Microelectronics I

Chapter 3: Introduction to the

Quantum Theory of Solids
Microelectronics I : Introduction to the Quantum Theory of Solids

Chapter 3 (part 1)

1. Formation of allowed and forbidden energy band

Qualitative and quantitative discussion

Kronig-Penney model

k-space diagram
(Energy-wave number diagram)

2. Electrical conduction in solids

Energy band model

Drift current, electron effective mass, concept of hole

Microelectronics I : Introduction to the Quantum Theory of Solids

Isolated single atom (ex; Si)

n=3
3p
n=2
3s
Quantized energy level
electron 2p (quantum state) + n=1
energy 2s

1s

Crystal (~1020 atom)

3p 3p 3p
3s 3s 3s
electron
energy 2p + 2p + …. 2p = ?
2s 2s 2s

1s 1s 1s

x 1020
Microelectronics I : Introduction to the Quantum Theory of Solids

Si Crystal

Tetrahedral structure
Diamond structure

energy
conduction band

Energy gap, Eg=1.1 eV

Valence band

Formation of energy band and energy gap

Microelectronics I : Introduction to the Quantum Theory of Solids

What happen if 2 identical atoms approach each other ?

Isolated atom
atom 1 atom 2

energy r
z
1s

x x
y
1s 1s
Probability density

x
y
1s Distance from center Wave function of two atom electron overlap

interaction
Microelectronics I : Introduction to the Quantum Theory of Solids

atom 1 atom 2

When the atoms are far apart
r
(r=∞), electron from different
atoms can occupy same
energy
energy level.
E1s,atom 1 =E1s, atom 2
1s

As the atoms approach each
r other, energy level splits
a
a ; equilibrium interatomic distance E1s,atom 1 ≠E1s, atom 2

energy
interaction between two overlap wave function
Consistent with Pauli exclusion principle
Microelectronics I : Introduction to the Quantum Theory of Solids

Regular periodic arrangement of atom (crystal)

ex: 1020 atoms

Total number of quantum states
do not change when forming a
energy 1020 energy levels system (crystal)

1s

energy
dense allowed energy levels “energy band”
Microelectronics I : Introduction to the Quantum Theory of Solids

Consider
energy

1 eV

1020 energy state

Energy states are equidistant

Energy states are separated by 1/1020 eV = 10-20 eV

(Almost) continuous energy states within energy band

Microelectronics I : Introduction to the Quantum Theory of Solids

1s

Probability density
energy

2s

2s
1s

Distance from center

atom 1 atom 2

r energy

2s

As the atoms are brought together,
electron from 2s will interact. Then electron “there is no energy level”
from 1s. forbidden band →
1s
energy gap, Eg
a
Microelectronics I : Introduction to the Quantum Theory of Solids

Ex;

Si: 1s(2), 2s(2), 2p(6), 3s(2), 3p (2) 14 electrons

Tightly bound to Involved in

nucleus chemical reactions

energy energy

3p Sp3 hybrid orbital

3s

Reform 4 equivalent states  4 equivalent bond (symmetric)

Microelectronics I : Introduction to the Quantum Theory of Solids

Si
Si Si Si
Si

energy

+ + + +

energy

empty

filled
Microelectronics I : Introduction to the Quantum Theory of Solids

Si crystal (1022 atoms/cm3)

energy energy

conduction band
empty
Energy gap, Eg=1.1 eV
filled
Valence band

4 x 1022 states/cm3
Microelectronics I : Introduction to the Quantum Theory of Solids

Actual band structure “calculated by quantum mechanics”

allowed band

Forbidden band
→band gap, EG

allowed band
Microelectronics I : Introduction to the Quantum Theory of Solids

Quantitative discussion
Determine the relation between energy of electron(E), wave number (k)

Ψ(x,t)= exp ( j(kx-ωt))

