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Diamond-like carbon

Dome coated with DLC for optical and tribological purposes.

A ta-C thin lm on silicon (15 mm diameter) exhibiting regions


of 40 nm and 80 nm thickness.

mixing these polytypes in various ways at the nanoscale


level of structure, DLC coatings can be made that at the
same time are amorphous, exible, and yet purely sp3
bonded diamond. The hardest, strongest, and slickest is
such a mixture, known as tetrahedral amorphous carbon,
or ta-C. For example, a coating of only 2 m thickness of
ta-C increases the resistance of common (i.e. type 304)
stainless steel against abrasive wear; changing its lifetime
in such service from one week to 85 years. Such ta-C
can be considered to be the pure form of DLC, since
it consists only of sp3 bonded carbon atoms. Fillers such
as hydrogen, graphitic sp2 carbon, and metals are used
in the other 6 forms to reduce production expenses or to
impart other desirable properties.[3][4]
The various forms of DLC can be applied to almost any
material that is compatible with a vacuum environment.
A Co-alloy valve part from a producing oil well (30 mm diame- In 2006, the market for outsourced DLC coatings was
ter), coated on the right side with ta-C, in order to test for added estimated as about 30,000,000 in the European Union.
resistance to chemical and abrasive degradation in the working In October 2011, Science Daily reported that researchers
at Stanford University have created a super-hard amorenvironment.
phous diamond under conditions of ultrahigh pressure,
Diamond-like carbon (DLC) is a class of amorphous which lacks the crystalline structure of diamond but has
carbon material that displays some of the typical prop- the light weight characteristic of carbon.[5][6]
erties of diamond. DLC is usually applied as coatings
to other materials that could benet from some of those
properties.[1]

1 Distinction from natural and

DLC exists in seven dierent forms.[2] All seven contain


synthetic diamond
signicant amounts of sp3 hybridized carbon atoms. The
reason that there are dierent types is that even diamond
can be found in two crystalline polytypes. The usual one Naturally occurring diamond is almost always found in
has its carbon atoms arranged in a cubic lattice, while the the crystalline form with a purely cubic orientation of sp3
very rare one (lonsdaleite) has a hexagonal lattice. By bonded carbon atoms. Sometimes there are lattice de1

3 PROPERTIES

fects or inclusions of atoms of other elements that give


color to the stone, but the lattice arrangement of the carbons remains cubic and bonding is purely sp3 . The internal energy of the cubic polytype is slightly lower than that
of the hexagonal form and growth rates from molten material in both natural and bulk synthetic diamond production methods are slow enough that the lattice structure has
time to grow in the lowest energy (cubic) form that is possible for sp3 bonding of carbon atoms. In contrast, DLC
is typically produced by processes in which high energy
precursive carbons (e.g. in plasmas, in ltered cathodic
arc deposition, in sputter deposition and in ion beam deposition) are rapidly cooled or quenched on relatively cold
surfaces. In those cases cubic and hexagonal lattices can
be randomly intermixed, layer by atomic layer, because
there is no time available for one of the crystalline geometries to grow at the expense of the other before the
atoms are frozen in place in the material. Amorphous
DLC coatings can result in materials that have no longrange crystalline order. Without long range order there
are no brittle fracture planes, so such coatings are exible and conformal to the underlying shape being coated,
while still being as hard as diamond. In fact this property has been exploited to study atom-by-atom wear at
the nanoscale in DLC.[7]

Production

There are several methods of producing DLC, which rely


on the lower density of sp2 than sp3 carbon. So the application of pressure, impact, catalysis, or some combination of these at the atomic scale can force sp2 bonded
carbon atoms closer together into sp3 bonds. This must
be done vigorously enough that the atoms cannot simply
spring back apart into separations characteristic of sp2
bonds. Usually techniques either combine such a compression with a push of the new cluster of sp3 bonded
carbon deeper into the coating so that there is no room for
expansion back to separations needed for sp2 bonding; or
the new cluster is buried by the arrival of new carbon destined for the next cycle of impacts. It is reasonable to envisage the process as a hail of projectiles that produce
localized, faster, nanoscale versions of the classic combinations of heat and pressure that produce natural and
synthetic diamond. Because they occur independently
at many places across the surface of a growing lm or
coating, they tend to produce an analog of a cobblestone
street with the cobbles being nodules or clusters of sp3
bonded carbon. Depending upon the particular recipe
being used, there are cycles of deposition of carbon and
impact or continuous proportions of new carbon arriving
and projectiles conveying the impacts needed to force the
formation of the sp3 bonds. As a result, ta-C may have
the structure of a cobblestone street, or the nodules may
melt together to make something more like a sponge or
the cobbles may be so small as to be nearly invisible to
imaging. A classic medium morphology for a ta-C lm

SEM image of a gold-coated replica of a ta-C diamond-like


coating. Structural elements are not crystallites but are nodules
of sp3 -bonded carbon atoms. The grains are so small that the
surface appears mirror smooth to the eye.

is shown in the gure.

