09 Chapter 2

Chapter 2
Basics of graphene and carbon nanotubes
This chapter reviews the theoretical understanding of the geometrical and elec-
tronic structure of graphene and carbon nanotubes which forms the basis for
many of their proposed applications in electronics. The chapter begins with
an overview of the basic physical structure of graphene and carbon nanotubes,
where the geometry of graphene in real and reciprocal space is discussed and
used to study the geometry of carbon nanotubes. The band structure of graphene
is derived using the tight-binding method and then used to derive the electronic
band structure of carbon nanotube. The energy dispersion relations for armchair
and zig-zag nanotubes are derived explicitly. The electronic structure of graphene
is used to study how energy gaps are formed when the graphene sheet is rolled
into a cylinder. In other words, how the chirality of nanotubes determines whe-
ther the tube is metallic or semiconducting. The chapter ends with a discussion
of the band structure near the Fermi points, where the energy spectrum is found
to be linear. This linear band spectrum is then used to derive the band gap and
the density of states of nanotubes.
35
36 BASICS OF GRAPHENE AND CARBON NANOTUBES
2.1 Physical structure of graphene and carbon nanotubes
Graphene is a single atomic layer of graphite and defined as a one-atom-thick

planar sheet of sp2 -bonded carbon atoms densely packed in a honeycomb crystal
lattice [6, 11] as shown in Fig. 2.1. This single layer structure makes graphene
a two-dimensional (2D) system. Graphene is considered as a building block for
all graphitic materials [11]. When several 2D graphene layers are stacked toge-
ther with an interplanar spacing of 0.34 nm, a three-dimensional (3D) graphite
is obtained. A one-dimensional (1D) carbon nanotube can be obtained by rol-
ling a graphene layer along a longitudinal axis and if the same graphene sheet is
wrapped in a ball structure, a zero-dimensional (0D) fullerene is obtained [11] as
illustrated in Fig. 2.1.
2.1.1 Graphene lattice in real and reciprocal space
The honeycomb lattice of graphene in real space is spanned by two lattice vectors
expressed as (√ ) (√ )
−
→
a1 =
3 a
a, , −
→
a2 =
3
a, −
a
, (2.1)
2 2 2 2
giving the relations
−
→
a1 .−
→
a1 = −
→
a2 .−
→
a2 = a2 ,
−
→ a2
a1 .−
→
a2 = . (2.2)
2
These lattice vectors form an angle of 600 between them and are of magnitude
√ √
a =|a⃗1 |=|a⃗2 |=acc × 3=1.42 × 3=2.46 Å, the lattice constant, where acc =1.42 Åis the
carbon-carbon bond length in graphene [29]. Figure 2.2(a) illustrates a hexagonal

lattice of a graphene sheet in real space with lattice vectors −
→
a 1 and −
→
a 2 . The
unit cell of the graphene sheet consists of two inequivalent carbon atoms, one
PHYSICAL STRUCTURE OF GRAPHENE AND CARBON NANOTUBES 37
(a) (b) (c)
Figure 2.1: A 2D graphene gives rise to three carbon materials of different dimensionalities. (a)
A 0D fullerene, (b) 1D carbon nanotube and (c) 3D graphite. Adapted from [11].
from the sublattice A (blue circle) and the other from sublattice B (green circle),
as emphasized with a dotted box in Fig. 2.2(a). The term inequivalent means that
the sites A and B in the unit cell can not be connected by unit vectors a1 and a2
[170].
The first Brillouin zone of graphene in reciprocal lattice is hexagonal with
−
→ −
→
corresponding lattice vectors b 1 and b 2 as shown by a shaded hexagon in Fig.
2.2(b). The direction of the reciprocal lattice vectors b1 and b2 are rotated by 900
from the real space unit vectors a1 and a2 [29]. The reciprocal lattice is constructed
from the real space unit vectors using the relationships,
a2 × a3 a3 × a1
b1 = 2π , b2 = 2π (2.3)
a1 .(a2 × a3 ) a1 .(a2 × a3 )
where −→a 1 and −

→
a 2 are defined above in Eq.(2.1) and −→
a 3 is the unit vector in the
−
→ −
→
z direction. Hence, the unit vectors b 1 and b 2 of the reciprocal lattice are given
by:
( ) ( )
−
→ 2π 2π −
→ 2π 2π
b1 = √ , , b2= √ ,− (2.4)
3a a 3a a
with a lattice constant of √4π in reciprocal space [29] and the relations:
3a
( )
−
→− → −
→− → 4 2π 2
b1 . b1 = b2 . b2 = ,
3 a
( )2
−
→− → 2 2π
b1 . b2 = − . (2.5)
3 a
The Brillouin zone consists of three types of high symmetry points: Γ, K(K′ ),
and M. Γ represents the center of the Brillouin zone, K and K′ represent the two
inequivalent corners of the hexagon, and M is the center of the line joining the
two corners [29].
2.1.2 Carbon nanotube in real space
The structure of a carbon nanotube (CNT) is that of a graphene layer as CNT can
be visualized as a hexagonal honeycomb lattice of a graphene sheet rolled into a
seamless cylinder [29] as shown in Fig. 2.1(b). The structure of a SWCNT can be
defined by a vector called the chiral vector Ch defined by the vector OA which
corresponds to a section of the nanotube perpendicular to the nanotube axis [29]

