 INTRODUCTION

 METHODS
 TYPES OF LASERS
 STEPS INVOLVED
 DIFFERENCES
 ADVANTAGES & DISADVANTAGES
 Arc discharge

 Laser ablation

 Chemical vapor deposition (CVD)

 Laser ablation is the process of removing or
evaporating material from a solid (or
occasionally liquid) surface by irradiating it
with a laser beam.
 A high powered pulsed laser is focused on
the surface of a (rotating) target. The energy
of each pulse is absorbed by the small
illuminated area causing a breakdown of the
chemical bonds within this region.
 Two methods:

1. Pulsed laser

2. Continuous wave
laser
 Pulsed • Continuous
◦ Much higher light --Much lower light
intensity (100 kW/cm2)
intensity (12 kW/cm2)
SWNT versus MWNT
 The condensates obtained by laser ablation are
contaminated with carbon nanotubes and carbon
nanoparticles. In the case of pure graphite
electrodes, MWNTs would be synthesised, but
uniform SWNTs could be synthesised if a mixture
of graphite with Co, Ni, Fe or Y was used instead
of pure graphite.
 Laser vaporisation results ropes' in a higher yield
for SWNT synthesis and the nanotubes have
better properties and a narrower size distribution
than SWNTs produced by arc-discharge.
 Nanotubes produced by laser ablation are purer
(up to about 90 % purity) than those produced in
the arc discharge process. The Ni/Y mixture
catalyst (Ni/Y is 4.2/1) gave the best yield.
 Because of the good quality of nanotubes produced
by this method, scientists are trying to scale up
laser ablation. However the results are not yet as
good as for the arc-discharge method, but they are
still promising.
 In the next two sections, two of the newest
developments on large-scale synthesis of SWNTs
will be discussed. The first is the ‘ultra fast Pulses
from a free electron laser method’, the second is
‘continuous wave laser-powder method’. Scaling
up is possible, but the technique is rather
expensive due to the laser and the large amount of
power required.
 Usually the pulses in an Nd:YAG system have
width of approximately 10 ns, in this FEL
system the pulse width is ~ 400 fs. The
repetition rate of the pulse is enormously
increased from 10 Hz to 75 MHz.
 To give the beam the same amount of energy
as the pulse in an Nd:YAG system, the pulse
has to be focused. The intensity of the laser
bundle behind the lens reaches ~5 x 1011
W/cm2, which is about 1000 times greater
than in Nd:YAG systems.
A jet of preheated (1000 °C) argon through a
nozzle tip is situated close to the rotating
graphite target, which contains the catalyst.
The argon gas deflects the ablation plume
approximately 90° away from the incident FEL
beam direction, clearing away the carbon
vapour from the region in front of the target.
The produced SWNT soot, is collected in a
cold finger.
 The yield at this moment is 1.5 g/h, which is
at 20 % of the maximum power of the not yet
upgraded FEL. If the FEL is upgraded to full
power and is working at 100 % power, a yield
of 45 g/h could be reached since the yield
was not limited by the laser power.
With this method the maximum achievable yield with the current lasers
is 45 g/h, with a NiCo or NiY catalyst, in argon atmosphere at 1000 °C
and a wavelength of ~3000 nm. The SWNTs produced in bundles of 8-
200 nm and a length of 5-20 microns has a diameter range 1-1.4 nm.
‣ This method is a novel continuous, highly productive
laser-powder method of SWNT synthesis based on
the laser ablation of mixed graphite and metallic
catalyst powders by a 2-kW continuous wave CO2
laser in an argon or nitrogen stream.
‣ Because of the introduction of micron-size particle
powders, thermal conductivity losses are significantly
decreased compared with laser heating of the bulk
solid targets in known laser techniques. As a result,
more effective utilisation of the absorbed laser power
for material evaporation was achieved.
‣ The established yield of this technique was 5 g/h. A
Ni/Co mixture (Ni/Co is 1:1) was used as catalyst, the
temperature was 1100 °C. In the soot a SWNT
abundance of 20-40% w as found with a mean
diameter of 1.2-1.3 nm.
 Developed by Dr. Richard Smalley and co-workers at Rice University

 Pulsed laser vaporizes a graphite target in a high-temperature reactor which has

inert gas

 Nanotubes develop on the cooler surfaces of the reactor as the vaporized

carbon condenses

 Water-cooled surface may be included in the system to collect the nanotubes

 The laser ablation method yields around 70% and

 Produces primarily single-walled carbon nanotubes with a controllable diameter

determined by the reaction temperature

 More expensive than either arc discharge or chemical vapor deposition

 - graphite pellet
containing the catalyst put
in an inert gas filled quartz
tube;
-oven maintained at a

temperature of 1,200 ◦C;

-energy of the laser beam

focused on the pellet;

-vaporize and sublime the

graphite

Sketch of an early laser vaporization apparatus

The carbon species are there after deposited as soot in different regions:
water-cooled copper collector, quartz tube walls.
 Vaporization of a target at a
fixed temperature by a
continuous CO2 laser beam (λ =
10.6μm). The power can be varied
from 100Wto 1,600 W.

