Chapter 3

Introduction to Quantum
Theory of Solids

W.K. Chen Electrophysics, NCTU 1

Outline

„ Allowed and forbidden energy bands

„ Electrical conduction in solid
„ Extension to three dimension
„ Density of state
„ Statistical mechanics

W.K. Chen Electrophysics, NCTU 2

 3.1 Allowed and forbidden energy bands
„ In one-electron atom
‰ Only discrete values of energy
are allowed
‰ The probability function shows that
the electron is not localized at a
given radius
‰ We can extrapolate these single-
atoms results to a crystal and
quantitatively derive the concepts of
allowed and forbidden energy
bands

− mo e 4
En =
(4πε o ) 2 2h 2 n 2

W.K. Chen Electrophysics, NCTU 3

3.1.1 Formation of energy bands

„ Fig. (a) shows the radial probability density function for the lowest
electron energy state of the single, non-interacting hydrogen atom Fig. (b)
shows the radial probability curves for two atoms that are in close proximity
to each other
„ Due to Pauli exclusion principle, no two electrons may occupy the same
quantum state, the interaction of two electrons give each discrete quantized
energy level splitting into two discrete energy levels

W.K. Chen Electrophysics, NCTU 4

„ By pushing the numbers of hydrogen type atoms together with a regular
periodic arrangement, the initial quantized energy level will split into a band
of discrete energy levels
„ The Pauli exclusion principle states that the joining of atoms to form a
system (crystal) does not alter the total number of quantum states
„ The discrete energy must split into a band of energies in order that each
electron can occupy a distinct quantum state

„ For a system with 1019 one-electron atoms with a width of allowed energy
band of 1 eV, if the discrete energy states are equidistant, then the energy
levels are separated by 10-19 eV, which is extremely small

W.K. Chen Electrophysics, NCTU 5

Example 3.1 Small change of kinetic energy

Consider an electron traveling at a velocity of 107 cm/s. Assume the velocity
increases by a value of 1 cm/s. Find the increase in kinetic energy
1 1 4.56 ×10 −21
E = mυ = (9.11× 10 )(10 ) = 4.56 ×10 J =
2 −31 5 2 − 21
−19
= 2.85 ×10 − 2 eV
2 2 1.6 ×10
1 1
ΔE = mυ 22 − mυ12
2 2
Let υ 2 = υ1 + Δυ
⇒ υ 22 = (υ1 + Δυ ) 2 = υ12 + 2υ1Δυ + (Δυ ) 2
1
⇒ ΔE ≈ m(2υ1Δυ ) = mυ1Δυ
2
ΔE ≈ mυ1Δυ = (9.11× 10 −31 )(105 )(0.01) = 9.11×10 −28 J
9.11×10 − 28
ΔE = −19
= 5.7 ×10 −9 eV
1.6 ×10

W.K. Chen Electrophysics, NCTU 6

 Discrete energy levels for a hydrogen atom

− mo e 4
En =
(4πε o ) 2 2h 2 n 2 E4
ΔE = 0.66 eV
E3
ΔE = 1.89 eV
E1 = −13.6eV E2
E1
E2 = = −3.4eV
22
ΔE = 10.2 eV
E
E3 = 21 = −1.51eV
3
E
E4 = 21 = −0.85eV E1
4

W.K. Chen Electrophysics, NCTU 7

„ For a atom contains electrons up through the n=3 energy level, when we
bought these atoms close together from initially far apart
‰ The n=3 energy shell will begin to interact initially, followed by n=2 energy shell
interaction and finally the innermost n=1 shell interaction
„ If ro is the equilibrium interatomic distance, then at this distance we have
‰ Bands of allowed energies (electrons may occupy)
‰ Bands of forbidden energies

allowed band
forbidden band

W.K. Chen Electrophysics, NCTU 8

 „ For silicon atoms, having 14
electrons,
‰ 2 electrons occupy n=1 energy
level
‰ 8 electrons occupy n=2 energy
level
‰ 4 remaining valence electrons
occupying n=3 energy level are
involved in chemical reactions
Isolated silicon atom
„ For silicon crystal
‰ 3s states corresponds to n=3 and
l=0 ( containing 2 quantum states)
(n=3, l=0, s=-1/2, +1/2)
‰ 3p states corresponds to n=3 and
l=1 ( containing 6 quantum states)
n=3, l=+1, m=1, s=-1/2, +1/2
m=0, s=-1/2, +1/2
m=-1, s=-1/2, +1/2