in Fig. 2.3. The chiral vector Ch represents the full circumference of the nanotube,
and the direction of the nanotube axis is represented by the vector OB which
defines the translational vector T of the tube. Thus T is defined as the unit vector
y
Unit Cell Brillouin Zone
x
b1
A B K
* M
a1
ky K’
a2
b2
kx
Figure 2.2: (a) The graphene lattice in real space with lattice vectors − →a 1 and −
→a 2 and the unit
cell (dotted box) with two sublattices A (blue circle) and B (green circle).(b) The reciprocal lattice
→
− −
→
of graphene with reciprocal lattice vectors b 1 and b 2 and the first Brillouin zone (shaded) with
three high symmetry points Γ, K, K′ , and M. Adapted from [29].
of the nanotube which is parallel to the nanotube axis and is perpendicular to Ch
[29]. The way the graphene sheet is rolled up to make nanotubes can be described
with the chiral vector defined as a linear combination of real space lattice vectors
−
→
a1 and −
→
a2 :
−
→
Ch = n−
→
a1 + m−
→
a2 = (n, m) (0 ≤ |m| ≤ n). (2.6)
The integers (n, m) indicate the number of lattice vectors along the two directions
in the lattice of graphene. In Fig. 2.3, a carbon nanotube can be constructed by
superimposing the two ends of the chiral vector Ch and the cylinder joint is made
−−→ −→
along the two lines OB and AB ′ both are perpendicular to the vector Ch at each
−
→ −
→
end of Ch . Such a tube is known as (n, m) SWCNT. The magnitude of Ch gives
the circumference of the tube
−
→ √
|Ch | = a n2 + m2 + nm, (2.7)
√
using the relations given in Eq. (2.2). Here the lattice constant a=acc × 3=1.44
√
Å× 3= 2.49 Å as the carbon-carbon bond length of carbon nanotubes is slightly
larger (1.44 Å) than that of graphite (1.42Å) [29].
−→
Figure 2.3: The unrolled (4,2) carbon nanotube. The chiral vector Ch and the translational vector
−
→ −→ −−→
T of the nanotube are defined by the vectors OA and OB, respectively. A nanotube is constructed
by connecting the lattice sites O and A, and B and B′ . The unit cell of the tube is represented by
the rectangle OAB′ B. Adapted from [29].
These two integers (n, m) determine the diameter dt and the chiral angle θ of
the tube. The tube diameter is defined as:
−
→
L | C h| a√ 2
dt = = = n + m2 + nm. (2.8)
π π π
The direction of the chiral vector is measured by the chiral angle θ, which is defi-
ned as the angle between vectors Ch and a1 , with values in the range 0 ≤ |θ| ≤ 300
because of the hexagonal symmetry of the lattice. The chiral angle θ is defined as:
Ch .a1 2n + m
cos θ = = √ . (2.9)
|Ch ||a1 | 2 n2 + m2 + nm
The translational symmetry of carbon nanotubes is characterized by a translatio-

nal vector T along the tube axis. The translational vector T (vector OB in Fig. 2.3)
can be expressed in terms of the lattice vectors −
→
a1 and −
→
a2 as:
−
→
T = t1 −
→
a1 + t2 −
→
a2 = (t1 , t2 ), (2.10)
where t1 and t2 are integers. The translational vector T is always perpendicular

−
→− →
to Ch , that is, T .Ch = (t1 −
→
a1 + t2 −
→
a2 ).(n−
→
a1 + m−
→
a2 )=0. Therefore using Eq. (2.2) t1
and t2 are given as:

2m + n 2n + m
t1 = , t2 = − , (2.11)
dR dR
where dR the greatest common divisor (gcd) of (2m + n) and (2n + m) given by
dR = d if (n − m) is not a multiple of 3d
= 3d if (n − m) is a multiple of 3d. (2.12)
with d, the gcd of n and m.

The rectangle OAB′ B constructed by the vectors Ch and T defines the unit cell
of a 1D carbon nanotube as shown in Fig. 2.3. The area of the unit cell of 2D
graphite is defined by the vectors a1 and a2 . The area of the nanotube unit cell
|Ch × T | divided by the area of a hexagon |a1 × a2 | gives rise to the number of
hexagon per unit cell N which is given by
|Ch × T | 2(m2 + n2 + nm)

N= = . (2.13)
|a1 × a2 | dR
Since each hexagon conatins two carbon atoms. Therefore, there are 2N carbon
atoms per unit cell of the carbon nanotube.
There are three distinct ways in which a graphene sheet can be rolled into a
tube as shown in Fig. 2.4. The first two of these are called “armchair" and “zig-
zag". The terms “armchair" and “zig-zag" refer to the arrangement of hexagons
around the circumference. These two nanotubes are known as achiral (symmor-
phic) nanotubes defined as carbon nanotubes having identical mirror image [29].
The third class of tube, which in practice is the most common, is known as chiral
(non-symmorphic), meaning that it can exist in two mirror-related forms [29].
• Armchair nanotube: when n=m, Ch =(n,n) and θ=300
• Zig-zag: when m=0, Ch =(n,0) and θ = 00
• Chiral: Ch =(n,m) and θ= 00 < |θ| < 300
2.2 Electronic structure of graphene and nanotubes
In the hexagonal structure of graphene, each of the carbon atom has four valence
electrons, where three of them are involved in sp2 hybridization forming σ orbi-
tals. However, the remaining fourth electron which makes pz bond and occupies
a π orbital determines the electronic transport properties of the structure. The
high symmetry of graphene makes it straightforward to carry out a tight-binding
(TB) calculation for the system. A tight-binding calculation provides a simplifed

