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Fraunhofer Institute for Surface Engineering and Thin Films IST, Braunschweig, Germany
AMG Coating Technologies, Hanau, Germany
a r t i c l e
i n f o
Article history:
Received 3 December 2013
Accepted in revised form 20 January 2014
Available online 25 January 2014
Keywords:
Diamond-like carbon
History
Industrial application
a b s t r a c t
Diamond-like carbon (DLC) lms combine several excellent properties like high hardness, low friction coefcients and chemical inertness. The DLC coating material can be further classied in two main groups, the hydrogenated amorphous carbon (a-C:H, ta-C:H) and the hydrogen free amorphous carbon (a-C, ta-C). By adding other
elements like metals (a-C:H:Me) or non-metal elements like silicon, oxygen, uorine or others (a-C:H:X), several
modications of the properties can be adjusted according to application requirements. First reports on hard
amorphous carbon lms were published in the 1950s and about 20 years later there began worldwide intensive
research activities on DLC. In the following years the number of publications increased continuously and the importance for industrial applications became more and more evident. Several deposition techniques were applied
to prepare a-C:H, ta-C, metal containing a-C:H:Me and non-metal containing a-C:H:X coatings. In parallel the
structure and deposition mechanisms of DLC coatings were extensively studied. An essential obstacle for a
broad industrial application was the high compressive stress level in a-C:H lms causing delamination and limiting the lm thicknesses. With metal based intermediate layer systems most adhesion problems could be solved
satisfactorily and thus from the mid-1990s the pre-conditions for a broad application especially in the automotive
industry were given. With modied a-C:H:X and a-C:X coatings a considerable friction reduction or surface energy adjustments could be achieved.
2014 Elsevier B.V. All rights reserved.
Contents
1.
2.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Initial developments . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Superhard hydrogen free ta-C and hydrogen containing ta-C:H coatings
2.3.
Structure and composition of a-C:H and ta-C . . . . . . . . . . . .
2.4.
Growth mechanisms of a-C:H and ta-C . . . . . . . . . . . . . . .
2.5.
Metal containing diamond-like carbon coatings . . . . . . . . . . .
2.6.
Modied of a-C:H and a-C lms incorporation of additional elements
3.
Transfer to industrial applications and mass production . . . . . . . . . .
4.
Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Amorphous diamond-like carbon (DLC) coatings are known for their
outstanding properties such as low friction coefcients, high hardness
and wear resistance, chemical inertness, optical transparency in the IR
spectral range and low electrical conductivities. These properties and
Corresponding author. Tel.: +49 531 2155 642; fax: +49 531 2155 900.
E-mail address: klaus.bewilogua@ist.fraunhofer.de (K. Bewilogua).
0257-8972/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.surfcoat.2014.01.031
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214
215
215
217
218
220
220
221
223
223
223
from Gillette should be mentioned. DLC lms are also applied for wear
protection of cutting and forming tools [6,7], for biomedical components [8,9], as IR antireection lms (Section 2.1), components of thin
lm sensors [10], barrier lms in PET bottles [9], or as a dielectric layer
[11]. For a summary of the most important applications of DLC coatings
a recent paper by Robertson [12] is recommended.
Currently the term DLC describes a large variety of carbon based
coating modications. In order to devise a classication regarding the
use of different names for DLC coatings, especially in Germany, Japan
and Korea attempts were made to describe the different modications
of DLC systematically. Here the German guideline VDI 2840 Carbon
lms Basic knowledge, lm types and properties should be mentioned
[13].
In this guide line it will be distinguished between the following
types of DLC coatings:
Hydrogen free amorphous carbon lms a-C
Hydrogen free tetrahedral amorphous carbon lms ta-C with a high
fraction of tetrahedral coordinated sp3 bonded carbon atoms
Metal containing hydrogen free amorphous carbon lms a-C:Me,
where the metal often is a carbide forming metal like titanium or
tungsten
Hydrogenated amorphous carbon lms a-C:H
Hydrogenated tetrahedral amorphous carbon lms ta-C:H
Metal containing hydrogenated amorphous carbon lms a-C:H:Me
Modied hydrogenated amorphous carbon lms a-C:H:X, where X
is related to such non-metal elements such as silicon, oxygen, nitrogen, uorine, and boron.
In order to obtain a comparison of DLC lms with diamond and
graphite in Table 1 some typical properties of both these crystalline
phases with ta-C and a-C:H are summarized.
