Handout 11

Energy Bands in Graphene: Tight Binding and the

Nearly Free Electron Approach

In this lecture you will learn: Energy

• The tight binding method (contd…)

• The π-bands in graphene

FBZ

ECE 407 – Spring 2009 – Farhan Rana – Cornell University

Graphene and Carbon Nanotubes: Basics

y a = 2.46 A
3a
• Graphene is a two dimensional
single atomic layer of carbon a
atoms arranged in a Honeycomb a
lattice (which is not a Bravais
lattice)
A B x
• The underlying Bravais lattice is v
a1
shown by the location of the black
dots and is a hexagonal lattice v
a2
• There are two carbon atoms per
primitive cell, A and B (shown in v ⎛ 3 1 ⎞ v ⎛ 3 1 ⎞
a1 = ⎜⎜ xˆ + yˆ ⎟⎟ a a2 = ⎜⎜ xˆ − yˆ ⎟⎟ a
blue and red colors, respectively) ⎝ 2 2 ⎠ ⎝ 2 2 ⎠

• Graphene can be rolled into

tubes that are called carbon
nanotubes (CNTs)

CNT CNT

ECE 407 – Spring 2009 – Farhan Rana – Cornell University

1
 Graphene: Sp2 Hybridization
Sp2 hybridization in carbon: y

r 1 r 1 r 1 r
ϕ1(r ) = φ2 s (r ) + φ2 px (r ) + φ2 py (r ) x
3 6 2
r 1 r 1 r 1 r
ϕ 2 (r ) = φ2 s (r ) + φ2 px (r ) − φ2 py (r )
3 6 2
r 1 r 2 r
ϕ 3 (r ) = φ2 s (r ) − φ2 px (r )
3 3

• All carbon atoms are all sp2 hybridized (one 2s orbital together with the 2px and
the 2py orbitals generate three sp2 orbitals)

• All sp2 orbitals form σ-bonds with the sp2 orbitals of the neigboring carbon atoms

• The bonding orbital associated with each σ-bond is occupied by two electrons
(spin-up and spin-down)

• There is one electron per carbon atom left in the 2pz orbital

ECE 407 – Spring 2009 – Farhan Rana – Cornell University

Graphene: 2pz orbitals

y

π-bonding:

• Each carbon atom contributes one

2pz-orbital that participates in x
bonding

⇒ Each primitive cell contributes

two 2pz-orbitals that participate in
bonding

• The 2pz orbital stick out of the plane of the chain and form π-bonds with
neigboring 2pz orbitals

• The π-bonding results in energy bands (π-bands) that we will study via tight
binding

ECE 407 – Spring 2009 – Farhan Rana – Cornell University

2
 Graphene: Some Useful Vectors
y
Basis vectors: 3a a = 2.46 A

y a
r r a
d1 d 2 x
A B A B x
r a r a v
d1 = − xˆ d2 = xˆ a1
2 3 2 3
v
a2
Nearest neighbor vectors:

r a
n1 = xˆ
r r 3
n2 n1
r a ⎛ 1 3 ⎞ These will be useful for
n2 = ⎜ − xˆ + yˆ ⎟
3 ⎜⎝ 2 2 ⎟⎠
rA B
n3 writing the final solution
in a compact form
r a ⎛ 1 3 ⎞
n3 = ⎜ − xˆ − yˆ ⎟
3 ⎜⎝ 2 2 ⎟⎠

ECE 407 – Spring 2009 – Farhan Rana – Cornell University

Graphene: Tight Binding Solution

y a = 2.46 A
• Each basis atom contributes one 2pz-orbital that 3a
participates in bonding

⇒ Each primitive cell contributes two 2pz-orbitals x

that participate in bonding A B

r r a
φ pzA (r ) ↔ Ep φ pzB (r ) ↔ Ep
a

One can thenr write the trial tight-binding solution for

wavevector k as:

r r
r
ψ kv (r ) = ∑
m
e i k . Rm
N
[
r r r
() r r r
(
r r r
) r r r
c pzA k e ik . d 1φ pzA r − Rm − d1 + c pzB k e ik . d 2 φ pzB r − Rm − d 2 () ( )]