W.K. Chen Electrophysics, NCTU

silicon crystal 9

„ As the interatomic distance decreases, the 3s and 3p states and

gradually merge together to form broad band
„ At the equilibrium interatomic distance, the broad band has again
split with 4 quantum states per atom in the lower band and 4
quantum states per atom in the upper band

„ The upper band is assigned as

conduction band
the lower band is call valence band
„ Since each Si atom has only 4
valence electrons
‰ At 0 K, electrons are in the lowest
wnergy states
all states in the valence band will be
full, and all states in the conduction
band will be empty

W.K. Chen Electrophysics, NCTU 10

 3.1.2 The Kronig-Penney Model
„ Fig. (a) shows potential function of a
single, noninteracting, one-electron atom
„ Fig. (b) shows potential function for the
case when several atoms are in close
proximity arranged, one-dimensional
array
„ Fig. (c) is the net potential function in Fig.
(b)
„ One-dimensional square periodic
potential function is used in K.P model

W.K. Chen Electrophysics, NCTU 11

Kronig-Penny Model
⎧0 0< x<a
V ( x) = ⎨
⎩Vo −b < x < 0

„ Block Theorem
„ The theorem states that all one-electron
wave functions involving periodically
varying potential energy functions must be
of the form
u ( x) : periodic function with period(a + b)
ψ ( x ) = u ( x )e jkx
e jkx :Q traveling wave
The general time-independent wave function
Ψ ( x, t ) = ψ ( x)φ (t )
E
= u ( x)e jkx ⋅ e − jωt ω= ( E = hω )
h
W.K. Chen Electrophysics, NCTU 12
 Time-independent Schrodinger wave equation

∂ 2ψ ( x) 2m
+ 2 ( E − V ( x))ψ ( x) = 0 ψ ( x) = u ( x)e jkx
∂x 2 h

∂ 2ψ ( x) 2mE
Region I : + 2 ψ ( x) = 0 (0 ≤ x ≤ a )
∂x 2 h
∂ 2ψ ( x) 2m( E − Vo )
Region II : + ψ ( x) = 0 (−b ≤ x ≤ 0)
∂x 2 h2

W.K. Chen Electrophysics, NCTU 13

Region I:

d 2u1 ( x) du ( x) 2mE
+ 2 jk 1 − (k 2 − α 2 )u1 ( x) = 0 α2 =
dx 2
dx h2

u1(x): the amplitude of the wave function in region I

Region II : if Vo > E

d 2u 2 ( x ) du ( x) 2m( E − Vo )
2
+ 2 jk 2 − (k 2 − β 2 )u2 ( x) = 0 β= = jγ
dx dx h2

u2(x): the amplitude of the wave function in region II

if E >Vo
u1 ( x) = Ae j (α − k ) x + Be − j (α + k ) x for 0 < x < a
2mVo
β2 =α2 −
h2
u2 ( x) = Ce j ( β − k ) x + Be − j ( β + k ) x for − b < x < 0

W.K. Chen Electrophysics, NCTU 14

 u1 ( x) = Ae j (α − k ) x + Be − j (α + k ) x for 0 < x < a

u2 ( x) = Ce j ( β − k ) x + Be − j ( β + k ) x for − b < x < 0

4 unknowns, 4 BCs

The wave function ψ(x) and its derivative ∂ψ/∂x

ψ ( x) = u ( x)e jkx
must be continuous ∂ψ ( x) ∂u ( x)
= e jkx + jku ( x)e jkx
⇒u(x) and its derivative ∂u/∂x must be continuous ∂x ∂x
− +
ψ ( x − ) = ψ ( x + ) ⇒ u ( x − )e jkx = u ( x + )e jkx ⇒ u ( x − ) = u ( x − )
∂ψ ( x) ∂ψ ( x)
=
∂x x − ∂x x+