All types of coatings mentioned, are usually prepared by physical
vapor deposition (PVD) methods like sputtering or arc evaporation or
by plasma-enhanced chemical vapor deposition (PECVD) methods.
PECVD techniques base on glow discharge processes applying hydrocarbon gases like acetylene (C2H2) and negatively biased substrates working at radio frequencies (r.f. 13.56 MHz) [14] or mid-frequencies
(m.f. some 10 to some 100 kHz) [15]. Besides the outstanding coating
properties of DLC it is an important aspect that these coatings can be
deposited at low substrate temperatures (b200 C), e.g. on temperature
sensitive steel components.
The aim of the present paper is to discuss historical developments of
preparation techniques, structure models, growth mechanisms, properties and applications of different types of DLC coatings. Furthermore examples for developments of industrial deposition processes and new
application elds of DLC coatings will be discussed.
Table 1
Comparison of typical properties of diamond, ta-C, a-C:H and graphite (references:
[12,38,39,55,56,68,87,102,145]).
Crystal system
3
Mass density/g/cm
sp3 Content/%
Hydrogen content/ at.%
Hardness/GPa
Friction coefcients
In humid air
In dry air
Band gap/eV
Electrical
resistivity/ cm
Thermal stability
in air/C
Diamond
ta-C
a-C:H
Graphite
Diamond cubic
Amorphous
Amorphous
Hexagonal
3.51
100
0
100
2.53.3
5090
~1
5080
0.1
0.1
5.5
1018
0.050.25
0.6
12.5
1061010
0.020.3
0.020.2
14
1041012
0.10.2
N0.6
0.04
106102
800
400600
300350
N500
1.52.4
2060
1050
1045
2.26
0
0
b5
215
2. History
2.1. Initial developments
Hard amorphous carbon lms were rst mentioned in 1953 by
Schmellenmeier in a paper on the inuence of an ionized acetylene
(C2H2) atmosphere on surfaces of tungstencobalt alloys [16]. The
main objective of his investigation was to nd out whether at relatively
low temperatures via a glow discharge in hydrocarbon atmospheres
tungsten carbide hard metal (so called Widia) surface layers can be
generated. As an additional observation the author found that black
and very hard amorphous lms were deposited on the cathode of the
d.c. glow discharge if the discharge current was not too high. In a second
paper published in 1956 Schmellenmeier [17] reported that these some
m thick hard lms consist of structure-less regions and, under specific process conditions, of crystallites which were identied by X-ray diffraction as diamond.
Already in 1951 Knig and Helwig [18] investigated direct current
(d.c.) glow discharge processes in a benzene (C6H6) atmosphere. However, they analyzed only the lms grown on the discharge-anode. These
lms were yellow and had a relatively low density (1.4 g/cm3). Later
Heisen [19,20], using nearly the same experimental set-up as Knig
and Helwig and also benzene as hydrocarbon precursor, observed on
the cathode of the discharge considerably higher deposition rates and
higher mass densities of the deposited lms than on the anode and concluded that the interaction cross sections of positive ions with adsorbed
gas molecules are much higher than those of electrons. Furthermore
Heisen [19] observed that the growth rates of the lms depend considerably on the substrate geometry as well as that insulating substrates
were charged under ion bombardment and consequently the lm
growth stops.
The next remarkable publication concerning hard amorphous carbon
lms was that of Aisenberg and Chabot [21] in 1971 where for the rst
time the term diamond-like carbon was used. These coatings were prepared by an ion beam deposition technique on room-temperature substrates. The ion beam consisted of carbon and argon ions generated in a
discharge system using graphite as material for the active electrodes.
Fig. 1 shows the scheme of this equipment. Positive carbon and gas ions
were extracted from the discharge region and deposited on a negatively
biased substrate and the ion energy could be adjusted by the substrate potential. The deposited lms were intensively investigated and specied
e.g. as scratch resistant, electrically insulating, optically transparent and
chemically resistant. The structure was described as partially crystalline
with lattice constants similar to those of diamond. Furthermore the
preparation of thin-lm transistors using the insulating carbon lms
was described. In 1973 the same authors reported that the cutting performance of paper cutting blades could be markedly increased by applying
diamond-like carbon lms. Wear tests with the coated blades revealed
that these lms apparently reduce the coefcient of friction [22].
In the 1970s several other papers on DLC were published. Spencer
et al. [23] analyzed DLC lms prepared by techniques similar to those
of Aisenberg and Chabot [21]. Using X-ray diffraction and transmission
electron microscopy (TEM) they found indications for small (size 5
10 nm) and large (up to 5 m) crystallites. The observed diffraction
reections were assigned to the diamond phase.