ECE 407 – Spring 2009 – Farhan Rana – Cornell University

3
 Graphene: Tight Binding Solution
y a = 2.46 A
Plug the solution into the Schrodinger equation: 3a

()
r r r
Hˆ ψ kr (r ) = E k ψ kr (r )
x
And then, one by one, multiply by from the left by A B
the bra’s corresponding to every orbital in one a
primitive cell to generate as many equations as the
number of orbitals per primitive cell
a
Step 1:
r
Multiply the equation with φ pzA (r ) and:
• keep the energy matrix elements for orbitals that are nearest neighbors, and
• assume that the orbitals on different atoms are orthogonal

( )
r r r r r r
() ()
v v r r
E p c pzA (k ) − Vppπ e i k . n1 + e i k . n2 + e i k . n3 c pzB (k ) = E k c pzA k

Notice that the final result can be written in

terms of the nearest neighbor vectors

ECE 407 – Spring 2009 – Farhan Rana – Cornell University

Graphene: Tight Binding Solution

y a = 2.46 A

3a

Step 2: x
r
Multiply the equation with φ pzB (r ) and: A B
• keep the energy matrix elements for orbitals that are a
nearest neighbors, and
• assume that the orbitals on different atoms are
orthogonal a

( )
r r r r r r
() ()
v v r r
E p c pzB (k ) − Vppπ e − i k . n1 + e − i k . n2 + e − i k . n3 c pzA (k ) = E k c pzB k

Notice that the final result can be written in

terms of the nearest neighbor vectors

ECE 407 – Spring 2009 – Farhan Rana – Cornell University

4
 Graphene: Tight Binding Solution
y a = 2.46 A
Write the equations obtained in a matrix form:
3a

()
r v v
⎡ Ep − Vppπ f k ⎤ ⎡c pzA (k )⎤ r ⎡c pzA (k )⎤
⎢
()
r ⎥ ⎢ v⎥=E k ⎢ v⎥ () x
⎣c pzB (k )⎦ ⎣c pzB (k )⎦
*
⎢⎣ − Vppπ f k Ep ⎥⎦ A B

a
()
r
Where the function f k is:

( ) a
r r r r r r
()
r
f k = e i k .n1 + e i k .n2 + e i k .n3

Solutions are:
() ()
r r
E k = E p ± Vppπ f k

And the corresponding eigenvectors are:

v v
⎡c pzA (k )⎤ 1 ⎡ 1 ⎤ ⎡c pzA (k )⎤ 1 ⎡ r1 r ⎤
() () () ()
⎢ v⎥ = r r ⎥ ⎢ v⎥ =
⎣c pzB (k )⎦ + ⎣c pzB (k )⎦ −
⎢ − f *
k f k ⎢ * ⎥
2⎣ ⎦ 2 ⎣f k f k ⎦

ECE 407 – Spring 2009 – Farhan Rana – Cornell University

Graphene: π-Energy Bands

Energy
ky
() ()
r r
E k = E p ± Vppπ f k
K

K’ K’

Γ M
M
FBZ kx
K K

K’
FBZ

• Bandgaps open at the M-points between the first and the second bands

• No bandgaps open at the K-points and the K’-points

• In the homeworks you showed (using nearly free electron approach) that bandgaps
can open at the K-points (or K’-points) if the inversion symmetry is broken

ECE 407 – Spring 2009 – Farhan Rana – Cornell University

5
 Graphene: π-Energy Bands

• Since graphene has two

electrons per primitive cell
contributing to π-bonding, the
lower π-band will be
completely filled at T ≈ 0K
3Vppπ
• The location of Fermi level
near T ≈ 0K is shown by the
dashed curve

In generating the plots I chose energy zero such that:

Ep = 0
And for graphene:
Vppπ = 3.0 eV

ECE 407 – Spring 2009 – Farhan Rana – Cornell University

Graphene: A Comparison of NFEA and TB

Scale normalized
2
h2 ⎛ 1 ⎞
to : ⎜ ⎟
2m ⎝ a ⎠
and offset by Vo

To compare the nearly free electron approach (NFEA) to tight-binding (TB) I assumed
the DC potential in NFEA to be:
Vo = E p − 3Vppπ
And in graphene:
Vppπ = 3.0 eV
ECE 407 – Spring 2009 – Farhan Rana – Cornell University