School of Electrical and Computer Engineering

Tuo-Hung Hou
A Density Functional Theory Study
of Schottky Barriers
at Metal-nanotube Contacts

Symposium on Quantum Mechanical Models of Materials
Outlines
Introduction
Whats carbon nanotube (CNT)?
Whats Schottky barrier ?
Whats DFT?
DFT simulation on (8,0) carbon nanotube
DFT simulation on CNT/Pd and CNT/Au contacts
Summary
Carbon Nanotube
Discovered by Dr. Sumio Iijima in NEC in 1991
Extraordinary properties:
1. Self-assemble nanostructure. (diameter 1 nm / aspect ratio as high as 10
7
)
2. 1-D carrier transport. Reduced scattering. Very high mobility (100x faster
than silicon)
3. Sustain current density as high as 10
9
A/cm
2
. (100x higher than copper)
4. Stiffer and stronger than steel.
Proc. IEEE, vol.91, p.1772, 2003
Carbon Nanotube
Graphene: a layer of graphite
(10,10) CNT
(20, 0) CNT
Chirality vector
C= na
1
+ ma
2

Proc. IEEE, vol.91, p.1772, 2003
semiconducting
metallic
Graphere: 2DEG (3,3) CNT: 1DEG
(4,2) CNT: 1DEG
Work Function & Schottky Barrier
Work Function:
Minimal energy necessary to extract an
electron from the metal
W = V
e
- E
F
Schottky Barrier:
The barrier formed at the metal-
semiconductor interface
u
BP
= E
F
E
v
; u
BN
= E
c
- E
F

vacuum
E
v
E
c
E
F
M S
e
|
BN
E
v
E
c
E
F
M S
e
|
BP
E
F
M M
e
Carbon Nanotube Field Effect Transistor
Bottleneck step of charge transport
The Schottky barrier at metal/ CNT interface determines the performance
of CNTFET.
S D
Back Gate
CNT
Proc. IEEE, vol.91, p.1772, 2003
A Closer Look of Schottky Barrier
E
v
E
c
E
F
E
vac
E
vac
M S
W
E
v
E
c
E
F
E
vac
E
vac
M S
No charge transfer
charge transfer
E
v
E
c
E
F
E
vac
E
vac
M S
- +
charge transfer &
finite separation
E
v
E
c
E
F
E
vac
E
vac
M S
- +
Ab-Initio Calculation of Schottky Barrier
Schottky barrier height u
BP

w/o interfacial interaction
= [E
F
]
metal
[ E
V
]
CNT

w/i interfacial interaction
= [E
F
<V>]
metal
[ E
V
-<V>]
CNT
+ [<V>
metal
- <V>
CNT
]
IF
E
F
E
V
E
F
E
V
[E
F
<V>]
metal
[E
V
<V>]
CNT
[<V>
metal
- <V>
CNT
]
IF
_
+
DFT takes into account the interfacial
interactions (dipole formation, geometry
relaxation etc. ) in first-principle. Thus, it
is very accurate in calculating Schottky
barriers heights.
J. Vc. Sci. Tech. A, vol.11, p.848, 1993
Brief Review of DFT
Density Functional Theory (DFT):
Describing electrons in a many-body system using the density instead of the
many-body wave function. It dramatically reduces the dimension of freedom
from 3N for N electrons to just 3.
1
st
Hohenberg-Kohn Theorem:
A one-to-one mapping exists between the ground-state charge density and
the ground-state many-body wavefunction.
2
nd
Hohenberg-Kohn Theorem:
There is a variational principle so that

So we can continuously refine the charge density to find the ground-state
energy.

0
) ( ) ( )] ( [ )] ( [ )] ( [ E dr r r v r E r T r E
ext e e
> + + =
}

Brief Review of DFT
0
) ( ) ( )] ( [ )] ( [ )] ( [ E dr r r v r E r T r E
ext e e
> + + =
}

Kohn-Sham Equation & Energy Minimization:


0 2 1
2 1
2 1
1
2 *
) ( ) ( )] ( [
) ( ) (
2
1
) ( ) (
2
1
)] ( [ E r d r r v r E r d r d
r r
r r
r d r r r E
ext xc
n
i
i i
> + +