Whitmell and Williamson [24] prepared hard and insulating lms
with thicknesses up to 4 m on different metallic substrates using a similar d.c. based deposition technique like that of Schmellenmeier and
Heisen but with a gas mixture of ethylene (C2H4) with 5% argon. Over
the substrates a domed aperture was placed (Fig. 2). Although the
deposited lms were insulating and a positive charge should be expected, surprisingly high thicknesses could be achieved. Holland [25]
explained this assuming that secondary electrons generated at the
edges of the domed aperture compensate for the positive charges.
Later such a compensation effect was veried for a d.c. based ion plating
a-C:H deposition process on insulating glass substrates [26].
216
217
Due to the combination of low friction coefcients with high hardness and wear resistance, a-C:H lms became very interesting for solving diverse engineering problems. Consequently the number of research
groups working on DLC began to increase considerably in the following
years. Fig. 6 shows, referring to the database Scopus, how the number of
publications from a small number up to the 1980s increased continuously and reached maximum output after the year 2000. In the period
from 1990 to 2000 DLC coatings became more and more interesting regarding industrial applications, especially for the automotive industry
where they are well established today.
Nowadays tribological and mechanical properties of DLC coatings are
of outstanding interest for industrial applications especially in the automotive industry. First references to the potential of DLC lms were, as
already mentioned, given by Aisenberg and Chabot [22] and by Enke
et al. [39,40]. As far back as the 1980s, more detailed studies followed,
discussing the dependence of friction coefcients on deposition conditions [42] and humidity or surrounding gas atmosphere [41,43,44]. Furthermore, in the following years, a lot of investigations on hardness,
wear and friction were presented whereas especially in the 1990s and
later, the number of research papers on these topics continuously increased (see e.g. the historical overview of Donnet and Erdemir and following contributions on Tribology of Diamond-like Carbon Films in [45]).
In the late 1970s and in the 1980s, several papers concerning data on
other than mechanical or tribological properties of a-C:H lms were
published. In this period, electrical conductivities as well as optical
constants (refractive indices and extinction coefcients) of a-C:H lms
prepared by r.f. glow discharge processes were investigated in depth
by Anderson [46] and Meyerson and Smith [47,48]. As well, already in
1980, Meyerson and Smith [49] investigated the electrical conductivity
of doped (B and P) a-C:H lms and found conductivity gains of 5 orders
of magnitude, for example for a coating deposited at 250 C from
10 12 1 cm 1 to 10 7 1 cm 1.
Similar data for the optical properties of a-C:H lms deposited by d.c.
magnetron sputtering in ArC2H2 gas mixtures were published in the
early 1980s by research groups from Sydney, Australia [5052]. The
characteristic of this unusual deposition technique was that metal targets (e.g. stainless steel) were over coated with carbon from the dissociation of hydrocarbon species in the plasma of the glow discharge.
Thus a-C:H lms could be prepared on different substrates.
It is noteworthy that also in 1980 Moravec [53] proposed Color
chart for DLC lms on silicon, a simple but rather helpful tool to measure the thicknesses of thin DLC lms (up to about 300 nm) considering
interference colors.
2.2. Superhard hydrogen free ta-C and hydrogen containing ta-C:H coatings
Superhard hydrogen free ta-C lms are characterized by a high fraction of tetrahedrally bonded (sp3) carbon atoms. To prepare such lms,
218
Fig. 6. Number of publications on diamond-like carbon coatings in four decades (data from Scopus database for all DLC modications described in the Introduction).
carbon species with energies in the range of 100 eV are needed (for a review see e.g. [54]). The most appropriate method to realize such conditions is the cathodic arc evaporation. The pioneer work in this eld was
done by Strel'nitskij and Aksenov and co-workers in Kharkov in the former Soviet Union (today Ukraine). In 1978 Strel'nitskij et al. [55,56] reported on extremely hard and electrically insulating ( 1010 cm)
diamond-like carbon lms deposited by arc evaporation using a pure
graphite cathode. Refractive indices n N 2.2 were another indication
for diamond-like properties (n of diamond: 2.4). The substrates were
powered by r.f. and d.c. voltages. The maximum measured lm hardness
was stated as near to or even higher than that of natural diamond. The
lms were nanocrystalline but a clear assignment of the X-ray diffraction peaks to known carbon phases was not possible.