and efficeint description of the electronic band structure of various crystalline
solids and organic molecules [29, 170]. The term tight-binding is used for the
atomic-like wavefunction, that are tightly bound to the atoms [170].
ELECTRONIC STRUCTURE OF GRAPHENE AND NANOTUBES 43
Armchair
Zig-zag
Chiral
Figure 2.4: Schematic view of armchair, zig-zag, and chiral carbon nanotubes. Taken from [171].
2.2.1 Tight-binding method for a crystalline solid
In the tight-binding method for a crystalline solid, the eigen functions Ψj (⃗k, ⃗r)
with j = 1, 2, · · · · · · , n, where n is the number of Bloch wavefunctions, are ex-

pressed as
∑
n
Ψj (⃗k, ⃗r) = Cjj ′ (⃗k)Φj ′ (⃗k, ⃗r), (2.14)
j ′ =1
where Cjj ′ (⃗k) are wavefunction coefficients for the function Φj ′ (⃗k, ⃗r), the Bloch
functions of the form
1 ∑ i⃗k.R⃗
N
Φj ′ (k, ⃗r) = √
⃗ e φj ′ (⃗r − R),
⃗ (2.15)
N ⃗
R
⃗ is the position of the atom and φj ′ denotes the atomic wavefunction in

where R
state j ′ , ⃗k is the wave vector, and r is the position vector [29]. The eigen functions
Ψj (⃗k, ⃗r) satisfy Bloch’s theorem, i.e. Ψj (⃗k, ⃗r) can be written in the form
Ψj (⃗k, ⃗r) = exp(ikr)u(r), (2.16)
where u(r) has the periodicity of the crystal lattice [172, 173].
The energy eigenvalue Ej (⃗k) of the j th state is given as

∫ ∗
< Ψ |H|Ψ > Ψj HΨj dr
= ∫ ∗
j j
Ej (⃗k) = , (2.17)
< Ψj |Ψj > Ψj Ψj dr
where H is the Hamiltonian of the solid. Using Eq. (2.14), the eigenvalue equation
can be further written as

∑n ∗
∑n ⃗ ∗
′ =1 Cij Cij ′ < Φj |H|Φj ′ > j,j ′ =1 Hjj ′ (k)Cij Cij ′
⃗
Ei (k) = ∑
j,j
∗
= ∑n , (2.18)
j,j ′ =1 Cij Cij ′ < Φj |Φj ′ >
n
⃗ ∗
j,j ′ =1 Sjj ′ (k)Cij Cij ′
where
Hjj ′ (⃗k) =< Φj |H|Φj ′ > and Sjj ′ (⃗k) =< Φj |Φj ′ > (j, j ′ = 1, · · · · · · , n), (2.19)
are the transfer and overlap integral matrices.

If the values of the n × n Hjj ′ (⃗k) and Sjj ′ (⃗k) matrices are fixed for a given value
of ⃗k, the coefficient Cij∗ is optimized so as to minimize Ei (⃗k) [29]. Note that the
coefficients Cij∗ is also a function of k, and therefore Cij∗ is determined for each
k [29]. Partial derivative of Ei (⃗k) with respect to Cij∗ while fixing the other C
coefficients, leads to zero for the local minimum condition
∑N ∑N
∂Ei (⃗k) ⃗
j ′ =1 Hjj ′ (k)Cij ′
⃗ ∗
j,j ′ =1 Hjj ′ (k)Cij Cij ′
∑ N
= ∑N − (∑ )2 Sjj ′ (⃗k)Cij ′ = 0.
∂Cij∗ ′ S ′ (⃗k)C ∗
C ′ N ⃗ ∗
j,j ′ =1 Sjj ′ (k)Cij Cij ′ j ′ =1
j,j =1 jj ij ij
(2.20)
∑N
Multiplying both sides of Eq. (2.20) by j,j ′ =1 Sjj ′ (⃗k)Cij∗ Cij ′ and using Eq.
(2.18), one obtains
∑
N ∑
N
Hjj ′ (⃗k)Cij ′ = Ei (⃗k) Sjj ′ (⃗k)Cij ′ . (2.21)
j ′ =1 j ′ =1
Now defining a column vector of the form

 
 Ci1 
 
 
 
Ci =  ... , (2.22)
 
 
 
CiN
Eq. (2.21) can be rewitten as
HCi = Ei (⃗k)SCi . (2.23)
This equation can be further expressed as [H − Ei (⃗k)S]Ci = 0, leading to the
secular equation
det[H − ES] = 0, (2.24)
provided that the inverse of the matrix [H −Ei (⃗k)S] does not exist. The solution of
the secular equation gives rise to all n eigevalues of Ei (⃗k) for a given ⃗k. Using Eqs.
(2.17) and (2.21 ) for Ei (⃗k), the coefficients Ci as a function of ⃗k can be determined
[29]. A more detailed tight-binding calculation can be found in references [8, 29,
170, 172, 173, 174, 175].
2.2.2 Electronic band structure of graphene
Within the tight-binding method, which includes one pz orbital per carbon atom
and the nearest-neighbor interaction, one can obtain the 2D energy dispersion
relations of graphene by solving the secular equation, Eq.(2.24), for a Hamiltonian

