Electronic structure of graphene

Graphene Monolayer
Graphene Bilayer
Title
Electronic Structure of Graphene
Oct 11, 2006
Hongki Min
Electronic structure of graphene
1. Introduction
2. Tight-binding Methods
3. Low Energy Effective Model
4. Ab initio Calculations
5. Graphene Bilayer
Outline
Electronic structure of graphene
1. Introduction
1) Carbon
2s, 2p
x
, 2p
y
and 2p
z
orbitals can mix with each other.
Example
sp
3
sp
3

*
sp
2
sp
2

*
p
z
p
z

*
s p
x
+p
y
sp
2
p
z
,
insulator metal
diamond : sp
3
graphite : sp
2
+p
z
s p
x
+p
y
+p
z
sp
3
(
6
C=1s
2
2s
2
2p
2
, group IV)
Electronic structure of graphene
1. Introduction
2) Graphene
Graphene is a two-dimensional honeycomb lattice of
carbon atoms.
The energy bands of graphene at low energies are
described by a 2D Dirac-like equation with linear
dispersion near K/K in k space.
I
K
K
'
M
k space
K
E
energy dispersion
1
a

2
a

A
B
real space
A 42 . 1 =
c c
a
Electronic structure of graphene
1. Introduction
3) Extraordinary properties of graphene
Dirac-like linear dispersion at low energies
Half-quantized quantum Hall effect
Quantum spin Hall effect
Excellent mechanical and electronic properties
|
.
|

\
|
+ =
2
1 4
2
n
h
e
xy
o
(n=0,1,)
Two-dimensional relativistic electronic system
A bulk gap with gapless spin filtered edge states
Future spintronic devices
Kane and Mele,
PRL 95, 226801 (2005)
Novoselov et al.
Nature 438, 197 (2005)
Electronic structure of graphene
2. Tight-binding Model
1) Simple tight-binding example
Consider a chain composed of two kinds of atoms.
(
(
(
(

|
.
|

\
|
|
.
|

\
|
=
B
A
t
ka
t
ka
t t
H
2
cos 2
2
cos 2
a
A B A B
t t t
A
t
B
0 = =
B A
t t
Electronic structure of graphene
2. Tight-binding Model
2) Tight-binding model with s and p orbitals
Hopping between two orbitals depends on the direction.
Example
Hamiltonian and overlap matrices can be constructed
using a few set of parameters such as
. , , t o o pp pp sp
n n n
] [n p p
z x
) ( t pp n n
z x
) ( o pp n n
z x
=

Electronic structure of graphene
2. Tight-binding Model
3) Band structure
Tight-binding model with nonorthogonal orbitals
decoupled to
sp
2
+ p
z
: sp
2
: p
z
*
,o o
*
, t t
I
K
K '
M
Electronic structure of graphene
3. Low Energy Effective Model
1) Generalized Haldane model
Kane and Mele, PRL 95, 146802 (2005)

> <
+
>> <<
+
> <
+
+ + =
j i
j z ij i R
j i
j z i ij
j i
j i
c d s c it c s c it c c t H
, ,
2
,
) (

v
band intrinsic spin-orbit Rashba spin-orbit

ij
=+1
ij
=-1
) (
) 2 (
s p z H
DEG
R

=
o
: creation/annihilation for orbitals at i
: Pauli matrices for spin
: unit vector along i and j
i i
c c ,
+
s

ij
d

Electronic structure of graphene

3. Low Energy Effective Model
1) Generalized Haldane model
Expand the tight-binding model near K/K
for A, B
for K, K
for ,
1 =
z
o
1 =
z
t
1 =
z
s
) ( ) (
x y y z x R z z z SO y y x z x F eff
s s s k k v H o t o t o o t o + + + =
Kane and Mele,
PRL 95, 226801 (2005)
(Dirac-like term) + (effective spin-orbit interactions)
2
3 3 t
SO
=
t
a
v
F
2
3
=

R R
t
2
3
=
, ,
Dirac-like intrinsic Rashba spin-orbit
Electronic structure of graphene
3. Low Energy Effective Model
2) Perturbation theory
Atomic spin-orbit interactions
are approximated by a local
atomic contribution.
External gate electric fields
are approximated by a local
atomic Stark-effect term.