+ V =
} }}

}
=







Plane Wave Basis Pseudopotential LDA
Errors:
1. LDA
2. Pseudopotential approximation
3. Energy cutoff of plane wave basis
4. K-point selection for BZ sampling
5. Finite unit cell size
Carbon Nanotube Unit Cell
(8, 0) CNT
Carbon nanotube 3-D coordinates: generated by the wrapping program.
Unit cell: A hexagonal close-pack lattice with larger enough separation
between tubes. Periodic in the z direction.
X
Y
Cross section the
hexagonal unit cell
a
Convergence
Plane wave energy cutoff Unit cell size
20 25 30 35 40 45
2.0x10
-4
4.0x10
-4
6.0x10
-4
8.0x10
-4
E
n
e
r
g
y

C
o
n
v
e
r
g
e
n
c
e


[

R
y
d

]


Energy Cutoff [Ryd]
Below 1 meV
Z
0
= 4.26
a = 22 Bohr
** Energy difference between a unrelaxed
and a relaxed structure.
Ecutoff = 40 Ryd
relaxed structure
4.18 4.20 4.22 4.24 4.26 4.28
-365.196
-365.194
-365.192
-365.190
-365.188
-365.186
a = 22 Bohr
a = 27 Bohr
T
o
t
a
l

E
n
e
r
g
y


[

R
y
d

]


Z
0
[]
Energy cutoff 40 Ryd, unit cell distance 22 Bohr and 11 special k-points along
the z direction are found to give good convergence.
Geometry Optimization of CNT
Z
Y
Z
0
= 4.221
4.18 4.20 4.22 4.24 4.26 4.28 4.30
-365.196
-365.194
-365.192
-365.190
-365.188
-365.186
-365.184
-365.182
-365.180
-365.178
T
o
t
a
l

E
n
e
r
g
y


[

R
y
d

]


Z
0
[]
Min. 4.221
(8, 0) CNT
X
Y
D = 6.29

Geometry optimization in the XY plane was carried
out for each Z
0
to find the most stable structure.
(Force < 20 meV/ in X,Y,Z directions)
Unrelaxed structure from the graphene sheet:
Z
0
= 4.26 , D = 6.26
Ecutoff = 40 Ryd
a = 22 Bohr
Band Structure of CNT
X
(8, 0) CNT
(8,0) CNT is semiconducting with E
G
0.6 eV, agreed with the value reported
by Blase etc. ( 0.62 eV by LDA, Phys. Rev. Lett. 72, 1878 (1994) )
E
G
= 0.6 eV
Work Function of CNT
VASP, Shan and Cho, Phys. Rev.
Lett. 94, 236602 (2005)
The potential and charge density are averaged over the z direction.
X
Y
Charge Density
High density
Potential
low potential
A A A A
A A
Total potential V = V
Ion
+ V
H-F
+ V
xc
Important!! Unit is Ry not eV
-10 -5 0 5 10
-10
-8
-6
-4
-2
0
2
4
WF
4.7eV
C
h
a
r
g
e

D
e
n
s
i
t
y


[

B
o
h
r
-
3

]
C
E
F
C
T
o
t
a
l

P
o
t
e
n
t
i
a
l


[

e
V

]


X []
1x10
-7
1x10
-5
1x10
-3
1x10
-1
1x10
1
Metal/Nanotube Contact Unit Cell
X
Y
Cross section the tetragonal unit cell
a
b
Z
Y
X
Y
The initial structure has a relaxed (8,0) CNT on top of (100) surface of a two
or three atomic-layer metal slab. The lattice parameters of metals are first
calculated from the bulk (Pd 3.88 , Au 4.05). The tensile strain is applied
on metal at the z direction to match the lattice constant of CNT. The strains
at x y directions are calculated by the Poisson ratio.
Geometry Optimization of Contact
u
0 5 10 15 20 25 30 35 40 45
-1122.94
-1122.93
-1122.92
-1122.91
-1122.90
-1122.89
-1122.88
-1122.87
T
o
t
a
l

E
n
e
r
g
y


[

R
y
d

]


u[
o
]
z
d = 2.0
z = 0
-0.5 0.0 0.5 1.0 1.5 2.0 2.5
-1122.97
-1122.96
-1122.95
-1122.94
-1122.93
-1122.92
-1122.91
-1122.90
-1122.89
-1122.88
T
o
t
a
l

E
n
e
r
g
y


[

R
y
d

]


