3

Electronic band structure of

graphene

The tight binding approximation for the hexagonal honeycomb lattice of graphene was
originally calculated by P. R. Wallace in 1947.1 He considered nearest and next nearest-
neighbor interaction for the graphene p* orbitals, but neglected the overlap between wave
functions centered at different atoms. FIG.3.1 shows the neighbor map in a graphene
sheet. The unit cell contains two carbon atoms A and B belonging to the two sub­
lattices. An atom Ao has three nearest neighbors Bn , six next- nearest neighbors A^ ,
and three second-nearest neighbors B3i. -

Figure 3.1: The nearest neighbor map in graphene sheet

69
tyj 3: Electronic band structure of graphene

3.0.1 Structure of graphene

Graphene has a two dimensional hexagonal structure with a space group of P6/mmm
having two atoms per unit cell (A and B of FIG.3.2), with the lattice vectors,

“i = |(3.V3),»! = 5(3,-V3) (3.1)

The nearest neighbour distance (carbon-carbon distance) is represented by the ‘a’ in

Figure 3.2: The Brillouin Zone of Graphene sheet

equation (3.1) and is approximately 1.42 A (a = 1.42 A). Graphene has lattice constants
of aj = a-2 = 2.46 A4’6 [FIG.3.2]. When extending the graphene layer, we consider the
other three next nearest neighbour vectors given by,

5x = |(l,^), *2 = |( 1,—\/3), <$3 =—a(l,0) (3.2)

3.0.2 Electronic structure of graphene

Figure 3.2 shows the tight binding calculated band structure for graphene which vanishes
at six K points when <pk = 0. Electrons in graphene have the unique property of possessing
extraordinary mobility Vf which plays a vital role in the applications of graphene. The
electronic structure of graphene was found to have the form of the relativistic Dirac
equation which is massless. The Brillouin zone of graphene consists of two momentum
positions (Dirac points) at the corners of the zone labelled as K and K’ respectively,
 71

given by
,2tv 27r . ,2tt 27t .
K= w5g)« k = - (3.3)
'3o’3\/3 3a’ 3>/3
These Dirac points are presented on figure [FIG.3.2], where the gamma (T) point is found
at the centre of the Brillouin zone and is non degenerate. The tight binding Hamiltonian
being written as,
H = -*E + (3.4)
n.iSi

Where t is the hopping parameter, a„ and bn+i are the annihilation operators and at and
bt are the creation operators corresponding to sublattices of graphene. After diagonalizing
the Hamiltonian equation [3.4], the operators are solved as follows:

<■« = -]?£ e*-*a( *), 6n+J( = 1£ e^b(k) (3.5)

iV k JV fc
where N is the number of primitive unit cells. Substituting the annihilation operators
into (3.4)
H = ~4t Z E
™ n,Si k
E e"ttnofcte<fl(B+i*)6, +
Q
(3.6)

=* H = -1 £
Nn,Sikq
EE (3.7)

= + (3.8)
Si k

=> H — -t^[e‘^2+fcv^) + + e<(*»°+M°))]afct6fc.

k
_^jg-<(fc*§+fc¥->f1)_|_ e“‘(fc»a+fc»-(0))]ofe5fct (3.9)

=> ** = -*E(2e<M«>s(^^a)+e-iA-a)afct6fc+(2e-<fe5cos(fc!/^a)+eifea)afc6Jtt (3-10)

fe 2 2

^’)U 1‘)(£) '3-n>

with
<j> = tetk*a(l + 2e~lkx3? cos(ky-~a)) (3.12)

Therefore, we obtain the wavefunctions of graphene as follows:

<f>(k) = —telkxa^[1 + 2e cos(^j^)] (3.13)

z
72 3: Electronic band structure of graphene

Theoretically, the energy bands are derived by the eigenvalues

E(k) = ±\m\ (3-14)

The equation (3.14) that leads to the band structure of graphene can be expressed as,

y/Zkyd \ ( 3kxa
Ek = ±|0*| = ±t 1 + 4cos2 y j + 4cos ^ ^ cos ------ (3.15)

Figure (3.3) shows the tight binding calculated band structure for graphene from equation
(3.15). which vanishes at six K points when <+ = 0, i.e.,

Band structure of graphene (tight-binding)

15

10
cn
energy (eV)

o cn
■

-15
K 1 M K
k space

Figure 3.3: The tight binding band structure of graphene

2e-(^)coShPyb =-l
(3.16)

These points are

., 2tt (1 1 \ 2n ( 2 \ 2jr 1 1
(k»ky) = ±T (s'ltlP^T'Vi)' ^ 3 ’ 3\/3
(3.17)
 73

These are connected by the reciprocal lattice vectors, and only two are inequivalent.
Expanding about ^ (o, , we get by Taylor expansion of Ek

Ek\(0,^-) = t + 4cos2 + 4cos 008 (yA*))

1+W (i^ + *»))+ 4OT (i^a + ^ 008 (f^V3-18)

- 3a .n 3dj o, 2 '■ 3a2„ 3a 2-^ + 0(**)
=< 1+ 1- + — ky + O(Aj)
8
(3.19)

, (. ■ 3a2.2 9a2.2 9a2,2 3a2,2 „ ,

t ^1 + 1 + 3a^y + -yA^ — 2 + y-A^ + y-A^ ~~ 3afcj, + 0(kx, A;y)J

((?a2«+^)) i (3.20)

- |atjfc| — (3.21)

where vp = ^ is the Fermi velocity. Note that energy is now linear in momentum and
hence the quasiparticles in graphene appear massless, and are ultra-relativistic at the
Dirac cones [FIG.8.1].

