Surface & Coatings Technology 242 (2014) 214225

Contents lists available at ScienceDirect

Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

History of diamond-like carbon lms From rst experiments to

worldwide applications
Klaus Bewilogua a,, Dieter Hofmann b
a
b

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

their combinations are very promising for a variety of technical

applications.
Today DLC lms are used worldwide on a large industrial scale to improve the performance of tools and of components, especially for automotive applications [13] with more than 100 million coated parts per
year and a market volume of several 100 million. Other application
elds with large market shares are protective DLC lms (a few nm
thick) for high storage density hard disks and recording heads [4,5] as
well as razor blades where thin DLC lms improve the performance of
sharp cutting edges. As an example the well-known Mach 3 razor

K. Bewilogua, D. Hofmann / Surface & Coatings Technology 242 (2014) 214225

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

K. Bewilogua, D. Hofmann / Surface & Coatings Technology 242 (2014) 214225

Fig. 1. Scheme of ion-beam deposition system.

Adapted according to [21].

Since the mid-1970s several research groups have published results

of a-C:H deposition experiments. Especially the work of Holland and
Ojha [27,25] can be regarded as a break through because they used a
radio frequency (r.f. 13.56 MHz) glow discharge in butane (C4H10)
gas to overcome problems with deposition of insulating a-C:H lms
(for a process-scheme see Fig. 3). Hard and insulating lms could be
prepared even on dielectric substrates such as glass. Furthermore it
seems to be important that similar equipment was available in many
laboratories and could be used simply to prepare DLC coatings. Besides
Holland and Ojha [25,27], Andersson, Berg and co-workers [28,29] used
the r.f. glow discharge method to prepare a-C:H lms and they considered aspects concerning the growth mechanism of a-C:H lms like the
initial phases of lm growth on different substrate materials [28]. Furthermore, different hydrocarbon precursors (methane CH4, ethane
C2H6, propane C3H8, n-butane C4H10 and iso-butane C4H10) were compared [29]. The highest deposition rates were observed for both butanes, the lowest one for methane. The authors stated that there was
no simple relationship between growth rate and precursor structure indicating complex ionization and dissociation processes of the hydrocarbon molecules.
In the early and mid-1980s profound work on a-C:H lms prepared
by r.f. glow discharge was done. Bubenzer et al. [30] from the Fraunhofer
Institute for Applied Solid State Physics in Freiburg, Germany, described
the negative r.f. self-bias VB of the substrate and the hydrocarbon gas
pressure P as the most important parameters controlling the deposition
process. E.g. the lm density ranged between 1.5 and 1.8 g/cm3 and

depended linearly on the term VB P0.5 which on the other hand

was found to be proportional to the average energy of the lm forming
energy. The objective of the research group in Freiburg was to develop
a-C:H as transparent wear resistant anti-reection coatings on infrared
(IR) optical components. On germanium and silicon substrates (refracting
index n 4) a-C:H lms with n 2 would be an ideal transparent
antireection layer [3032]. Catherine and Couderc [33] compared a-C:
H glow discharge deposition processes and growth kinetics both for
r.f. (13.56 MHz) and m.f. (50 kHz) plasma excitation. The lm properties
were found to be related to the product VB P0.5 for the r.f. process (likewise Bubenzer et al. [30]) and to the product J P0.5 for the m.f. process
where J is the mean current density.
In the period since the mid-1970s also other techniques for a-C:H
deposition were developed and the lms were characterized in detail.
Weissmantel and co-workers [34,35] reported on two different
methods for the preparation of DLC coatings. With the so called dual
beam technique, a carbon target was sputtered with argon ions and
the carbon lm growing on the substrate was simultaneously
bombarded by a second ion source operated at about 1 kV with argon
and methane (Fig. 4). The deposited carbon lms were hard and the
structure was characterized as amorphous with crystallites embedded
in the substrate regions exposed to the highest ion current densities
[35].
On the other hand in the Weissmantel group a-C:H coatings were
prepared applying a completely d.c. based ion plating process where
hydrocarbon ions were generated in a benzene atmosphere by hot

Fig. 2. Scheme of d.c. glow discharge deposition technique.

