Introduction to Molecular

Electronics
Lecture 1
 Why Molecular Electronics?
• Low-cost devices (OLED, RF-ID,
chemical sensors etc.)
• Beyond the Moor’s law: more devices
per unit area and not only
• Self-assembly: new old way to
assemble complicated devices
• Complex (designer) logical functions
• Interacting with living organisms: e.g.
linking biological functions and
electronic readout
Conductive organic molecules
“Plastic can indeed, under certain circumstances, be made to behave
very like a metal - a discovery for which Alan J. Heeger, Alan G.
MacDiarmid and Hideki Shirakawa are to receive the Nobel Prize in
Chemistry 2000”.
 Particle in a box
• The technique:
– Solve Schrodinger equation
between the walls (V=0)
– Impose boundary condition at the
walls and find the coefficients

∂
2
Hˆ ψ = Eψ Hˆ = −
2m ∂x 2
k2 2
ψ k = Aeikx + Be − ikx Ek =
2m
ψ k (0, L) = 0

ψ n ( x) = C sin(nπ x / L) n = 1, 2,...
 Particle in a box: example
• Electronic absorption of b-carotene

0.294nm

22 electrons fill states up to n=11

( )
2
h
∆E = E12 − E11 = ( n + 1) − n 2
2

8mL
 Energy bands in solids

Metal Semiconductors

• Metal – Fermi level lies within a band

• Semiconductor (or dielectric) – Fermi level lies in a gap
 p- and n-doped semiconductors

•• n-doped
n-doped
P,
P,As,
As,Sb,
Sb,Bi
Bi

•• p-doped
p-doped
(B,
(B,Al,
Al,Ga,
Ga,In)
In)
Intermediate case: molecules
 Molecular structure
• The Born-Oppenheimer
approximation:
nuclei can be treated as a
stationary
• Valence bond theory:
key concepts: spin pairing, s
and p bonds, hybridization.
• Bonding-Antibonding orbitals
ψ = A(1) B(2) ± A(2) B(1)
Diatomic molecules
Hybridization
 Hydrogen molecule
Antibonding
unbounds more
• Bonding-Antibonding than bonding
bounds!

Bond order – a measure of net bonding in a diatomic molecule:

1
b = (n − n*)
2
The greater the bond order the shorter the bond and the greater the bond strength
 Diatomic molecules
antibonding

bonding

• s-orbitals are built from atomic s-orbitals and pz-orbitals.

• p-orbitals are built from atomic px and py orbitals
Diatomic molecules
 Peierls distortion
• 1D delocalized
system is expected
to be metallic,
lowering energy
however
• Monoatomic metallic
chain will undergo a
metal-insulator
transition at low
temperature;
• period doubling
leads to opening a
gap at p/2
 Peierls distortion
• Peierls transition in
polyacetylene
 Charge-transfer complexes
• Charge transfer compounds are formed by two or more types of neutral
molecules one of which acts as a donor and the other is an electron
acceptor
Mixed stacks: not highly conductive
→ ⎡⎣ D +• ⎤⎦ ⎡⎣ A−• ⎤⎦
D + A ⎯⎯

Segregated stacks:
strong p-overlap results in
delocalizing and high conductivity
 Charge-transfer complexes
• Example: pyrene (10-12 S·m-1)
and iodine (10-7 S·m-1) form a
high conductivity complex with
1 S·m-1.

• Example:
TTF (tetrathiafulvalene) and TCNQ
(tetracyanoquinodimethane)
• 1:1 mixture shows conductivity of
about 5·102 S·m-1 and metallic
behaviour below 54K.
 Doping of organic semiconductors
• As in inorganic semiconductors, impurities can be
added to either transfer an electron to LUMO (p*) or
remove electron from HOMO (p).

→ ⎡⎢( CH ) ( I 3− ) ⎤⎥
3ny
[CH ]n +
y+
I 2 ⎯⎯
2 ⎣ y ⎦n

[ ]n ⎡ ( ) Na + ⎤
y−
CH + nyNa ⎯⎯→ CH
⎣ ⎦n

• Large doping concentration is required 1-50%

• Counter ions are fixed while charge on the polymer
backbone is mobile
 Quantum Mechanical Tunneling
• the wave nature of electrons allows penetration into a
forbidden region of the barrier
• at low voltages (V<<barrier height):

σ = A exp(− Bd )
• at higher voltages the barrier tilt should be taken into
account:

⎡ π CkT ⎤ ⎛ CV ⎞
I = 2I0 ⎢ ⎥ exp( − BV 2
) sinh ⎜ ⎟
⎣ sin(π CkT ) ⎦ ⎝ 2 ⎠
 Variable range hopping
• for disordered materials the charge transfer goes by
a process similar to diffusion as the mean free path is
of the order of interatomic distance
• Mott equation
1/3
1/3for
for2D
2Dand
and½
½for
for1D
1D
⎛ ⎛ T0 ⎞1/ 4 ⎞
σ = σ 0 exp ⎜ − ⎜ ⎟ ⎟
⎜ ⎝T ⎠ ⎟
⎝ ⎠
 Charge-space separation

m
⎛V ⎞
J ∼d⎜ 2 ⎟
⎝d ⎠
 Shottky and Poole-Frenkel effects
• At high applied electric fields (>107 V/m)

⎛ E β 0.5 ⎞
J ∝ exp ⎜ ⎟
⎝ kT ⎠