∂u ( x) − − ∂u ( x) + +
⇒ e jkx + jku ( x − )e jkx = e jkx + jku ( x + )e jkx
∂x x − ∂x x +
∂u ( x) ∂u ( x)
⇒ =
∂x x − ∂x x +
W.K. Chen Electrophysics, NCTU 15

u1 ( x) = Ae j (α − k ) x + Be − j (α + k ) x for 0 < x < a

u2 ( x) = Ce j ( β − k ) x + Be − j ( β + k ) x for − b < x < 0

B.C.1 : u2 (0 − ) = u1 (0 + ) ⇒ A+ B = C + D

∂u2 ∂u2
B.C.2 : = ⇒ (α − k ) A − (α + k ) B − ( β − k )C + ( β + k ) D = 0
∂x 0 − ∂x 0 +

B.C.3 : u1 (a) = u2 (−b) Ae j (α − k ) a + Be − j (α + k ) a = Ce − j ( β − k )b + Be + j ( β + k )b

∂u1 ∂u2 (α − k )e j (α − k ) a + (α + k )e − j (α + k ) a
B.C.4 : =
∂x x=a ∂x x =−b
= ( β − k )e − j ( β − k ) b − ( β + k )e + j ( β + k ) b

W.K. Chen Electrophysics, NCTU 16

From the above 4 eq, derived from 4 BCs, we obtain the parameter k in
relation of the total energy E (through the parameter α)and the potential
function Vo (through the parameter β)

Kronig-Penny Model

− (α 2 + β 2 )
(sin α a )(sin β b) + (cos α a )(cos β b) = cos k (a + b)
2αβ

⎧0 0< x<a
V ( x) = ⎨
⎩Vo −b < x < 0

W.K. Chen Electrophysics, NCTU 17

3.1.3 The k-space diagram

− (α 2 + β 2 )
(sin α a)(sin β b) + (cos α a )(cos β b) = cos k (a + b)
2αβ

2mE 2m(Vo − E )
α= β = jγ = j , γ >0
h2 h2

Case 1: Free particle:

bVo is finite value, and
b=0
Vo=0

V(x)
2mE
β =α = E
h2

W.K. Chen Electrophysics, NCTU 18

 0 1
− (α + α )
2 2
(sin α a)(sin α b) + (cos α a )(cos α b) = cos k (a + b)
2α 2

cos αa = cos ka (free particle) ⇒ α =k

2mE 2m( 12 mυ 2 ) mυ p 2mE

α= = = = = k ⇒ =k
h2 h2 h h h2

⎧ p = hk
⎪ p: particle momentum
⇒⎨ p 2 h 2k 2 k: wave number
⎪E = =
⎩ 2m 2m

For the case of free particle, parabolic relation is

valid between energy E and momentum p.

p: momentum of wave motion

W.K. Chen Electrophysics, NCTU 19

Case 2: bound electrons in crystal:

bVo is finite value, but
b→0
Vo→∞ ⇒ E<<Vo Periodic δ function potential barrier

V(x)

Periodic δ function potential barrier

W.K. Chen Electrophysics, NCTU 20

 − (α 2 + β 2 )
(sin α a )(sin β b) + (cos α a )(cos β b) = cos k (a + b)
2αβ
2mE 2m(Vo − E )
α= Q E << Vo ⇒ β = jγ = j , γ >0
h2 h2
decaying wave at barrier region
(γ 2 − α 2 )
(sin α a)(sinh γ b) + (cos α a)(cosh γ b) = cos k (a + b)
2αγ
1 1
b→0 ⇒sinhγb≈ γb & coshγb→1 Q sin θ = [e jθ − e − jθ ] cos θ = [e jθ + e − jθ ]
2j 2
mVoba sin α a
+ (cos α a) = cos ka
h2 αa
mVoba
sin α a P' =
E - k equation P' + (cos α a) = cos k a h2
αa
2mE
α=
h2
energy term momentum term
The above eq does not lend itself to an analytical solution, but must be solved
using numerical or graphical techniques to obtain the relation between k, E
and Vo.
W.K. Chen Electrophysics, NCTU 21

