Surface and CoatingsTechnology 100~101 (1998) 180-186

Recent progress on the tribology of doped diamond-like and

carbon alloy coatings: a review
C. Donnet *
l&ok Centrale de Lyon. Laboratoire de Trihologie et Dynamique des Syst&nes. UMR 5513. BP 163, 69 131 lh~lly, Crde.y, France

Abstract

Diamond-like carbon (DLC) coatingshave beenwidely recognizedas beinga wear-resistantsolid lubricant with a low friction
coefficient. Its tribological behavior strongly dependsboth on the tribotesting conditions and the nature of the coating, which in
turn dependson the technique usedfor film deposition. Recently, there have beenseveralattempts to improve the tribological
behavior of DLC coatings by the addition of elements.such as silicon, nitrogen, fluorine and various metals.The paper will
presentan updated review of the tribological propertiesof doped DLC, in comparisonwith the conventional hydrogenatedand
non-hydrogenatedcarbonaceousfilms. 0 1998ElsevierScienceS.A.

Keywords: Diamond-like carbon (DLC); Doped DLC; Carbon alloy coatings;Friction; Wear

1. Introduction nature and properties (electrical conductivity, surface

Diamond-like carbon (DLC ) coatings have been the
subject of intensive studies for the last 20 years. Recent
reviews summarize the knowledges on film deposition,
characterization, properties and tribological behavior
[l-4]. The general term DLC describes hydrogenated
and non-hydrogenated carbon materials prepared by a
variety of methods (PVD and PACVD techniques) and
presenting of wide range of structure, composition and
properties, such as low friction, high wear resistance,
chemical inertness, a relatively high optical gap and high
electrical resistivity. DLC films present a noteworthy
example of thin films whose tribological behavior
strongly depends both on the nature of the coating
(controlled by the deposition procedure) and the testing
conditions, including mechanical (contact pressure), cin-
ematic (speed), physical (temperature) and chemical
(nature of the environment) parameters. In particular,
for varied deposition methods, the hydrogen concen-
tration ranges from less than a few at.% to about
50 at.%. Hydrogen is important for obtaining a wide
optical gap and a high electrical resistivity, removing
midgap defect states, stabilizing the random network
and preventing its collapse into a graphitic phase. The
* Tel: + 334 72 18 62 80; fax: 334 78 43 33 83;
e-mail: donnet@ec-lyon.fr
energy, etc.) of the DLC may also be modified by
controlling the incorporation of dopants, such as silicon,
fluorine, nitrogen and various metals. For example, an
increase of the water wetting angle, associated with a
decrease of the surface energy, is observed with the
incorporation of Si or F in the DLC, whereas the
opposite behavior is observed with the incorporation of
0 or N [51. The effect of Si or F on the surface energy
of the DLC films is attributed to the reduction of mainly
of the polar part of the surface energy, due to the loss
of sp’ C hybridization and dangling bonds. These
carbon-based multicomponents films may also be com-
bined to obtain property-controlled multilayer coatings
[6], including:
(1) interface layers, to improve the adhesion;
(2) large number of repeated layers, with different
intrinsic mechanical properties; and
(3) diverse property layers, to combine several protec-
tive functionalities, such as corrosion protection,
wear resistance,thermal isolation, electrical conduc-
tivity. diffusion barrier and adhesion to the
substrate.
The present paper reviews and summarizes the basic
and latest understanding on the tribology of doped DLC
films. A short review on the undoped DLC (a-C and
a-C:H) coatings is provided for comparison at the
beginning.

0257~8972/98/$19.00 0 1998 Elsevier Science B.V. All rights reserved.

PII SO’57-897X(97)00611-7
 C. Donnef / Surface and Coatings
2. Tribology of conventional a-C and a-C:H coatings
Improvements in the tribological behavior and expan-
sion of the use of DLC films for tribological protection
in new applications have required an enhancement of
the understanding of the friction and wear of these films
and their dependence on the operating environment and
film properties. Since review papers have recently been
published on this subject [3,4], the tribology of DLC
will be summarized here only in general terms. To be
used as tribological coatings, DLC films must adhere
well to the substrate material, the adhesive forces having
to overcome the high internal stresses that otherwise
would cause film delamination. Adhesion depends on
the substrate material and can be affected by the depos-
ition method. Good adhesion of DLC films to carbide-
and silicide-forming substrates has been found. The
adhesion of DLC coatings to silicide forming metals can
be improved by depositing an interfacial layer of amor-
phous silicon (2-4 nm thick) between the metal and the
carbon film, thus forming an interfacial silicide layer
promoted by the plasma even at a relatively low sub-
strate temperature [ 71.
