INTRODUCTION

Laser ablation is the process of removing material from a solid surface

by irradiating it with a laser beam.
 The pulse laser vaporization synthesis system, basically, consist of three
part the laser, the optical Delay and the Reactor.
 Laser vaporization is an established nanomaterial synthesis tool.
 It is possibly the best method to grow high-quality, high-purity single-
wall carbon nanotubes (SWNTs).
 As typically employed, a small amount of material (~ 10 16 carbon atoms
and ~1014 metal catalyst atoms, e.g. ~ 1 at. % Ni, Co, Fe, Y, etc.) is laser-
vaporized inside a hot oven with gently-flowing inert gas.
 On a single laser shot, this material self-assembles to form an
astounding fraction of SWNT (70-90 vol.% yield) under the correct
conditions.
PULSE LASER
Pulsed lasers are lasers which emit light not in a continuous
mode, but rather in the form of optical pulses.
Ultra short optical pulses can in principle be generated by
starting with a continuous light source and using a
fast modulator, which lets the light pass only for a short
period of time.
Mode locking in active or passive form is used for
generating ultra short pulses (with
typical durations between 30 fs and 30 ps), having
megahertz or gigahertz pulse repetition rates and
moderate pulse energies
 Nd: YAG LASER
 YAG is the acronym for yttrium aluminum garnet , a synthetic crystal
material which became popular in the form of laser crystals in the 1960s.
 The term YAG laser is usually used for solid-state lasers based on
neodymium-doped YAG.
 YAG is a host medium with favorable properties, particularly for high-
power lasers and Q-switched lasers emitting at 1064 nm.
 Usually the pulses in an Nd:YAG system have width of approximately 10
ns.
 The repetition rate of the pulse is enormously increased from 10 Hz to 75
MHz.
 A jet of preheated (1200 °C) argon through a nozzle tip is situated close to
the rotating graphite target, which contains the catalyst. The produced
SWNT , is collected in a cold finger
What are Nd:YAG lasers
Nd:YAG (neodymium-doped yttrium aluminium
garnet; Nd:Y3Al5O12) is a crystal that is used as
a lasing medium for solid-state lasers. The dopant,
triply ionized neodymium, Nd(III), typically replaces
a small fraction (1%) of the yttrium ions in the host
crystal structure of the yttrium aluminium
garnet (YAG), since the two ions are of similar size. It
is the neodymium ion which provides the lasing
activity in the crystal, in the same fashion as red
chromium ion in ruby lasers.
http://en.wikipedia.org/wiki/Nd:YAG_laser
Why the femtosecond lasers
Using the ultra-short pulse length Femtosecond (~10 -
 seconds) lasers, which can produce power densities
15

as high as 1015 W/cm2.
The energy forms a plasma that explodes and
vaporizes material directly without forming a liquid
phase. However, the average power available from
these ultra fast lasers is low (1-10W) and component
throughput is slow compared to that available from a
Q-switched Nd:YAG laser, for example, with two
orders of magnitude higher average power.
http://www.twi-global.com/technical-knowledge/faqs/process-faqs/faq-what-
is-laser-vaporisation/
Fig. 1. Schematic of the 2’’ -diameter quartz tube and hot furnace used
for laser vaporization growth of SWNT with in situ LIL-imaging and
spectroscopy diagnostics.
Plume dynamics
During the condensation of the Co atoms for ∆t > 1 ms,
only the leading edge of the atomic-Co plume overlaps
the carbon clusters. Assuming that Co clustering initiates
nanotube formation, it appears that nanotubes grow from
a feedstock of aggregated nanoparticles during seconds of
time, confined first within the vortex ring and then by
thermophoresis and fluid flow in the quartz tube.
Thermophoresis, or thermodiffusion is a
phenomenon observed in mixtures of mobile particles
where the different particle types exhibit different
responses to the force of a temperature gradient
EXPERIMENTAL SET UP
In 1995, Smalley's group at Rice University reported the
synthesis of carbon nano tubes by laser vaporization. The laser
vaporization apparatus used by Smalley's group . A pulsed, or
continuous laser is used to vaporize a graphite target in an
oven at 1200 °C. The main difference between continuous and
pulsed laser, is that the pulsed laser demands a much higher
light intensity (100 kW/cm2 compared with 12 kW/cm2). The
oven is filled with helium or argon gas in order to keep the
pressure at 500 Torr. A very hot vapor plume forms, then
expands and cools rapidly. As the vaporized species cool, small
carbon molecules and atoms quickly condense to form larger
clusters, possibly including fullerenes
Reference:-http://www6.physik.uni-greifswald.de/
 GRAPHITE
TARGET