Z []
Major degrees of freedom are first sampled before full ab-initio optimization
to avoid trapping at local minima.
Rotational Angel Translational Distance
d = 2.0
u = 0
o
Binding Energy
E
Binding
= E
CNT
+ E
Metal
E
CNT/Metal
Total Energy (Ryd) Pd Au
(8,0) CNT -365.1943 -365.1943
Metal slab -757.5965 -667.9404
CNT/Metal -1122.9598 -1033.1867
Binding Energy (meV) 12.4285 3.8194
The equilibrium interfacial distance between CNT and Pd is smaller
than CNT and Au with stronger binding energy.
1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0
-1123.00
-1122.95
-1122.90
-1122.85
-1122.80
-1122.75
-1122.70
-1122.65
-1122.60
Au
Pd
T
o
t
a
l

E
n
e
r
g
y


[

R
y
d

]


d []
-1033.40
-1033.35
-1033.30
-1033.25
-1033.20
-1033.15
-1033.10
-1033.05
-1033.00
d
Interfacial Distance
z = 0
u = 0
o
Full ab-initio Optimization
Step1
Z
Y
X
Y
Step25
fixed
Energy = -1502.0944 rdy
Energy = -1502.1555 rdy
All force < 0.02 eV/
CNT/Pd
Potential Energy
CNT / Au
CNT / Pd
A
A
A
A
-10 -5 0 5 10
-20
-10
0
10
Pd Pd Pd C C
E
F
T
o
t
a
l

P
o
t
e
n
t
i
a
l


[

e
V

]


Y []
-10 -5 0 5 10
-20
-10
0
10
Au Au Au C C
E
F
T
o
t
a
l

P
o
t
e
n
t
i
a
l


[

e
V

]


Y []
No physical tunneling
barrier existed
between CNT and
either Pd or Au.
Although Au with
larger interfacial
distance does show
an additional bump.
The carrier
transportation across
the interface is then
determined by the
band lineup, i.e.
Schottky barrier.
Charge Density
C
Pd
Less charge density between C / Au due to the additional bump in the potential
profile.
C
Au
CNT / Pd CNT / Au
Charge Transfer
+
+ +
_ _
_
Electron transfers from CNT to Pd and Au. More dipole formation at CNT/Pd is
due to its proximity, but the dipole moment is not necessarily larger (p=Eqd).
_ _ _
+ +
Charge difference = [e]
CNT/Metal
[e]
CNT
[e]
Metal
Schottky Barrier
-10 -5 0 5 10
-80
-70
-60
-50
-40
-30
-20
-10
0
10
-65.2
-65.0
-64.8
-64.6
T
o
t a
l P
o
t e
n
t i a
l [ e
V
]

-3.8
-3.6
-3.4
-3.2
T
o
t a
l P
o
t e
n
t i a
l [ e
V
]


CNT/Au CNT Au
Au Au Au C C
T
o
t
a
l

P
o
t
e
n
t
i
a
l


[

e
V

]


Y []
u
BP
= [E
F
]
metal
[ E
V
]
CNT
w/o interaction

= [E
F
<V>]
metal
[ E
V
-<V>]
CNT

+ [<V>
metal
- <V>
CNT
]
IF
w/i interaction
Pd WF = -4.79 eV; CNT E
V
= -5.01 eV;
w/o interaction AEp = 0.22 eV
w/i interaction AEp = 0.185 eV

Au WF = -5.27 eV; CNT EV= -5.01 eV;
w/o interaction AEp = -0.26 eV
w/i interaction AEp = 0.39 eV

-10 -5 0 5 10
-80
-70
-60
-50
-40
-30
-20
-10
0
10
20
-64.8
-64.6
-64.4
-64.2
T
o
t a
l P
o
t e
n
t i a
l [ e
V
]

4.6
4.8
5.0
5.2
5.4
T
o
t a
l P
o
t e
n
t i a
l [ e
V
]


CNT/Pd CNT Pd
Pd Pd Pd C C
T
o
t
a
l

P
o
t
e
n
t
i
a
l


[

e
V

]


Y []
Summary
1. Review the theory of the ab initio Schottky barrier calculation based on DFT.
The method is applicable for many interfacial problems in nanoscale.
2. Detailed DFT calculations on (8,0) carbon nanotube are performed,
including the geometry optimization, band structure, and work function.
3. Geometry optimization at CNT/metal contacts are carefully examined
though a 2-step process. The major degrees of freedom are first optimized,
and followed by the ab initio relaxation.
4. CNT is more closely bounded to Pd than Au with larger binding energy and
shorter interfacial distance.
5. Although the number of dipoles is larger in CNT/Pd, the total dipole moment,
which is responsible for the potential shift across the interface is larger in
CNT/Au, which therefore shows larger Schottky barrier.
6. Very good quantitative agreement in this study in comparison with previous
works and experimental results.