Diamond & Related Materials 17 (2008) 1685–1688

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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

Investigation on wear and adhesion of graded Si/SiC/DLC coatings deposited by

plasma-enhanced-CVD
Ch. Schwarz, J. Heeg, M. Rosenberg, Marion Wienecke ⁎
Hochschule Wismar, Institute of Surface and Thin Film Technology, Germany

a r t i c l e i n f o a b s t r a c t

Available online 4 March 2008 In this work Si/SiC/DLC graded layer systems, with thickness up to 20 μm were prepared on Titan-substrates by
the PECVD-method, using Ethyne (C2H2, g) and HMDSO (l) as reactants. During the process the parameters of
Keywords: bias power, working pressure and mixing ratio of the gas flows were modified to achieve graded interfaces.
DLC Vickers and Martens hardness measurements were performed to obtain hardness and elasticity respectively.
SiC Wear resistance measurements were performed by ball-on-disc method grinding calottes with defined
PECVD
geometry. EDX-measurements have been analysed to reveal the depth concentration profiles. The increased
Wear
adhesive strength of the graded layers was obtained by bending tests (DIN EN ISO 1519). The results show, that
Adhesion
EDX graded and in particular thick layers with hardness up to 1200 HV and low elastic module (30–80 GPa) could
be used as adhesive wear resistance layers. The adhesive strength depends on thickness and gradient of
elasticity.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction layer or even transformation to a composite material in order to

DLC films are considered for widespread clinical use as biocompa-
tible coating for cardiovascular applications because of its excellent
bio- and haemocompatibility. Recent reviews on DLC coatings for
biological applications summarized the advantages offered by this
class of materials [1–3]. Although DLC has proven its outstanding
tribological properties in many technical applications, contradicting
results are reported on DLC coated load bearing implants. Increased
wear and coating delamination and corrosion are reported e.g. for
joint implants. High internal stress in the hard DLC films and low
adhesion at relative soft substrate materials like Ti-alloy originate
these failures. An innovative concept in the development of advanced
tribological systems involves coatings with graded interfaces. How-
ever, reported film thickness usually does not exceed 1–2 μm.
The main drawback of the DLC coatings is the high intrinsic
compressive stress (7–10 GPa, associated with the high hardness, up
to 50 GPa [4]), which alter the adherence and limits the thickness of
the films. Because the stresses in DLC films are directly correlated
with the fraction of sp3 bonded carbon, the parameters which control
the hybridization type will control also the mechanical stability of the
films. It was found that the sp3/sp2 ratio increased with decreasing
the substrate temperature during deposition [5], and with increasing
the hydrogen content in the material [6].
Numerous papers reported incorporation of different elements
into the DLC films, deposition of composition graded intermediate
⁎ Corresponding author.
E-mail address: m.wienecke@et.hs-wismar.de (M. Wienecke).
increase the mechanical stability, without affecting the other proper-
ties of the material. The most frequent used doping element was
silicon/silicon oxide, allowing reduction of internal stresses up to 30%
[7–12]. The Ti-base alloy valve claimed in [13] has a composite coating
comprising the structure: metal alloy/metal-silicide/Si/SiC/DLC, which
provided better mechanical stability due to strong SiC bonds. Further
improvement of the mechanical stability and properties of the films
was attained with functionally gradient films TiN/Ti(N,C)/DLC [14], or
superhard nanocomposite (Ti,Cr)CN/DLC coatings [15]. A silicon doped
diamond like nanocomposite biocompatible coating for an intravas-
cular stent is disclosed in [16]. The layer has a minimum thickness of
50 nm and compressive stress lower than 150 MPa, allowing a high
degree of flexibility and a complete expandability of the stent.
For load bearing implants such as joint implants increased wear
and partial coating delamination are reported [2] and in vivo inves-
tigations show lower survivorships for DLC coated hip implant heads
compared to Al2O3 implants [17]. Besides the stress in the coatings an
enhanced corrosion in the implant coating interface are discussed [2].
Electrochemical corrosion investigation showed that thicker DLC
coatings offer improved corrosion protection [18].
In this work thick (6 to 20 μm) graded Si/SiC/DLC layers have been
prepared and their wear and adhesion behaviour is investigated.
2. Experimental
Graded Si/SiC/DLC multilayer systems were prepared on Titan-
substrates by the PECVD-method, using Ethin (C2H2) and hexam-
ethyldisiloxane (HMDSO) as reactant gases. The liquid HMDSO was