Friction coefficients of adherent DLC films, typically
ranging from 0.01 to more than 0.5, depending on the
nature of the DLC film and the tribotesting conditions
[3], are strongly governed by tribochemical effects [8-
10]. The build-up of a transfer film, followed by easy
shear within the interfacial material is the most fre-
quently observed friction-controlling mechanism for
DLC films. However, the shearing ability strongly
depends on the nature of the surrounding gas present
in the contact. From the pioneering experiment of Enke
et al. [ll], DLC coatings are known to be extremely
sensitive to the presence of oxidizing species (oxygen,
water vapor) during friction, which give rise to a notice-
able tribo-oxidation of the topcoats, generally increasing
the friction and wear. Wear rates may reach extremely
low values (down to 10e6 mm3 Nm-‘) but also very
high values, which can inhibit the use of the coating in
any applications. Liu et al. [ 121 have shown that the
steady-state low friction of DLC films in ambient air is
due to wear induced graphitization, i.e. formation of a
low friction graphitized tribolayer. Both sliding velocity
and applied load influence the graphitization process,
due to temperature rise at contact asperities facilitating
hydrogen release from the DLC structure. Lower friction
coefficients ( lop2 range) have been frequently observed
in dry and/or inert environments. However, the absence
of a systematic control of oxygen and water vapor
partial pressures in the reported experiments prevents
precise identification of the partial pressure thresholds
at which the friction changes. In the absence of oxidizing
gas, as in an ultrahigh vacuum (UHV ), a large spread
of friction values is observed in published results, from
less than 0.01 up to 0.3 or more [3]. The ultralow
Technology 100-101 (1998) 180-186 181
friction of smooth DLC layers in inert environments is
attributed by Gardos [ 131 to the high surface finish and
the presence of ultrathin hydrocarbon-polymerlike top-
coats with weak Van der Waals interactions between
hydrogenated carbonaceous chains. The lo-fold, humid-
ity and oxidation-caused, increase in friction from the
lo-’ range to the lo- ’ range corresponds to an increase
in bond strength from about 0.08 eV per bond, for Van
der Waals bonding of hydrocarbons, to about 0.21 eV
per bond, for hydrogen bonding at C=O sites by water
molecules. Thus, most of the DLC films present a
friction behavior evolution similar to MoS,, from UHV
to ambient air, whereas diamond and graphite exhibit
both higher friction in UHV (>0.5) but comparable
friction values in ambient air, as mentioned by
Buckley [ 141.
The difficulty in correlating the properties of DLC
with their tribological behavior, as determined by the
preparation process, stems from the generally poor
definition of all deposition conditions of a specific film,
the difficulty of structural characterization of the amor-
phous materials, and the lack of any standardization of
tribological characterization. Films with various
hydrogen contents exhibit different physical properties,
such as carbon hybridization, refractive index, hardness,
stress, and tribological behaviors in controlled condi-
tions. Recently, Donnet and Grill [ 151 have shown how
to control the friction and wear of DLC films in high
vacuum conditions, depending on the nature of the film.
High-impact energy during the deposition (controlled
directly by the bias and gas pressure in d.c. PACVD
systems or by the power and the gas pressure in r.f.
PACVD systems) induces high precursor dissociation
and thus a more cross-linked carbon network, with a
lower sp3 fraction, lower hydrogen content, and lower
fraction of hydrogen bonded to carbon. Films deposited
under such conditions are harder, with a higher stress
and index of refraction, and a lower surface energy, and
are characterized by a very high degree of friction (> 0.5)
in UHV conditions. Ultralow friction and wear may be
reached in UHV for DLC films if the hydrogen content
is high enough (about 40 at.%), but with a carbon
network sufficiently cross-linked and having a noticeable
fraction of hydrogen (about 0.3) unbounded to carbon.
With the deposition system used by the authors, an
absolute bias increase from 500 to 800 V is sufficient to
lower the hydrogen content (by about 6 at.%), and the
fraction of hydrogen bounded to carbon in films depos-
ited from acetylene, thus enhancing the friction in UHV
from less than 0.01 to more than 0.5. This shows how
the friction behavior of DLC films is sensitive to their
structure and composition.
