Paolo ALLIA

Politecnico di Torino
DISAT

SOLID STATE PHYSICS 04

Atomic and Band Structure of Graphene

(mostly a graphic support)

Paolo Allia - SOLID STATE PHYSICS

Explicit calculations for graphene band structures are done using blackboard & chalk.
Here, some images are given as a visual support and some results are highlighted as
a memo.

Paolo Allia - SOLID STATE PHYSICS

Graphene unit cell

is a lozenge of side
31/2a
B
A

There are 2 atoms

per unit cell.
We call them A , B.

Paolo Allia - SOLID STATE PHYSICS

Each A atom has:

A
A

- 3 nearest neighbors
at a distance a from
A; these are all B
atoms

Paolo Allia - SOLID STATE PHYSICS

Each A atom has:

A
A

Paolo Allia - SOLID STATE PHYSICS

- 3 nearest neighbors
at a distance a from
A; these are all B
atoms
- 6 next-nearest
neighbors at a
distance 31/2a from
A : these are all A
atoms

A
A

Paolo Allia - SOLID STATE PHYSICS

The reference
atom is one of
the A atoms in
(0,0)

AIV
AV

A
B
B

AVI

Paolo Allia - SOLID STATE PHYSICS

The reference
atom is one of
the A atoms in
(0,0)

Co-ordinates of the
three n.n. B atoms:

AIV
AV

A
B
B

B: (a,0)

AVI

B: (-a/2,3a/2)
x

B: (-a/2,-3a/2)

Paolo Allia - SOLID STATE PHYSICS

The reference
atom is one of
the A atoms in
(0,0)

Co-ordinates of the
six n.n.n. A atoms:

AIV
AV

A
B
B

A: (3a/2,3a/2)

AVI

A : (0,-3a)
x

A: (-3a/2,-3a/2)
AIV: (0,3a)
AV: (-3a/2,3a/2)

AVI: (3a/2,-3a/2)
Paolo Allia - SOLID STATE PHYSICS

Sketchy representation of pz orbitals

in-plane px,y orbitals determine the structure of the layer (covalent bonds)
pz orbitals are out of plane (greenish electronic clouds in the above figure)
There is one electron per pz orbital (each orbital can host up to two
electrons)
Paolo Allia - SOLID STATE PHYSICS

10

Sketchy representation of pz orbitals

Hopping mechanism of in-plane electronic conduction

Paolo Allia - SOLID STATE PHYSICS

11

Energy bands of two-dimensional graphite

E H '11 | H '12 |

H '11 ?

Paolo Allia - SOLID STATE PHYSICS

| H '12 |2 ?

12

Energy bands of two-dimensional graphite

E H '11 | H '12 |

H '11 E0 '0 f (k )

| H '12 |2 02 3 f (k )

k kxi k y j

linear momentum of electrons

moving in the xy plane

3
3
f (k ) 2cos 3ak y 2 cos ak y cos
ak x
2
2

Paolo Allia - SOLID STATE PHYSICS

13

Energy bands of two-dimensional graphite

0 X * (r rA ) H X (r rB )d 0
0 / h: hopping rate for A B hopping
of electrons ( 3 n.n. of A)

'0 X * (r rA ) H X (r rA' )d 0

A
A

0 / h: hopping rate for A A hopping

of electrons (6 n.n.n. of A)

Paolo Allia - SOLID STATE PHYSICS

B
A

14

Band structure of two-dimensional graphite

(graphene)

E (k ) E0 0 3 f k '0 f k
E0 0

1 0 = 0

(i.e, A-B hopping only; no A-A hopping)

Paolo Allia - SOLID STATE PHYSICS

B
A

15

Paolo Allia - SOLID STATE PHYSICS

16

Paolo Allia - SOLID STATE PHYSICS

17

Paolo Allia - SOLID STATE PHYSICS

18

Paolo Allia - SOLID STATE PHYSICS

19

This is the colour map of the lower band. Blue: lower energy; red: higher energy.
The vertexes of the cones are the red spots in the reciprocal plane of graphene.

