Carbon Nanotubes Synthesis Via the Catalytic CVD Method

Submitted by

Submitted To

Dr. Muhammad Azam

A REPORT SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS

FOR THE DEGREE OF
MASTER OF SCIENCE
IN
PHYSICS

DEPARTMENT OF PHYSICS

FACULTY OF SCIENCES

UNIVERSITY OF AGRICULTURE
 FAISALABAD

2023

Chapter 1

INTRODUCTION
A carbon nanotube is a substance that resembles a tube and is formed of carbon. Its
diameter is measured in nanometers. One billionth of a metre, or 10,000 times smaller than a
human hair, is a nanometer. Since the atoms' bonds are so strong and the aspect ratios of the
tubes can be extremely high, CNTs are special. A carbon nanotube can range in thickness from a
few nanometers to hundreds of microns in length. To put this into perspective, a single strand of
your hair would be over 40 metres long if it had the same aspect ratio. Nanotubes have been built
with length-to-diameter ratios up to 132,000,000:1, which is much bigger than for any other
material. This is due to the material's extraordinary strength and rigidity.

Moreover, carbon nanotubes are used as additions in a variety of structural materials

because of their exceptional mechanical, electrical, and thermal conductivity. For instance, a
small amount of materials, mostly carbon fibre, is made up of nanotubes in some baseball bats,
golf clubs, vehicle parts, and damascus steel. A new era in materials research began in 1991 with
the discovery of carbon nanotubes (CNT). Many unique electrical, magnetic, and mechanical
properties are present in these amazing formations. Nanotube fibres could reinforce practically
any material because CNT are at least one-sixth as heavy as steel while being at least 100 times
stronger. More better than copper, nanotubes can conduct heat and electricity. CNT are already
used to anti-static packaging and utilised in polymers to regulate or improve
The structural family of fullerene includes nanotubes. Its name comes from the long, hollow
structure whose walls are made of graphene, or carbon sheets that are just one atom thick. The
combination of the rolling angle and radius determines the nanotube properties, such as whether
the individual nanotube shell is a metal or semiconductor. These sheets are rolled at particular
and discrete ("chiral") angles. Single-walled nanotubes (SWNTs) and multi-walled nanotubes are
two types of nanotubes (MWNTs). Van der Waals forces, more precisely, pi-stacking, hold
individual nanotubes in place as "ropes" that naturally align themselves.

Carbon nanotubes can be found in a variety of shapes that vary in length, thickness, and the
number of layers. Depending on how the graphene sheet is rolled up to produce the nanotube,
which can result in it acting either metallically or as a semiconductor, the characteristics of
nanotubes can vary. The graphite layer that makes up the nanotube has an uninterrupted
hexagonal mesh and carbon molecules at the hexagonal apexes, giving it the appearance of
rolled-up chicken wire. [1]

Figure 1.1: Schematic of carbon nanotube made from rolled graphene sheet

Graphene

Many variations of CVD can be utilized to synthsize graphene. Although much advancement
have been made, the processes listed below are not commercially viable yet.

• Carbon source

The most popular carbon source used to produce graphene is methane gas. Less popular
choices include petroleum asphalt, notable for being inexpensive but more difficult to work with.
• Use of catalyst

The use of catalyst is viable in changing the physical process of graphene production.
Notable examples include iron nanoparticles, nickel foam, and gallium vapor. These catalysts
can either be used in situ during graphene buildup, or situated at some distance away at the
deposition area. Some catalysts require another step to remove them from the sample
material.The direct growth of high-quality, large single-crystalline domains of graphene on a
dielectric substrate are of vital importance for applications in electronics and optoelectronics.
Combining the advantages of both catalytic CVD and the ultra-flat dielectric substrate, gaseous
catalyst-assisted CVD paves the way for synthesizing high-quality graphene for device
applications while avoiding the transfer process.

Physical conditions

Physical conditions such as surrounding pressure, temperature, carrier gas, and chamber
material play a big role in production of graphene. Most systems use LPCVD with pressures
ranging from 1 to 1500 Pa. However, some still use APCVD. Low pressures are used more
commonly as they help prevent unwanted reactions and produce more uniform thickness of
deposition on the substrate. On the other hand, temperatures used range from 800–1050 °C. High
temperatures translate to an increase of the rate of reaction. Caution has to be exercised as high
temperatures do pose higher danger levels in addition to greater energy costs.

