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SWNTs

History and Overview

The first reports of carbon nanotubes (CNTs) and single walled carbon nanotubes (SWCNTs)
first emerged in early 1990s. Since then, the research efforts in the field of carbon nanotubes
has continued to increase, making it arguably the known nanomaterial in the field of
nanotechnology. This is because of the excellent electrical and optical properties that are
exhibited by this nanomaterial [6]. CNTs are allotropes of carbon in which the atoms of
carbon form a hexagonal sheet which is seamlessly rolled up to form a cylindrical structure
with a few nanometres in diameter and only microns long. It is the hexagonal shape formed
when the C-C atoms bond to each that leads to some unique properties that can find use in
many applications [9].

There are three distinct categories of CNTs based on the number of walls they have. These
are: (i) SWCNTs are made of a single-atom-thick wall, (ii) Double-walled CNTs (DWCNTs)
are made of a two-atom-thick wall, and (iii) Multi-walled CNTs (MWCNTs) are made of two
or more coaxial SWCNTs with one SWCNT inside the diameter of another [3]. The structure
of the three types of CNT is shown in the figure below:

A B C

Figure 1: Structure of the three types of CNT: (A) SWCNT, (B) DWCNT, (C) MWCNT

The electronic properties of CNTs is highly dependent on how the grapheme sheets are rolled
up (chirality).
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Figure 2: Theoretical construction of a SWCNT by rolling grapheme sheet

The chiral vector, C, completely describes SWCNTs, except for length. The chiral vector C is
created using two atoms on unrolled planar sheet of grapheme, with one atom taken as the
origin, and is defined as:

C h=na1 +ma 2

The vectors a1 and a2 are unit cell vectors for the hexagonal 2-D grapheme lattice, while
n and m are integers [4]. The chiral vector Ch is the peripheral length of the nanotube and is
defined as:

C h=√ 3ac −c √ n2 +nm+m 2 , where ac-c is the length of C-C bond.

The electronic properties of carbon nanotubes can easily be determined given that:

|𝑛−𝑚|=3𝑞

If q is an integer, then the nanotube is metallic. If otherwise, the nanotube will have a
semiconductor. The pattern of the CNT can be described using the chiral angle. This is the
angle between the chiral vector C hand nearest zigzag of carbon atom bonds, and is defined as:

0° ≥ θ ≤30° .

For armchair nanotube (m=n), θ=30°

For zigzag nanotube (m=0), θ=0 °
The chiral, zigzag, and armchair nanotubes are shown in figure 3 below.
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Zigzag Armchair Chiral

Figure 3: Chiral, zigzag, and armchair nanotubes

SWCNTs exhibit quasi-1D properties. The 1D confined electrons in k-states lead to Van
Hove singularities (VHSs) in electronic density states.

Band Structures
The band structure of graphene sheet is shown in figure 4 (a, b). Graphene sheet is a
semiconductor with no band gap, as determined by the tight binding method. Here, the top of
the valence band and the bottom of the conduction band have the same energy which equals
to the Fermi energy for a single special wave vector – the K-point of the 2D Brillouin zone.

Figure 4(a,b): Band structures of graphine in reciprocal space as determined by the tight
binding method
When the graphene sheet is rolled up to form a SWCNT, a periodic boundary condition is
imposed on the nanotube. This periodic boundary condition is given by: . k =2 πq , where C is
the chiral vector representing the circumference of the nanotube, while qis an integer. The
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condition gives rise to quantisation of the wave factor k which leads to formation of a series
of sub-bands (shown as yellow bands in figure 4 (c, d)). For metallic nanotubes, |𝑛−𝑚|=3𝑞
and k passes through a K-point, creating a CNT with no energy gap in the band structure.
Conversely, for semiconducting nanotubes, |𝑛−𝑚|≠3𝑞 and k does not pass through a K-point,
creating a CNT with a finite energy gap in the band structure.

Figure 4 (c, d): (c) Metallic SWCNT (4, 4), (d) semiconducting SWCNT (5,3) showing
yellow lines as wave vectors, and red dots as K-points.

The electronic density of states (DOS) of CNTs

The DOS of SWCNTs depends on whether the nanotube is metallic or semiconducting. The
DOS close to the Fermi level are directly related to the energy levels of the states that are
found near the corners of the Brillouin zone [8]. Semiconducting SWCNTs with the same
diameter have the same DOS within the vicinity of the Fermi level. This extension holds
between chiral metallic and achiral CNTs and is analogous to metallic nanotubes [7].