1 jθ 1
Q sin θ = [e − e − jθ ] cos θ = [e jθ + e − jθ ]
2j 2

e x + e− x e x − e− x e x + e− x
cosh x = sinh x = cosh x =
2 2 2

e x − e− x
sinh x =
2

W.K. Chen Electrophysics, NCTU 22

 sin αa
f (αa) = P' + (cos αa)
αa

− 1 ≤ f (αa ) = cos ka ≤ +1

a is fixed, k varies
2mE
The parameter α is related to the total energy E of the particle α=
h2

W.K. Chen Electrophysics, NCTU 23

W.K. Chen Electrophysics, NCTU 24

 E-k diagram

„ The right figure shows the

energy E as a function of the
wave number k
„ The plot shows the concept of
allowed energy bands for
particle propagating in the
crystal lattice
„ Since the energy E is
discontinuities, we also have
the concept of forbidden
energy for particles in the
crystal

W.K. Chen Electrophysics, NCTU 25

Example 3.2 bandwidth

Coefficient P’ =10, potential width a=5Å
sin αa
f (αa) = P' + (cos αa) = cos ka
αa
Solution
The lowest allowed band occurs as ka changes from 0 to π

sin αa
For ka=0 P' + (cos αa) = +1
αa
Using numerical technique (trial and error), we find αa = 2.628

2mE 2mEupper
α= ⇒ α a = a = 2.628
h2 h2
(2.628) 2 h 2 (2.628) 2 (1.054 ×10−34 ) 2
Elower = = −31 −10 2
= 1.68 ×10−19 J = 1.053 eV
2ma 2
2(9.11×10 )(5 ×10 )

W.K. Chen Electrophysics, NCTU 26

 For ka=π, as seen form the figure it happens αa=π

2mEupper
αa = a =π
h2
π 2h 2 π 2 (1.054 ×10−34 ) 2
Eupper = =
2ma2 2(9.11×10−31 )(5 ×10−10 ) 2
= 2.407 ×10−19 J = 1.50 eV

ΔE = Eupper − Elower = 1.50 − 1.053 = 0.447 eV

W.K. Chen Electrophysics, NCTU 27

sin αa
P' + (cos αa ) = cos ka cos ka = cos(ka + 2nπ ) = cos(ka − 2nπ )
αa
energy term momentum term
Displacement of portions of the curve in left figure by 2π still satisfy the E-k
equation

W.K. Chen Electrophysics, NCTU 28

„ The entire E versus k plot is contained within -
π/a<k<π/a
„ For free electron, the particle momentum and
the wave number k are related by

momentum p = hk (free electron)

„ Given the similarity between the free electron

solution and the results of the single crystal,
The parameter ħk in a single crystal is
referred to as the crystal momentum, which
is not the actual momentum of the electron in
the crystal , but is a constant of motion that
includes the crystal interaction

crystal momentum : hk

W.K. Chen Electrophysics, NCTU 29

3.2 Electrical conduction in solids

„ For covalent bonding of silicon crystal,
each silicon atom is surrounded by 8
valence electrons. 4 from itself, 4 from the
4 nearest Si neighbor
„ For N silicon atoms in the crystal, there are
4 N energy states in lower valence band
and 4N energy states in higher conduction
band. Each energy state allow only one
electron to reside
„ At T=0K, all valence electrons are lying in
their lowest energy states, valence band,
i.e. the valence band is fully occupied and
the conduction band is completely empty

W.K. Chen Electrophysics, NCTU 30

 Covalent bond breaking
„ At T>0K, a few valence band (VB) electrons may gain enough thermal
energy to break the covalent band and jump into conduction band (CB)
‰ VB: covalent bonding position
‰ CB: elsewhere
„ Since the pure semiconductor is neutrally charged, as the negatively
charged electron breaks away from its covalent bonding position, a
positively charged “empty state” is created in the original covalent
bonding position in the VB

CB

VB

W.K. Chen Electrophysics, NCTU 31

„ At T=0K, the energy states in the VB in E-k diagram are completely full,
and the states in CB are empty (Fig. (a))
„ At T>0K, a few valence band (VB) electrons may gain enough thermal
energy to break the covalent band and jump into CB (Fig (b))

W.K. Chen Electrophysics, NCTU 32

 3.2.3 Drift current
l l N: total number of flow charge
n: volume density of flow charge
A: cross-sectional area
A υ: average drift velocity
l: traveling length of carrier per Δt