Carrier gas

Hydrogen gas and inert gases such as argon are flowed into the system. These gases act as a
carrier, enhancing surface reaction and improving reaction rate, thereby increasing deposition of
graphene onto the substrate.

• Chamber material

Standard quartz tubing and chambers are used in CVD of graphene. Quartz is chosen
because it has a very high melting point and is chemically inert. In other words, quartz does not
interfere with any physical or chemical reactions regardless of the conditions.[2]
• Methods of analysis of results

Raman spectroscopy, X-ray spectroscopy, transmission electron microscopy (TEM), and

scanning electron microscopy (SEM) are used to examine and characterize the graphene
samples. Raman spectroscopy is used to characterize and identify the graphene particles; X-ray
spectroscopy is used to characterize chemical states; TEM is used to provide fine details
regarding the internal composition of graphene; SEM is used to examine the surface and
topography. Sometimes, atomic force microscopy (AFM) is used to measure local properties
such as friction and magnetism.Cold wall CVD technique can be used to study the underlying
surface science involved in graphene nucleation and growth as it allows unprecedented control of
process parameters like gas flow rates, temperature and pressure as demonstrated in a recent
study. The study was carried out in a home-built vertical cold wall system utilizing resistive
heating by passing direct current through the substrate. It provided conclusive insight into a
typical surface-mediated nucleation and growth mechanism involved in two-dimensional
materials grown using catalytic CVD under conditions sought out in the semiconductor industry.
[3]

Graphene nanoribbon

In spite of graphene's exciting electronic and thermal properties, it is unsuitable as a

transistor for future digital devices, due to the absence of a bandgap between the conduction and
valence bands. This makes it impossible to switch between on and off states with respect to
electron flow. Scaling things down, graphene nanoribbons of less than 10 nm in width do exhibit
electronic bandgaps and are therefore potential candidates for digital devices. Precise control
over their dimensions, and hence electronic properties, however, represents a challenging goal,
and the ribbons typically possess rough edges that are detrimental to their performance.

Types of carbon nanotubes

There are many different types of carbon nanotubes, but they are normally categorized as
either single-walled (SWNT) or multi-walled nanotubes (MWNT). A single-walled carbon
nanotube is just like a regular straw. It has only one layer, or wall. Multi-walled carbon
nanotubes are a collection of nested tubes of continuously increasing diameters. They can range
from one outer and one inner tube (a double-walled nanotube) to as many as 100 tubes (walls) or
more. Each tube is held at a certain distance from either of its neighboring tubes by interatomic
forces.

• Single-walled
• Multi-walled
• Double-walled carbon nanotubes
• Junctions and crosslinking
• Extreme carbon nanotubes
• Mechanical
• Electrical
• Optical.
Single-walled carbon nanotubes
Single-walled carbon nanotubes (SWNTs) are seamless cylinders comprised of a layer of
graphene. They have unique electronic properties which can change significantly with the chiral
vector, C = (n, m), the parameter that indicates how the graphene sheet is rolled to form a carbon
nanotube.

Figure 1.2. single walled tubes

Multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWNTs) consist of multiple rolled layers of graphene.

MWNTs have not been well-defined due to their structural complexity and variety when
compared to SWNTs. Nonetheless, MWNTs exhibit advantages over SWNTs, such as ease of
mass production, low product cost per unit, and enhanced thermal and chemical stability. In
general, the electrical and mechanical properties of SWNTs can change when functionalized, due
to the structural defects occurred by C=C bond breakages during chemical processes. However,
intrinsic properties of carbon nanotubes can be preserved by the surface modification of
MWNTs, where the outer wall of MWNTs is exposed to chemical modifiers.

