PREPARATION OF CNT

BY PECVD
 PLASMA ENHANCED CVD
 PECVD uses electrical energy to generate a glow discharge
(Plasma) in which energy is transferred into a gas mixture.

 Transform the gas mixture into reactive radicals, ions, neutral

atoms, molecules and other highly excited species.

 Activation energy of the chemical reaction is lowered due to

plasma state of reactive gases, which is induced by injecting RF
power.

 A gas in the plasma state is already ionized, which means it does

not need the extra energy that is used for freeing up its outer
electrons. This makes the gas more reactive hence a lower activation
energy.
 Lower activation energy means gases would require less external
energy to perform the chemical reaction.

Since this external energy is generally supplied through the high

temperature of the medium lower activation energy would result in
lower processing temperatures.

 Ability to perform CVD at lower temperatures is the main motivation

behind using PECVD instead of thermal CVD.
SYNTHESIS OF CNT BY PECVD
 Chemical vapor deposition (CVD) technique can fabricate the aligned CNT
on a selected area on the substrate.

 Aligned CNT would be able to fabricate at lower substrate temperature by

using plasma enhanced CVD (PECVD) technique.

 Various plasma sources have been used for the growth of CNT such as
microwave, direct current, and inductive coupled radio frequency.

 However, radio frequency PECVD (rf-PECVD) method has a possibility for

the large area deposition, because the plasma is very stable and
homogeneous.

 However, the quality of CNT synthesized by rf-PECVD method is

comparatively poor.
EXPERIMENT
 The iron (Fe) nanoparticle was used as a catalyst for CNT growth.

 First, Fe film with a 10nm thickness was deposited onto 100-nm thick SiO2
layer on the n-Si (100) wafer by rf-sputtering method.

 Next, Fe film was heated in Ar atmosphere at 700 deg C for 30 min.The Fe

film transformed to Fe nanoparticles with diameter of 10-30 nm.

 CNTs were synthesized by the rf-PECVD apparatus, which consists of two

parallel plane electrodes with diameter of 50 mm and separated by 80 mm.

 The rf power of 13.56 MHz was applied to the lower electrode and the other
was grounded. The substrate was fixed to the grounded electrode, which
equipped with lamp heater.

 Acetylene gas (C2H2) diluted in Hydrogen gas (H2) was used as a source gas.
Schematic of rf-PECVD apparatus
SEM image of the sample synthesized
by r.f. power of 100 W
Region A, which was exposed to the plasma directly.

 Region B, which was covered with screw and washer to fix the substrate.

 In the region A, the 50-100 nm diameter fiber with large amount of carbon
soot was obtained on the substrate. However, the aligned fiber was obtained in
the region B.

 We covered the substrate with a metal plate to make the condition equal to
the region B. The stainless steel metal plate with 70 mm diameter was
perpendicularly installed from the substrate.
The sample prepared with metal plate at the r.f. power of
100W
(a)SEM image
(b)High resolution SEM image of the tip of CNT
(c) High resolution TEM image and electron diffraction
pattern
SEM images of the CNT
synthesized at the r.f. power
of (a) 10 W, (b) 30 W and (c)
50 W, and high resolution
SEM images of the tip of the
CNT synthesized at the r.f.
power at (d) 10 W, (e) 30 W
and (f) 50 W
SWCNT PRODUCED BY PECVD
 We attempt to produce SWNTs using radio-frequency (RF, 13.56 MHz)
magnetron plasma-enhanced chemical vapor deposition (RFM-PECVD).

 PECVD is advantageous to individual and well-aligned nanotube growth at

a low temperature.

 However, all the carbon nanotubes produced by PECVD are only multi-
walled carbon nanotubes(MWNTs).

 Therefore, in order to control the tube diameter, we adopt the nonporous

and well crystallized materials, Faujasite-type zeolites, as a support material
for the Fe/Co catalyst.
Schematic illustration of the RFM-PECVD apparatus
RF glow-discharge apparatus consisting of an RF electrode, a substrate with
a heater, a matching box (MB), a blocking condenser (BC), and magnetic coils.

 The RF electrode and a substrate holder placed on the heater are made of
Cu, while the substrate on the holder is made of Ni.