The synthesis yield is controlled

by three parameters: the
cooling rate of the medium
where the active, secondary
catalyst particles are formed,
the residence time, and the
temperature (in the 1,000–
2,100K range) at which SWNTs
nucleate and grow.

Fig. 3.10 Sketch of a synthesis reactor with a

continuous CO2 laser device
 In the absence of catalysts in the target, mainly c-
MWNTs with a length up to 300nm are produced.
 The best quality is obtained for an oven temperature
of 1,200 ◦C.
 When catalysts (less than 1% of transition metals like
Co or Ni) are added, SWNTs are formed.
 These SWNTs have remarkably uniform diameter and
they self-organize into rope-like crystallites 5–20 nm
in diameter and tens to hundreds of micrometers in
length.
 The ends of all SWNTs appear to be perfectly closed
with hemispherical end caps.
 Finding the two tips of a SWNT is rather challenging,
considering the huge aspect ratio of the nanotube
and their entanglement.
TEM image of raw SWNT material obtained from the laser
vaporization technique.
• This method is a highly productive laser-powder method of
SWNT synthesis based on the laser ablation of mixed
graphite and metallic catalyst powders by a 2-kW
continuous wave CO2 laser in an argon or nitrogen stream
at a temperature by 1100 °C
• Because of the introduction of micron-size particle powders,
thermal conductivity losses are significantly decreased
compared with laser heating of the bulk solid targets in
known laser techniques.
• As a result, more effective utilization of the absorbed laser
power for material evaporation was achieved. The set-up of
the laser apparatus is shown in Figure.
 The established yield of this technique was 5 g/h. A
Ni/Co mixture (Ni/Co is 1:1) was used as catalyst, the
temperature was 1100 °C.
 In the soot a SWNT abundance of 20-40% w as found

with a mean diameter of 1.2-1.3 nm.

 An HRTEM-picture of this sample is shown in Figure .
Step 1: In laser ablation, a pulsed laser vaporizes a
graphite target in a high-temperature reactor.
Step 2: The target was placed in a tube-furnace
heated to 1200°C.
Step 3: while an inert gas is blend into the
chamber.
Step 4: Nanotubes develop on the cooler surfaces
of the reactor as the vaporized carbon condenses.
Step 5: A water-cooled surface may be included in
the system to collect the nanotubes.
• In this method two-step laser ablation was used. Initial
laser vaporization pulse was followed by second pulse to
vaporize target more rapidly. The two step process
minimizes the amount of carbon deposited as soot. Tubes
grow in this method on catalysts atoms.
• Tubes grow in this method on catalysts atoms and
continued to grow until to many catalyst atoms aggregate
at the end of the tube.
 They produced high yields (>70%) of Single walled Carbon
Nanotubes . 
 Typical by-products include fullerene, graphitic
polyhedrons with enclosed metal particles, and amorphous
carbon in the form of particles or over-coating on the CNT
sidewalls
• A controllable diameter determined by the
reaction temperature.
• By varying temperature, catalyst composition and
other process parameters average diameter and
length of car-bon nanotube could be varied.
• The tubes produced by this method are in the
form of mat of ropes 10 - 20 nm in diameter and
up to 100 micron or more in length
• However, it is more expensive than either arc
discharge or chemical vapor deposition and
requires high temperatures.
Advantages
 Good diameter control
 Few defects
 Pure product

Disadvantages
Expensive because of lasers and high
powered equipment
 The laser ablation method is one of the three
methods currently used to prepare SWNTs as
commercial products.
 Market situation:

◦ December 2002: 1000$/g raw material.

◦ Prediction: 0.03$/g
 scientists replaced the metals with graphite
to create multi-walled carbon nanotubes.
 Later the team used a composite of graphite

target containing 0.5 atomic percent of

nickel and cobalt to synthesize single-walled
carbon nanotubes.
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