0925-9635/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.diamond.2008.02.039
1686 Ch. Schwarz et al. / Diamond & Related Materials 17 (2008) 1685–1688

vaporised with a vapour pressure from 30–44 Pa by heating the liquid

reservoir. The plasma was excited using a parallel-plate capacitive
coupled RF system. Samples have been mounted on the powered
electrode. Before deposition the samples have been cleaned by Argon
plasma. During the deposition process the RF power, the C2H2 and
HMDSO gas flows, respectively, and thus the working pressure were
changed stepwise. The aim was to crate an appropriate combination of
an adhesive layer with improved elastic properties and a wear pro-
tective layer with increased hardness on the top. To analyse the process
parameter influence on the mechanical and elastic properties of each
layer, different samples series have been prepared. Representative
samples and process parameters are summarized in Table 1. For
deposition of Si adhesion layers HMDSO was excited in the plasma
(all samples 30 min). The growing rate depends on RF power as
revealed by thickness measurements (see Table 1). SiC layers have
been deposited with equal C2H2 and HMDSO partial pressures, the
working pressure kept nearly constant and the RF power was varied Fig. 1. EDX-excitation-profile of a SiC layer on Ti substrate (sample SiC4).
(see Table 1). All SiC coatings have been grown for 30 min. The
growing rates of these samples are slightly increasing with increasing
applied to the same probing parameters. All measurements have been
RF power. A further group of samples have been prepared by
performed with 0.54 N, 1.1 m/s for 30 min.
deposition SiC (all 30 min) subsequently to a Si adhesion layer (all
EDX-measurements (Roentec® detector) at the calottes surfaces
have been grown for 10 min), thus these samples are named Si/SiC
and with changing excitation energies have been analysed to create
(Table 1). In these experiments the RF power kept constant and the
the depth profiles. Depending on the materials density and excitation
partial pressure ratio of C2H2:HMDSO during SiC deposition was
energy E0 which was varied between 4 and 25 keV the penetration
varied by increasing the C2H2 gas flow (0.4:1 for sample Si/SiC7, 0.5:1
depth R of exciting electrons is given according Eq. (1) [19].
for sample Si/SiC8, 0.75:1 for sample Si/SiC9), thus for these samples
the working pressure is increasing. Under this HMDSO rich plasma 4120 ð1:2650:0954lnE0 Þ
constitution the average growing rate is much higher and thus larger R¼  E0 ð1Þ
q
layer thickness is obtained and the growing rate is increasing with
working pressure (see Table 1). For samples named DLC subsequently The layers thickness was estimated by SEM (Zeiss DSM 962)
to the Si/SiC deposition (as described above) HMDSO flow was measurement tools or by analysing the grinded calottes in light optical
switched off, thus pure C2H2 plasma was applied (for all DLC samples microscope.
30 min). The process parameters like applied RF power and working The adhesive strength of the layers could be demonstrated with
pressures are summarized in the table too. bending tests (DIN EN ISO 1519). Coated Ti-substrates have been
Vickers and Martens measurements were performed to obtain bended at 90°. Bending velocity kept constant. The samples have been
hardness and elasticity respectively using FISCHERSCOP HM2000. The classified qualitatively into five classes (class 0 for no blistering, class 5
Martens Hardness is acquired by penetration load and — depth taking for complete blistering).
into account. The layer Elastic Module is yielded by calculating the
ratio of penetration depths under applied penetration load and after 3. Results and discussion
releasing load. An appropriate choice of penetration load in
consideration of layer thickness, expected hardness and elastic The EDX-measurements with the changing excitation energies
module is critical. revealed a Si/C concentration gradient in all deposited SiC and Si/SiC
Wear resistance measurements were performed by grinding films. Fig. 1 shows the results for the SiC4 sample and Fig. 2 for Si/SiC8
calottes according to DIN EN 1071-2 using the precision probe device for example. According Eq. (1) and assuming an average materials
“kaloMAX NT” which was purposely developed for wear measure- density of 1.5 g/cm3 and excitation energy of 20 keV approximately
ments of thin layers by cooperation of BAQ GmBH and Fraunhofer correspond to an excitation depth of about 4 μm, thus no Ti
Institut für Schicht- und Oberflächentechnik. A 100Cr6 steel ball of concentrations from the substrate have been detected. The beam
30 mm diameter and under 60° angle of support were used to create energy E0 was changed from 20 down to 4 keV. Fig. 1 reveals for SiC an
grinding calottes with defined geometry. Al2O3 suspension was used 1:1 atomic concentration ratio in the range of 20 down to 13 keV. At
as grinding medium. Wear resistance measurements are comparison lower energies, respective closer to the surface, one can see a
measurements allowing related statements within a series of samples gradually changing concentration ratio towards higher carbon

Table 1
Mechanical tests results, RF power, working pressures and samples thickness of graded SiC, Si/SiC and Si/SiC/DLC layers; for Si mechanical properties have not been measured

Sample no. RF power/W Working pressure/Pa Wear/mm3/Nm Hardness HV E-module/GPa Thickness/μm Bending test/category

