiroyuki Miki c, Toshiyuki Takagi c,
a
b
c

Institute for International Advanced Interdisciplinary Research, Tohoku University International Advanced Research and Education Organization, Japan
Graduate School of Engineering, Tohoku University, Japan
Institute of Fluid Science, Tohoku University, Japan

a r t i c l e

i n f o

Available online 24 January 2009

Keywords:
DLC
Metal-doped DLC
Friction
Double-layered structure

a b s t r a c t
Tribological properties of a diamond-like carbon (DLC) coating with an adhesive tungsten-containing DLC
(W-DLC) layer were investigated. The coatings were deposited onto AISI316L steel substrates and Si wafers
using plasma enhanced chemical vapor deposition and tungsten co-sputtering of the metal target. Methane
and argon gases were used as the precursor of the coatings. In this study, three types of coatings were
evaluated: DLC/W-DLC on AISI316L (DLC-1), DLC/W-DLC on Si wafer (DLC-2), and DLC on Si wafer (DLC-3).
The structural characterizations were performed by transmission electron microscopy and tapping mode
atomic force microscopy. At the boundary between the W-DLC layer and the AISI316L substrate, microscopic
decohesion or delamination was not observed. The surface roughness of the DLC-1 coating was greater than
that of the DLC-2 coating. This feature was derived from the surface roughness of the initial surface of the
AISI316L substrate. Friction tests were performed using a rotation-type ball-on-at conguration tribometer.
The observed friction of the DLC-1 coating was unstable compared with the DLC-2 or DLC-3 coatings. This
was due to wear debris which had risen to the friction surface resulting in unstable friction on the DLC-1
coating. During the friction studies, the top DLC layer was removed from the adhesive W-DLC layer because
the adhesive strength at this part was not enough. In order to achieve the low and stable friction of the DLC
coating with the W-DLC layer on AISI316L, it is necessary to improve the smoothness of the surface and the
adhesion between the DLC coating and the W-DLC layer.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Many attempts have been made to achieve a good adherence
between DLC coatings and steel substrates, since DLC coatings have a
wide range of applications. The major techniques to obtain a good
adhesive strength include the fabrication of an intermediate glue
layer between the coating and substrates, and the reduction of the
internal stress of the coating. Resent developments have been mainly
focused on the former case. Intermediate metal or compound layers
such as Ti, Zr, W, Nb, or WC have shown potential to improve the
adhesive strength [1].
However, even if an intermediate layer is fabricated, it does not
work as an adhesive layer for DLCs deposited by the CVD technique.
Wei et al. systematically investigated the adhesiveness of DLC coatings
on Si substrates, sputter-deposited Cr on Si, and sputter-deposited Ti
on Si [2]. Although the DLC coating could be deposited on the Si
substrate without a metallic intermediate, the DLC coatings on sputterdeposited metal intermediates were readily delaminated. This feature
Corresponding author. Institute of Fluid Science, Tohoku University, 2-1-1 Katahira,
Aoba-ku, Sendai 980-8577, Japan. Tel./fax: +81 22 217 5248.
E-mail address: takagi@ifs.thoku.ac.jp (T. Takagi).
0925-9635/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.diamond.2009.01.029

was also conrmed by our own experiments on a sputtered W layer as

the intermediate layer. The sudden delamination or peeling of the DLC
coating was observed just after the deposition. Possibly, the stress level
of the DLC coatings deposited by CVD is higher than that deposited
by other techniques, and the metal intermediate layer does not
have enough strength to adhere the DLCs with high residual stress.
Thus a reduction of the residual stress of the DLC coating is one of
the important issues in obtaining a good adherence to the metallic
substrates.
The residual stress of the DLC coating has been reduced by
including additional elements. Both light and heavy elements have
been considered as dopants. Ban et al. investigated silicon as a dopant
for the reduction of the compressive stress in the DLC coating [3].
Their group used SiH4 gas as a precursor of the silicon element. The
stress reduction from 2.5 GPa to 1.0 GPa was achieved when the SiH4
ow ratio was 36.4%. Another work was performed by Rabbani et al.
on N2-doped a-C:H coatings [4]. Their group also doped nitrogen from
the gas phase and investigated how the degree of stress was reduced
in view of the nitrogen and argon concentration in the coatings. The
most stressful coating was obtained in the case of the Ar inert gas
(1.6 GPa), and the minimum stress level (~0.9 GPa) of the coating was
achieved by a certain mixture ratio of Ar and N2 gases. Therefore,

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T. Takeno et al. / Diamond & Related Materials 18 (2009) 10231027