As a result, much attention should be paid to the
deposition process for controlling both friction and wear
of DLC films. The main results related to the tribology
of a-C and a-C:H films may be summarized as follows:
(1) relative high values of compressive stress (up to
3 GPa) result in poor adhesion to most of the
substrates, requiring the deposition of adhesion-
promoting interlayers,
(2) transfer film build-up followed by easy-shear within
the interfacial material is systematically observed,
whatever the nature of the film and tribotesting
conditions;
( 3 ) friction in ambient conditions (presence of oxygen
and water vapor) leads to tribochemical oxidation
of the DLC topcoats, confining the friction coeffi-
cients in the 10-r range; and
(4) wear in ambient conditions as well as friction and
wear in inert environments (including high vacuum
conditions) are strongly affected by the deposition
conditions.
Therefore, the main objectives of the studies related
to doped or alloyed carbon coatings are both to modify
some of the surface-related properties of the films (i.e.
surface energy) and to overcome tribological limitations,
mainly by reducing the internal stress and inhibiting the
triboreactivity of the coating regards oxygen and/or
water vapor responsible for high friction and low wear
resistance.
3. Tribology of silicon-containing DLC coatings
Oguri et al. [ 16,171 deposited a-C:H:Si coatings with
a hydrogen content of about 40 at.% and a Si/C +Si
ratio between 10 and 30 at.%, by a d.c. PACVD.
Tribological tests (load lo-50 N, speed 0.2-3.0 m s- ‘)
in ambient air (relative humidity RH=50-70%) gave
wear rates lower than 1O-7 mm3 Nmt and friction
coefficients ranging between 0.03 and 0.1. that is the
lowest friction values observed with DLC films in ambi-
ent air conditions. The tribological behavior was attrib-
uted to the formation of SiO, wear particles and
their interaction with the humid environment through
tribochemical effects. Goranchev et al. [18] obtained
a-C,:H:Si,-, films from r.f. reactive sputtering, with a
carbon fraction .K ranging between 0.5 and 0.9. An
increase in internal stress was associated with an increase
in silicon content. Contrary to metal-containing films,
the a-C,:H:Si, -x films were systematically amorphous
and exhibited friction coefficients lower than 0.1. Hioki
et al. [ 19,201 studied Si containing DLC films deposited
from ion beam-assisted deposition (IBAD) with a com-
position C:Si:O =0.8:0.1:0.1 with the exception of
10 at.% of hydrogen. With relative humidities varying
from 20 to 70% in air or nitrogen. friction coefficients
ranged between 0.04 and 0.07. At higher humidities,
friction increased up to 0.2. Ultralow friction values
down to 0.02 or less were observed in dry nitrogen. A
transfer film build-up was systematically observed on
the steel counterpart. The same kinds of friction results
were already observed by Braun et al. [21] with films
deposited by the same technique. The authors found
also that for tool steel samples coated with an a-C:H:Si
( 100 nm thick) immersed in aqueous solutions of acetic
acid or NaCl, the initiation of pitting corrosion com-
pared to the bare substrate was delayed by a factor
greater than 1000. Therefore, the coating was believed
to have potentialities for corrosion protection. a-C:H:Si
films with a silicon content ranging between 10 and
25 at.% were obtained from electron cyclotron resonance
ECR-PCVD by Miyamoto and Miyake et al. [22-251.
During microtribological tests (0.1 -mm diamond tip
with a normal load of 10 mN), the films exhibited a
high degree of wear resistance and low friction values.
However, friction increased up to 1 when the load was
decreased down to 0.5 mN. A low degree of friction was
observed during macroscopic sliding tests against steel
in ambient air conditions. Ultralow friction (0.007) was
achieved when the film was rubbed with a steel ball in
a high vacuum. Polarized microinfra-red spectroscopy
revealed that high lubrication performance is attributed
to hydrocarbons transferred from the rubbed film to the
ball surface and oriented along the sliding direction
[22]. Dorfman [26] obtained so-called diamond-like
nanocomposites ( DLN ) films containing silicon from
various deposition techniques, with a structure con-
sisting of a mixture of diamond-like (a-C:H ) and quartz-
like (a-Si) atomic-scale random networks. The DLN
films combined low internal stress, high degree of hard-
ness and elasticity together with low friction. In a review
paper, Meneve et al. [27] investigated the tribological
behavior of a-Sir-,:C,:H films deposited from r.f.
PACVD, with 0.7 <s ~0.9. They found that addition of
silicon to an a-C:H film reduces the hardness, elastic
modulus and internal stresses by values of 15-30%.