N nAl nA(υΔt ) #
Flux Φ = = = = nAυ ( )
Δt Δt Δt sec
Φ #
Flux density φ = = nυ ( )
A sec ⋅ cm 2

A
Drift current density J = qφ = qnυ d ( ) Ampere
cm 2
n
J = q ∑υi υi: the velocity of the ith charged carrier
i =1

W.K. Chen Electrophysics, NCTU 33

E-k diagram under external bias

„ Under no external force, the electron
distribution in CB is an even function of k,
since the net momentum is zero under
thermal equilibrium.
„ Under applied force, electrons in CB can
gain energy and a net momentum

Work - Eenergy Theorem

dE = Fdx = Fυdt

W.K. Chen Electrophysics, NCTU 34

3.2.3 Electron effective mass
The movement of an electron in a lattice is different
from that of an electron in free space
Ftotal = Fext + Fint = ma
r r
Fext Fext
Fint: due to the interaction between the moving
electron and other charged particles, such as ions,
protons and else electrons in the lattice

Fext = m*a

m*: effective mass

Which takes into account of the particle mass
Free space crystal and the effects of internal forces
r r
Fext = ma Fext = m*a

W.K. Chen Electrophysics, NCTU 35

E-k diagram and particle mass in free space

1
E = moυ =
2 p2
=
(hk ) (parabolic curve)
2

2 2mo 2mo
( p = hk )
∂E 2h 2 k hp hmoυ
⇒ = = =
∂k 2mo mo mo
1 ∂E
⇒ velocity : υ = (free electron)
h ∂k

∂ 2 E ∂ h 2k h2 „ The first derivative of E with k is

= ( )= related to the velocity of free
∂k 2 ∂k 2mo mo particle
1 1 ∂2E „ The second derivative of E versus
⇒ mass : = k is inversely proportional to the
mo h 2 ∂k 2 mass of free particle

W.K. Chen Electrophysics, NCTU 36

 Electron effective mass & E-k diagram in crystal
Conduction band
The energy near the bottom of CB may
be approximated by a parabola, just as
that of free particle
E − Ec = C1k 2 , C1 > 0

1 1 ∂2E 1 1 ∂2E
mass : = effective mass : * = 2
mo h 2 ∂k 2 mn h ∂k 2
(free electron) (Block electron)

W.K. Chen Electrophysics, NCTU 37

∂E ∂2E
= 2C1k (C1 > 0), = 2C1
∂k ∂k 2
1 1 ∂ 2 E 2C1
⇒ * = 2 = 2
mn h ∂k 2 h
Thus acceleration of Block electron with external force is Fext = mn a
*

If we apply an electric field, the acceleration is

Fext − eE
a= = *
mn* mn a
Fext
E: electric field E
E: total energy
„ Effective mass parameter is used to relate quantum mechanics and
classical mechanics
„ The larger the bowing of E-k diagram, the small the effective mass is

W.K. Chen Electrophysics, NCTU 38

 3.2.4 Concept of hole
„ The empty state is created when a covalent bond is broken
„ The movement of a valence electron into the empty state is equivalent to the
movement of a positively charged empty state itself
„ The above positive charge carrier is called “hole”
„ The crystal now has a second equally important charge carrier, hole, that
can give rise to a current

W.K. Chen Electrophysics, NCTU 39

The drift current in VB

Under external biased voltage, it is the electrons that moving in the VB, not
the positively charged ions
The drift current due to electrons in VB

∑υ
n
J = ( − e) i Q J = q ∑υi , q = −e for electron
i ( filled )
i =1

J = ( − e) ∑ υ i + ( + e) q = +e for + ion
i ( full )
∑υ
i ( empty )
i

= +

filled emptyfilled

W.K. Chen Electrophysics, NCTU 40

 (−e) ∑υi = ? (full valence band)
i ( full )

The velocity of individual electron is given

1 ∂E
υe (E ) =
h ∂k
„ The valence band is symmetric in k and every state in VB is occupied
so that every electron with a velocity lυ l, there is a corresponding
electron with a velocity -lυ l
„ Since the valence band is full, the distribution of electrons with respect
to k has no chance to be changed by an external applied. The net drift
current density generated from a completely full band electrons, then, is
zero