 This system is operated at RF power of PRF =900 W. A magnetic field BZ

(=340 G) is externally applied in order to achieve a magnetron-type discharge.

 A gas mixture of methane (CH4) and hydrogen (H2) is filled during the
discharge, where the pressure ratio is expressed by PCH4/PH2 .

 The substrate is heated up to a desirable temperature (Tsub =550–850 deg

C), which is measured by a thermocouple directly connected to the copper
substrate holder. After which, the gas mixture of CH4 and H2 is fed, and then
the total pressure is kept at 0.5 Torr.
 At first, nanotube growth is performed simply using the Ni plate as a catalyst
on the substrate. After 10 min, plasma discharge with the Ni plate heated
under the condition of Tsub = 850 deg C and PCH4/PH2 =9/1. Individually
separated and one-way aligned MWNTs are produced.

 Now Faujasite-type zeolites are placed on the Ni plate. Individually grown

or thin bundles of SWNTs which bridge zeolite particles are evidently
observed by FE-SEM.
 It is, worthy to note that the individual tube diameter exactly coincides with
the zeolite pore size (~7.4 Å).

FE-SEM image of SWNTs produced

by PECVD on the zeolites under the
condition of Tsub =850 deg C and
PCH4 /PH2 =9/1

FEG-TEM image showing

individual SWNT and well
crystallized zeolites
CONCLUSION
 CNTs synthesized by rf-PECVD method and well-aligned CNT obtained on
the Fe deposited substrate.

 Good crystallized CNT without carbon soot was obtained by covering the
substrate with metal plate and grew at the substrate temperature below 500
deg C. Therefore, the aligned CNT will be obtained on a large area below 600
deg C by using rf-PECVD method.

 Moreover some of these SWNTs have the same diameter as that of the
zeolite pore used as a catalyst supporter.

 These results indicate that the advantage of PECVD in the synthesis stage
could be applied to the SWNTs, i.e., individually separated and one-way
aligned SWNTs with the same diameter might be produced
at a quite low temperature.

 It might be possible to control the electric property of SWNTs by changing

the zeolite pore size.
 Importance of PECVD method

Remarkable feature of PECVD is its capability to grow

vertically aligned CNTs (VACNTs).

Large area growth of CNTs is also possible by PECVD.

These are desirable features for the growth process of
CNTs in nanoelectronics applications

Direct growth of CNTs with high efficiency at a

relatively lower temperature is possible than other
methods.
 Role of Plasma on CNT
Growth
Plasma is a collection of free charged
particles, i.e., ions and electrons, formed
by gas discharges.

There are two types of plasma currently

used in PECVD:
Arcdischarge plasma.
Glow discharge plasma.
Effect of plasma on CNT
 Effect of plasma on CNT growth is high-electric field generation in
the sheath region.

 This electric field stems from the potential difference between the
plasma and the substrate, and sheath thickness.

 The electric field applied to the substrate serves as a driving force

for CNT directional growth toward the electric field, which results
in perpendicular CNT growth on the substrate.

 The mechanism of alignment probably stems from van der Waals

interaction among the CNTs that are densely grown to each other.
 Catalyst Preparation
CNT growth by PECVD requires a metal catalyst where CNTs grow. A metal
catalyst must first be deposited on the substrates on which CNTs are grown

Transition metals such as iron, cobalt, nickel and the alloys of these metals
are commonly used as catalyst.

Preparation method includes steps such as- Dissolution, Stirring,

Precipitation, Separation, Cooling, Gel Formation,
Reduction/Drying/Annealing/Calcination etc.

The film thickness typically used for CNT growth is less than 100 nm.

Film thickness strongly influences CNT growth because film thickness is

closely correlated with catalyst particle size.
Contd..
Under layer formation between the catalyst film and the
substrate is quite common in PECVD-CNT growth.

Metal films such as Al, Ti, Mo and other high-melting

point metals are often used.

