Universit` degli Studi di Trieste a Department of Physics Density of State in Graphen: Periodic Boundary Condition A project work for

the course Electronic Structure of Materials Submitted to Prof. Rafael Resata

Degaga Gemechis Dereje April 20, 2012

Abstract This project work is devoted to the numerical study of DOS Graphene with periodic boundary condition using the energy dispersion relation obtained from two-band Tight-Binding Model. In the calculation of the energies, 1000X100 Kpoints were generated on the rst Brillouin zone FBZ by the help of M onkhorst P ack way . Depending on the oset it was possible to include or not to include the singular Dirac points. Since the density of state D() is obviously a singular function at any nite grid , it was regularized by replacing the Dirac delta function with a normalized Gaussian by using a Gaussian width larger than energy levels spacings.

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tight-Binding model for Graphene . . . . . . . . . . . . . . . . . . . . 2 3

Introduction
Graphene is a one-atom-thick planar sheet of sp2 bonded carbon atoms that are densely packed in a honeycomb crystal lattice. Its unit cell can be represented in two possible ways as shown in the Figure-1. The carbon-carbon bond length in graphene, usually denoted by a and is approximately 0.142 nm. Graphene is the basic structural element of all carbon allotrope including graphite, carbon nanotubes and fullerenes. The structure can be seen as a triangular lattice with a basis of two atoms per cell. The direct lattice vectors can be expressed as a1 = a a (3, 3) a2 = (3, 3) 2 2 (1)

The corresponding reciprocal lattice vectors are written as b1 = 2 2 (1, 3) b1 = (1, 3) 3a 3a (2)

Of crucial importance for the study of graphene are the two points k and k at the corners of the graphene Brillouin Zone (BZ). These are named as Dirac points because of the fact that electrons of energy dispersion of this point behave like Dirac Fermions. Their position in momentum space is given by k=( 2 2 , ) 3a 3 3a k = ( 2 2 , ) 3a 3 3a (3)

Figure 1: Possible Unit cells Together with the direct and the indirect lattice vectors the Dirac points can be shown as the in Figure-2. The three nearest-neighbor vectors in real space are given by a a (1, 3) 2 = (1, 3) 3 = a(1, 0) (4) 2 2 and the six second-nearest neighbors are located at 1 = a1 , 2 = a2 , 3 a1 a2 1 =

Figure 2: Honeycomb 2D, direct and reciprocal lattice vectors along with the Dirac points of Graphene In atomic units h = me = 40 = 1, the TB Hamiltonian for electron in graphene, considering that electron can hop to both nearest- and next-neighbor atoms, has the form H = t
i,j ,

(a b,j + H.c.) t ,i
i,j ,

(a a,j + b b,j + H.c.) ,i ,i

(5)

where ai, and a respectively annihilates and creates an electron with i, spin ( =, ) on the site Ri on sub-lattice A , same denition is applied for the sub-lattice B, t(= 2.8eV ) is the nearest -neighbor hopping energy i.e hopping between dierent sub-lattices, and t is the next nearest-neighbor hopping energy i.e hopping in the same sub-lattice. The energy band derived from this Hamiltonian have the form W allace, 1947 (k) = t 3 + f (k) t f (k) where f (k) = 2cos( 3ky a) + 4cos( 3 3 ky a)cos( kx a) 2 2 (7) (6)