( − e) ∑ υ i = 0
i ( full )

W.K. Chen Electrophysics, NCTU 41

The net drift current density due to electrons in VB

0
J = ( − e) ∑ υ i + ( + e) ∑υ i = ( + e) ∑υ i
i ( full ) i ( empty ) i ( empty )

„ The net drift current due to electrons in VB is entirely equivalent to placing a

positively charged particle in the empty state (assigned as hole) and
assuming all other states in the band are neutrally charged
„ The associated hole velocity is exactly the velocity of the electron who
occupy the empty state

neutral hole neutral

W.K. Chen Electrophysics, NCTU 42

 Effective mass & E-k diagram in crystal
Valence band
The energy near the bottom of VB may
be approximated by a parabola, just as
that of free particle

Eυ − E = C2 k 2
∂E ∂2E
= −2C2 k (C2 > 0), = −2C2
∂k ∂k 2
1 1 ∂ 2 E − 2C 2
⇒ *= 2 = <0
me h ∂k 2
h 2

„ An electron moving near the top of valence band behaves as if it has a

negative mass

W.K. Chen Electrophysics, NCTU 43

Thus acceleration of Block electron near the top of VB with external force is

Fext = me*a = (−e) E me: negative quantity

a
We may rewrite F F
a = ext* = ext* > 0 Fext
me me E
− eE + eE
= = *
me* mp filled emptyfilled

m*p = − me*
a
1 1 1 ∂2E Fext
=− * =− 2 E
m*p me h ∂k 2
neutral hole neutral
1 ∂E
υ h ( E ) = −υ e ( E ) = −
h ∂k

W.K. Chen Electrophysics, NCTU 44

„ Now we can model VB as having particles with a positive electronic charge
and a positive effective mass, so it will move in the same direction as the
direction of applied field
„ The new particle is the hole
„ The density of hole is the same as the density of empty states in VB

W.K. Chen Electrophysics, NCTU 45

3.2.5 Metals, insulators and semiconductors

„ Insulator:
‰ The allowed bands are either completely empty or completely full
‰ Since empty band and full band contribute no current at all, the resistivity of an
insulator is very large
‰ The bandgap of insulator is usually on the order of 3.5 to 6 eV or larger

W.K. Chen Electrophysics, NCTU 46

„ Semiconductor:
‰ The allowed bands are at conditions either almost empty or almost full
‰ Both the electrons in CB and holes in VB can contribute the current
‰ The bandgap of semiconductor is on the order of 1 eV
‰ The resistivity of semiconductor can be controlled and varied over many orders of
magnitude

W.K. Chen Electrophysics, NCTU 47

„ Metal:
‰ The band diagram for a metal may be in one of two forms
partially full band
overlapped conduction and valence bands
‰ In the case of partially full band, many electrons are available for conduction, so
that the material can exhibit a large electrical conductivity
‰ For overlapped conduction and valence bands , there are large numbers of
electrons as well as large numbers of holes can move, so this material can also
exhibit a very high electrical conductivity

W.K. Chen Electrophysics, NCTU 48

 3.3 Extension to three dimensions
„ The basic concept of allowed and forbidden energy bands comes from the
electrons moving in periodic potential arrangement in crystal lattice
„ For three dimensional crystal, the distance between atoms varies as the
direction through the crystal changes

W.K. Chen Electrophysics, NCTU 49

„ The E-k diagram is symmetric in k so that no new information is obtained by

displaying the negative axis
„ In following plot of E-k diagrams, E-k diagrams at two directions are plotted.
[100] portion of the diagram with +k to the right and [111] portion of the
diagram with +k to the left are plotted

W.K. Chen Electrophysics, NCTU 50

„ Direct bandgap
the minimum conduction band is at k=0 so that the transitions for electron
between CB & VB can take place with no change in crystal momentum
„ Indirect bandgap
the minimum conduction band occurs not at k=0 so that the transitions for
electron between CB & VB includes an interaction with the crystal