An obvious drawback of the used arc technique was the appearance
of macro particles in the growing lms. To overcome this, Aksenov et al.
[57,58] proposed an arc system equipped with a curvilinear separating
lter allowing a drastic reduction of the macro particles. The carbon species arriving at the substrate were completely ionized, predominantly
single charged [58]. The diamond-like-carbon coatings prepared by
this technique had highly pure surfaces and were still extremely hard
[58].
A few years later several papers concerning cathodic arc deposition
of superhard hydrogen free DLC lms were published. Martin, McKenzie
and co-workers [59,60] used a ltered arc system similar to that introduced by Aksenov and co-workers (see [58]) and discussed the atomic
structure of the deposited tetrahedral amorphous carbon (ta-C) lms
in detail, taking into account the data of electron energy loss spectroscopy (EELS) and electron diffraction analyses. In the very comprehensive
paper of McKenzie and co-workers [60], in addition to the atomic structure, the data on the compressive stress (up to 8 GPa) as a function of
the ion energy as well as a model for the stress development was presented. Furthermore optical properties and possible electronic devices
built with ta-C lms were discussed.
Another concept for the arc deposition of ta-C lms, the so called
laserarc technique, was proposed in the early 1990s by a research
group in Dresden, Germany, led by Pompe and Scheibe [61,62]. They
used short pulses (b1 ms) of a Nd:YAG laser to ignite a vacuum arc
realizing a time and position controlled arc of about 50 ms duration.
The deposited carbon lms were amorphous, very hard and had
refractive indices between 2.05 and 2.5. An additional advantage of
the laserarc technique is that by moving the target against the laser
beam the material to be deposited can be selected. Thus multilayer
Table 2
Examples for mass densities, hydrogen contents, number densities (calculated according
to reference [75]) and hardsoft classication of diamond, graphite diamond-like carbon
lms and a polymer.
Diamond
Graphite
ta-C
a-C:H (1)
a-C:H (2)
a-C:H (3)
Polystyrene
(C8H8)
Mass density
(g/cm3)
Hydrogen
content (at.%)
Number density
(1/cm3)
Hard/soft
3.51
2.25
3.2
2.3
2.0
1.4
1.05
0
0
1
11
17
60
50
0.29
0.19
0.27
0.21
0.20
0.26
0.16
Superhard
Soft
Superhard
Hard
Hard
Soft
Soft polymer
219
Fig. 7. Relation between sp3/sp2 ratio and hydrogen concentration in a-C:H lms, calculated according to [76], experimental data, derived from Kaplan et al. [86], Robertson [12],
and Hofmann et al. [145].
from infrared absorption spectra and the total hydrogen content was estimated by an effusion technique. With increasing self-bias voltages the
structure changed from weakly bonded benzene-like rings to graphitic
ring structures. After annealing the number of sp2 bonded carbon
atoms increased and above 600 C hydrogen was released.
An interesting model for a-C:H was presented in 1990 by Tamor and
Wu [80] who proposed defected graphitic networks where hydrogen
atoms saturate open bonds in vacancies of graphite clusters. Applying
this model nearly the same lower (20 at.%) and upper (60 at.%) limits
of the hydrogen content like those from Angus and Jansen [76] were
estimated.
In 1993 Mller and co-workers [81,82] described structure and composition of different hydrocarbon lms by a ternary phase diagram
which assumed as the three phases in these lms sp3 and sp2 hybridized
carbon and hydrogen. This ternary phase diagram was afterward used
in many papers concerning a-C:H lms (e.g. [67,83]). Fig. 8 shows an example for such a phase diagram.
Beginning in the late 1980s, Australian research groups investigated
the structure of arc deposited ta-C in detail using electron optical
methods especially EELS [59,84,85] and electron diffraction [60,85]. It
was proved that in these lm sp3 bonded carbon dominates. In the
low energy part of the EELS spectra, the plasmon peak was found in
the range of the diamond peak (33 eV) and from electron diffraction,
nearest neighbor distances (r1)and coordination numbers (n1) as well
as the bond angles () were determined as very near to the diamond
values (diamond: r1 = 0.154 nm, n1 = 4 and = 109.47).
For structure characterization of DLC lms beside electron diffraction, EELS, IR spectroscopy [70] or nuclear magnetic resonance (NMR)
[86] the Raman spectroscopy was an important characterization tool
[8789]. An essential advantage of the Raman spectroscopy is that no
extensive sample preparation is necessary. Although the interpretation
of Raman spectra is rather complex [83], this technique allows comparison of different phases of carbon materials and estimation of sp3/sp2
ratios [83,90].