Tight-Binding model for Graphene

Tight-Binding model is a quantum mechanical model used to describe the properties of electrons tightly bound to the atom they belong to and these are assumed to have weak interaction with states and potentials on surrounding atoms of the solid. As a result the wave function of the electron will be rather similar to the atomic orbital of the free atom it belongs to. The energy of the electron will also be rather close to the ionization energy of the electron in the free atom or ion because the interaction with potentials and states on neighboring atoms is limited. In this model, the calculation of electronic band structure is through an approximate set of wave functions for isolated atoms located at each atomic site. In general sense the model is so related to the LCAO method. In graphene, each carbon atom forms a double bond with each of its three nearest neighbors. since carbon is quadravalent atom, this leaves an electron 3

per each carbon atom which is not used to form these double bonds. This extra valence electron occupies a band formed by pz orbitals which is 2p orbitals on each carbon which point out of the page. The crystal Hamiltonian H, in the case of TB, is written as H = Hat + U (r) (8)

where Hat is the Hamiltonian of a single atom located at the lattice point and U (r) is the term that contains all correction to the atomic potential required to produce the full periodic potential of the crystal. In order to build a Tight-Binding description of graphene, let us consider Block states of the form k (r) =
R

(c1 (r r d1 ) + c2 (r R d2 ))eik.R

(9)

Here (r R ds ) is normalized the atomic pz orbital associated with the carbon at the R + ds for s = 1, 2. The coecients c1 and c2 can be illuminated through the calculation, we are keeping just for general formulation. For H is the full Hamiltonian for an electron in graphene the time independent Shrdinger o equation becomes Hk = k (10) By taking the inner product of both sides of the Shrdinger equation with states o (r d1 ) and (r d2 ) one can obtain the following system of equations,
R

(c1 12 (R) + c2 12 (R))eik.R (c1 21 (R) + c2 22 (R))eik.R

R

=
R

(c1 11 (R) + c2 12 (R))eik.R (c1 21 (R) + c2 22 (R))eik.R

R

(11)

where ss ss = =

d3 (r ds )H(r ds ) d3 (r ds )H(r ds )

(12)

An approximation can be made to the and integrals. For the , since the overlap of pz orbitals on neighboring lattice sites is small we can express the approximation as ss (R) ss R,0 (13)

Following the same reasoning, for R = 0 and s = s the approximation to the takes the form 11 (0) = 22 0 p (14)

where p is the energy of an atomic pz orbital. For the other ss (R) one needs only to keep those matrix elements of H between pz orbitals on nearest neighbor carbon atoms. Furthermore, all the matrix elements will have the same value denoted by t. Eventually, the coupled equation 10 can be rewritten as
p c1 t(1 + 2e 3Ky 2 cos kx a )c2 2 a t(1 + 2e 3Ky 2 cos kx a )c2 + c1 2

= =

c1 c2

(15)

and solving this eigenvalue problem results in the energy dispersion relation of the conduction and valence band which is given by (k) = p t 1 + 4 cos2 kx a kx a + 4 cos cos 2 2 3ky a 2 (16)

Making the rst term zero point energy and considering that t = 0, this equation is precisely equivalent to the the energy dispersion relation of Eq. 6(this is used for the project work).

Monkhorst-Pack way
Consider a lattice dened by the primitive transilation vectors a1 , a2 , a3 . A general lattice point is given by R = R1 a 1 + R2 a 2 + R3 a 3 where R1 R3 are integers. The associated primitive reciprocal-lattice vectors are given by
b1 = 2 2 2 a 2 a 3 b2 = a 3 a 1 b3 = a1 a2 (18)

(17)

is the unit cell volume, and b1 b3 span the reciprocal lattice with BZ 3 volume 8 . For a sequence of numbers ur = (2r q 1)/2q (r = 1, 2, 3, ...., q) (19)

where q is an integer that determines the number os special points in the set. With the above ur s we now dene kprs = up b1 + ur b2 + us b3 This gives q 3 distinct points uniformly spaced in the BZ. (20)

Results and Discussion

For graphene, using the relation in the Eq. 1 and Eq. 2, together with Eq. 20 one obtains 2 3 2 (up + ur ) ky = (up ur ) (21) kx = 3a 3a This way one can generate a M M in the reciprocal cell, in the MonkhorstPack way. For any chosen grid, an histgram of N (), the number of states with energy lower than
2 M2

N () = 2
n=1 m=1

( nkm ).

(22)