ARGON GAS CHAMBER

WATER COOLED
COPPER
COLLECTOR
Nd:YAG
LASER FURNACE AT 1200 CELSIUS

Reference :-http://www.phy.mtu.edu
Dr. Gerald Caneba Department of Chemical Engineering, Michigan Technological University Houghton, Michigan
 The catalysts also begin to condense, but more slowly at
first, and attach to carbon clusters and prevent their
closing into cage structures. Catalysts may even open cage
structures when they attach to them. From these initial
clusters, tubular molecules grow into single-wall carbon
nano tubes until the catalyst particles become too large, or
until conditions have cooled sufficiently that carbon no
longer can diffuse through or over the surface of the
catalyst It is also possible that the particles become that
much coated with a carbon layer that they cannot absorb
more and the nano tube stops growing. The SWNTs
formed in this case are bundled together by van der Waals
force
Fig. a .Field-emission SEM image of SWNT bundles
b. TEM images of the raw SWNT collected
Reference:-A.A. Puretzky, D.B. Geohegan, X. Fan, S.J. Pennycook “Dynamics of
single-wall carbon nanotube synthesis by laser Vaporization” Appl. Phys. A 70, 153–
CONCLUSION
Laser vaporization is arguably the best method to grow
high-quality, high-purity SWNTs. As typically employed, a
small amount of material ( e16 carbon atoms and e14
metal catalyst atoms) is laser-vaporized inside a hot oven
with gently flowing inert gas. On a single laser shot , this
material self-assembles to form of SWNTs (70–90 % yield)
under the correct conditions . Despite the wide range of
metal catalyst nano particle diameters produced during
pulsed-LV, only SWNTs are formed. Although SWNTs
grow easily by nanosecond time-scale laser vaporization
followed by annealing in a hot oven, they can also be
grown by LV at room temperature where it appears that
sufficient heating of the target or ejecta is accomplished by
high-repetition-rate or long-pulse ( 10 ms) lasers.
Prelude
Pulsed Laser Vaporisation is a technique
where a high-power pulsed laser beam is
focused inside a vacuum chamber to strike a
solid carbonaceous target from which CNT is
to be synthesised.
This material is vaporized from the target and
deposits as a solid product. This process can
occur in the presence of a background gas,
such as argon used to transport the final
product.
 EXPERIMENTAL SETUP
A typical reactor chamber consists of a cylindrical quartz tube
within a furnace.
In order to successfully produce SWNTs the temperature of the
reactor chamber must be heated and the temperature maintained
between 800-1200C. This heated region contains the target.
The vaporized material travels down the quartz tube under
flowing Argon.
When the vaporized material exits the heated portion of the
furnace, product condenses on the walls of the quartz reactor
tube.
Often times a cold condenser will be used to collect the product.
 Process
This process gives high yields of Single walled Carbon
Nanotubes by vaporising graphite rods containing small
amounts of Ni and Co at 1200°C using a laser beam.
In this method Initial laser vaporization pulses are followed
by pulses to vaporise target more rapidly. This process
minimizes the amount of carbon deposited as soot.
CNT aggregate at the end of the tube. The tubes produced by
this method are in the form of ropes 10 - 20 nm in diameter
and up to 100 micron or more in length. By varying
temperature, catalyst composition and other process
parameters average diameter and length of CNT can be
varied.
 Laser ablation of the target
material
 Incident laser pulse penetrates into the surface of
the material within the penetration depth which is
up to 10nm, this dimension depends on laser
wavelength and refraction index of material
The strong electrical field generated by the laser
light is sufficiently strong to remove the electrons
from the bulk material of the penetrated volume.
The free electrons oscillate within the
electromagnetic field of the laser light and can
collide with the atoms of the bulk material thus
transferring some of their energy to the lattice of
the target material within the surface region. The
surface of the target is then heated up and the
material is vaporized.
TECHNICAL ASPECTS
Some factors that influence the synthesis rate of CNT:
Target material
Temperature of chamber
Catalyst used
Pulse energy of laser
Type of gas and pressure in chamber (argon,
nitrogen, etc.)
 DESCRIPTION OF PHYSICAL
PHENOMENA
Minimum laser intensity or the vaporisation
threshold necessary for bulk material evaporation
can be computed from the following equation

where Cp, χ and ρ are, respectively, the heat

capacity, specific mass, and the thermal diffusivity of
the target material, R is the reflectivity of target
surface, Tvap - vaporization temperature and To -
ambient temperature, τlas is the laser pulse duration
 DESCRIPTION OF PHYSICAL
PHENOMENA(cont)
 To get high quality CNT, particle formation should be avoided. Two
main causes for particle formation during laser evaporation are the
breakaway of surface defects under thermal shock and splashing of
liquid material due to superheating of subsurface layers. The last
phenomenon appears for fast heating rates. To avoid superheating,
the laser intensity must be lower than that needed to evaporate a
mass volume The superheating threshold is given by

 α - the absorption coefficient, tr - the relaxation time of hot

electrons on the surface, ΔHvap - the enthalpy change per mass
unit including latent heat for fusion and vaporisation and heating
from ambient temperature to the vaporization point.
 Advantages Disadvantages
This same technique can be applied
to form solid nanorods and
nanowires of many other materials.
• The throughput of the
Unique process of source material technique decreases as
transfer which limits the amount of the reactor
heated material virtually only to that temperature is
which is liberated; its pulsed nature reduced.
which affords high controllability of • Many other
the CNT formation rate, the ease of compounds of carbon
source material replacement and it
are formed along with
allows for easy handling.
the SWNTs.
Reference
MECHANISMS OF SINGLE-WALL CARBON
NANOTUBE GROWTH BY THE LASER
VAPORIZATION TECHNIQUE: IN SITU IMAGING
AND SPECTROSCOPY-D. B. GEOHEGAN*, A. A.
PURETZKY**, X. FAN*, M. A. GUILLORN*, M. L.
SIMPSON*, V. I. MERKULOV*, S. J. PENNYCOOK*
Oak Ridge National Laboratory, Oak Ridge, TN 37831,
odg@ornl.gov
**Dept. of Materials Science and Engineering,
University of Tennessee