Adapted according to [24].

Fig. 3. Scheme of r.f. glow discharge deposition technique.

Adapted according to [25,27].

K. Bewilogua, D. Hofmann / Surface & Coatings Technology 242 (2014) 214225

217

Fig. 4. Scheme of dual beam deposition technique.

Adapted according to [34,35].

cathode ionization. The a-C:H lms were grown by acceleration of these

ions to a negatively d.c. biased (up to 800 V) substrate [35,36]. Fig. 5
shows the scheme of this deposition method. These lms were hard,
partially optically transparent and electrically insulating. The structure
was described as a mixture of nanocrystalline components consisting
of graphite-like and diamond-like elements [36].
In the early 1990s Martinu et al. [37] increased the effectiveness of
the r.f. glow discharge processes by applying a simultaneously operating
microwave (MW 2.45 GHz) radiation. With this combined r.f.MW
process increased ion uxes on the substrate, higher deposition rates,
lower hydrogen contents and increased hardness of the deposited a-C:
H lms were achieved.
Enke, Dimigen and co-workers reported in the early 1980s on very
low friction coefcients of hard diamond-like carbon lms against
steel counterparts [3840]. The investigated a-C:H lms were prepared
by a r.f. glow discharge technique similar to that of Holland and Ojha
[27]. In contrast to graphite, these lms had extremely low friction coefcients () at low humidity (0.01) and under normal atmosphere
the values remained rather low (b0.2). Memming et al. [41] measured
friction coefcients of the same type of a-C:H lms against steel in ultrahigh vacuum ( 0.02), humid air or nitrogen (0.25) as well as in dry
nitrogen (0.02) and dry oxygen (0.6) and explained the differences
with different developments of the transfer layers which is generated
between the sliding partners.

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

Fig. 5. Scheme of d.c. ion plating deposition technique.

Adapted according to [35,36].

Superhard hydrogen free ta-C lms are characterized by a high fraction of tetrahedrally bonded (sp3) carbon atoms. To prepare such lms,

218

K. Bewilogua, D. Hofmann / Surface & Coatings Technology 242 (2014) 214225

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

lms can be prepared [61]. Later industrially utilizable laserarc

techniques to deposit ta-C were developed [63].
Other PVD techniques were revealed to be principally appropriate to
prepare carbon lms with high sp3 contents. Here the pulsed laser deposition (PLD for an overview see [64] and references therein), the
unbalanced magnetron sputtering (UBM) [65,66], should be mentioned.
Weiler et al. [67] reported on tetrahedral hydrogenated DLC lms (taC:H) prepared from a plasma beam source based on a r.f. (13.56 MHz)
discharge at relatively low working gas pressures (0.05 Pa) and a
magnetic connement allowing generation of a highly ionized plasma
beam. The prepared lms had a sp3 fraction up to 0.75, a maximum
mass density of 2.9 g/cm3 and hydrogen contents between 22 and
28 at.%. High hardness (N 60 GPa) but also high compressive stress
(8.5 GPa) corresponded to the high sp3 contents.
Although the properties of tetrahedrally coordinated DLC lms, like
high hardness and wear resistance and low friction coefcients under
ambient conditions and under oil lubrication [68], are very attractive,
a broad breakthrough of ta-C deposition techniques in the industrial
mass production is still outstanding.
2.3. Structure and composition of a-C:H and ta-C
In the abovementioned rst publications on diamond-like carbon
lms their structure was specied as amorphous with crystalline
regions [17] or partially crystalline where the crystalline phase
corresponded to diamond [21,23]. Anderson [46] found that highly insulating a-C:H lms prepared by r.f. glow discharge are amorphous
and proposed a structure model consisting of three- and four-fold coordinated carbon atoms where the latter prevent the formation of extended graphite-like components.
In the 1980s, detailed investigations on the structure of a-C:H were
presented. Craig and Harding [52] analyzed composition and structure
of magnetron sputtered a-C:H lms (see Section 2.1.). The hydrogen
content, determined by pyrolysis, was in all as-deposited lms higher
than 32 at.% and the oxygen content (from residual gas) higher than
6 at.%. The proposed structure model consisted of a random network
of tetrahedral coordinated carbon atoms modied by carboncarbon
double bonds and carbonhydrogen bonds. This model was consistent
with the low densities (1.0 to 1.6 g/cm3) and high resistivities (N107
cm). McKenzie et al. [50,51,69] developed an a-C:H model where
threefold coordinated carbon clusters are embedded in an insulating
polymer-like hydrocarbon material containing many methyl groups.