Figure 1.3. multi walled tubes

Double-walled carbon nanotubes

Double-walled carbon nanotubes (DWNTs) are a synthetic blend of both single-walled

and multi-walled nanotubes, showing properties intermediate between the two types. DWNTs
are comprised of exactly two concentric nanotubes separated by 0.35 – 0.40 nm, with sufficient
band gaps for use in field-effect transistors. The inner and outer walls of DWNTs have optical
and Raman scattering characteristics of each wall. Theoretically, if each wall behaves like a
SWNT, DWNTs can consist of four combinations based on the electronic type (metallic or
semiconducting) according to (n,m) values of their inner and outer walls, e.g., metallic-metallic
(inner-outer) and metallic-semiconducting.
 Figure.2.4.double walled tube

Multi-walled CNT

Currently, the most popular use for carbon nanotubes is in structural reinforcement. The
high strength and low weight of CNT combined with their flexibility allow for them to be added
to other materials like rebar to concrete. Advances are being made using carbon nanotubes to
extract power from sunlight and even as a heat source. Carbon nanotubes are unique in that they
are thermally conductive along their length but not across the tube itself. This lets carbon
nanotubes play a role on both sides of thermal insulation. CNT are also highly electrically
conductive, which could potentially make for an extremely cost effective replacement for metal
wires. The semiconducting properties of CNT make them candidates for the next generation of
computer chips. Other applications under investigation are their use as chemical carriers for
pharmaceutical applications. Specific drugs can be attached to CNT that can target and attack
only certain types of cells, including cancer cells, for example.

It is important to note that growth of carbon nanotubes in general always requires the
presence of a catalyst. The catalyst is usually predeposited on the surface on which growth will
take place. The catalyst can also be suspended in a hot gas stream and nanotube formation will
occur that way as well, though the latter is a very inefficient way to do so. It also should be
mentioned that it is possible to inject both a hydrocarbon compound and a catalyst-bearing
compound simultaneously into a CVD system and get growth without prepatterning the
substrate. An example would be injecting toluene and ferrocene simultaneously, in which case
the growth is characterized as a two-source process and would require two injection mechanisms
operating simultaneously as well as a carrier gas injection assembly. The single source precursor
that comes with the SSP354 is much simpler, less expensive and more reliable to use.
Figure 1.5.multi walled CNT
Chapter 2 Material and Methods

Syn
thesis
CNT Synthesis

Carbon nanotubes are made every time you light a match. The problem is that there are
so few of them and they are mixed in with other forms of carbon so they just aren’t useful. The
focus of carbon nanotube synthesis is in making a considerable quantity of pure nanotubes with
minimal contamination. It takes a great deal of effort with highly specialized equipment to
ensure that the tubes are the same width and length. As a result, most high volume synthesis
methods do not provide much control over tube diameter or length.

Arc Discharge

This technique involves biasing a sharp carbon rod to many thousand volts. The voltage
is then discharged from the rod, rapidly heating the rod and vaporizing some of the carbon. This
carbon vapor is allowed to cool, and as it does CNTs are produced. The arc discharge method
generally involves the use of a vacuum chamber and an inert gas supply. Even single-walled
nanotubes can be produced if the proper metal ions are introduced. When optimized, this method
can turn roughly 30% of the carbon into carbon nanotubes.
 Figure.1.6. Arc Discharge schematic for CNT synthesis

Laser Ablation

Laser ablation works through the same mechanism as arc discharge, but instead of
producing heat through electrical discharge a laser is used. A focused and powerful laser is used
to rapidly heat carbon and vaporize it. The additional benefit of this is that the temperature and
pulse times can be precisely controlled. Because of these strict controls the parameters of the
CNTs can be finely tuned and up to 70% of the carbon can be turned into CNTs.[4]

Figure.1.7. Laser ablation schematic for CNT synthesis

Chemical Vapor Deposition

Chemical vapor deposition (CVD) oxide is a linear growth process where a precursor gas
deposits a thin film onto a wafer in a reactor. The growth process is low temperature and has a
much higher growth rate when compared to thermal oxide. It also produces much thinner silicon
dioxide layers because the film is deposted, rather than grown. This process produces a film with
a high electrical resistance, which is great for use in ICs and MEMS devices, among many other
applications. Chemical vapor deposition (CVD) oxide is performed when an external layer is
needed but the silicon substrate may not be able to be oxidized.