3 Properties
As implied by the name, diamond-like carbon (DLC),
the value of such coatings accrues from their abilities to
provide some of the properties of diamond to surfaces
of almost any material. The primary desirable qualities are hardness, wear resistance, and slickness (DLC
lm friction coecient against polished steel ranges from
0.05-0.20[8] ). DLC properties highly depends on plasma
treatment (,[9] ([10] ) deposition parameters, like eect
of bias voltage ([11] ), DLC coating thickness ([12] ),([13] ),
interlayer thickness ([14] )etc.
However, which properties are added to a surface and to
what degree depends upon which of the 7 forms are applied, and further upon the amounts and types of diluents
added to reduce the cost of production. In 2006 the Association of German Engineers, VDI, the largest engineering association in Western Europe issued an authoritative
report VDI2840[15] in order to clarify the existing multiplicity of confusing terms and trade names. It provides a
unique classication and nomenclature for diamond-likecarbon (DLC) and diamond lms. It succeeded in reporting all information necessary to identify and to compare

3.1

Hardness

dierent DLC carbon lms which are oered on the market. Quoting from that document:
These [sp3 ] bonds can occur not only with
crystals - in other words, in solids with longrange order - but also in amorphous solids
where the atoms are in a random arrangement.
In this case there will be bonding only between
a few individual atoms and not in a long-range
order extending over a large number of atoms.
The bond types have a considerable inuence
on the material properties of amorphous carbon lms. If the sp2 type is predominant the
lm will be softer, if the sp3 type is predominant the lm will be harder.
A secondary determinant of quality was found to be the
fractional content of hydrogen. Some of the production
methods involve hydrogen or methane as a catalyst and
a considerable percentage of hydrogen can remain in the
nished DLC material. When it is recalled that the soft
plastic, polyethylene is made from carbon that is bonded
purely by the diamond-like sp3 bonds, but also includes
chemically bonded hydrogen, it is not surprising to learn
that fractions of hydrogen remaining in DLC lms degrade them almost as much as do residues of sp2 bonded
carbon. The VDI2840 report conrmed the utility of locating a particular DLC material onto a 2-dimensional
map on which the X-axis described the fraction of hydrogen in the material and the Y-axis described the fraction of sp3 bonded carbon atoms. The highest quality
of diamond-like properties was armed to be correlated
with the proximity of the map point plotting the (X,Y)
coordinates of a particular material to the upper left corner at (0,1), namely 0% hydrogen and 100% sp3 bonding.
That pure DLC material is ta-C and others are approximations that are degraded by diluents such as hydrogen,
sp2 bonded carbon, and metals. Valuable properties of
materials that are ta-C, or nearly ta-C follow.
STM image of surfaces at the edge of a 1 m thick layer of ta-C

3.1

Hardness

Within the cobblestones, nodules, clusters, or


sponges (the volumes in which local bonding is sp3 )
bond angles may be distorted from those found in either
pure cubic or hexagonal lattices because of intermixing
of the two. The result is internal (compressive) stress that
can appear to add to the hardness measured for a sample
of DLC. Hardness is often measured by nanoindentation
methods in which a nely pointed stylus of natural
diamond is forced into the surface of a specimen. If
the sample is so thin that there is only a single layer
of nodules, then the stylus may enter the DLC layer
between the hard cobblestones and push them apart
without sensing the hardness of the sp3 bonded volumes.
Measurements would be low. Conversely, if the probing
stylus enters a lm thick enough to have several layers

diamond-like coating on 304 stainless steel after various durations of tumbling in a slurry of 240 mesh SiC abrasive. The rst
100 min shows a burnishing away from the coating of an overburden of soft carbons than had been deposited after the last
cycle of impacts converted bonds to sp3 . On the uncoated part of
the sample, about 5 m of steel were removed during subsequent
tumbling while the coating completely protected the part of the
sample it covered.

of nodules so it cannot be spread laterally, or if it enters


on top of a cobblestone in a single layer, then it will
measure not only the real hardness of the diamond
bonding, but an apparent hardness even greater because
the internal compressive stress in those nodules would
provide further resistance to penetration of the material
by the stylus. Nanoindentation measurements have
reported hardness as great as 50% more than values for
natural crystalline diamond. Since the stylus is blunted in

4 APPLICATIONS

such cases or even broken, actual numbers for hardness


that exceed that of natural diamond are meaningless.
They only show that the hard parts of an optimal ta-C
material will break natural diamond rather than the
inverse. Nevertheless, from a practical viewpoint it
does not matter how the resistance of a DLC material
is developed, it can be harder than natural diamond in
usage. One method of testing the coating hardness is by
means of the Persoz pendulum.