Relation of E and k for free electron

E h 2k 2
E =
2m
K-space diagram

Continuous value of E

k
Microelectronics I : Introduction to the Quantum Theory of Solids

E-k diagram for electron in quantum well

2
h2  π  2
E =   n
2m  L 
h 2k 2 π 
E = k =  n
2m L En=3
E
En=2

En=1
x=0 x=L

k
π/L 2π/L

E-k diagram for electron in crystal? The Kronig-Penney Model

Microelectronics I : Introduction to the Quantum Theory of Solids

The Kronig-Penney Model

− e2
V (r ) =
4πε 0 r
+ + + +
Periodic potential

V0

II I II I II I II I II

-b a
Potential tunneling
well L Wave function overlap

Determine a relationship between k, E and V0

Microelectronics I : Introduction to the Quantum Theory of Solids

Schrodinger equation (E < V0)

∂ 2ϕ I ( x) 2mE
Region I + α 2
ϕ I ( x) = 0 α2 =
∂x 2 h2

∂ 2ϕ II ( x) 2m(V0 − E )
Region II − β 2
ϕ II ( x) = 0 β2 =
∂x 2 h2

Potential periodically changes

Bloch theorem
k; wave number [m-1]
V ( x) = V ( x + L)

Wave function ϕ ( x) = U ( x)e jkx Phase of the wave

amplitude U ( x) = U ( x + L)
Microelectronics I : Introduction to the Quantum Theory of Solids

Boundary condition

U I (0) = U II (0) Continuous wave function

U I (a ) = U II (−b)

' '
U I (0) = U II (0)
' ' Continuous first derivative
U I (a ) = U II (−b)
Microelectronics I : Introduction to the Quantum Theory of Solids

From Schrodinger equation, Bloch theorem and boundary condition

β 2 −α 2
sinh( βb) ⋅ sin(αa ) + cosh( βb) ⋅ cos(αa ) = cos(kL)
2αβ

B  0, V0  ∞ Approximation for graphic solution

 mV0ba  sin(αa)
 2  + cos(αa) = cos(ka)
 h  αa
sin(αa) ' mV0ba
P '
+ cos(αa ) = cos(ka) P =
αa h2

Gives relation between k, E(from α) and V0

Microelectronics I : Introduction to the Quantum Theory of Solids

Left side
sin(αa)
f (αa ) = P ' + cos(αa )
αa

Right side
f (αa ) = cos(ka)
Value must be
between -1 and 1

Allowed value of αa
Microelectronics I : Introduction to the Quantum Theory of Solids

2 mE
α2 =
h2
α 2h 2
E=
2m

Plot E-k

Discontinuity of E
Microelectronics I : Introduction to the Quantum Theory of Solids

Right side
f (αa ) = cos(ka) = cos(ka + 2nπ ) = cos(ka = 2nπ )

Shift 2π
Microelectronics I : Introduction to the Quantum Theory of Solids

From the Kronig-Penney Model (1 dimensional periodic potential function)

Allowed energy band

Forbidden energy band

Allowed energy band

Forbidden energy band

Allowed energy band

First Brillouin zone

Microelectronics I : Introduction to the Quantum Theory of Solids

Electrical condition in solids

1. Energy band and the bond model

energy

conduction band
-
Energy gap, Eg=1.1 eV

+ Valence band

Breaking of covalent bond

Generation of positive and negative charge
Microelectronics I : Introduction to the Quantum Theory of Solids

E versus k energy band

conduction band

Valence band

T=0K T>0K

When no external force is applied, electron and “empty state” distributions are
symmetrical with k
Microelectronics I : Introduction to the Quantum Theory of Solids

2. Drift current

Current; diffusion current and drift current

When Electric field is applied

dE = F dx = F v dt
“Electron moves to higher empty state”
E E

No external force E

k k

n
Drift current density, J = −e ∑ υ i [A/cm3]
i =1
n; no. of electron per unit volume in the conduction band
Microelectronics I : Introduction to the Quantum Theory of Solids

3. Electron effective mass

Electron moves differently in the free space and in the crystal (periodical potential)

Fext + Fint = ma

External forces Internal forces

(e.g; Electrical field) + (e.g; potential)
= mass acceleration

Internal forces
(e.g; potential)