Modeling of a-C structures started in 1984 by Beeman et al. [91]
using hand models with several 100 carbon atoms and in 1989 by
Galli et al. [92,93] using rst-principle molecular-dynamic methods. In
the 1990s several groups carried out extensive computer modeling of
pure a-C [94], ta-C [95,96] or both pure and hydrogenated amorphous
carbon [9799] and compared the results with experimentally determined data like mass densities, hydrogen contents or interference functions and radial distribution functions. The best points of concurrence
of experiment and model could be used to draw conclusions e.g. on
the contributions of sp3, sp2 and sp1 bonds (sp1: one-dimensional,
acetylene-like), and made it possible to calculate electronic densities
of states [95,97,98]. Fig. 9 shows an example for an a-C:H lm model
with a dominant sp2 share and 30 at.% hydrogen.
220
Fig. 8. Ternary phase diagram adapted according to and using data from [8183,12,145].
Fig. 9. Structure model of an a-C:H lm with a density of 1.7 g/cm3, 30 at.% hydrogen, 65%
sp2, 20% sp3 and 15% sp1 bonds. A cluster consisting of graphite-like rings is accented.
Image: with kind permission of Thomas Frauenheim, Bremen Center of Computational
Materials Science.
In the 1980s and still in the 1990s the main reason of the retarding
industrial applications of DLC as tribological coatings was their disappointing adhesion caused by relatively high compressive stresses in
the range of some GPa. To overcome this obstacle, Dimigen and coworkers [111,112] prepared metal containing DLC lms (Me-DLC,
today abbreviated as a-C:H:Me) by reactive r.f. sputtering of a metal in
a hydrocarbonargon atmosphere. Alternatively, instead of pure metal
targets, metalcarbon (metal carbide) targets could be utilized. Such
Me-DLC lms with metal to carbon ratios in the range Me/C = 0.10.2
were found to have, under non-lubricated conditions, similar low friction coefcients like a-C:H. In comparison to a-C:H, not only their hardness and wear resistance, but also the compressive stress was slightly
lower but, on the other hand, due to a strongly cross-linked carbon
hydrogen matrix, considerably higher than the hardness of metal containing polymers [44]. Another essential advantage of the Me-DLC process was that the metal target could simply be used in a rst process
step to prepare an adhesion improving metallic interlayer. Moreover,
it was remarkable that the electrical conductivity of Me-DLC was several
orders of magnitude higher than that of a-C:H [113]. Later Benndorf
221
Fig. 10. Ion-lm interactions during growth of ta-C and a-C:H: direct (a) and indirect (b) subplantations, scheme of a-C:H growth (c).
Adapted according to [109,110,105].
et al. [114] developed a structure model which explained the high electrical conductivities even at relatively low metal contents. The authors
assumed that metal, not bonded in carbides, modies the carbide surrounding a-C:H matrix.
The reactive sputter deposition technique was developed and applied in the same period and even earlier by Australian scientists for
the preparation of solar absorbing surfaces. Ritchie and Harding [115]
prepared FeC lms by d.c. diode sputtering in an ArCH4 mixture.
Wilson et al. [116] used a dual-post cathode sputter coater with two independently controlled cathodes consisting of different materials operating with acetylene so that graded metalcarbon lms could be
produced.
The most important factors for industrial applications of Me-DLC (or
a-C:H:Me) coatings were the tribological properties, the good adhesion
and especially the high potential for transferring the deposition processes to industrial dimensions (see Section 3). Industrially relevant deposition processes could not be realized with r.f. processes. Therefore
transferring the process to magnetron sputter techniques was
demanded. Bergmann and Vogel [117] used a magnetron sputter machine equipped with four planar targets to prepare W-DLC coatings
from a tungsten carbide target as well as Ti-DLC and Cr-DLC coatings
from the corresponding metal targets. Deposition rate, hardness and
stress of the coatings depended on the reactive gas (acetylene) ow
during sputter deposition and these properties were clearly different
for the three investigated metals.
A summary of the situation at the end of the 1980s concerning deposition processes, structure and composition as well as optical, electrical,
mechanical and tribological properties of Me-DLC lms was presented
by Klages and Memming [44].