The underlayer may serve as a barrier layer that

prevents reaction between the catalyst and the
substrats or provides active nucleation sites.
 WHY PECVD?
 Chemical vapour deposition (CVD) has been widely used
to grow CNTs
 CVD is amenable for nanotube growth on patterned
surfaces where controlled growth over masked areas is
needed
 Recently, plasma enhanced chemical vapour deposition
(PECVD) has been investigated for its ability to
produce vertically-aligned nanotubes.
 The plasma enhancement in CVD first emerged in
microelectronics because certain processes cannot
tolerate the high wafer temperatures of the thermal
CVD.
CONTD..
 The plasma CVD allows an alternative at substantially lower
wafer temperatures (room temperature to 100˚C) for many
processes.
 The low temperature operation is possible because the
precursor dissociation is enabled by the high energy
electrons in an otherwise cold plasma.
 The electric field in the plasma enables more individual,
free-standing and vertically-oriented CNTs are possible with
PECVD.
 The advantage of PECVD is being able to grow the carbon
nanotubes on the desired substrate, control growth sites by
arranging the catalyst and being able to be produced on an
industrial scale efficiently and economically.
 CATALYST
PREPARATION
 Transition metal catalysts are needed for CNT growth
by PECVD
 For PECVD, the catalyst on the substrate must be in
the form of particles instead of smooth, continuous
films
 Because the diameter of CNT depends on the particle
size of the catalyst being used
 The metals used to date as catalysts include Fe, Ni,
Co, and Mo. It is possible to apply these onto the
substrate from solutions containing them or they can
be directly deposited using some physical techniques
 The film thickness typically used for CNT growth must
be less than 100nm
A typical preparation includes steps such as
dissolution , stirring, precipitation, separation,
cooling, gel formation, reduction,
drying/annealing/calcination etc.
 GROWTH OF CNT
 CNT growth does not need precursor
dissociation in the gas phase
 The precursor dissociation occurs at the
surface of catalyst particles producing the
carbon needed for nanotube growth
 Typical hydrocarbon sources used in plasma-
based growth of CNTs include methane,
ethylene and acetylene as feedstock
 Carrier gases such as Hydrogen, Argon and etc
are used
 Initially when the plasma was on, the MWCNTs
are vertical; when growth was continued with
plasma off, the nanotubes were found to be
curly or randomly oriented
Deposition (a) without (b) with Plasma
SCHEMATIC
 GROWTH MECHANISM
 Nanotube growth on catalyst particles is similar
to a traditional gas–solid interaction process
such as thin film deposition on substrates.
 The growth proceeds according to the following
sequence of steps and one or more of these steps
may be rate controlling, which varies from case
to case and requires careful experimental
analysis:
(i) Diffusion of precursor(s) through a thin
boundary layer to the substrate.
(ii) Adsorption of species onto the surface.
(iii) Surface reactions leading to film growth.
(iv) Desorption of product species.
(v) Diffusion of species through the boundary layer
into the bulk stream.
GROWTH OF CNT USING Fe
CATALYST

Deposition of Fe metal film using RF

magnetron sputtering
◦ The RF sputtering process was carried out using Fe
catalyst target and deposited onto the Si substrate
◦ The working pressure used is 15 mTorr, base pressure
in the order of 10^-6 mTorr, with 100W of RF power
and a deposition time of 45mins.
Synthesis
◦ Several samples were then placed onto the heating
element in the PECVD chamber and pumped down to high
vacuum and the CVD process started.
◦ After the entire process has completed, the heating
element is switched off to allow the samples to cool
down before retrieval.
◦ The RF power used is 90W, and working pressure set
to 1000 mTorr.
Result
◦ The CNT grown has a diameter of 20 nm, and were
vertical-aligned.
◦ The nanotubes have length ~39 um, and a growth rate
of 7.2 nm/sec.
◦ It is generally believed that CNTs grown in a high
density will be aligned due to the steric
interaction between adjacent nanotubes which enables
them to grow only upward from the substrate.
SEM images of CNT
 CONCLUSION
 Thus by varying the synthesis parameters can affect
the diameter of the CNT as well as its alignment.
 There is only a small range of growth parameters
under which the CNT can be vertically aligned.
A suitable set of growth parameters has to be
found, and then can be further optimized to allow
good controllability of its morphology and
structural composition.