3.2

Bonding of DLC coatings

The same internal stress that benets the hardness of


DLC materials makes it dicult to bond such coatings
to the substrates to be protected. The internal stresses
try to pop the DLC coatings o of the underlying samples. This challenging downside of extreme hardness is
answered in several ways, depending upon the particular
art of the production process. The most simple is to exploit the natural chemical bonding that happens in cases in
which incident carbon ions supply the material to be impacted into sp3 bonded carbon atoms and the impacting
energies that are compressing carbon volumes condensed
earlier. In this case the rst carbon ions will impact the
surface of the item to be coated. If that item is made
of a carbide-forming substance such as Ti or Fe in steel
a layer of carbide will be formed that is later bonded to
the DLC grown on top of it. Other methods of bonding
include such strategies as depositing intermediate layers
that have atomic spacings that grade from those of the
substrate to those characteristic of sp3 bonded carbon. In
2006 there were as many successful recipes for bonding
DLC coatings as there were sources of DLC.

3.3

Tribology

DLC coatings are often used to prevent wear due to their


excellent tribological properties. DLC is very resistant
to abrasive and adhesive wear making it suitable for use
in applications that experience extreme contact pressure,
both in rolling and sliding contact. DLC is often used
to prevent wear on razor blades and metal cutting tools,
including lathe inserts and milling cutters. DLC is used
in bearings, cams, cam followers, and shafts in the automobile industry. The coatings reduce wear during the
'break-in' period, where drive train components may be
starved for lubrication.
DLCs may also be used in chameleon coatings that are designed to prevent wear during launch, orbit, and re-entry
of land-launched space vehicles. DLC provides lubricity at ambient atmosphere and at vacuum, unlike graphite
which requires moisture to be lubricious.

change in hardness. This phenomenon prevents the use


of DLC coated machine tool on steel.

3.4 Electrical
If a DLC material is close enough to ta-C on plots of
bonding ratios and hydrogen content it can be an insulator
with a high value of resistivity. Perhaps more interesting
is that if prepared in the medium cobblestone version
such as shown in the above gure, electricity is passed
through it by a mechanism of hopping conductivity. In
this type of conduction of electricity the electrons move
by quantum mechanical tunneling between pockets of
conductive material isolated in an insulator. The result
is that such a process makes the material something like
a semiconductor. Further research on electrical properties is needed to explicate such conductivity in ta-C in
order to determine its practical value. However, a different electrical property of emissivity has been shown to
occur at unique levels for ta-C. Such high values allow for
electrons to be emitted from ta-C coated electrodes into
vacuum or into other solids with application of modest
levels of applied voltage. This has supported important
advances in medical technology.

4 Applications
Applications of DLC typically utilize the ability of the
material to reduce abrasive wear. Tooling components,
such as endmills, drill bits, dies and molds often use DLC
in this manner. DLC is also used in the engines of modern
supersport motorcycles, Formula 1 racecars, NASCAR
vehicles, and as a coating on hard-disk platters and harddisk read heads to protect against head crashes. Virtually
all of the multi-bladed razors used for wet shaving have
the edges coated with hydrogen-free DLC to reduce friction, preventing abrasion of sensitive skin. It is also being
used as a coating by some weapon manufacturers/custom
gunsmiths. Some forms have been certied in the EU for
food service and nd extensive uses in the high-speed actions involved in processing novelty foods such as "chips"
and in guiding material ows in packaging foodstus with
plastic wraps. DLC coats the cutting edges of tools for the
high-speed, dry shaping of dicult exposed surfaces of
wood and aluminium, for example on automobile dashboards.