Under humid conditions, potential applications of these
films are limited to contact pressure levels below approx-
imately 1 GPa. For higher pressures. however, the lower
wear resistance of the Si containing films compared to
typical DLC becomes increasingly unacceptable. Under
dry conditions, the friction and wear behaviors of pure
DLC cannot be surpassed, whatever the contact
pressure.
In summary, silicon incorporation in the DLC struc-
ture is recognized to affect most of the film properties
(including a decrease of the surface energy and internal
stress) and the tribological behavior. Friction appears
to be significantly reduced (below 0.1) compared to
conventional undoped DLC in ambient humid air, with
a comparable high wear resistance. However, this tribo-
logical behavior seems to be observed when the contact
pressure remains low enough, that is below 1 GPa. At
higher contact pressures, conventional a-C and a-C:H
films cannot be surpassed. Consequently, a-C:H:Si films
may be used in applications requiring both low friction
(co.1 ), high wear resistance (< 10m7 mm3 Nm-‘) under
 C. Donrwt 1 Swftice
moderate mechanical conditions, for the protection of
low-stress aerospace or automotive components,
precision ball bearings and gears, sliding bearings and
magnetic recording media.
4. Tribology of fluorine-containing DLC coatings
As mentioned in the introduction, fluorine and silicon
both induce a significant reduction of the surface energy
of the DLC films [5]. Indeed, since F and Si are unable
to form double bonds, the authors claim that these
elements force carbon into an sp3 bonding state.
However, there is no reason that fluorine would prevent
-C=C- bonds. Anyway, whereas the addition of silicon
is able to reduce the polar part of the surface energy, it
is unable to reduce also the dispersive component, as
fluorine is able to do. As claimed by the author in
Ref. [5], the main difference in the film formation is
that with the addition of the Si-containing precursor
[Si(CH,), in the study], a high amount of hydrogenated
carbon is still present in the network structure, while
with fluorine, many -CF, and -CF, groups are present
with the deposition conditions used. This reduces the
density of the network structure, resulting in a reduced
dispersive component of the surface energy. Con-
sequently, it is not surprising that the surface energy of
a-C:F:H films was found to be intermediate
(20 mN m-i), compared to PTFE (used for non-sticking
purposes, with a surface energy of 18 mN rn- ‘),
a-C:H:Si (31 mN m-‘) and a-C:H (43 mN m-r).
Therefore, an advantage of the a-C:H:F films is to
combine a low surface energy (comparable to the value
of PTFE) with a hardness slightly lower but in the same
range (between 5 and 20 GPa) than values related to
undoped a-C:H and significantly higher than the hard-
ness of PTFE (0.3 GPa). For some applications (i.e.
magnetic recording media). the friction has to be further
reduced by applying lubricants on the top surface of the
protective DLC coating. It was shown that surface
fluorination can reduce the friction and microwear of
DLC [28]. However, fluorination in that case was
applied subsequent to the deposition of DLC and there-
fore had a limited effect since its lubricating property
was lost after a relatively short wear time, due to the
localization on the topmost layer of the coating.
Consequently, studies have used fluorinated hydro-
carbons or their mixture with hydrocarbons or hydrogen
to deposit fluorine-containing films by RF PACVD. Soft
polymerlike fluorinated carbon films, with a small frac-
tion of fluorine chemically bonded to the carbon matrix
and the rest being trapped in the graphitic structure of
the films, have been reported [29]. Other authors also
reported deposition of fluorine-containing carbon films,
some claiming that the films are abrasion-resistant but
without reporting any abrasion results [30], and others
and Coatings Trchnolog~ 100-101 (1998) 180-186 183
obtaining soft and easily scratchable films [31]. Recently,
Grill et al. [32] have reported on fluorinated DLC films
prepared by d.c. PACVD from pure difluorobenzene
(DFB) or hexafluorobenzene (HFB) with various dilu-
tions. The films deposited from DFB contained lessthan
10 at.% fluorine and had a wear resistance similar to
that of non-fluorinated DLC. The films deposited from
HFB contained 45 at.% fluorine but were very soft and
had no wear resistance at all. Argon dilution of the
precursor reduced the fluorine concentration in the films,
but had no effect on the wear resistance of the films. In
contrast, films deposited from HFB diluted with
hydrogen had lower fluorine concentrations and had a
wear resistance that increased with increasing hydrogen
dilution. At a sufficient dilution (71% hydrogen in the
HFB + HZ), films containing 18 at.% fluorine and with
a wear resistance similar to that of diamond-like carbon
were obtained. Recently, Donnet et al. [33] have studied
a:C:F:H films deposited by r.f. PACVD from hexafluor-
obenzene diluted with hydrogen. For a given precursor
mixture, the wear rates of the a-C:F:H films can be
controlled by the average impact energy of the ions on
the growing film. Depth wear rates as low as 1 A per
1000 rotations, comparable to those observed for hard
non-fluorinated DLC, have been obtained for films
containing up to 20 at.% fluorine and 10 at.% hydrogen.