Table 1
Deposition parameters for the coatings investigated in this study.
DLC/W-DLC on AISI316L
Sample ID
Substrate
Initial pressure

Gas
Substrate self bias
Operation pressure
Gas
Substrate self bias
Operation pressure
Sputtered target
Target DC power

Gas
Substrate self bias
Operation pressure

DLC-1
AISI316L

DLC/W-DLC on Si

DLC on Si

DLC-2
DLC-3
Single crystal Si wafer
4
4.0 10 Pa

Pretreatment of the substrates

Ar = 10.0 sccm
400 V
3.3 Pa
Deposition of the adhesive layer (W-DLC)
Ar/CH4 = 10.0/3.0
400 V
3.3 Pa
Tungsten (W)
40 W

Deposition of the DLC layer

CH4 = 10.0 sccm
400 V
3.3 Pa

doping of additional elements into the DLC matrix is one of the ways
to reduce the residual stress of the coatings.
The inclusion of metal nanoclusters into the DLC matrix is also a
good candidate. Our previous reports have shown that metalcontaining DLC (Me-DLC) coatings can be made by the hybrid
deposition technique of CVD and PVD [5,6]. The structure of the
coating is dened by the metal clusters of several nanometer-sizes
which are dispersed into the amorphous carbon host matrix. The
inclusion of metal clusters into the DLC coating is expected to reduce
the residual stress of the coating, which may result in the successful
deposition of metallic substrates without an intermediate layer.
Even if a Me-DLC coating can be deposited onto a metal substrate,
there is another issue to be solved. Concerning tribological properties,
Me-DLC coatings sometimes show high wear as the number of friction
cycles increases [7]. The friction behavior of the W-DLC layers against
the AISI304 stainless steel ball shows that a drastic increase in friction
coefcient occurred in the early stage of friction cycling, and the
coatings were worn by the sliding. However, double-layered structures like DLC/W-DLC on Si show excellent friction behavior, and the
average friction coefcient in ambient nitrogen was under 0.1. Thus
this double-layered structure on stainless steel substrates is a very
promising combination in terms of industrial application. Thus our
concept is that the W-DLC layer is used as an intermediate and the DLC
coating is used as a coating showing good tribological performance.
In this study, a DLC coating with an adhesive W-DLC layer
deposited onto AISI316L stainless steel substrates was investigated.
Experiments were performed for three types of coatings; DLC/W-DLC
on AISI316L, DLC/W-DLC on Si wafer, and DLC on Si wafer. The crosssectional microstructure and surface morphology of the coatings was
analyzed. Then, friction tests were carried out. The tribological
properties of the coatings are discussed in terms of the cross-sectional
structure and surface morphology of the coatings.

target. The parameters used in this study were determined from our
preliminary results. The deposition procedure is as follows. Substrates
were evacuated up to 4.0 10 4 Pa. Before the deposition, the substrates were cleaned by RF-discharged Ar plasma in order to remove
surface contamination. The investigated coatings were fabricated onto
AISI316L stainless steel in two steps. First, the W-DLC adhesive layer
was fabricated onto the well-polished substrates by RF discharged
methane plasma and DC magnetron co-sputtering of a tungsten metal
target. Secondary, a DLC coating was deposited onto the W-DLC
adhesive layer using methane plasma. The detailed deposition
parameters used in this study are summarized in Table 1. In this
study, three types of coatings were investigated for the tribological
properties.
The boundary structure between the adhesive layer and the metal
substrate was analyzed by transmission electron microscopy (TEM)
using a JEOL JEM-3010 instrument under an acceleration voltage of
300 kV. The sample for TEM observation was prepared by an ion slicer
using a JEOL EM-09100IS instrument.
Friction tests were performed at room temperature using a rotation
type ball-on-disk type tribometer manufactured by CSM Instruments.
A ball of 6 mm in diameter made of AISI304 stainless steel was used as a
counter material. The normal load of 1 N was applied to the ball and the
linear sliding speed was set at 12 cm/s. The testing apparatus was
enclosed within an acrylic chamber. The chamber was rst evacuated
and then, dry air or nitrogen was introduced into the chamber. The
friction coefcient was measured in two types of ambient conditions:
in air with a well-controlled humidity (40 RH%), and in a nitrogen
atmosphere condition (RH b 10%). The humidity during the friction test
was monitored using a commercial hygrometer and the uctuation
was within 5%, as measured from the start of the experiment. After the
friction test, the surface of the ball was analyzed by using Scanning
Electron Microscope equipped with Energy Dispersive X-ray spectrometer (Hitachi High-Technologies S-4700 Scanning Electron
Microscope).
3. Results and discussions
3.1. Characterization of the coatings
Fig. 1 shows the cross-sectional TEM image of the boundary
structure between the W-DLC adhesive layer and AISI316L substrate.
The thickness of the adhesive layer was about 1 m. No microscopic