Fext = m*a

External forces
(e.g; Electrical field)
= Effective mass acceleration

Effect of internal force

Microelectronics I : Introduction to the Quantum Theory of Solids

From relation of E and k

h 2k 2
E =
2m
d 2E h2
2
=
dk m

Mass of electron, m
h2
m=
 d 2E 
 2
 Curvature of E versus k curve
 dk 

E versus k curve Considering effect of internal force (periodic potential)

m from eq. above is effective mass, m*

Microelectronics I : Introduction to the Quantum Theory of Solids

E versus k curve
E
Free electron

Electron in crystal B

Electron in crystal A

Curvature of E-k depends on the medium that electron moves in

Effective mass changes

m*A > m > m*B

Ex; m*Si=0.916m0, m*GaAs=0.065m0 m0; in free space

Microelectronics I : Introduction to the Quantum Theory of Solids

4. Concept of hole

Electron fills the empty state

Positive charge empty the state

“Hole”
Microelectronics I : Introduction to the Quantum Theory of Solids

When electric field is applied,

hole

electron

Hole moves in same direction as an applied field

Microelectronics I : Introduction to the Quantum Theory of Solids

Metals, Insulators and semiconductor

10-8 103

Insulator Semiconductor Metal Conductivity,

σ (S/cm)

Conductivity; no of charged particle (electron @ hole)

carrier
1. Insulator

Conduction
e
empty band

No charged particle can contribute to
a drift current
Big energy gap, Eg
Eg; 3.5-6 eV

full Valence
band
Microelectronics I : Introduction to the Quantum Theory of Solids

2. Metal

Many electron for

Partially
e filled conduction
e

full
No energy gap

3. Semiconductor

T> 0K
Conduction
Almoste empty
band
Conduction band; electron

Valence band; hole
Eg; on the order of 1 eV

e full Valence
Almost band
Microelectronics I : Introduction to the Quantum Theory of Solids

from E-k curve , 1. Energy gap, Eg

2. Effective mass, m*

Q. 1;

Eg=1.42 eV

Calculate the wavelength and

energy of photon released when
electron move from conduction band
to valence band? What is the color
of the light?
Microelectronics I : Introduction to the Quantum Theory of Solids

Q. 2;

E (eV)
B
A
0.7

0.07
k(Å-1)
0.1

Effective mass of the two electrons?

Microelectronics I : Introduction to the Quantum Theory of Solids

Extension to three dimensions

1 dimensional model (kronig-Penney Model)

1 potential pattern

[110]
direction
Different direction

Different potential patterns

[100]
direction

E-k diagram is given by a function of the direction in the crystal

Microelectronics I : Introduction to the Quantum Theory of Solids

E-k diagram of Si

Energy gap; Conduction band minimum –

valence band maximum

Eg= 1 eV

Indirect bandgap;
Maximum valence band and minimum
conduction band do not occur at the same k

Not suitable for optical device application

(laser)
Microelectronics I : Introduction to the Quantum Theory of Solids

E-k diagram of GaAs

Eg= 1.4 eV

Direct band gap

suitable for optical device application

(laser)

Smaller effective mass than Si.

(curvature of the curve)
Microelectronics I : Introduction to the Quantum Theory of Solids

Current flow in semiconductor ∝ Number of carriers (electron @ hole)

How to count number of carriers,n?

Assumption; Pauli exclusion principle

If we know
1. No. of energy states Density of states (DOS)

2. Occupied energy states The probability that energy states is

occupied
“Fermi-Dirac distribution function”

n = DOS x “Fermi-Dirac distribution function”

Microelectronics I : Introduction to the Quantum Theory of Solids

Density of states (DOS)

3/ 2
4π (2m)
g (E) = 3
E
h

A function of energy

As energy decreases available quantum states decreases

Derivation; refer text book

Microelectronics I : Introduction to the Quantum Theory of Solids

Q.
Calculate the density of states per unit volume with energies between 0 and 1 eV

Solution

1eV
N= ∫ g ( E )dE
0
1eV
4π (2m)3 / 2
=
h3 ∫
0
E dE

4π (2 × 9.11× 10 −31 )3 / 2 2 −19 3 / 2

= −34 3
(1 .6 × 10 )
(6.625 × 10 ) 3
= 4.5 × 10 21 states / cm3
Microelectronics I : Introduction to the Quantum Theory of Solids