Si 2 50 4.4 – – – 0.4 1
Si 3 80 4.6 – – – 0.9 0
SiC 2.1 50 4.0 1.6 10− 4 260 29 6.9 1
SiC 3.1 80 4.3 0.8 10− 4 640 54 7.6 5
SiC 4.1 100 4.7 1.0 10− 4 380 40 8.1 5
SiC 5.1 30 4.3 3.6 10− 4 230 28 – 0
Si/SiC 7 50/50 4.8/4.7 1.8 10− 4 270 20 17 3
Si/SiC 8 50/50 4.6/5.8 3.7 10− 4 340 27 23 3
Si/SiC 9 50/50 4.3/6.3 – 405 43 – 4
DLC 1 50/50/50 4.4/4.3/4.3 0 330 26 9.9 4
DLC 2 50/80/100 4.4/4.5/3.7 0 620 40 11 5
 Ch. Schwarz et al. / Diamond & Related Materials 17 (2008) 1685–1688
Fig. 2. EDX-excitation-profile of a Si/SiC layer on Ti substrate (sample Si/SiC8).
content. This constitution gradient can be only explained by the
growing process: the SiC deposition starts stoichiometrically, see Fig. 1,
but during the growing the plasma becomes more and more carbon
rich and the growing film changes its composition. For Si/SiC samples
(compare Fig. 2 for sample Si/SiC8) the process starts with HMDSO
and for SiC deposition C2H2 is added after 10 min. Thus the plasma
composition in this case changes from Si-rich to carbon rich during
the film growth. Figs. 1 and 2 reveal, that the obtained layer systems
should be discussed as gradually doped systems, such as Si:O:C/SiC:O/
a-C:Si:O.
The obtained oxygen content results from the HDMSO precursor
are always connected with the Si-concentration. Depending on Si-
content the oxygen concentration in the graded layers is up to 40%.
However the measurements reveal continuously changing Si and C-
concentrations, up to 70% C and 12% Si and oxygen respectively at
the sample surface. For Si/SiC/DLC samples the carbon concentra-
tions achieved 100% at the surface and Si as well oxygen 0%,
respectively.
Hardness and E-module of the DLC samples (Si/SiC/DLC as
explained above) are shown in Fig. 3 for different proof loads and
thus for different indentation depths. The DLC layers have been
grown with different RF bias power: lowest (50 W) for sample
DLC1, highest for DLC2 (100 W). Highest values for hardness and
elasticity appear for sample DLC2 (1200 HV, E-module 85 GPa),
what corresponds to our other findings, that hardness and E-
module of pure DLC-coatings increase with increasing bias power.
Fig. 3. Microhardness (straight lines) and Elastic Module (dashed lines) of DLC-covered
Si/SiC layer on Titanium substrate vs. applied proof load.
1687
Fig. 4. Grinding calotte of sample SiC3; the calottes diameter is 46 μm.
All measured hardness and elastic modules are much lower as have
been achieved for single DLC films (up to 4000 HV). The values
decrease with increasing proof load. The maximum indentation
depth for the maximum proof load was about 2 μm, what was for
the samples more than 10% of the layer thickness, thus the
measured results should be influenced by the metal substrate
material. For comparison hardness and E-modules measured with
300 mN proof loads are summarized for all investigated samples in
Table 1, revealing an average hardness and elasticity of the coating
system. Table 1 also compares the process parameters (applied RF
power, working pressures for Si, SiC and DLC deposition respec-
tively), the sample thickness and the results of bending tests. The
values show, that thin Si layers have an excellent adhesion. The
adhesion of the graded SiC layers depends on the elasticity: best
bending test category is achieved with samples having E-modules
lower than 30 GPa having a thickness of about 7 μm. Thicker
samples (sample Si/SiC7 and Si/SiC8, 17 or 23 μm, respectively) peel
off (bending test category 3) although they have low E-modules
too. This is because of the huge thickness resulting in high inner
stress in the layers. Samples with high E-modules show bad
adhesion, SiC samples grown with higher RF power as well as the
DLC samples.
However, the Si/SiC/DLC layer systems show excellent wear
resistance, what is demonstrated by calotte grinding tests (Figs. 4
and 5). Fig. 4 shows the calotte for a SiC graded layer, which is one of
the lowest wear abrasions for SiC samples (see Table 1, Sample SiC 3).
Fig. 5 shows the test result for a Si/SiC/DLC graded layer (sample
DLC2), performed under same conditions as for the sample in Fig. 4.
The improved wear resistance is obviously. The treated surface area
appears polished. Si/SiC/DLC protective layers do not show abrasion or
blistering during abrasion tests.
Fig. 5. Attempt to wear at same conditions like on sample in Fig. 4 on top of a DLC
covered SiC sample (Si/SiC/DLC 2); there is no visible grinding calotte but a polished
(black) range with some scratches.
1688 Ch. Schwarz et al. / Diamond & Related Materials 17 (2008) 1685–1688

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