Diamond-Like Carbon (DLC)

coatings
Tribological applications

Daniel MUNTEANU
 What is diamond-like carbon ?
Diamond-like carbon (DLC) refers to a metastable form of amorphouse carbon
containing a predominant fraction of sp3 bonds. DLC is an umbrella term for 7
forms of amorphous carbon material that exhibit some of the unique properties
of diamond.

Source: Fraunhofer – IST institute

Index of Carbon Coatings http://www.ist.fraunhofer.de/english/c-products/tab/complete.html

Predominant sp2 sp3 sp2 sp2 or sp3 sp3 sp2 sp2

C-C-bond type

Film # 2.1 2.2 2.3 2.4 2.5 2.6 2.7

Hydrogen free Tetrahedral Metal Hydrogenated Tetrahedral Metal Modified
amorphous hydrogen free containing amorphouse hydrogenated containing hydrogenated
carbon films amorphous hydrogen free carbon films amorphous hydrogenated amorphous
carbon film amorphouse carbon film amorphous carbon films
Designation carbon films carbon films

Abbreviation a-C ta-C a-C:Me a-C:H ta-C:H a-C:H:Me a:C:H:X

Me= W, Ti, ... Me= W, Ti, ... X= Si, O, N, F,

B, ...
 What is diamond-like carbon ?
In the sp3 configurion, a carbon atom’s four valence electrons form σ bonds, the
strongest type of covalent bonding. In the sp2 configuration, three of the four carbon
atom’s valence electrons form σ bonds, in a plane (graphite), with the other remaining
electron forming a weaker π bond.
 What is diamond-like carbon ?
The VDI 2840 standards report,
produced by the Association of
German Engineers, classifies
and assigns nomenclature for
diamond-like-carbon (DLC) and
diamond films. The report includs
a map that allows classification of
the carbon film based on the
fraction of H and sp3 bonded
carbon atoms. ‘Pure’ DLC thus
exists near the top left corner.
(See: ta-C and ta-C:H)
 What is diamond-like carbon ?
- Unlike diamond, which is crystal with which
has long-range order of the sp3-bonded
carbons arranged in a cubic lattice, DLC is
not crystalline with no long-range order,
including the grains at right.

- The grains are amorphous and contain a

random combination of cubic and hexagonal
lattices.
What is diamond-like carbon ?
Yield stress, hardness and brittleness
It is often believed that all hard materials are brittle, and there is
sometimes confusion when considering mechanical properties like
hardness and brittleness.

In fact, a material is brittle when the transition from the elastic

behaviour (limited by the yield strength) to the fracture strength
at which the material breaks, is narrow (i.e., there is little plastic
deformation).

This is generally the case with many hard materials, but it should
not be forgotten that hard materials can also support high loads
and high stress without breaking (even if the eventual failure is
brittle in nature).
Yield stress, hardness and brittleness
Under the action of a stress, the resulting strains in bulk hard
materials are small, even when the deforming forces are quite
high, because of the high associated elastic modulus (a
consequence of the high binding energies between the atoms).

The elastic modulus (E) and the yield stress (Y) (which is close to
the breaking tensile strength in a brittle material) are typically
correlated to the hardness (H) by an empirical formula of the form
H/Y=0.07+0.6 ln (E/Y).

In order to forecast the loading conditions at which a coating

material will fail, it is necessary to know the thickness, yield
stress and elastic modulus of all materials involved in the coating
system (substrate, interface and coating material itself).
Yield stress, hardness and brittleness

It has been shown that optimised anti-wear properties

occur for coatings with high H/E (hardness/elastic
modulus) ratios.
 Differences among DLC films
The main groups are a-C (non-hydrogenated amorphous
carbon), a-C:H (hydrogenated amorphous carbon) and
polymeric a-C:H (highly hydrogenated amorphous
carbon).
 Differences among DLC films
All the diamond-like carbon contains significant fraction of C-C
sp3 bonds.

The a-C:H films contains sp3 fraction smaller than 50%, on the
other hand a-C films may contain up to 85% or more sp3 type
of bonds .

Hydrogenated amorphous carbon can be classified into

following classes:
 Differences among DLC films
1. Polymer-like a-C:H (PLCH): This type of films have the
highest hydrogen content of above 40%. The sp3 content
may be up to 60%. Hydrogen prefers to bond in a sp3
configuration. These films are soft and most of the sp3
bonds are terminated by hydrogen.

2. Diamond-like a-C:H (DLCH): a-C:H film with intermediate

hydrogen contents between 20-40% and sp3 content of
40-60% are known as diamond-like a-C:H (DLCH). They
have higher C-C sp3 bond than that of PLCH.
 Differences among DLC films
(3)Tetrahedral amorphous carbon (TAC or ta-C:H): This class
of a-C is characterized with highest C-C sp3 content up to
60-85% and hydrogen content close to 25%. TAC films may
be hydrogenated or hydrogen free. TAC films have closest
resemblance to the microstructure of the diamond films
due to high sp3 content.

(4) Graphite-like amorphous carbon (GAC): These types of

amorphous carbon have low hydrogen content (less than
20%). They have high sp2 content and sp2 clustering. The
band gap is less than 1(0-0.6 eV) eV. The conductivity of
graphite-like amorphous carbon is very high close to that of
graphite.
Radio-frequency plasma-enhanced
chemical vapor deposition (RF-PECVD)

Radio-frequency plasma-enhanced chemical vapor deposition

(RF-PECVD) is one of the most popular techniques for the
synthesis of DLC films. DLC can be deposited from a variety of
precursors such as CH4, C6H6, C6H12, C2H4 and C2H2 as well
as mixture of these gases with Ar or H2.