H associated with two carbon atoms in the unit cell.
The Bloch functions for graphene can be constructed from the atomic orbitals
for the two carbon atoms at sites A and B in the unit cell using Eq. (2.15) as
follows
1 ∑ i⃗k.R⃗ A(B)
N
Φj (k, ⃗r) = √
⃗ e φj (⃗r − R
⃗ A(B) ). (2.25)
N ⃗
RA(B)
Only nearest-neighbor interactions are considered in the Bloch phase factor. Since
within the same A or B sublattice the nearest-neighbor interactions are absent,
the diagonal elements HAA and HBB of the transfer integral matrix defined as
< ΦA |H|ΦA > and < ΦB |H|ΦB > from Eq. (2.19) can be parameterized as a
single value ϵ2p by substituting Eq. (2.25) into Eq. (2.19) [29]. Whereas, the off-
diagonal matrix elements HAB and HBA can be obtained by adding up hopping
contributions from the three nearest-neighbor B atoms relative to an A atom [29,
⃗ 1, R
176]. These three nearest-neighbor B atoms are denoted by the vectors R ⃗ 2,
⃗ 3 in Fig. 2.5. Hence, substituting Eq. (2.25) into Eq. (2.19) the off-diagonal
and R
matrix element HAB is obtained as:
⃗ ⃗ ⃗ ⃗ ⃗ ⃗
HAB =< ΦA |H|ΦB >= γ0 (eik.R1 + eik.R2 + eik.R3 ) = γ0 f (k), (2.26)
where γ0 =< φA |H|φB > is the nearest-neighbor C-C tight-binding transfer inte-
gral with positive value and φA and φB are pz orbitals centered on atoms A and
B, and H is the Hamiltonian of the system [29, 176]. The function f (k) is the sum
of the phase factors of eik.Rj and can be explicitly calculated using Fig. 2.5, and is
x
B R2
R1
B
A R3
a
B
Figure 2.5: The hexagonal lattice of graphene, where the carbon atom A (blue) is surrounded by
⃗ 1, R
three nearest-neighbor B atoms (green), each placed at positions R ⃗ 2 and R
⃗ 3 , respectively.
given as:
⃗ ⃗ ⃗ ⃗ ⃗ ⃗
f (k) = eik.R1 + eik.R2 + eik.R3
−a
√ kx − a ky ) −a
√ kx + a ky )
i( i( i √a kx
= e 2 3 2 +e 2 3 2 +e 3
(k a)
i √a kx −i a
√ kx y
f (k) = e 3 + 2e 2 3 cos . (2.27)
2
The off-diagonal matrix element HBA is the complex conjugate of HAB (HBA =
∗
HAB ) and hence HBA is given as γ0 f (k)∗ .
Similarly, the matrix elements of the overlap integral matrix can be defined.
The diagonal matrix elements SAA and SBB are 1 as the overlap integral of a wa-
vefunction is 1 [29, 176]. The off-diagonal element SAB is given as:
SAB =< ΦA |ΦB >= sf (k), (2.28)
where s =< φA |φB > is the overlap integral and the matrix element SBA is given
as sf (k)∗ .
Hence the transfer integral matrix H and overlap integral matrix S are given
as:  
 ϵ2p γ0 f (k) 
H=

,
 (2.29)
γ0 f (k)∗ ϵ2p
 
 1 sf (k) 
S=

.
 (2.30)
sf (k)∗ 1
Solution to the secular equation det[H - ES]=0 using H and S leads to the
energy dispersion relation of graphene
ϵ2p ± γ0 |f (k)|
Eg,2D (⃗k) = , (2.31)
1 ± s|f (k)|
where v (√ )
u ( ) ( )
u 3k a ky a ky a
t
|f (k)| = 1 + 4cos
x
cos + 4cos2 . (2.32)
2 2 2
The + and - signs in Eq. (2.31) correspond to the conduction and valence bands,
respectively.
It should be noted that the on-site energy parameter ϵ2p is an arbitrary refe-
rence energy point for the Fermi level. In the orthogonal tight-binding model, it
is set equal to zero because in the unit cell there are two carbon atoms and the on-
site energy is the same for both A and B sites. If there were two different atoms
at sites A and B (e.g., the case of B and N), then the on-site energy would be dif-
ferent and a gap would appear. The overlap integral s is also set equal to zero.
As a result, the valence and conduction bands become symmetrical which can be
seen from Eq. (2.31) [29, 170]. Therefore, the energy dispersion relation for a 2D
graphene sheet reduces to a simpler form given as

v (√ )
u ( ) ( )
u 3k a ky a k a
t
Eg,2D (kx , ky ) = ±γ0 |f (k)| = ±γ0 1 + 4cos
x
cos + 4cos2
y
.
2 2 2
(2.33)
Figure 2.6: The energy dispersion relations for 2D graphene with γ0 =2.5 eV. The Fermi level
is located at the six corner points (two are marked K and K′ ) where the valence and conduction
bands touch. Adapted from [177].
Fig. 2.6 depicts the energy dispersion relations calculated from Eq. (2.33). The
mesh plot represents the whole region of the Brillouin zone. The two resulting
upper half and lower half bands of the energy dispersion plot correspond to the
conduction (π ∗ -energy anti-bonding) and valence (π-energy bonding) bands, and
are the consequence of two carbon atoms per unit cell. The conduction band
touches the valence band at the corners K and K′ of the first Brillouin zone, also
known as Dirac points. The touching points are called Fermi points denoted as
kF and kF′ through which the Fermi level passes. There are six Fermi points which
can be derived by setting the phase factor f (k) = 0, and given as
K(K′ ) = kF (kF′ ) = ±(b⃗1 − b⃗2 )/3, ±(2b