2. Experimental procedure
The coatings were deposited by plasma-enhanced chemical vapor
deposition technique and DC magnetron co-sputtering of tungsten
metal target. The DC magnetron sputter locates upside of the
deposition chamber. The substrate holder is at the bottom of it, and
the RF power is applied to the holder. The distance between the target
and the holder is xed as 100 mm. The nozzle end of argon gas is faced
to the target and the gas blows against it. On the other hand, methane
is introduced from the backside of the deposition chamber. These
techniques allow us to avoid the possible poisoning of the tungsten

Fig. 1. Cross-sectional transmission electron micrograph of the W-DLC adhesive layer on

a AISI316L substrate.

T. Takeno et al. / Diamond & Related Materials 18 (2009) 10231027

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size of the tungsten clusters and the degree of dispersiveness in the

amorphous carbon host matrix. But, once the surface of the W-DLC
layer is covered with DLC coating, the surface roughness of the nal
form of the coating decreases compared with the single W-DLC layer
[7]. The DLC coating grows as lling the bumpy surface of the W-DLC
layer. However, the surface roughness of the DLC-1 coating is greater
than that of the DLC-2 coating. Assuming that the same DLC coating
and W-DLC adhesive layer were fabricated even if the substrate
material is different, the rough surface in the DLC-1 coating may be
derived from the initial surface morphology of the AISI316L substrate.
3.2. Tribological properties
The ball-on-at conguration has been used to investigate the
tribological properties of three types of coatings. The results of the
friction tests are shown in Fig. 3. The DLC-1 sample (Fig. 3(a))
exhibited an average friction coefcient within the range of 0.150.20
under nitrogen condition after the running-in process. In the case of
air condition, an unstable friction coefcient was observed as the
number increases. The friction coefcient of the DLC-2 sample showed
a stable behavior (Fig. 3(b)) in both air and nitrogen atmosphere
condition. After the running-in process, the average friction coefcient
in the steady-state regime was 0.07. The third set of experimental
results of DLC-3 (Fig. 3(c)) showed a gradual increase in the friction
coefcient. After the 40 103 cycles, the friction was very noisy.
Fig. 4 shows a photograph of the wear tracks and the balls of the
DLC-1 and DLC-2 coatings at the contact point after the friction test. In

Fig. 2. Surface morphology of the coatings: (a) DLC-1 and (b) DLC-2. The calculated
surface roughness (Ra) of the DLC-1 and the DLC-2 coatings were 1.675 nm and
0.487 nm, respectively.

decohesion was observed between the layer and substrate. The

crystallographic structure of the W-DLC layer indicates that tungsten
metal clusters of several nanometers in size are well dispersed in the
amorphous carbon host matrix, which was conrmed by the
magnied TEM image [6]. The dispersive metal clusters lead to a
reduction of the stress in the DLC coating and helped to achieve a good
adherence to the stainless steel substrates. The successful deposition
of the W-DLC intermediate layer was conrmed by adding the
tungsten metal clusters into the amorphous carbon host matrix.
The surface morphologies of the DLC-1 and DLC-2 coatings were
obtained by tapping mode AFM and the results are shown in Fig. 2. The
images were obtained in 10 10 mm2 in area. The surface roughness of
the DLC-1 and DLC-2 coatings was calculated as Ra = 1.675 nm and
Ra = 0.487, respectively. After the deposition of the W-DLC layer, a
rather rough surface was obtained, which resulted from the average

Fig. 3. Friction behavior of three types of coating: (a) DLC-1, (b) DLC-2 and (c) DLC-3.
Red and blue lines represent the results in the case of air and nitrogen atmosphere
condition. (For interpretation of the references to colour in this gure legend, the reader
is referred to the web version of this article.)

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T. Takeno et al. / Diamond & Related Materials 18 (2009) 10231027

Fig. 4. Optical images of the balls and the wear tracks: (a) ball and (b) wear track of the DLC1 coating, and (c) ball and (d) wear track of the DLC-2 coating after a friction test in
nitrogen atmosphere condition.