Properties and applications of CNTs

The CNTs have properties that are directly related to the nature and geometrical shape of the
carbon atom bonding within their structure. Many studies have demonstrated that CNTs
exhibit exceptional mechanical, electrical, thermal, and optical properties which open the
world for their applications in various fields.
Mechanical properties: Theoretical and experimental studies have shown that CNTs have a
Young’s modulus of approximately 1 TPa. This value has been found to depend on chirality
and diameter of a nanotube, except for small diameters when the carbon bonds are fully
strained. CNTs have been found to withstand a tensile strength of up to 150 GPa. This is
arguably 100 times greater than that of steel. These mechanical properties make CNTs
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suitable or applications in composite reinforcement [10]. They are light, strong and can
produce high performance composites in bicycle frames, aircraft and automobile parts, etc.
Electronic properties: The electrical properties and 1D nature of CNTs creates resistance
that depends on the contact between CNT and other electrodes. Studies have demonstrated
that a perfect CNT contact can act as ballistic transporters – making CNTs conductive
without resistance or scattering. Ballistic transport in CNTs is disrupted by defects within the
lattice structure, creating scattering [5]. Many scattering collisions (due to high defect
population or a long CNT) limits the diffusion of carrier mobility, although it can still be as
high as 105 cm2 V-1S-1 , which is typically 1000 times greater than that of bulk Silicon. CNTs
can carry large currents, with a maximum current density of about 109 A cm-2, which is
approximately 100 times larger than that of Copper. Metallic CNTs find applications in
integrated circuits as ballistic transporters. In semiconducting CNTs, the carrier transport can
be switched on/off, an effect that can be used in field effect transistors (FET) which provide
an opportunity to reduce the size of transistors in integrated circuits [2].

Synthesis of CNT
CNTs can be synthesized using three main methods: Chemical vapour deposition (CVD), arc
discharge, and laser ablation.
i. Chemical vapour deposition (CVD)
This method involves flowing carbon feedstock over NPs of a transition metal at
temperatures of 500oC – 1200oC. Under these conditions, the NPs catalyse and act as
nucleation sites for growth of CNTs. CNTs are collected after the system is cooled to room
temperature. The type of carbon feedstock, catalyst, or temperatures at which the process
occurs can alter the length, diameter, chirality, purity, orientation, and the type of CNT
produced [1].
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Figure 4 (a): Summary of the CVD method

ii. Arc discharge

In this method, a direct current bias is applied between two electrodes of graphite in an inert
atmosphere to produce a plasma which vaporises carbonaceous material. The carbonaceous
material reforms into CNTs. SWCNTs can be synthesized by incorporating catalyst NPs into
carbon electrodes and applying specific pressures and gases [1].

Figure 4(b): Summary of arc discharge method

iii. Laser ablation
Laser ablation involves vaporisation of a graphite rod loaded with cobalt and nickel in small
amounts at 1200oC. CNTs are collected on a collector plate after cooling with water [1].
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Figure 4(c): Summary of laser ablation method

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References

1. Aqel, Ahmad, et al. "Carbon nanotubes, science and technology part (I) structure,
synthesis and characterisation." Arabian Journal of Chemistry (2012): 1-23.

2. Avouris, P., Z. Chen and V. Perebeinos. "Carbon-based electronics." Nature

nanotechnology (2007): 605-615.

3. Eatemadi, Ali, et al. "Carbon nanotubes: properties, synthesis, purification, and

medical applications." Nanoscale research letters (2014): 393-393.

4. Endo, M. and M.S. Dresselhaus S. Iijima. "Carbon nanotubes." Elsevier (2013).

5. Green, Alexander A. and Mark C. Hersam. "Properties and Application of Double-

Walled Carbon Nanotubes Sorted by Outer-Wall Electronic Type." ACS Nano (2011):
1459–1467.

6. Iijima, S. "Helical microtubules of graphitic carbon." Nature Nanotechnology (1991):

p. 56.

7. Inoue, Satoshi, et al. "Density of States of Single-Walled Carbon Nanotubes Grown

on Metal Tip Apex." The Japan Society of Applied Physics (2009).

8. Mintmire, J. W. and C. T. White. "Universal Density of States for Carbon

Nanotubes." Physical Review Letters (1998): 2506-2509.

9. Mostofizadeh, Ali, et al. "Synthesis, Properties, and Applications of Low-

Dimensional Carbon-Related Nanomaterials." Journal of Nanomaterials (2011): 1-21.

10. Varshney, Kalpna. "Carbon Nanotubes: A Review on Synthesis, Properties and

Applications." International Journal of Engineering Research and General Science
(2014): 660-676.