Diamond like carbon (DLC)

Diamond vs DLC
Hybridisation of Carbon
DLC
Carbon exist in SP
3
, SP
2
, SP hybridised states
SP
3
Diamond, SP
2
- Graphite
DLC is a metastable form of amorphous carbon, with or
without hydrogen, which contains a significant fraction
of sp
3
bonded carbon atoms.
DLC has network of graphitic clusters linked into islands
by SP
3
bonds.
DLC has similar properties of diamond, but these are
achieved by the isotropic thin films with no grain
boundaries.
structurally they are amorphous in nature with sp
2
and
sp
3
bonded carbon atoms

Carbon-Hydrogen alloys
Ternary phase diagram of bonding in amorphous carbon-hydrogen alloys
ta-C Tetrahedral amorphous carbon
ta-C:H Hydrogenated ta -C
a-C:H amorphous hydrogenated -C
DLC
Mixture of SP
3
and SP
2
sites. DLC has always SP
2
sites
ta-C with > 70% of SP
3

Properties depend on the composition of films

Schematic of SP
2
clusters in a-C:H
DLC - properties
The structure and properties of DLC films are largely
dependent on the hydrogen content and the ratio of sp
2
to
sp
3
bonded carbon atoms
Hydrogen content reduces hardness and density
Hydrogen content increases the band gap and the electrical
resistivity
Hydrogen content also affect the optical properties and
decreases the refractive index
Dopants ( B, N, O, F, Si, Ti, W, Nb) manipulate the properties
of DLC films
DLC has high mechanical hardness, very low surface
roughness, chemical, optical transparency, electrochemical
inertness and a wide band gap semiconductor.



DLC-Properties
Unlike Diamond, DLC can be p and n doped
At high N content, band gap reduces and new SP
2
sites
increases.
DLC has low surface energy
Density dependent on number of SP
3
sites
Mechanical properties depend on the local C-C
coordination. SP
3
increases youngs modulus increases.
Electronic properties depend on number of SP
2
sites, this
controls the band gap. All DLC have bonds.
Optical band gap decreases with increase in SP
2
fraction




Comparison of different C forms
DLC
Preparation of DLC
DLC films may contain significant amounts of
hydrogen depending on the source of carbon
and deposition process.
Hydrogen-free DLC coatings are prepared by
solid carbon or graphite targets with arc
physical vapor deposition, pulsed laser
deposition, and magnetron sputtering
techniques
Preparation of DLC
DLC are easy to prepare compared to diamond
DLC contains amorphous (a-C), hydrogenated
alloys (a-C:H)
Deposition methods like Plasma enhanced
chemical vapour deposition (PECVD),
sputtering are used to prepare a-C with with
higher SP
3
content
More SP
3
with less hydrogented films were
deposited by PECVD.
General deposition methods
Chemical vapour deposition (CVD) High
temperature, specific choice of substrates,
polycrystalline film, more hydrogen content
and more grain boundaries.

Physical vapour deposition (PVD) Sputtering,
ion beam, mass selected ion beam (MSIB)
plasma, Pulse laser, cathodic vacuum arc
DLC deposition methods
Ion beam
PECVD
Sputtering
Cathodic vaccum arc
Pulse laser deposition
Deposition techniques
Deposition mechanism
Diamond like carbon deposition takes place with optimum ion
( carbon or hydrocarbon ions) energy bombardment ~ 100 eV
SP
3
fraction and H contents of DLC films depends mainly on
ion energy
Ion beam deposition
Carbon or hydrocarbon ions are generated by plasma sputtering of graphite
cathode or gas (methane) ionization in a plasma.

Ions are extracted and accelerated using power grids

Ion beam were directed into deposition vacuum chamber

Deposition on the substrate


Mass selected Ion beam (MSIB)
Controlled deposition from single ion species
with well-defined ion energy
Accelerated ions passed are through the
magnetic filters
It filter out neutral species and selects the C
+

Ions can be decelerated to desired ion energy
using electrostatic lens and deposited on the
substrate

Sputtering
Most common method for depostion of DLC

Ar Plasma generation

Magnetron sputtering is used to increase the yield (magnets are placed behind the
target causes the Electron to achieve higher path length and thereby It increases
the plasma ionisation).