The latter appears to be unbound to carbon. The highest
wear resistance was achieved for films deposited at the
highest deposition bias and lowest gas pressure. These
films exhibited a more cross-linked structure with a
lower fraction of unbound fluorine and higher compres-
sive stresses,compared to lesswear-resistant films. The
steady-state friction of the fluorinated films is in the
same range as the steady-state friction of most of the
typical DLC coatings. Contrary to wear, friction appears
to be independent of the bias and gas pressure within
the studied range, but depends very much on the contact
pressure during friction.
The combination of silicon and fluorine in a-C:F:Si:H
films obtained by ECR-PCVD has been studied by
Miyake et al. [24]. The microtribological behavior of
the silicon-containing film was improved by fluorination.
The surface energy is found to decreasedue to fluorina-
tion, in agreement with the results reported by Grischke
et al. [ 51. The micro-wear is reduced on an atomic scale
by fluorination. Moreover, the adhesion to the silicon
substrate and strength of the carbon film is greatly
improved by adding small quantities of silicon. Films
containing silicon also have a significantly longer lubri-
cating life. Miyake [34] has elucidated the complex
frictional behavior of the investigated a-C:F:H films in
ambient air: a running-in period (the first 100 sliding
cycles) with coefficients of friction in the 0.21-0.35
range, a stable period (the next 300 cycles) in which the
coefficient stabilized at 0.20, a transient period (the next
600 cycles) in which the value increased from 0.20 to
184 C. Donnet 1 Surfice and Contings
0.65, and finally a failure period characterized by decom-
position of the coating. Ex-situ I.R. measurements at
the end of each friction regime provided a correlation
of these frictional fluctuations with molecular trans-
formations of the C:F structure. It was found that the
halogenated carbon framework decomposed into amor-
phous carbon and activated carbon, which then reacted
with fresh metal through bond cleavage between halogen
and carbon. The carboncarbon bond cleavage also
reduced the molecular size of carbonaceous chains. The
low friction state occurred during the decomposition
process, due to the presence of molecules containing
fluorinated C =C moieties, such as polydifluorinateda-
cetylene (PDFA), that were oriented in the sliding
direction (as seen by the polarized I.R. probe).
In summary, like silicon, fluorine incorporation in the
DLC structure affects the surface properties. The reduc-
tion in stress compared to conventional DLC is in the
same range as with a-C:H:Si. However, the reduction in
surface energy is higher with fluorine than with silicon.
Highly fluorinated DLC [F/( F + C) > 0.41 appear to be
soft with no wear resistance. Moderate fluorination
[(F/( F + C ) < 0.21 can be controlled by the deposition
conditions to obtain films with a comparable wear
resistance and friction level than conventional a-C:H
film, but with a lower degree of stress and surface energy.
5. Tribology of nitrogen-containing DLC coatings
From the prediction of Liu et al. [35], several groups
have attempted to synthesize the b-C,N, crystalline
phase, which would have a bulk modulus comparable
to that of diamond. To achieve this goal, one way has
been to incorporate nitrogen in the DLC structure by
several methods summarized by Wan et al. [36].
Consequently, numerous published papers are dedicated
to the analytical investigations of the composition, struc-
ture and properties of the a-C:N and a-C:H:N films.
The main results indicate that the films are generally
amorphous, with no unambiguous identification of the
formation of the crystalline C,N, phase. However, it
has been found that nitrogen incorporation in the DLC
structure decreases the fraction of C sp3 hybridization.
Indeed, the presence of the C=N and C=N bonds has
often been detected by infra-red or electron energy loss
spectroscopies. Consequently, the surface energy of
a-C:H:N films should be significantly increased, and this
has been confirmed by the results of Grischke et al. [5],
showing a drastic increase from 43 mN rnF (for a typical
a-C:H) to 59 mN rnk for the nitrogen-containing film
due to the increase of the polar component. A N/(N + C )
atomic ratio up to 0.4 can be incorporated into the film
structure, generally reducing the stress but preserving
the hardness and wear resistance, even if the results do
not agree systematically from one study to another [37-
Teclmolog~ 100-101 (19%‘) 180-186
431. In 1993, Yeh et al. [37] obtained a protective
coating for magnetic rigid disks by r.f. diode sputtering
using a mixture of argon and nitrogen gases. In a
continuous drag test with thin film head sliders, they
showed that the CN, films have a better wear perfor-
mance than a-C films obtained in similar conditions
but without the nitrogen gas during deposition. Li et al.