K. Bewilogua, D. Hofmann / Surface & Coatings Technology 242 (2014) 214225

Assuming such a structure, the results of annealing experiments which

led to properties similar to those of glassy carbon, could be simply explained. More or less simultaneously Dischler et al. [70] analyzed IR absorption spectra and developed similar structural concepts for as-grown
as well as for annealed a-C:H lms prepared by r.f. glow discharge.
It had been proved reasonable to compare structural features of a-C:
H lms with those of evaporated a-C lms. Bewilogua, Weissmantel
et al. [7173] revealed by electron diffraction and electron energy loss
spectroscopy studies a high similarity of ion plated a-C:H lms [35]
and of evaporated a-C lms. The best t for the experimentally derived
electron diffraction intensity functions was obtained assuming small
clusters (b 1 nm) consisting of puckered hexagonal and of pentagonal
rings. To explain the remarkable differences of the a-C:H and a-C
properties (hardness, electrical conductivity) for a-C:H, strong sp3 containing cross-linkages between the clusters were assumed which in a-C
do not exist. A corresponding hand built model was presented by
Weissmantel [73].
Robertson and O'Reilly [74] discovered that the optical gaps of a-C
(~0.5 eV) and a-C:H (1.52.5 eV) are clearly different. Analyses of the
gaps of hydrocarbon ring structures indicated that the gap varies roughly inversely to the cluster size. Considering this relation, evaporated a-C
lms dominantly consist of disordered graphite clusters with dimensions up to 1.5 nm. On the other hand a-C:H lms contain a high amount
of sp2 sites in ring structures and the observed gap sizes are in accordance with the existence of clusters consisting of four or more aromatic
rings.
Angus [75] proposed an empirical categorization of DLC lms by
their gram atom number density N and their hydrogen fraction xH
where N is the quotient of the mass density m and molar mass:
N = m / (xH + 12(1 xH)) with the atomic masses 1 for hydrogen
and 12 for carbon. In Table 2 some examples for N and cH data are
summarized. Films with N N 0.2 g atom/cm3 were called dense carbonaceous (hard) lms or with signicant hydrogen amounts dense
hydrocarbon (soft) lms.
In 1988 Angus and Jansen [76] applied random covalent network
concepts to dense hydrocarbon lms. The theories suitable to describe
random covalent networks were developed some years ago by Phillips
[77] and Dhler et al. [78]. Accordingly a random covalent network is
completely constrained if the number of constraints per atom is equal
to the number of degrees of freedom per atom. Applied to hydrocarbon
systems containing sp2 and sp3 bonded carbon and hydrogen atoms, for
completely constrained structures, hydrogen contents between 17 and
62 at.% were derived [76]. In Fig. 7 the described relation (sp3/sp2 ratio
vs. hydrogen fraction xH) and an extended set of experimental data
are shown. This mode of representation allows a very clear distinction
between soft (high hydrogen content) and hard (low hydrogen content) coatings.
Fink et al. [79] analyzed as-deposited and annealed a-C:H lms by
high-resolution EELS. The lms were prepared by r.f. glow discharge
in benzene vapor. The content of bonded hydrogen was determined

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.

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K. Bewilogua, D. Hofmann / Surface & Coatings Technology 242 (2014) 214225

Fig. 8. Ternary phase diagram adapted according to and using data from [8183,12,145].

For a survey of the different structure characterization methods of

amorphous and nanocrystalline carbon lms a paper of Chu and Li
[100] is recommended.