⃗ 1 + b⃗2 )/3, and ± (b⃗1 + 2b
⃗ 2 )/3. (2.34)
At the Fermi level, the density of the electronic states (DOS) becomes zero, there-
fore graphene is a zero-gap semiconductor. This zero gap at the K points exists
because of the symmetry requirement of two equivalent carbon sites A and B in
the unit cell of hexagonal lattice as discussed above.
Now, the graphene energy dispersion relations will be used to derive the
energy dispersion relations for carbon nanotubes.
2.2.3 Electronic band structure of carbon nanotubes
The electronic structure of CNTs is that of graphene modified by the tube struc-
ture and reduced dimensionality. Carbon nanotubes possess excellent electronic
properties because of their nanometer dimension and unique electronic struc-
tures. Although graphene is a zero-gap semiconductor, both experimental and
theoretical studies have shown SWCNTs can be either metallic or semiconduc-
ting depending on the diameter and chirality (degree of twist) of the tube [174,
175, 178, 179, 180] and various types of SWCNTs can be formed on the basis of
chirality as discussed in section 2.1. The dependence of electronic properties of
CNTs on their structure is due to the unique electronic band structure of graphene
as discussed in subsection 2.2.2.
The electronic band structure of CNTs can be derived from the graphene elec-
tronic band structure. When making a tube by rolling a graphene sheet, periodic
⃗ h ) direction. As a re-
boundary conditions are imposed in the circumferential (C
⃗ h direction becomes quantized but remains a conti-
sult, the wave vector in the C
nuous wave vector along the tube axis (T ). Hence, only a certain set of k (energy)
states of the graphene sheet is allowed which depend on the diameter and chira-
lity of the tube. These allowed k states of the tube are the lines mapped onto the
graphene Brillouin zone. The electronic structure of the carbon nanotube can be
understood in detail in the following manner:
Carbon nanotubes in reciprocal space: consider the graphene reciprocal lat-
tice as constructed in Fig. 2.2(b), let the reciprocal lattice vector corresponding
to the chiral vector Ch be K1 and the reciprocal lattice vector corresponding to
the translational vector T be K2 . In carbon nanotubes, Ch and T play the role
of graphene real space unit vectors a1 and a2 , whereas K1 and K2 play the role
of graphene reciprocal space unit vectos b1 and b2 [170]. Since K1 is along the cir-
cumferential direction Ch , hence it is perpendicular to the tube axis T and parallel
to Ch . The vector K2 is aligned with the tube axis T and is thus parallel to T and
perpendicular to Ch . Expressions for K1 and K2 can be derived using the relation
Ri .Kj = 2πδij , where Ri and Kj are the lattice vectors in real and reciprocal space,
respectively. Hence K1 and K2 satisfy the relations,
Ch .K1 = 2π, T.K1 = 0, Ch .K2 = 0, T.K2 = 2π. (2.35)
Using Eqs. (2.6), (2.10), (2.11), and (2.13) and the above definition, K1 and K2 are
given by
1 1
K1 = (t1 b2 − t2 b1 ), K2 = (mb1 − nb2 ). (2.36)
N N
The length of K1 and K2 are defined as
2π 2 2π
|K1 | = = and |K2 | = . (2.37)
|Ch | dt T
From the definition of K1 , two vectors differ by N K1 are equivalent, as this corres-
ponds to a reciprocal lattice vector of graphene. Therefore, N wavevectors of type

µK1 , where µ = 0, 1, · · · · · · , N − 1, lead to N discrete lines or k vectors of length

|K2 | and spacing |K1 |, in the graphene Brillouin zone [29, 170]. There are N one-
dimensional energy bands corresponding to N discrete values of the k vectors
[29]. Hence, the nanotube reciprocal space can be viewed as the result of sectio-
ning the graphene Brillouin zone into a set of N one-dimensional Brillouin zone
or cutting lines, such that the possible k values in the carbon nanotube Brillouin
zone are given as [170]
K2 −π π
k = µK1 + kz , where (µ = 0, 1, · · · , N − 1) and < kz < . (2.38)
|K2 | T T
For any (n, m) nanotube k follows the relation
k.Ch = 2πq, (q = 1, · · · , 2n), (2.39)
which is the periodic boundary condition imposed in the circumferential direc-
tion Ch with q an integer. Equation (2.38) shows that the values of µ are discrete
in K1 direction, while because of the translational periodic boundary condition

along the tube axis, the wave vectors kz along the cutting lines change conti-
nuously [29, 170]. The allowed states in a nanotube thus correspond to parallel
lines in the graphene Brillouin zone.
With the help of Eq. (2.38) the elctronic band structutre of carbon nanotubes
can be calculated by considering the dispersion only along these cutting lines,
which is known as the zone-folding method, that is, sectioning the dispersion
relation of graphene E2D,g (kx , ky ), Eq. (2.33), along the cutting lines [29, 170].
Hence, for any (n, m) carbon nanotubes the dispersion relations are given as
( K2 )
E(µ, kz ) = E2D,g µK1 + kz . (2.40)
|K2 |
2.2.3.1 Energy dispersion relations for armchair and zig-zag nanotubes
In the case of the (n, n) armchair SWCNT, the periodic boundary condition is
applied on the wave vector kx in the circumferential direction, Fig. 2.7, which
leads to
kx,q .Ch = 2πq