[38] synthesized nitrogen-containing DLC using d.c.
unbalanced magnetron sputtering of graphite in a
N,-containing plasma. Tribological tests indicated that
the friction and wear behavior were both in the same
range as for typical DLC films. Dekempeneer et al. [39]
synthesized a-C:H:N films using r.f. PACVD and
obtained a nitrogen content in the range of O-35 at.%,
depending on the deposition conditions. The nitrogen
incorporation led to softer, less stressed materials with
a lower wear resistance than classical DLC films, and a
steady-state friction remaining in the range of 0.2 in
ambient air conditions. These results were explained on
the basis of a structural model in which nitrogen atoms
are arranged between the aromatic clusters, thereby
modifying the sp3:sp2 ratio. More recently, Prioli et al.
[40] deposited a-C:H:N films from PACVD and found
a friction coefficient of 0.22 in air, against silicon nitride,
for nitrogen concentration up to 11 at.%. A slight
increase in the surface roughness of the top surface was
observed due to the nitrogen incorporation increasing
significantly the number and size of graphitic domains.
Cutiongco et al. [41] presented promising results with
CN, films (22 at.% of N) deposited on magnetic disks
by sputtering in an argon/nitrogen plasma. The amor-
phous coatings exhibited hardness in the range of
22-28 GPa, better contact start-stop performances and
three to four times better pin-on-disk contact durability
compared with amorphous carbon overcoats. The IBAD
technique has also been used by Khurshudow et al. [42]
by argon-sputtering of a carbon target with concomitant
bombardment of the growing film by nitrogen ions in
the 0.5510-keV range. The intrinsic stresses could be
varied from tensile to compressive, depending on the
deposition conditions (current and energy of the ion
beam). Some films exhibited friction coefficients as low
as 0. IO-O. 12 in ambient air against a silicon nitride ball.
However, no clear correlation was observed between the
hardness, stress and wear resistance of the coatings.
Koskinen et al. [43] deposited CN, films by the pulsed
vacuum arc method, on silicon and metallic substrates.
Friction and wear were measured with a pin-on-disk
apparatus with various relative humidities (RH = 12 and
50%) and sliding speeds ( 1.4 and 14 cm s- ‘). After a
run-in period with a friction decrease from 0.4 to
0.1-0.2, the steady-state friction ranges between 0.2 and
0.3. The wear rates remain near lo-’ mm3 Nm-i irre-
spective of nitrogen content. However, friction was
found to increase with increasing nitrogen content,
especially at lower values of the relative humidity. No
 C. Donnet J Surjbce and Coatings Technology 100-101 (1998) 180-186 185

friction-induced modification of the film structure was should bear in mind that the optimization of the material
identified by micro Raman spectroscopy inside the combination and deposition parameters is a challenging
wear tracks. subject for each element or combination of elements.
In summary, less work has been performed on the When it is achieved, the metal-containing DLC films
tribological investigation of the nitrogen-containing may exhibit promising tribological properties in terms
DLC films, due to their recent discovery compared to of steady-state friction level and wear rates for many
conventional DLC and other doped DLC. If the nitro- applications.
gen incorporation has an opposite effect on the surface
energy than the silicon or fluorine incorporations, stress
seems to be also systematically reduced, whereas the 7. Conclusion
hardness evolution is more discussed. The first tribologi-
cal investigations do not show any significant differences The literature survey presented above shows how the
in terms of friction level and wear resistance, in com- incorporation of dopants in the DLC structure may be
parison to undoped DLC. However, more work is used to achieve precise combinations of design surface-
encouraged to identify relationships between the related properties with a low friction and high wear
nature/structure of the films, their properties and tribo- resistance. However, the need for correlating between
logical behavior, in relation with the deposition process doped DLC film processing, their properties and tribo-
and conditions. logical behavior becomes more pressing, taking into
account the diversity of coatings that can be produced
by the deposition technology. The ultimate goal is to
6. Tribology of metal-containing DLC coatings identify a limited seriesof significant coating properties
that are easily measurable, which may be correlated
Alloying DLC films has been obtained with different with the tribological behavior quantified through stan-
metals (Ti, Nb, Ta, Cr, MO, W, Ru, Fe, Co, Ni, Al, dardized and reproducible procedures. This will afford,
Cu, Au, Ag) to form a-C:H:M coatings [43-491. The finally, a control and monitoring of the tribological
structure of these films has not been systematically behavior in given experimental conditions, directly from
investigated, but in many cases, metals are in the form the control of the deposition process. Such a direct link
of small nanocrystallites of pure metal or metal carbide between coating designers and end-users offers a great
(depending on the nature and concentration of the opportunity for a significant increase in mass market
metal) dispersed throughout the carbon network. This applications of tribological coatings in the next future.