order to avoid the oxygen in air for the friction behavior, these pictures
show the results of the nitrogen condition. The sizes of the transfer
lms on the balls were approximately 130 m in both cases, and the
wear tracks of both cases were shown to have almost the same size. In
addition to that, wear debris was observed on the surface along the
wear track. Although the generation of debris was observed to have
occurred, no ruptures inside the wear track were observed in either
sample.
After the friction tests, the ball surface was analyzed by the SEM
equipped with Energy Dispersive X-ray Spectrometer. Fig. 5 shows the
surface image and elemental mapping results on the ball after the
100,000 cycles in ambient air condition on DLC-1. One can see that
transferred lm contains carbon, tungsten and oxygen. Observed
carbon element come from the top DLC layer and the W-DLC adhesive
layer, and tungsten and oxygen elements come from the W-DLC layer

and ambient air, respectively. These results indicate that the coating
was worn and the ball surface reached to the adhesive W-DLC layer. In
addition to that, it can be considered that tungsten react with the
oxygen and form the tungsten oxide debris.
Focusing on the effect of the surface roughness on the friction
coefcient, its contribution was considered to be large. The rough
surface led to the high friction in the W-DLC coating and a minimum
friction coefcient of ~0.1 was obtained in Ra = 7 nm in air condition
after 100,000 cycles [8]. The same feature was also shown in this paper
for the Cr-DLC coatings. Ohana et al., reported on the effect of the
surface roughness of the DLC coating on a steel substrate [9]. They
investigated the friction tests in water. The minimum friction coefcient was achieved in Ra = 34 nm. Their group also investigated the
coating deposited onto a smoother surface (Ra = 2 nm), but the
measured friction coefcient was somewhat higher compared with

Fig. 5. SEM/EDX results on the ball after the 100,000 cycle friction test in ambient air condition of DLC-1. The images were obtained in 800 magnication.

T. Takeno et al. / Diamond & Related Materials 18 (2009) 10231027

the result with Ra = 34 nm. These results indicated that the surface
roughness and the test environment are key factors for low friction,
where low friction can be achieved when the coating surface is
smooth. In our case, the friction tests were carried out in a gaseous
atmosphere and low friction was achieved in the DLC-2 coating. The
results agreed with the above-mentioned papers for the surface
roughness of the DLC-2 coating. However, the friction coefcient of
the DLC-1 coating was unstable. In case of the unstable friction shown
in Fig. 3(a), the behavior can be due to the rolling effect of brittle and
hard tungsten oxides. The idea as a possible mechanism comes from
the consideration as follows. After the ball reached to the W-DLC layer,
the tungsten in the W-DLC layer could react chemically with the
oxygen in ambient air during the friction, and the tungsten oxides was
formed. The oxides came to the contact point easily because of the
rough surface, and were inserted into the contact point. The debris
possibly played a role like a roller. However, the debris was sometimes
come out from the wear track. By continuous insertion and exclusion,
unstable friction behavior observed.
On the other hand, stable friction shown in Fig. 3(b) is due to the
smooth surface of the coating. Possibly, the ball also approached to the
W-DLC layer. However, the debris may not be inserted in the contact
point because of the very smooth surface. The debris was just come
out from the wear track and could not be inserted into the contact
point even if the oxides were formed. Thus, it can be considered that
the friction behavior is stable since no roller effect is available.
The above consideration seems reasonable when we focus on the
amount of the wear debris at the edge of the wear track. From the
optical photographs shown in Fig. 4(b) and (d), large amount of the
wear debris was observed in case of DLC-2 compared to that of DLC-1.
The results also could be the evidence for the above mechanisms.
Thus, the increase in adhesive strength and the decrease in surface
roughness are required for the low and stable friction. From the
discussion above, the decrease in the surface roughness and the
increase in the adhesive strength are important for the low friction.
4. Summary
In this study, a DLC coating with an adhesive W-DLC intermediate
was deposited onto steel substrates and its tribological properties

1027

investigated. The adhesive W-DLC intermediate was successfully

deposited onto an AISI316L substrate and no microscopic decohesion
or delamination was observed. The surface roughness of the DLC
coating with adhesive intermediate was greater than that of the
coating deposited onto a Si substrate. The rough surface was derived
from the surface roughness of the AISI316L substrate. The tribological
property of the DLC-1 coating showed variation of the friction
coefcient. Such an unstable friction was caused by wear debris on
the surface. Comparing the friction behavior of the DLC-1 coating with
the previous reports and the data of the DLC-2 coating, low friction
can be realized in the case of coatings with a smoother surface and
strong adhesive strength between the DLC coating and the adhesive
W-DLC layer.
Acknowledgments
This work was partly supported by a Grant-in-Aid for Young
Scientists (B) (No.20760095) and a Grant-in-Aid for Scientic
Research (B) (20360380) of Japan Society for the Promotion of
Science (JSPS). The authors express their great appreciation to Mr.
Takeshi Sato from the Institute of Fluid Science at Tohoku University
for his technical assistance.
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