√
kx,q .a n2 + n2 + n2 = 2πq
2πq
kx,q a = √ , (q = 1, · · · , 2n). (2.41)
n 3
Discreteness of the kx,q values leads to a one-dimensional dispersion relation of
the armchair nanotube by substituting Eq. (2.41) into Eq. (2.33) giving
√ ( ) ( )
( qπ ) ka ka
(armchair)
Eq,1D (k) = ±γ0 1 + 4cos cos + 4cos2 , (2.42)
n 2 2
(−π < ka < π), (q = 1, · · · , 2n).
Here k is a one dimensional wave vector in the direction of the vector K2 .
In a similar manner, the energy bands for the (n, 0) zig-zag nanotube can be
derived using Eq. (2.33) by applying the periodic boundary condition on ky Fig.
2.7, as follows:
2πq
ky,q a = , (q = 1, · · · , 2n), (2.43)
n
which gives rise to the 1D dispersion relations for the zig-zag nanotube
v (√ )
u ( qπ ) ( qπ )
u 3ka
(k) = ±γ0 t1 + 4cos
(zig−zag)
Eq,1D cos + 4cos2 , (2.44)
2 n n
(− √π3 < ka < √π ),

3
(q = 1, · · · , 2n).
(a)
Armchair
(b)
Zig-zag
Figure 2.7: The periodic boundary condition only allows quantized wave vectors around the
circumferential direction, which leads to one dimensional band structure of carbon nanotubes (a)
Armchair and (b) Zig-zag. Taken from [181].
Figure 2.7 represents the schematic of the periodic boundary condition ap-
plied in the circumferential direction which gives rise to one dimensional band
structure of (a) armchair and (b) zig-zag nanotube.

As shown in Fig. 2.8 (a), if for a particular nanotube of chirality (n, m) the
cutting line passes through a K point in the 2D Brillouin zone of graphene, then
the one-dimensional energy bands of the nanotube have no bandgap, hence the
tube is metallic. Later, it will be shown that the density of states near the Fermi
point has a finite value for these carbon nanotubes. If the cutting lines do not pass
through a K point, then the nanotube is semiconducting with a finite bandgap,
Fig. 2.8 (b), where the density of states is zero [28, 29].
Figure 2.9 represents the one-dimensional dispersion relations for (a) armchair
(5, 5), (b) zig-zag (9, 0), and (c) zig-zag (10,0) SWCNTs. For armchair nanotubes,
Fig. 2.9(a), the band structure is gapless indicating the tube is metallic. The va-
K2 K2
K1 K1
Figure 2.8: The one-dimensional wave vectors k are shown in the two dimensional Brillouin zone
of graphene as bold lines for (a) metallic and (b) semiconducting carbon nanotubes. In the direc-
tion of K1 , discrete k values are obtained by periodic boundary conditions for the circumferential
direction of the carbon nanotubes, while in the direction of the K2 vector, continuous k vectors are
shown in the one dimensional Brillouin zone. (a) For metallic nanotubes, the bold line intersects a
K point at the Fermi energy of graphite. (b) For the semiconductor nanotubes, the K point always
appears one-third of the distance between two bold lines. Here, only a few of all the possible bold
lines are shown near the indicated K point. Adapted from [28].
lence and conduction bands cross at K and K′ points where k = ±2π/3a. The
bandstructure consists of six dispersion relations for the conduction band and
the same number in the valence band. In each valence and conduction band, two
bands are nondegenerate bands as shown in red color, and the four bands are
doubly degenerate, giving rise to 10 levels in each case [182]. For zig-zag nano-
tube, the band structure does not show a gap for (9,0) nanotube in Fig. 2.9 (b),
but the bands cross at k = 0, showing the metallic behavior of the tube, whereas
the (10,0) nanotube has a gap, indicating the tube is semiconducting. In general,
the nanotube with chirality (n, m) is metallic if n − m is a multiple of 3 and it is
semiconducting otherwise. Note, the curvature effect of the tube is neglected, if
it is taken into account then the condition that determines whether the tube is
metallic or semiconducting would not be valid [183] as the (9,0) nanotube does
show a tiny gap in the dispersion spectrum due to the curvature effect [182].
Condition for metallic versus semiconducting nanotubes. To obtain the
condition for a metallic or semiconducting nanotube the expression for the chi-
ral vector Eq.(2.6) and Fermi points Eq.(2.34) are substituted into the boundary
condition Eq.(2.39), and using the relation bi .aj = 2πδij one can get the condition:
1 ⃗
kF .Ch = (b1 − b⃗2 ).(na⃗1 + ma⃗2 ) = 2πq
3
2π(n − m)/3 = 2πq
(n − m)/3 = q. (2.45)
If n − m is a multiple of 3 then the allowed k states or lines intersect the K

and K′ points and the nanotube is metallic. The tube is semiconducting with a
bandgap if n − m is not a multiple of 3 and k states miss the K and K′ points.
Therefore, if the curvature effects are excluded all armchair nanotubes (n, n) are
always metallic, and zig-zag nanotubes (n, 0) are metallic if n is a multiple of 3
(a) (b)
E/J0
E/J0
k k
( c)
E/J0
Figure 2.9: One-dimensional dispersion relations for different CNTs (a) An armchair (5,5) nano-
tube exhibiting metallic behavior, (b) A zig-zag (9,0), and (c) zig-zag (10,0) nanotube exhibiting
semiconducting and metallic characters. Adapted from [182].
and semiconducting otherwise. As a consequence, 1/3 of SWCNT are metallic

and 2/3 semiconducting [175] as shown in chirality map of Fig. 2.10 for different
types of CNTs, where the metallic nanotubes are denoted by blue hexagons and
semiconducting tubes by yellow hexagons. Experimental studies on SWCNTs by
Odom et al. [179] and Wildoer et al. [180] using scanning tunneling microscopy
(STM) confirmed these theoretical predictions.
Zig-zag; (n,0); chiral angle =0
Ar
mc
ha
ir;
(n=
m)
;c
hir
al
an
gle
Semiconducting nanotubes =3
0
Metallic nanotubes
Figure 2.10: Chirality map displaying the different types of SWCNTs that can be formed by
rolling a graphene sheet. The carbon nanotubes (n,m) denoted by blue color are metallic and
yellow color are. Adapted from [184].
2.2.4 Electronic band structure near the Fermi points (K = kF )
For carbon nanotubes, a coordinate system for the reciprocal vectors based on the
circumferential vector Ch and translational vector T is chosen [185]. In order to
study the band structure of carbon nanotube near the Fermi point the origin of
the new coordinate system is reset to the Fermi point, giving the new wave vector
as
⃗k ′ = ⃗k − ⃗kF = k ′ C⃗h + k ′ T⃗ , (2.46)