type of composite film, mainly obtained by reactive
sputtering, differs from films constituted by multilayers,
such as the superposition of DLC and metal carbide
Acknowledgement
thin layers, even if the global composition [M/(M + C)]
may be in the same range for both types of coatings.
The author gratefully acknowledges Dr A. Grill for
Generally, the metal incorporation reduces the compres-
valuable comments on the manuscript.
sive stress (< 1 GPa) compared to conventional undoped
DLC. Most of the tribological tests have been performed
in ambient air conditions and exhibited steady-state
friction in the range of 0.10-0.20, with a slight depen- References
dence on the humidity, load and metal concentration.
For Ta and W incorporation in DLC obtained by [I ] A. Grill, B.S. Meyerson, in: K.E. Spear, J.P. Dismuke (Eds.).
Synthetic Diamond: Emerging CVD Science and Technology,
reactive sputtering, frictions below 0.1 have been
Wiley, New York, 1994. p. 91.
observed with lower wear rates than TIN and TiAlN [3] A. Grill, Wear 168 (1993) 143.
coatings in the same testing conditions [45]. Interesting [3] C. Donnet, Condensed Matter News 4 (1995) 9.
optimum wear rates may be obtained for each type of [4] A. Grill, Surf. Coat. Technol. 94-95 (1997) 507.
metal dopant, with a concentration that seems to depend [5] M. Grischke. K. Bewilogua, K. Trojan, H. Dimigen, Surf. Coat.
Technol. 7475 ( 1996) 739.
on its nature. The tribological behaviors of the metal-
[6] K. Holmberg. A. Matthews, in: D. Dowson (Ed.), Coatings
containing DLC films have been explained by a combi- Tribology. Tribology Series, 28, Elsevier. Amsterdam, 1994,
nation of ceramic-like properties (high hardness, H) p. 241.
and polymer-like properties (high elasticity, E, and low [7] A. Grill, B. Meyerson, V. Patel. J. Mater. Res. 3 (1988) 214.
surface energy, S), thus leading to high H/E values and [8] IL. Singer, in: I.L. Singer, H.M. Pollock (Eds.). Fundamentals
of Friction: Macroscopic ant Microscopic Processes. Vol. 220,
low S/H values.
NATO-AS1 Series. Kluwer. Dordrecht. 1992, p. 237.
In summary, the number of different material com- [9] C. Donnet, M. Belin, J.C. Auge, J.M. Martin, A. Grill, V. Patel,
positions and structures appears to be enormous when Surf. Coat. Technol. 6869 ( 1994) 626.
one starts to coat metal-containing DLC coatings. One [IO] C. Donnet, M. Belin. T. Le Mogne, A. Grill, V. Patel, in: Y.
 Pauleau. P.B. Barna (Ed%), Protective Coatings and Thin Films, [30] R.E. Sah. B. Dischler. P. Koidl, A. Bubenzer, Appl. Phys. Lett.
NATO-AS] Series Vol. 21. Kluwer, Dordrecht, 1997, p. 229. 46 (1985) 739.
[ 1 I] K. Enke, H. Dimigen. H. Hubsch, Appl. Phys. Lett. 36 ( 1980) 291. [3l] J. Seth. S.V. Babu, Thin Solid Films 230 (1993) 90.
[I?] Y. Liu, A. Erdemir. E.I. Meletis. Surf. Coat. Technol. 8687 [32] A. Grill. V. Patel, Diamond Films Technol. 6 ( 1996) 13.
( 1996) 564. [33] C. Donnet, J. Fontaine, A. Grill, V. Pate], C. Jahnes, M. Belin,
[ 131 M.N. Gardos, in: K.E. Spear. J.P. Dismuke (Eds.). Synthetic Surf. Coat. Technol. 94495 (1997) 531.