Electronic Density of States of Graphene

Figure 3.4: Electronic density of states (DOS) of graphene

74 3: Electronic band structure of graphene

FIG.(8.1) depicts the electronic DOS of graphene showing semimetallic behaviour. This
DOS of graphene is completely different from that of diamond which has a wide band gap.
It shows that the density of states for graphene has a zero band gap between the valence
and conduction band. The DOS is derived from (3.22) and its expression is written as
follows:
4 \E\ 1 7r
P(E) (3.22)
7T2 t2 v/2o 2’
The function g denotes the elliptic integral while Z0 and Z\ are the phases of the graphene.

E±(q)~±v,(9)+0{(ln (3.23)

The equation(3.23) is approximated by equation (3.24) near the Dirac point. The function
q is the momentum obtained relative to the Dirac points. This approximation reduces
the DOS of graphene to
2A,\E\
/>(£) = (3.24)
7T iff

Chiral Dirac Fermions

A peculiarity of graphene is that its charge carriers do not show the typical parabolic
dispersion relation E(k) = characteristic of free electrons or electrons in metals
and semiconductors. Instead, due to the honeycomb lattice, graphene shows a linear
dispersion relation:
E(k) = ±h\k\fiF (3.25)

in the vicinity of the K and K’ points, as shown in Figure 3.15 (vp = 106 m/s) is the
Fermi velocity). Such a linear energy relation is also described by the Dirac equation,
where
+ ^0^)<3-26>
is the Dirac hamiltonian (er are the 2x2 Pauli matrices and k is the quasiparticle mo­
mentum. Because of the formal analogy to the Dirac equation, the electrons in graphene
are often referred to as Dirac Fermions, and the comers of the Brillouin zone are called
Dirac points. If we calculate the (isotropic) effective mass,

PE
m* h2 (3.27)
Sk2
 75

using the energy from Eq.(3.25), we find that m vanishes. The same result is ob­
tained by comparing the energy of a Dirac particle (3.25) to the relativistic energy
E = yijfic2 + 7Tio2c4). If one substitutes the particles momentum p = k and the ef­
fective speed of fight c = vp,2,3 the rest mass mo vanishes. The zero effective mass for
a range of wave vectors implies that for low energies (E less than leV ), electrons and
holes do. not interact with the crystal lattice.4-6

Comparison of NNTB with First principles Calculations

The nearest- neighbor tight-binding model for the 7r and 7r* bands of graphene predicts
the electronic bands correctly only for a very limited range of wave vectors. If up to
third-nearest neighbours are included, the tight-binding approximation quite accurately
reproduces first principles results over the entire Brillouin zone as shown in FIG. [3.5a].
The agreement is not restricted to high-symmetry fines only.7 The point to be noted
here is that the linear dispersion relation of the bands at the K- point of graphene,
remains unchanged irrespective of the level of sophistication of the electronic structure
implemented for the calculation FIG.[3.5b]. Such a ‘topologically rugged’ behaviour of
graphene at the Fermi level is a unique feature that has given birth to a new class of
materials known as ‘topological insulators’.8

3.0.3 Conclusion

In conclusion, in this chapter we have discussed the tight-binding approximation for the
7r and 7r* bands of graphene. The valence band and conduction band of graphene meet at
a point to form a Dirac cone at the Fermi level, as a result of which the electrons at the
Fermi level acts as massless Dirac Fermions. Thus, graphene shows ballistic transport and
finite minimum conductivity at room temperature (as also discussed in the Introduction
of this thesis). In the succeeding chapters of this thesis, we shall discuss the effect
of functionalization on the electronic structure of graphene (Chapter-4). We shall also
discuss the effect of mechanical strain on the band structure of hydrogenated/ fluorinated
graphene sheet in the Chapter-6 of this thesis.
76 3: Electronic band structure of graphene

Figure 3.5: Ab initio and nearest-neighbor tight-binding dispersions of graphene, (a) The
converged ab initio calculation of the graphene w and w* electronic bands is shown by
the full lines. The dashed lines represent the tight-binding dispersion, (b) Difference A E
between the ab initio and tight-binding band structures.7
 Bibliography

[1] P. R. Wallace, Physical Review 71 622 (1947).

[2] M. Ishigami et al, Nano Lett 7 (6) 1643 (2007).

[3] E. Stolyarova et al, Proceedings of the National Academy of Sciences 104 (22) 9209
(2007).

[4] G. W. Semenoff, Phys. Rev. Lett. 53 (26) 2449 (1984).

[5] P. Avouris, Z. Chen and V. Perebeinos, Nature Nanotechnology 2 (10) 605 (2007).

[6] K. S. Novoselov et ai, Nature 438 (7065) 197 (2005).

[7] S. Reich, J. Maultzsch, and C. Thomsen, Physical Review B 66, 035412 (2002).

[8] C. L. Kane and E. J. Mele Phys. Rev. Lett. 97, 226801 (2005); L. Fu and C. L. kane
98,106803 (2007).

77