Already in 1980, Richie [118] investigated the structure of Ti-DLC
lms prepared by reactive d.c. magnetron sputtering applying an
argonmethane mixture and a pure titanium target and reported on titanium carbide particles of 510 nm diameter embedded in an amorphous carbon matrix. In the 1990s some very detailed studies on MeDLC growth processes and the structure were published. Wang et al.
[119,120] analyzed the structure and composition of Ti-, Ta- and WDLC lms prepared by reactive r.f. sputtering and measured thereby
the hydrogen contents by elastic recoil detection (ERD). Sjstrm et al.
[121] investigated the structure of Mo-DLC and W-DLC lms by highresolution transmission electron microscopy, X-ray diffraction and
Auger electron spectroscopy. In the amorphous a-C:H matrix small crystallites with dimensions of few nm were embedded. In the case of molybdenum, metallic bcc Mo clusters (14 nm) and of tungsten 1 nm
clusters, probably consisting of tungsten carbide, were identied. A
comparative study on the structure and cluster distribution in Me-DLC
lms for carbide forming metals (W, Fe) and non-carbide forming
metals (Au, Pt) was published by Schiffmann et al. [122] in 1999.
To control reactive magnetron sputter deposition processes and to
prevent excessive target poisoning a plasma emission monitor could
be used [123,124]. Using this control tool it was revealed that the
main contribution to lm growth originates from target near discharge
222
Fig. 11. Scheme morphology of a Me-DLC coating grown in a sputter machine with rotating substrates.
Adapted according to [130].
for lms with Si/C ratios between 0.15 and 0.4 the friction coefcients
were extremely low (b0.05) and thereby clearly lower than those of
pure a-C:H coatings in humid air (0.120.2). To explain the low friction
coefcients in humid air it was assumed that ne silica particles formed
during the sliding process will be surrounded by a water layer and the
silica-sol acts as a liquid lubricant [139]. Miyake [140] found a similar
friction behavior under vacuum conditions. As-deposited lms and
lms annealed at 400 C exhibited the extremely low values (markedly lower than 0.1) for a Si concentration range around 10%. After annealing at 600 C the friction coefcients increased drastically (N 0.2). A
comparison of a-C:H:Si, a-C:H:Ge and a-C:H:Ti revealed that obviously
only a silicon incorporation leads to a drastic reduction of the friction coefcients [141]. In the following years many details on structure and
properties of silicon containing a-C:H:Si and other doped coatings, especially with respect to their tribological properties, were reported (for an
overview see [142] and references therein).
Another remarkable property of a-C:H:Si is the clearly higher thermal stability compared to that of pure a-C:H. For a-C:H:Si lms prepared
by r.f. PECVD the temperature at which structural changes started could
be considerably increased by adding silicon to a-C:H [143,144]. It was
assumed that higher silicon contents lead to more sp3 bonded carbon
and thus the carbon network will be stabilized against graphitization
[144]. Recently also for sputter deposited a-C:H:Si a clearly higher thermal stability compared to that of a-C:H was reported by Hofmann et al.
[145]. Both hardness and friction coefcients remained nearly constant
even after annealing at 500 C in air whereas a-C:H coatings already
failed at temperatures below 400 C.
Fig. 12. Typical dependencies of hardness, wear (a) and friction coefcients (b) on metal/carbon ratios, shown for a-C:H:W and a-C:H:Ti.
Adapted according to [130], hardness of a-C:H:Ti from [132].
223
C:H and other components like tappets and piston pins will be routinely
coated with a continuously increasing proportion [2].
4. Summary and outlook
The rst experimental evidence of DLC coatings was reported about
60 years ago. From the mid-1970s the research activities on DLC coatings continuously increased until the end of the 1990s and thereafter
remained on a high level. During the course of this development, new
deposition methods like reactive sputtering and cathodic arc processes
as well as modications of diamond-like amorphous carbon-based
lms were created. After reliably solving the adhesion problems the
number of industrial applications increased continuously. Today a
large number of applications, especially in the automotive industry,
are established and, for example for diesel injection systems, DLC coatings are indispensable.
Future developments of coating deposition processes should take
into consideration the following points:
Reliable homogeneous deposition of DLC-based coatings on threedimensional parts in industrial scale deposition machines,
Reduction of the costs of ownership for the coatings by optimization
of the deposition processes, which is connected with higher deposition rates and reliable processes at retaining coating quality,
Optimization of DLC based coatings with respect to operation under
lubricated conditions, aiming to a further reduction of friction
effects,
And increase in the thermal stability of DLC coatings by optimization
of modied coating types including multilayer coatings designs.
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