2.4. Growth mechanisms of a-C:H and ta-C

Already Heisen [19] (see Section 2.1.) presented rst considerations
on the growth of hydrocarbon lms on discharge cathodes. Later, beginning in the 1980s, the roles of ions and radicals on the growth behavior
of a-C:H lms were considered more in detail by Catherine and Couderc
[33] and by Bubenzer et al. [30] and Koidl et al. [101] for r.f. based a-C:H
deposition processes. Koidl et al. [101] investigated different process
gases as precursors (benzene, cyclo-hexane, n-hexane, methane) and
found that the lm properties are nearly independent of the used
precursor gas if the bias voltage is high enough for an effective fragmentation of the hydrocarbon molecules. On the other hand, the nding
that the deposition rates depended clearly on the precursor gas
corresponded to the results reported by Andersson et al. [29]. The deposition rates increased with increasing molecule masses. Furthermore,
the ionization energy was seen as another rate-determining factor
(see also [102]).

In the 1990s, several theoretical studies on deposition mechanisms

both of hydrogen free ta-C and of hydrogen containing a-C:H lms
were published. Mller [103,104] from the Max-Planck Institute for
Plasma Physics in Garching, Germany analyzed the elementary mechanisms of the growth of a-C:H lms from low-pressure methane plasmas
and developed models which predicted the sp3/sp2 ratios for varying
ion energies [103] and explained, amongst others, the dependence of
the hydrogen content on the energy of the ions striking the substrates,
depth proles of carbon and hydrogen in an a-C:H lm and the inuence of the substrate temperature on the deposition rate [104]. In the
following years several papers on deposition experiments and modeling
of a-C:H lm growth were published by the research group from the
Max-Planck Institute for Plasma Physics in Garching, Germany, for example by von Keudell et al. [105] who discussed the processes in the
near surface growth zones and the mechanisms of hydrogen release
from growing a-C:H lms under ion bombardment. Hydrogen ions
have a considerably higher penetration depth than carbon ions and
form via recombination H2 molecules, which can desorb and thus
lower the hydrogen content in the lms. Additionally, such a mechanism explains the experimental ndings that the composition and properties of a-C:H lms prepared from very different precursors like
methane CH4 or benzene C6H6 are often rather similar.
For more details, a review of von Keudell [106] on Formation of
polymer-like hydrocarbon lms from radical beams of methyl and
atomic hydrogen is recommended.
In 1989 and 1990 Lifshitz et al. [107,108] suggested a subplantation
model to describe the ion-enhanced growth of carbon lms where
subplantation means the penetration of impinging hyperthermal species (11000 eV) into the top layers of the bombarded sample causing
phase transformations. In the case of carbon this model explained the
high sp3 contents assuming a considerable difference of the displacement energies Ed between graphite (25 eV) and diamond (80 eV) leading to preferred displacement of the low-Ed and remaining high-Ed
carbon.
Robertson [109] developed a similar model where ions enter the
subsurface region which will be densied. The experimentally determined density maxima of ta-C lm at ion energy around 100 eV were
interpreted as a consequence of a densication due to the ion striking
the surface and, at higher energies, to an energy dissipation accompanied by an annealing and density decrease. The impact of the ions can
be direct (carbon ion) into the surface near region or indirect by displacement of a surface atom into an interstitial site (Fig. 10).
In a continuative publication Robertson [110] extended the lm
growth model to plasma deposited a-C:H lms.
2.5. Metal containing diamond-like carbon coatings