1 2
where k2′ is the wave vector along the tube axis (T ) and k1′ is the wave vector
⃗ h ), which is quantized due to the periodic
along the circumferential direction (C
boundary condition. k1′ is defined as the projection of k⃗′ to the unity vector in the
circumferential direction [185]. Using |C

⃗ h | = πd, bi .aj = 2πδij , Eqs. (2.34) and
(2.39) k1′ is given as:
′ ⃗ ⃗
⃗h
C ⃗k.C
⃗ h − ⃗kF .C
⃗h 2[ n − m]
k1,q = (k − kF ). = = q− . (2.47)
|C
⃗ h| |C
⃗ h| d 3
To derive the band structure near the Fermi point, the expression for the E(⃗k)
relation of graphene, Eq. (2.33) is simplified by using Taylor series expansion for
the cosine function near the Fermi point [185, 186]. This results in
√
3acc γ0 3acc γ0 ⃗ ⃗
E(⃗k) = ± (⃗kx − ⃗kF x )2 + (⃗ky − ⃗kF y )2 = ± |k − kF |. (2.48)
2 2
E(⃗k) is linear near a Fermi point and hence this is called the linear band ap-
proximation. A derivation of this equation can be found in the Appendix A.
Equation (2.48) can be rewritten using the coordinate system for the nanotube,
Eq. (2.46), as:

√
3acc γ0 ′
E(⃗k) = ± + k ′2 .
2 2
k1,q (2.49)
2
′
The minimum value of k1,q gives rise to the lowest band of the nanotube. Next,
the metallic and semiconducting tubes will be discussed explicitly and Eq. (2.49)
will be used to derive the band gap and density of states of the nanotubes.
Metallic carbon nanotubes- The condition for a nanotube to be metallic states

′
(n − m)/3 = q. In this case, k1,q = 0 in Eq. (2.47). Hence the E(⃗k) relation becomes:
3acc γ0 ′
E(k⃗2′ ) = ± k2 = ~vF k2′ , (2.50)
2
where vF is the Fermi velocity defined as
1 ∂E(k) 1 3acc γ0
vF = = . (2.51)
~ ∂k ~ 2
This is a one-dimensional linear dispersion relation for the lowest band inde-
pendent of (n, m).

Semiconducting carbon nanotubes- In this case, (n−m)/3 ̸= q and the minimum
′
value of k1,q = 2/3dt is obtained from Eq. (2.47), leading to E(⃗k) relation
√
3acc γ0
E(k⃗2′ ) = ± k ′ 22 + (2/3dt )2 , (2.52)
2
which is a one-dimensional dispersion relation independent of (n, m) but de-
pends on the tube diameter dt . It is a parabola with a direct band gap expressed
as:
2acc γ0
Egap = . (2.53)
dt
Hence, the larger the tube diameter, smaller the bandgap [29].
2.2.5 Density of states of carbon nanotubes
The density of states of the carbon nanotube determines its electrical properties.
In general, the density of states, ρ(E), is defined as the derivative of the available
states with respect to energy and expressed as [186]:
∫ ∂E −1
∂k g∑
ρ(E) = = dkδ(k − ki ) , (2.54)
∂E l i ∂k
where, g is the degeneracy factor and g = 4 for graphene because of spin and val-
√
ley degeneracies, ki are the roots of the equation E−E(ki ) = 0, l = (4π/ 3)|Ch |/a2
is the length of the 1D Brillouin zone, which corresponds to a normalization over
the graphene sheet unit cell and is calculated as the ratio of the total area of the
Brillouin zone to the interline spacing 2π/|Ch |, and k is the total number of elec-
tron states per unit cell below a given energy E [186]. Using Eq.(2.49) the inverse
of the derivative of the states with respect to energy is given by
√
∂E −1 2
′2
k1q + k2′
2

′ = . (2.55)
∂k2 3acc γ0 k2′
Now using Eqs. (2.47) and (2.49) the above equation can be rewritten as
∂E −1 |E|
2
′ = √ , (2.56)
∂k2 3acc γ0 E 2 − E 2
1q
where
acc γ0
|E1q | = (3q − (n − m)), (2.57)
2r
and r is the radius of the nanotube.