Types of CVD Processes

CVD covers processes such as:

• Atmospheric Pressure Chemical Vapour Deposition (APCVD)

 • Low Pressure Chemical Vapour Deposition (LPCVD)

• Metal-Organic Chemical Vapour Deposition (MOCVD)

• Plasma Assisted Chemical Vapour Deposition (PACVD) or Plasma Enhanced Chemical

Vapour Deposition (PECVD)

• Laser Chemical Vapour Deposition (LCVD)

• Photochemical Vapour Deposition (PCVD)

• Chemical Vapour Infiltration (CVI)

• Chemical Beam Epitaxy (CBE)

Chemical Vapor Deposition Growth:

CVD growth occurs when a gas or vapor (precursor) is introduced into a low temperature
reactor where wafers are arranged either vertically or horizontally. The gas moves through the
system and distributes evenly across the surface of the wafers. As these precursors move through
the reactor, the wafers begin to absorb them onto their surface. Once the precursors have
distributed evenly throughout the system, chemical reactions begin along the surface of the
substrates. These chemical reactions start as islands, and as the process continues, the islands
grow and merge to create the desired film. Chemical reactions create biproducts on surface of the
wafers, which diffuse across the boundary layer and flow out of the reactor, leaving just the
wafers with their deposited film coating.
 Figure.1.8.

Benefits of Chemical Vapor Deposition:

• Low temperature growth process.

• Fast deposition rate (especially APCVD).

• Does not have to be a silicon substrate.

• Good step coverage (especially PECVD)

The most popular and simplest way to grow carbon nanotubes in the laboratory is to use
chemical vapor deposition (CVD). A CVD system for CNT growth injects a vaporized
hydrocarbon compound (methane or ethane are common) into a high temperature zone in a
furnace. The hot zone contains a substrate on which has been pre-deposited a thin film of iron,
nickel or cobalt that has either separated or been pre-patterned into nanoscale islands of the
metal. These nanoscale islands catalyze the growth of the carbon nanotubes. The catalyst is the
key to the whole process and careful attention must be given to its deposition. Both single and
multi-walled CNTs can be produced via CVD.
 Figure1.9. Chemical Vapor Deposition (CVD) schematic for CNT synthesis

A variant of CVD developed by scientists at the NASA Glenn Research Center, and
embodied by the Nanotech Innovations SSP354 reactor involves injecting a liquid precursor that
already contains both the carbon and catalyst atoms in it into a two temperature zone reactor
tube. The first zone vaporizes the liquid and the iron and carbon atoms are swept into a second,
higher temperature zone where the growth occurs. The iron atoms from the vapor congregate
into nanoparticle islands and the CNT growth takes place from those. This allows for the entire
inside of the hot zone of the reactor tube to be used as a growth surface, both simplifying the
process and greatly increasing yield. Since this technique eliminates the need for pre-patterned
catalyst deposition prior to carbon atom injection by using a single compound that contains both
atoms it is often called a “single source precursor” method. It saves both time and money when
making multi-walled nanotubes. At present the single source precursor method is used to
produce only multi-walled tubes. Work is underway to extend the technique to include growth of
single-walled nanotubes.[5]

Uses of CVD

CVD is commonly used to deposit conformal films and augment substrate surfaces in
ways that more traditional surface modification techniques are not capable of. CVD is extremely
useful in the process of atomic layer deposition at depositing extremely thin layers of material. A
variety of applications for such films exist. Gallium arsenide is used in some integrated
circuits (ICs) and photovoltaic devices. Amorphous polysilicon is used in photovoltaic devices.
Certain carbides and nitridesconfer wear-resistance. Polymerization by CVD, perhaps the most
versatile of all applications, allows for super-thin coatings which possess some very desirable
qualities, such as lubricity, hydrophobicity and weather-resistance to name a few. CVD of metal-
organic frameworks, a class of crystalline nanoporous materials, has recently been
demonstrated. Applications for these films are anticipated in gas sensing and low-k
dielectrics CVD techniques are adventageous for membrane coatings as well, such as those in
desalination or water treatment, as these coatings can be sufficiently uniform (conformal) and
thin that they do not clog membrane pores.

Properties and Applications of Carbon Nanotubes

Carbon nanotube technology can be used for a wide range of new and existing applications:
 • Micro- and nano-electronics

• Structural composite materials

• Flat-panel displays

• Conductive plastics

• Atomic Force Microscope (AFM) tips

• Ultra-capacitors

• Radar-absorbing coating

• Technical textiles

• Gas storage

• Power applications (e.g. batteries with improved lifetime, photovoltaic applications)

• Sensors and Biosensors

• Extra strong fibers

Overall, carbon nanotubes show aunique combination of stiffness, strength, and tenacity
compared to other fiber materials which usually lack one or more of these properties. Thermal
and electrical conductivity are also very high and are comparable to other conductive materials.
[6]

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