Medical applications: The wear, friction, and electrical properties of DLC make it an appealing material for
medical applications. Fortunately, DLC has proved to
have excellent bio-compatibility as well. This has enabled many medical procedures, such as Percutaneous
Despite the favorable tribological properties of DLC it coronary intervention employing brachytherapy to benet
must be used with caution on ferrous metals. If it is used from the unique electrical properties of DLC. At low voltat higher temperatures, the substrate or counter face may ages and low temperatures electrodes coated with DLC
carburize, which could lead to loss of function due to a can emit enough electrons to be arranged into dispos-

5
able, micro-X-ray tubes as small as the radioactive seeds
that are introduced into arteries or tumors in conventional brachytherapy. The same dose of prescribed radiation can be applied from the inside, out with the additional possibility to switch on and o the radiation in the
prescribed pattern for the X-rays being used. DLC has
proved to be an excellent coating to prolong the life of
and reduce complications with replacement hip joints and
articial knees. It also has been successfully applied to
coronary artery stents, reducing the incidence of thrombosis. The implantable human heart pump can be considered the ultimate biomedical application where DLC
coating is used on blood contacting surfaces of the key
components of the device.
The Space Black stainless steel Apple Watch[16] is coated
with diamond-like carbon.

Environmental
benets
durable products

of

The increase in lifetime of articles coated with DLC that


wear out because of abrasion can be described by the formula f = (g) , where g is a number that characterizes the
type of DLC, the type of abrasion, the substrate material
and is the thickness of the DLC coating in m.[17] For
low-impact abrasion (pistons in cylinders, impellers in
pumps for sandy liquids, etc.), g for pure ta-C on 304
stainless steel is 66. This means that one-m thickness
(that is ~5% of the thickness of a human hair-end) would
increase service lifetime for the article it coated from a
week to over a year and two-m thickness would increase
it from a week to 85 years. These are measured values;
though in the case of the 2 m coating the lifetime was
extrapolated from the last time the sample was evaluated
until the testing apparatus itself wore out.

7 References
[1] Robertson, J. (2002). Diamond-like amorphous carbon.
Materials Science and Engineering: R: Reports 37 (46):
129. doi:10.1016/S0927-796X(02)00005-0.
[2] Name Index of Carbon Coatings
[3] Kran, B.; et al.
(2009).
Tribological behavior of tungsten-doped DLC coating under oil lubrication.
Tribology International 42 (2): 229.
doi:10.1016/j.triboint.2008.06.011.
[4] Evtukh, A.A; et al. (2001). Silicon doped diamondlike carbon lms as a coating forimprovement of electron eld emission.
Proceedings of the 14th International Vacuum Microelectronics Conference: 295.
doi:10.1109/IVMC.2001.939770.
[5] Louis Bergeron (Oct 17, 2011). Amorphous Diamond,
a New Super-Hard Form of Carbon Created Under Ultrahigh Pressure. Science Daily. Retrieved 2011-10-21.
An amorphous diamond -- one that lacks the crystalline
structure of diamond, but is every bit as hard -- has been
created by a Stanford-led team of researchers. ... That
uniform super-hardness, combined with the light weight
that is characteristic of all forms of carbon -- including
diamond -- could open up exciting areas of application,
such as cutting tools and wear-resistant parts for all kinds
of transportation.
[6] Yu Lin, Li Zhang, Ho-kwang Mao, Paul Chow, Yuming Xiao, Maria Baldini, Jinfu Shu, and Wendy L. Mao.
Amorphous diamond: A high-pressure superhard carbon
allotrope. Physical Review Letters, 2011
[7] Achieving ultralow nanoscale wear
[8] DLC Coatings
[9] Argon plasma treatment on metal substrates and eects on
diamondlike carbon (DLC) coating properties By Abdul
Wasy ZIA et al. DOI: 10.1002/crat.201300171

There are environmental arguments that a sustainable


[10] Eect of Physical and Chemical Plasma Etching on Sureconomy ought to encourage articles not engineered to
face Wettability of Carbon FiberReinforced Polymer
lower performance or to fail prematurely. This in turn
Composites for Bone Plate Applications By Abdul Wasy
will reduce the need to support greater production of units
ZIA et al. DOI: 10.1002/adv.21480
and their frequent replacement, which might provide an
economic disincentive to manufacturers of such devices. [11] Evaluation of bias voltage eect on diamond-like carbon
coating properties deposited on tungsten carbide cobalt By

Currently there are about 100 outsource vendors of DLC


Abdul Wasy ZIA et al. DOI: 10.1002/sia.5400
coatings that are loaded with amounts of graphite and hydrogen and so give much lower g-numbers than 66 on the [12] Thickness dependent properties of diamond-like carbon
coatings by ltered cathodic vacuum arc deposition by
same substrates.
Abdul Wasy Zia et al, DOI: http://dx.doi.org/10.1179/
1743294414Y.0000000254

See also
Chemical vapor deposition
Cathodic arc deposition
poly(hydridocarbyne)

[13] Eect of Diamond like Carbon Coating Thickness on


Stainless Steel Substrate by Abdul Wasy Zia et al,
[14]
[15] Pressemitteilungen
[16] .
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