=
i
i i SO
S L H

=
i
i EF
z eE H
What is the low energy effective model at K
and K in the presence of atomic spin-orbit
interactions and external gate electric fields?
Electronic structure of graphene
2) Perturbation theory
Treat spin-orbit and electric fields as a perturbation.
E=0 eigenstates are fourfold degenerate at K/K.
Second-order degenerate perturbation theory
H H H
band
A + =
EF SO
H H H + = A
3. Low Energy Effective Model

e

A A
=
D l
l D
mn
E E
n H l l H m
H
) 0 (
) 0 ( ) 0 ( ) 0 ( ) 0 (
) 2 (
D :
| z
p A,
+ z
p A,
| z
p B ,
+ z
p B ,
, , ,
) , ( D n m e
Electronic structure of graphene
3. Low Energy Effective Model
2) Perturbation theory
Effective Hamiltonian at K/K
Intrinsic and Rashba spin-orbit coupling constants
Energy gap opens when
2
2
) ( 18

o

sp
s
SO
=

o

) ( 3
0
sp
eEz
R
=
) (
x y y z x R z z z SO SO eff
s s s H o t o t o + + =
for A, B
for K, K
for ,
1 =
z
o
1 =
z
t
1 =
z
s
K 01 . 0 ) ( 2 s =
R SO gap
E
R SO
>
Min et al. PRB 74, 165310 (2006)
Electronic structure of graphene
1) Density functional theory
4. Ab initio Calculations
| | | |
i i i xc ion
n V x d
x x
x n e
n V
m
| c | =
|
|
.
|

\
|
+
'
'

'
+ + V
}

) (
2
2
2
2

) 2 ( ) 2 ( ) 1 ( ) 1 (
| | n n
Self-consistent method :
| | n V
eff
Mapping of the interacting many-electron system
onto a system of non-interacting electrons moving
in an effective potential due to all the other electrons
Kohn and Sham,
Phys.Rev.140, A1133 (1965)
xc
V
: exchange-correlation potential

e
=
occ i
i
x x n
2
) ( ) (

|
,
Electronic structure of graphene
4. Ab initio Calculations
2) Band structure
Ab initio density functional calculations with spin-orbit
interactions
: atomic carbon
spin-orbit strength
0

Energy gap
opens when 0
I
K
K '
M
Electronic structure of graphene
4. Ab initio Calculations
3) Energy gap as a function of spin-orbit interactions
Increase spin-orbit coupling
by decreasing the speed of
light.
Energy gaps from ab initio,
tight-binding and perturbation
theory are consistent.
Min et al. PRB 74, 165310 (2006)
2
2
0
) ( 9
2
o

sp
s
E
SO gap
R
= =
=
0 =
R

Electronic structure of graphene

5. Graphene Bilayer
1) Graphene Bilayer
Graphene bilayer is composed of a pair
of coupled graphene monolayers.
A band gap opens if on-site energy
difference U between two layers is non-zero.
U can be controlled by doping or external electric fields.
U=0
E
K
U 0
K
E
E
gap
=U
A
B A
B
A 42 . 1 =
c c
a
A 35 . 3 = d
bottom
top
d
Electronic structure of graphene
5. Graphene Bilayer
2) Controlling the band structure of graphene bilayer
Angle-resolved photoemission spectroscopy (ARPES)
Change U by doping.
Ohta et al. Science 313, 951 (2006)
ARPES tight-binding
Electronic structure of graphene
5. Graphene Bilayer
2) Controlling the band structure of graphene bilayer
Ab initio density functional calculations
Change U by applying external electric fields,
V
ext
=0 , E
gap
=0 V
ext
=0.4 eV, E
gap
=0.17 eV
V
ext
=eEd.
switch semimetal-insulator transition
Electronic structure of graphene
Summary
In graphene monolayer, the energy
bands at low energies are described by
a 2D Dirac-like equation with linear
dispersion. Atomic spin-orbit interactions
open a band gap quadratically.
In graphene bilayer, the band structure
can be controlled by on-site energy
difference U between two layers.
K
E
K
E
E
gap
=U