Extension to semiconductor

Our concern; no of carrier that contribute to conduction (flow of current)

Free electron or hole

1. Electron as carrier
T> 0K Can freely moves
Conduction
e band
Ec

Ev
Valence
e
band

Electron in conduction band contribute to conduction

Determine the DOS in the conduction band

Microelectronics I : Introduction to the Quantum Theory of Solids

3/ 2
4π (2m)
g (E) = 3
E − EC
h
Energy

Ec
Microelectronics I : Introduction to the Quantum Theory of Solids

1. Hole as carrier

Conduction
e band
Ec

Empty Ev
state Valence
e
band
freely
moves

hole in valence band contribute to conduction

Determine the DOS in the valence band

Microelectronics I : Introduction to the Quantum Theory of Solids

3/ 2
4π (2m)
g (E) = 3
Ev − E
h
Energy

Ev
Microelectronics I : Introduction to the Quantum Theory of Solids

Q1;
Determine the total number of energy states in Si between Ec and Ec+kT at
T=300K

Solution;

Ec + kT
4π (2mn )3 / 2
g=
h3 ∫
Ec
E − EC dE Mn; mass of electron

4π (2mn )3 / 2  2  3/ 2
=   ( kT )
h3 3
4π (2 ×1.08 × 9.11×10 −31 )3 / 2  2  −19 3 / 2
= −34 3   ( 0. 0259 × 1 .6 × 10 )
(6.625 ×10 ) 3
= 2.12 ×1019 cm −3
Microelectronics I : Introduction to the Quantum Theory of Solids

Q2;
Determine the total number of energy states in Si between Ev and Ev-kT at
T=300K

Solution;

4π (2m p ) 3 / 2 Ev
g=
h 3 ∫
Ev − kT
Ev − E dE Mp; mass of hole

4π (2m p )3 / 2  2  3/ 2
=   ( kT )
h3 3
4π (2 × 0.56 × 9.11×10 −31 )3 / 2  2  −19 3 / 2
= −34 3   ( 0. 0259 × 1 .6 × 10 )
(6.625 ×10 ) 3
= 7.92 ×1018 cm −3
Microelectronics I : Introduction to the Quantum Theory of Solids

The probability that energy states is occupied

“Fermi-Dirac distribution function”

Statistical behavior of a large number of electrons

Distribution function

1
f F (E) =
 E − EF 
1 + exp 
 kT 
EF; Fermi energy

Fermi energy;
Energy of the highest occupied quantum state
Microelectronics I : Introduction to the Quantum Theory of Solids

For temperature above 0 K, some electrons jump to higher energy level.

So some energy states above EF will be occupied by electrons and some
energy states below EF will be empty
Microelectronics I : Introduction to the Quantum Theory of Solids

Q;
Assume that EF is 0.30 eV below Ec. Determine the probability of a states being
occupied by an electron at Ec and at Ec+kT (T=300K)

Solution;

1. At Ec 2. At Ec+kT

1 1
f = f =
 EC − ( EC − 0.3eV )   E + 0.0259 − ( EC − 0.3eV ) 
1+   1+  C 
 kT   kT 
1 1
= =
 0.3   0.3259 
1+   1+  
 0. 0259   0.0259 
= 9.32 ×10 −6 = 3.43 × 10 −6

Electron needs higher energy to be at higher energy states. The probability

of electron at Ec+kT lower than at Ec
Microelectronics I : Introduction to the Quantum Theory of Solids

1
f F (E) = electron
 E − EF 
1 + exp 
 kT 

Hole?

The probability that states are being empty is given by

1
1 − f F (E) = 1 −
 E − EF 
1 + exp 
 kT 
Microelectronics I : Introduction to the Quantum Theory of Solids

Approximation when calculating fF

1
f F (E) =
 E − EF 
1 + exp 
 kT 
When E-EF>>kT
1
f F (E) ≈
 E − EF 
exp  Maxwell-Boltzmann approximation
 kT 

Approximation is valid in this range