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

K. Bewilogua, D. Hofmann / Surface & Coatings Technology 242 (2014) 214225

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

processes and that the contribution of direct plasma polymerization at

the substrates is small [124]. For reactive r.f. sputter processes the
same two contributions to the a-C:H:Me lm growth were revealed
for Ag-DLC lms [125].
Me-DLC coating preparation using magnetron sputter machines
with rotating substrates caused a columnar morphology with characteristic multilayer structures consisting of oscillating metal rich and carbon
rich single layers coatings [126130]. These oscillations could be explained by periodical changes of the substrate position compared to
the targets with a maximum metal content deposited directly in front
of the metal target. Fig. 11 shows a scheme of such a multilayer MeDLC coating with a columnar structure.
Me-DLC coatings consist of an a-C:H matrix with embedded carbides
which commonly are even harder than a-C:H [130]. Therefore it is
somewhat surprising that Me-DLC coatings are generally softer and exhibit higher wear rates than metal free a-C:H lms [126,131]. An explanation for this observation is that the a-C:H matrix of Me-DLC has
weaker cross-linkages, higher hydrogen contents and therefore a
lower mechanical stability [131].
The properties of a-C:H:Me coatings depend considerably on the
metal content which can be simply adjusted by the reactive gas content
in the sputter gas. Fig. 12 illustrates typical dependencies for hardness
and abrasive wear (a) and for the friction coefcients of tungsten and titanium containing a-C:H:Me coatings (b). The pronounced hardness
maxima (Fig. 12 a) can be interpreted as an effect of a MeC/a-C:H
nanocomposite structure consisting of metal carbide nanocrystals
surrounded by an amorphous carbon binder phase [132,130].
2.6. Modied of a-C:H and a-C lms incorporation of additional elements
In this section the so-called modied or doped DLC lms, according
to the VDI 2840 guideline [13] denoted as a-C:H:X where X is related to
non-metal elements, will be considered.
In the mid-1970s and 1980s several authors reported on silicon containing a-C:H:Si lms which were prepared by glow discharge decomposition of silane (SiH4) and hydrocarbon gases (C2H4 [133], CH4
[134,135]) as well as by sputter techniques [135,136]. McKenzie et al.
[136] applied the d.c. magnetron technique to prepare a-SixC(1 x)Hy
lms. The same magnetron sputter technique had already been previously successfully used for the deposition of pure a-C:H lms [5052]
(see also Section 2.1.). The working gas for the a-SixC(1x)Hy deposition
was a silaneacetyleneargon mixture. Because the motivation of this
research was to develop low emittance solar selective coatings on copper substrates, the optical properties were studied in detail. It is remarkable that, beside single layer coatings, also a-C:H/a-C:Si multilayer
coatings were prepared by varying the parameter x [136].
In the early 1990s Japanese research groups investigated friction coefcients () of silicon containing a-C:H:Si coatings prepared by
plasma-enhanced CVD methods. Oguri and Arai [137,138] measured
values using a ball-on disk tester under un-lubricated conditions at
room temperature in humid and dry atmospheres. In both atmospheres

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K. Bewilogua, D. Hofmann / Surface & Coatings Technology 242 (2014) 214225

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.

In the mid-1990s it was discovered that incorporation of non-metal

elements into the a-C:H can alter the surface energies of a-C:H coatings
to lower (X: F, Si, Si+O) and also to higher (B, N, O) values [146]. Thus it
became possible to combine the high mechanical stability of diamondlike carbon with low surface energies comparable with those of the
well-known hydrophobic material polytetrauorethylene (PTFE
surface energy about 19 mN/m, hardness b1 GPa). Grischke et al.
[147,148] reported on low surface energies of modied a-C:H:Si
(31 mN/m, 1015 GPa), a-C:H:Si:O (24 mN/m, 710 GPa) and a-C:H:F
(20 mN/m, 2 GPa) coatings. To realize these modications in r.f.
PECVD deposition processes the precursors TMS (Si(CH3)4), HMDSO
(OSi2(CH3)6) and C2F4 were used. For the corresponding pure a-C:H
coatings the surface energy was 41 mN/m and the hardness of
2030 GPa. Potential applications of this type of a-C:H:X lms were
demonstrated for example for heat exchanger surfaces [149,150].
Also hydrogen free modied a-C:X coatings were found to be hydrophobic. Schulz et al. [151] investigated a-C:F and a-C:Al lms prepared
by laserarc technology (see Section 2.2.). In both cases not only the
surface energy, but also the Young's modulus decreased with increasing
X-content.
Also in the mid-1990s Meneve et al. [152,153] reported on a-C:H/aSi1 x Cx:H multilayers prepared in a r.f. PECVD process using methane
and alternatively added silane as process gas. Under optimum process
conditions remarkable properties like low friction coefcients of a-C:
H:Si combined with low wear rates of pure a-C:H could be achieved.
The high potential of DLC based multilayers was conrmed by later publications in the 2000s [154156].