DC bias is applied to the substrate to vary the ion energy

a-C:H produced by Reactive sputtering ( Ar, and H or CH
4
)

a-CNx can be produced by using ( Ar + N plasma)

Disadvantage Less ratio of Ions to neutral species (less hard)




Ion assisted sputtering
A beam of Ar ion is used to sputter the graphite traget

Additional Ar beam can be used to bombard the growing film
to densify the film or encourage SP
3
bonding
Cathodic vacuum arc
Touching graphite cathode with carbon striker
electrode and withdrawing initiate the arc. (In vacuum)

High ion density (10
13
cm
3
)plasma is generated
by above process

Low voltage, high current density power supply
(cathode spot is very small [1-10 m])

Particulate and plasma can be filtered by using magnetic filter ducts. (Filtered
Cathodic Vacuum Arc[FCVA]) (Shown in the next slide)

FCVA are used to prepare highly ionised plasma with an energetic species low ion
energy distribution and high growth rate (1 nm/s)

Unlike ion beam deposition, the depositing beam in FCVA is neutral plasma beam,
which can be deposited on the insulating substrates.
Filtered Cathodic vacuum arc (FCVA)
Particulates cannot follow the field. they hit the walls of the filters. ( S
bends gives improved filtration)
Neutral species also hit the walls, so the filters raises the ionisation of
plasma from 30% to 100 %.
Finally plasma beam are condensed on the substrate to produce ta-C

Single bend
S bend
Plasma deposition
Plasma decomposition of hydrocarbons ( acetylene)

Two electrodes with different area

Higher mobility of electrons than ions create a
sheath next to electrode with excess of ions

For DLC deposition the plasma has to operated at
lowest possible pressure

This will increase the fraction of ions to radical
of the plasma

In pressure plasma, use of magnetic field, increase
the path length of electron and the ionisation efficiency
Pulsed laser deposition
A very short pulse of intense laser vaporise materials as intense plasma

The expanding ions in plasma strikes the substrate and deposit as film

This is used to coat many different materials

Characterisation methods
Raman spectroscopy
IR Spectroscopy
Nuclear magnetic resonance ( C
13
NMR)
Electron energy loss spectroscopy
Electron spectroscopy for chemical analysis
(ESCA)
UV spectroscopy
Ellipsometry
X Ray reflectivity, Neutron diffraction

Applications
Optical windows - a-C:H forms transparent thin films. (UV,
Visible)

Magnetic storage disks higher capacity and less wear of
disk materials. No pinholes even with 1.2 nm thick film

Antifuses - as the high current passes it affords less
resistance. DLC acts as semiconductor, hence increase in
temperature increases the conductivity. Nitrogen doped
DLC are better antifuses

Low dielectrics films Device dimension decreases with
DLC films. Lower dielectric constant than SiO
2
Applications
Field emission Emission of electrons under ambient
temperature. FE Devices made of DLC shows emission
at low applied field. Thin film carbon emitters are
better than the tips of Si, Mo in chemical, physical
stability and their cost.

Field effect transistors ta-C can be used in thin film
transitors. Now Carbon nanotubes are found to be
better than DLC.

Nitrogen doped ta-C retain its electrochemical stability
as boron doped diamond electrodes






Applications

DLC have low friction coefficient- unlubricated DLC on steel
has same friction as lubricated steel on steel

High wear resistance ta-C has low rate of wear.

tribological properties depends on the chemical
composition of the surface film, method of preparation.

Useful in precision machining and manufacturing

Keeps razor blade tips very sharp



Applications

Microelectromechanical devices (MEMs)

Biomedical coatings biocompatible coatings
replacement hip joints, heart valves and stents. (
hydrogenated DLC films)

Protective coatings - Automobile coatings, corrosion
resistant coatings, abrasion resistant coatings, ultra smooth
surfaces

Ultra-hydrophobic surfaces fluorinated DLC films
Applications
References
Diamond-like amorphous carbon. J.Robertson,
Material science and Engineering, R(37), 2002,
129-281