Diamond: Emerging CVD Science and Technology, Wiley, New [34] S. Miyake, in: K. Miyoshi. Y.W. Chung (Eds.), Surface Diagnos-
York, 1994, p. 419. tic in Tribology. Series in Modern Tribology. Vol. I, World Scien-
[ 141 D.H. Buckley, in: Surface Etfects in Adhesion, Friction, Wear and tific, Singapore, 1993, p. 183.
Lubrication, Elsevier, New York, 198 1, p. 574. [35] A.Y. Liu. M.L. Cohen. Science 245 (1989) 841.
[l5] C. Donnet, A. Grill, Surf. Coat. Technol. 94-95 ( 1997) 456. [36] L. Wan, R.F. Egerton. Thin SoIid Films 279 ( 1996) 34.
[ 161 K. Oguri. T. Arai, Surf. Coat. Technol. 47 (1991) 710. [37] T.A. Yeh. C.L. Lin, J.M. Sivertsen. J.H. Judy, J. Magnetism
[ 171 K. Oguri, T. Arai. Thin Solid Films 208 ( 1992) 158. Magnetic Mater. 120 (1993) 314.
[I81 B. Goranchev. K. Reichelt. J. Chevallier, P. Hornshoj, H. [38] D. Li, V.P. Dravid, Y.W. Chung. M.Y. Chen, M.S. Wong, W.D.
Dimigen, H. Htibsch, Thin Solid Films 139 (1986) 275. Sproul, Diamond Films Technol. 4 (2) ( 1994) 99.
[ 191 T. Hioki. Y. Itoh, A. Itoh. S. Hibi, J. Kawamoto. Surf. Coat. [39] E.H.A. Dekempeneer. J. Meneve. J. Smeets, S. Kuypers, L.
Technol. 46 ( 1991) 233. Eersels, R. Jacobs, Surf. Coat. Technol. 6869 ( 1994) 621.
[20] Y. Itoh, S. Hibi, T. Hioki. J. Kawamoto. J. Mater. Res. 6 [40] R. Prioli, S.I. Zanette, A.O. Caride, D.F. Franceschini. F.L. Freire
(1991) 871. Jr, J. Vat. Sci. Technol. A 14 (1996) 2351.
[21] M. Braun. Nucl. Instrum. Meth. B 39 (1989) 556. [4l] E.C. Cutiongco, D. Li. Y.W. Chung, C.S. Bhatia, Trans. ASME
[22] 1. Sugimoto, S. Miyake, Appl. Phys. Lett. 56 (19) (1990) 1868. I18 (1996) 543.
[23] T. Miyamoto, R. Kaneko. S. Miyake. J. Vat. Sci. Technol. B 9 [42] A. Khurshudov, K. Kato. D. Sawada, Tribal. Lett. 2 (1996) 13.
(1991) 1336. [43] H. Dimigen, H. Htibsch. R. Memming, Appl. Phys. Lett. 36
[24] S. Miyake, R. Kaneko, Y. Kikuya, 1. Sugimoto, Transactions of (1987) 1056.
the ASME, J. Tribol. 113 (1991) 384. [44] C.P. Klages, R. Memming, Mater. Sci. Forum 5253 ( 1989) 609.
[25] S. Miyake. R. Kaneko. Thin Solid Films 212 (1992) 256. [45] H. Dimigen. C.P. Klages. Surf. Coat. Technol. 49 ( 1991) 543.
[36] V.F. Dorfman, Thin Solid Films 212 (1992) 267. [46] M. Wang, K. Schmidt, K. Reichelt. H. Dimigen. H. Htibsch,
[27] J. Meneve, E. Dekempeneer, J. Smeets, Diamond Films Technol. J. Mater. Res. 7 (1992) 667.
4(1)(1994)23. [47] D. Klaffke, R. Wasche, H. Czichos, Wear 153 (1992) 149.
[28] K. Trojan, M. Grischke, H. Dimigen. Phys. Status Solidi A 145 [48] M. Grischke, K. Bewilogua. H. Dimigen. Mater. Manufact.
(1994) 57. Processes 8 ( 1993) 407.
[29] R. D’Agostino, R. Lamendola. P. Favia, A. Giquel, J. Vat. Sci. [49] H. Sjostrom, L. Hultman, J.E. Sundgren, L.R. Wallenberg, Thin
Technol. A 12 (1994) 308. Solid Films 232 ( 1993) 169.