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].

K. Bewilogua, D. Hofmann / Surface & Coatings Technology 242 (2014) 214225

3. Transfer to industrial applications and mass production

In the late 1980s and early 1990s Me-DLC processes were transferred to large scale d.c. magnetron sputter machines, mostly equipped
with 4 targets, and became applicable for industrial applications
[157,158]. To prepare hard and wear resistant Me-DLC coatings high
ion current densities at the rotating substrates were necessary. This
was realized by applying special magnetic eld arrangements like the
so called Plasma Booster [157,159] or closed eld unbalanced magnetron (CFUBM) arrangements [158,160]. Furthermore, multi-chamber
systems allowing in-line processes to prepare tungsten containing DLC
(W-DLC or a-C:H:W) coatings were developed [161,162].
Hydrogen free carbon and metal containing carbon coatings for tribological applications were developed by Teer and co-workers using industrial CFUBM machines [163,164]. The tribological properties of
carbon/chromium (C/Cr) multilayers depend considerably on the Cr
contents, and it was found that pure carbon coatings have good wear
properties at low loads while coatings with optimum Cr contents have
excellent tribological performances at high loads [164].
Increasing tribological stresses of engineering components required
a replacement of Me-DLC by the harder and more wear resistant metal
free pure a-C:H coatings [1,162]. At the end of the 20th and beginning of
the 21st century the adhesion problems of pure a-C:H coatings could be
solved reliably for industrial scale deposition processes by preparation
of interlayer systems based on metal and metal nitride layers (see
e.g. [165167]). In industrial practice, hybrid deposition processes became established. These hybrid processes consisted of a sputter deposition of the interlayer system followed by a PECVD process (m.f. glow
discharge) for deposition of the a-C:H top layer (see e.g. [167,162]).
For industrial applications in large scale deposition machines, m.f. processes will be preferred because adequate bias voltages cannot be generated at large substrate surface areas [165].
Alternatively the a-C:H top layer can be deposited by a reactive magnetron sputter process using graphite targets and acetylene as reactive
gas [145,168].
Thus the a-C:H coatings could complete the spectrum of available
DLC coatings especially in the application area of highly loaded components where a-C:H:Me coatings are no longer sufcient. On the other
hand, the mentioned complex interlayer systems are often too thick
(clearly more than 1 m) and their preparation is not compatible with
economic deposition processes. In fact in many cases for industrial
applications of DLC coatings interlayers thinner than 1 m are required.
Another approach to realize a high adhesion level is based on the
HIPIMS (high power impulse magnetron sputtering) [168,169]. High
energy metal ions were used to etch the substrates before starting the
deposition process and the rst part of the interlayer (tungsten carbide
WC) was deposited using HIPIMS.
Arc technologies for ta-C preparation on an industrial scale are still
not widely established. However, now laserarc modules which can
be added to industrial coating machines are available [170].
In the late 1990s [171] and intensively in the 2000s the tribological
behavior of DLC coatings under lubricated conditions was investigated
because such conditions are found in industrial applications of coated
components. It became obvious that friction and wear sensitively depend on the system coating lubricant- (oil + additive) counterpart
[172] and that modications of pure carbon lms can lead to superior
tribological properties as shown for chromium containing a-C:H lms
[173,174]. Kano [175] tested a-C:H and ta-C coatings in two different lubricants and detected at boundary lubrication a maximum friction reduction for ta-C lms operating in an ester containing oil. For an
overview considering the type of DLC coating, the inuence of additives
and contact conditions can be seen in [172].
Examples for the industrial exploitation especially of a-C:H and a-C:H:
Me coatings in the automotive industry (diesel injection systems, tappets,
piston pins and others) have been reported many times [1,162,176,177].
Today nearly all high pressure diesel injection systems are coated with a-

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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