Substituting Eq. (2.56) into Eq. (2.54) the expression for the DOS becomes
4 ∑
∞
2 |E|
ρ(E) = √ , (2.58)
l q=−∞ 3acc γ0 E 2 − E 2
1q
after putting the value of l, ρ(E) becomes

√
3acc ∑
∞
ρ(E) = 2 g(E, E1q ), (2.59)
π γ0 r q=−∞
where
√
g(E, E1q ) = |E|/ E 2 − E1q
2
, |E| > |E1q |;
0, |E| < |E1q |. (2.60)
For E1q ̸= 0 and |E| = |E1q |, g(E, E1q ) shows a divergent van Hove singularity,
while for |E1q | = 0, g(E, 0) is constant and equal to 1, this refers to the case of
metallic nanotubes [186]. In the case of semiconducting carbon nanotubes, the
density of states is zero inside the bandgap. The density of states contributed
by the lowest band of a semiconducting nanotube can be expressed in a more
compact form as
√
3acc ∑
∞
|E|
ρ(E) = 2 √ Θ(|E| − Egap /2), (2.61)
π γ0 r q=−∞ E − (Egap /2)2
2
where Egap /2 = E1q and the step fuction Θ(|E| − Egap /2) = 1 if |E| > (Egap /2)
and 0 otherwise [185]. Figure 2.11 shows the electronic density of states for (a) a
semiconducting (5,0) carbon nanotube and (b) a metallic (5,5) carbon nanotube.
2.3 Summary
In this chapter, the physical and electronic structure of carbon nanotubes was de-
rived from graphene. The unique structure of graphene and carbon nanotubes
make them wonder materials. Moreover, carbon nanotubes possess various crys-
tal structures depending on the chirality, which results in a variety of nanotube

types. Using the tight-binding method the electronic band structure of graphene
was discussed and then used to explain the geometry-dependent electronic band
structure of carbon nanotubes. The energy dispersion relations for armchair and
SUMMARY 63
(a) (b)
Figure 2.11: Density of states for (a) a (5,0) nanotube which shows semiconducting behavior and
(b) a (5,5) nanotube which shows metallic behavior. Adapted form [170].
zig-zag nanotubes were explicitly derived and discussed for some special chira-
lity. The predictions on the metallic or semiconducting behavior of carbon nano-
tubes using (n, m) indices were also derived and discussed. The linear dispersion
relation of the CNT in the vicinity of the K points was also derived and used to
calculate and understand the energy gap and the density of electronic states of
carbon nanotubes.

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Chapter 2

Basics of graphene and carbon nanotubes

many of their proposed applications in electronics. The chapter begins with

an overview of the basic physical structure of graphene and carbon nanotubes,

2.1 Physical structure of graphene and carbon nanotubes

Graphene is a single atomic layer of graphite and defined as a one-atom-thick

is obtained. A one-dimensional (1D) carbon nanotube can be obtained by rol-

wrapped in a ball structure, a zero-dimensional (0D) fullerene is obtained [11] as

illustrated in Fig. 2.1.

2.1.1 Graphene lattice in real and reciprocal space

giving the relations

carbon-carbon bond length in graphene [29]. Figure 2.2(a) illustrates a hexagonal

(a) (b) (c)

where −→a 1 and −

two corners [29].

2.1.2 Carbon nanotube in real space

corresponds to a section of the nanotube perpendicular to the nanotube axis [29]

of the nanotube which is parallel to the nanotube axis and is perpendicular to Ch

the tube. The tube diameter is defined as:

The translational symmetry of carbon nanotubes is characterized by a translatio-

where t1 and t2 are integers. The translational vector T is always perpendicular

and t2 are given as:

= 3d if (n − m) is a multiple of 3d. (2.12)

with d, the gcd of n and m.

|Ch × T | 2(m2 + n2 + nm)

(non-symmorphic), meaning that it can exist in two mirror-related forms [29].

• Armchair nanotube: when n=m, Ch =(n,n) and θ=300

• Zig-zag: when m=0, Ch =(n,0) and θ = 00

• Chiral: Ch =(n,m) and θ= 00 < |θ| < 300

2.2 Electronic structure of graphene and nanotubes

(TB) calculation for the system. A tight-binding calculation provides a simplifed

2.2.1 Tight-binding method for a crystalline solid

with j = 1, 2, · · · · · · , n, where n is the number of Bloch wavefunctions, are ex-

⃗ is the position of the atom and φj ′ denotes the atomic wavefunction in

Ψj (⃗k, ⃗r) = exp(ikr)u(r), (2.16)

The energy eigenvalue Ej (⃗k) of the j th state is given as

can be further written as

are the transfer and overlap integral matrices.

(2.18), one obtains

Now defining a column vector of the form

Eq. (2.21) can be rewitten as

HCi = Ei (⃗k)SCi . (2.23)

This equation can be further expressed as [H − Ei (⃗k)S]Ci = 0, leading to the

2.2.2 Electronic band structure of graphene

relations of graphene by solving the secular equation, Eq.(2.24), for a Hamiltonian

within the same A or B sublattice the nearest-neighbor interactions are absent,

matrix element HAB is obtained as:

SAB =< ΦA |ΦB >= sf (k), (2.28)

graphene sheet reduces to a simpler form given as

can be derived by setting the phase factor f (k) = 0, and given as

K(K′ ) = kF (kF′ ) = ±(b⃗1 − b⃗2 )/3, ±(2b

the unit cell of hexagonal lattice as discussed above.

2.2.3 Electronic band structure of carbon nanotubes

ture and reduced dimensionality. Carbon nanotubes possess excellent electronic

properties because of their nanometer dimension and unique electronic struc-

tures. Although graphene is a zero-gap semiconductor, both experimental and

theoretical studies have shown SWCNTs can be either metallic or semiconduc-

the translational vector T be K2 . In carbon nanotubes, Ch and T play the role

respectively. Hence K1 and K2 satisfy the relations,

Ch .K1 = 2π, T.K1 = 0, Ch .K2 = 0, T.K2 = 2π. (2.35)

The length of K1 and K2 are defined as

ponds to a reciprocal lattice vector of graphene. Therefore, N wavevectors of type

µK1 , where µ = 0, 1, · · · · · · , N − 1, lead to N discrete lines or k vectors of length

For any (n, m) nanotube k follows the relation