4
3
2

0
-0.3542
-0.7083
-1.062
-1.417
-1.771
-2.125
-2.479
-2.833
-3.187
-3.542
-3.896
-4.250
-4.604
-4.958
-5.312
-5.667
-6.021
-6.375
-6.729
-7.083
-7.438
-7.792
-8.146
-8.500

kya

1
0
-1
-2
-3
-4
-4

-3

-2

-1

Kxa
Paolo Allia - SOLID STATE PHYSICS

20

A standard shape of electron energy bands near to a band edge: parabolic

dependence, bandgap in between

Paolo Allia - SOLID STATE PHYSICS

21

Around any of the touching (Dirac)points

Paolo Allia - SOLID STATE PHYSICS

22

Paolo Allia - SOLID STATE PHYSICS

23

Paolo Allia - SOLID STATE PHYSICS

24

Paolo Allia - SOLID STATE PHYSICS

25

Paolo Allia - SOLID STATE PHYSICS

26

Paolo Allia - SOLID STATE PHYSICS

27

Paolo Allia - SOLID STATE PHYSICS

28

 2 2
KD
,
5 others
3a 3 3a
E0 0

KD is any of the
the positions of
the cone vertexes
in the reciprocal
plane
4
3
2
1

kya

3 0 a
E (q)
| q | vF | q |
2
q k KD

0
-1
-2
-3
-4
-4

-3

-2

-1

Kxa

Velocity of electrons moving with wavevectors around KD :

3 0 a
1 E
E
v

|q| |q|
2
independent of: a) electron energy; b) magnitude and direction of
linear momentum (most unusual for electrons in solids).
This is basically the Fermi velocity of electrons in graphene (the energy of the Dirac
point is the Fermi energy of undoped graphene)
Paolo Allia - SOLID STATE PHYSICS

29

Band structure of two-dimensional graphite

(graphene)

E (k ) E0 0 3 f k '0 f k
E0 0

1 0 0

(i.e, both A-B and A-A hopping allowed)

0 = - 0.2 0
Paolo Allia - SOLID STATE PHYSICS

B
A

30

Paolo Allia - SOLID STATE PHYSICS

31

Paolo Allia - SOLID STATE PHYSICS

32

Paolo Allia - SOLID STATE PHYSICS

33

Paolo Allia - SOLID STATE PHYSICS

34

Around any of the touching (Dirac)points

Paolo Allia - SOLID STATE PHYSICS

35

Paolo Allia - SOLID STATE PHYSICS

36

Paolo Allia - SOLID STATE PHYSICS

37

Paolo Allia - SOLID STATE PHYSICS

38

Paolo Allia - SOLID STATE PHYSICS

39

Paolo Allia - SOLID STATE PHYSICS

40

Paolo Allia - SOLID STATE PHYSICS

41

3 0 a
E (q) 3 '0
|q|
2
q k KD
2 2
KD
,
5 others
3a 3 3a
E0 0
Velocity of electrons moving with wavevectors around KD :

3 a
1 E
0
|q|
2

Same definitions and properties as in the case 0 = 0.

Paolo Allia - SOLID STATE PHYSICS

42

 In intrinsic (undoped) graphene the Fermi level is exactly at the

connection points (vertexes) of the cones.
The density of states of the material is zero at the Fermi level;
therefore the conductivity of intrinsic graphene is rather low.
However, the Fermi level can be changed by an electric field:
depending on the applied polarity the material becomes either
electrically n-doped (electrons populate the conduction band
above the Dirac points) or electrically p-doped (electrons populate
the valence band without reaching the vertex of the cone so there
are holes left in the valence band).

Paolo Allia - SOLID STATE PHYSICS

43

 The conductivity for electrically doped graphene is expected to be

high; at room temperature it may be higher than that of copper.

Electrical
resistance of
graphene as a
function of bias

Paolo Allia - SOLID STATE PHYSICS

44

 Close to the Fermi level the dispersion relation for electrons (and holes) is
linear.

This is analogous to what happen for massless photons in vacuum, where

E= (h/2)ck. A linear dispersion relation between E and k is the hallmark of
a massless quantum particle.
This applies for electrons in graphene as well, when q is small (k close to
any KD [Dirac point] ). The usual expression for the effective mass, which would imply in
this case an infinite (instead of zero) effective mass, cannot be applied because it implicitly
assumes a parabolic band dispersion - which is not the case here.

The expression describing excitations in graphene is formally identical to

the Dirac equation for massless fermions which move at a constant speed.
This is why the connection points (vertexes) of the cones are called Dirac
points. This gives way to interesting analogies between graphene and
particle physics.

Paolo Allia - SOLID STATE PHYSICS

45