Laser Assisted Thermal CVD method

can be used for promising and fast

local growth of carbon nano tubes.
As the name suggests, laser is used
to locally heat the substrate. Laser
CVD differs from conventional CVD
in that, the area of growth can be
limited to that of where the laser
beam passes.
 Typical Parameters:
Pressure: 1atm
Temperature: 700 ° - 900°C
Substrate: Si, mica, quartz, or alumina.
Carbon supply: CH4 or CO2 gas
Common catalysts: Ni, Fe, or Co.
 Commercial method for production of carbon
nanotubes

 Substrate is prepared with a layer of metal catalyst

particles(commonly nickel, cobalt, iron, or a
combination)

 Diameters of the nanotubes depends on the size of the

metal particles
 Two gases are bled into the reactor:
 a process gas (such as ammonia, nitrogen or
hydrogen) and
 a carbon-containing gas (such as acetylene,
ethylene, ethanol or methane)

 This can be controlled by patterned (or masked)

deposition of the metal, annealing, or by plasma
etching of a metal layer

 Substrate is now heated to ~ 700°C which initiate

the growth of nanotubes
 Nanotubes grow at the sites of the metal catalyst;
the carbon-containing gas is broken apart at the
surface of the catalyst particle, and the carbon is
transported to the edges of the particle, where it
forms the nanotubes.

 Catalyst particles can stay at the tips of the

growing nanotube during the growth process, or
remain at the nanotube base, depending on the
adhesion between the catalyst particle and the
substrate

 One issue in this synthesis route is the removal of

the catalyst support via an acid treatment, which
sometimes could destroy the original structure of
the carbon nanotubes. However, alternative
catalyst supports that are soluble in water have
proven effective for nanotube growth
 Where A is the species to be deposited and B
is the carrier.

 The high temperatures needed to induce

these reactions are generated within the
small volume surrounding the focus of a laser
beam that is perpendicularly irradiating the
surface of a substrate immersed in the
precursor. By having the laser focus at the
substrate surface,molecules at the solid-gas
interface within this hot zone are dissociated
allowing for the adsorption of species A onto
the surface.
 Two types of laser CVD, pyrolytic and photolytic.

 In Pyrolytic LCVD, an incident laser beam heats

the substrate to a high temperature and precursor
molecules adjacent to this hot surface are
thermally decomposed to form a deposit. In
photolytic LCVD, however, the incident laser
energy is directly absorbed by the reaction gas to
selectively excite precursor molecules. Generally,
pyrolytic LCVD is more advantageous in achieving
good electrical property, high deposition rate,
high resolution, and high purity of a deposit than
the photolytic LCVD except that the substrate
temperature in pyrolytic LCVD is much higher than
that in photolytic LCVD.
Fig.LCVD process
 consists of two steps:
 (1) the deposition of catalyst material on the
substrate, followed by
 (2) the actual synthesis of nanotubes by
laser-induced chemical vapor deposition.

LCVD is a method to deposit microscale solid

patterns or three dimensional structures on
the surface of a substrate by a localized,
single step process. For the deposition of
solid by LCVD, a focused laser beam
irradiates on the surface of a substrate
 placed in a chamber filled with precursor gas
to locally raise its surface temperature.
Then, the precursor gas adsorbed on the
heated substrate surface undergoes a
thermally-induced chemical decomposition
into solid deposit and gaseous byproducts
Because a focused laser beam is used for the
substrate heating, the size of heated surface
and thus the deposited pattern can be
controlled to the order of a few micrometer.
LCVD has been applied to the repair of
electrical circuits or photolithographic mask
patterns and also to the fabrication of three-
dimensional micro structures.
Fig.Schematic representation of the Laser-assisted CVD growth setup
 High deposition rates of typically 100–1000 times
greater than maximum rates obtained by CVD
techniques, which is favorable for scale-up
production of carbon nanotubes.
 Minimum substrate and grown nanotube damage is
observed due to highly localized heating and
excellent spatial resolution and process control.
 Temperatures involved in laser chemical processing
are generally higher than conventional CVD
processes, therefore one would expect lower defect
densities and a higher degree of graphitization for
LCVD produced carbon nanotubes.
 LCVD technique has the capability to make carbon
nanotube networks and patterns by selected area
deposition and laser direct writing techniques.
 Minimal gas phase reactions are involved in LCVD
because the precursors are selected such that they
do not absorb at the laser wavelength.
 Inability to control the size of metal particle
catalysts
 Difficulties associated with controlling laser-
induced gas phase reactions which complicate
for scale-up production and may potentially
lower nanotube quality by gas phase
contamination.
 The density and the size of the catalytic metallic
nanoparticles previously deposited onto the
substrate mostly determine the subsequent CNTs
density and size .One of the main challenge in
the preparation of CNTs-based devices to address
catalytic particle of controlled size at a
controlled location.
  In Pyrolytic LCVD, an incident laser beam heats the
substrate to a high temperature and precursor
molecules adjacent to this hot surface are
thermally decomposed to form a deposit. In
photolytic LCVD, however, the incident laser energy
is directly absorbed by the reaction gas to
selectively excite precursor molecules. Generally,
pyrolytic LCVD is more advantageous in achieving
good electrical property, high deposition rate, high
resolution, and high purity of a deposit than the
photolytic LCVD except that the substrate
temperature in pyrolytic LCVD is much higher than
that in photolytic LCVD.
Techniques of LACVD Contd.
 The synthesis of CNTs is highly dependent on the
process parameters such as temperature, process
gases, catalyst, substrate, and time.
 Depending upon catalyst and substrate interaction
there are two types of growth :
 Tip Growth - interaction is weak.
 Base Growth- interaction is strong.
Laser types Substrate Catalyst Temperatur Results
e range
CO2 focused Silicon, Fe(CO)5 1130 C MWNT
Graphite

Nd:YAG Silicon Co 800 C SWNT

focused

Nd:YVO4 Quartz Al-Cr Ni 650–770 C MWNT

focused aligned/SWN
T

Solid state Si/glass Au 1180 C SWNT

focused
 LACVD CVD
Localized growth Complete substrate growth
•Temperature Sensitive •High quantity growth of CNTs
components/substrates •Necessity for prepatterning
•Versatile process
•Writing patterns
•Direction control
Fast heating/temperature Low heating rate
Response •Catalyst prepatterning step
•Catalyst structuring and activation in
situ
Non-uniform temperature Uniform temperature distribution
Distribution (hot wall)
No direct control of temperature Temperature set
Small amount of CNTs Large amount of CNTs
•Fast response to changes in •High inertial environment
Environment