W.K. Chen Electrophysics, NCTU 51

Effective mass concept in 3-dim crystal

W.K. Chen Electrophysics, NCTU 52

 3.4.1 Density of states for free electron
„ To determine the density of allowed quantum states as a function of energy,
we need to consider an appropriate mathematical model
„ Consider a free electron confined to a three-dimensional cubic with length a
with infinite potential well
a
V ( x, y , z ) = 0 for 0 < x < a
for 0 < y < a a
for 0 < z < a
V ( x, y, z ) = ∞ elsewhere a

Using the separation of variables technique in 3 dimensional Schrodinger’s

wave equation, we can have r
k r
kz
2mE r
2
= k 2 = k x2 + k y2 + k z2 r ky
h kx
W.K. Chen Electrophysics, NCTU 53

Two-dimensional plot of allowed quantum states in k space

π π π
k x = nx , k y = ny , k z = nz
a a a

nx, ny, nz: positive integers

Positive and negative values of

kx,ky or kz have the same energy
and represent the same quantum
state

The volume Vk of a single quantum state in k-space is

π
Vk = ( ) 3
a

W.K. Chen Electrophysics, NCTU 54

The density of quantum state in k-space for whole cubic box is

1 4πk 2 dk
gT (k )dk = 2( )
8 Vk
2: due to two spin states allowed for each quantum state
1/8: due to the positive values of kx,ky, and kz

k 2 dk
gT (k )dk = ⋅ a3
π2

W.K. Chen Electrophysics, NCTU 55

Density of quantum states versus energy

k 2 dk 4π (2m) 3 / 2
g k (k )dk = ⋅a 3
⇒ g ( E )dE = E dE
π2 h3
2mE 1
Qk2 = , 2mE k=
h2 h
1 1 1 1 m
dk = 2m ⋅ ⋅ dE = dE
h 2 E h 2E
The number of energy states for whole cubic box between E and E+dE, i.e.,
between k and k+dk is given by
k 2 dk
g k (k )dk = ⋅ a 3 = g ( E )dE
π 2

2mE 1 1 m 4πa 3
g ( E )dE = 2 ⋅ 2 ⋅ dE ⋅ a = 3 ⋅ (2m) 3 / 2 ⋅ E dE
3

h π h 2E h
W.K. Chen Electrophysics, NCTU 56
 The density of quantum states per unit energy per unit volume of the crystal
gT ( E )dE gT ( E )dE
g ( E )dE = =
V a3

4π (2m) 3 / 2
g ( E )dE = E dE
h3

g(E)

„ The density of states is proportional to the energy E. As the energy of free

particle becomes large, the number of available quantum states increase
„ The density of states is dependent on the mass of the free particle

W.K. Chen Electrophysics, NCTU 57

Example 3.3 Density of states

Calculate the total density of states for free electron per unit volume with
energies between 0 and 1 eV
1eV 4π (2m) 3 / 2 1eV
N =∫ g ( E )dE = ∫0 E dE
0 h3
4π (2m) 3 / 2 2 3 / 2
N= ⋅ ⋅E
h3 3
4π [2 ⋅ (9.11×10 −31 )]3 / 2 2
N= −34 3
⋅ ⋅ (1.6 ×10 −19 ) 3 / 2 = 4.5 ×10 27 m −3
(6.625 ×10 ) 3
N = 4.5 × 10 21 states/cm −3
„ The density of states is typically a large number ranging from 1018 to 1022
cm-3
„ The density of quantum states in semiconductor is usually less than the
density of atoms in semiconductor crystal

W.K. Chen Electrophysics, NCTU 58

 3.4.2 Density of states for semiconductor
The parabolic relationship between energy and momentum of a free electron
is
p 2 h 2 k2
E= =
2m 2m
The E-k curve near k=0 at conduction band can be approximated as a
parabola, so we have

p 2 h 2 k2
E − Ec = =
2m 2m
The density of states in CB is

4π (2mn* ) 3 / 2
g c ( E )dE = E − Ec dE
h3

W.K. Chen Electrophysics, NCTU 59

Similarly, the E-k parabolic relationship for a free hole in VB

p2 h 2 k2
Eυ − E = =
2m*p 2m*p

The density of states for holes (electrons) in VB is

4π (2m*p ) 3 / 2
gυ ( E )dE = Eυ − E dE
h3

W.K. Chen Electrophysics, NCTU 60

 3.5 Statistical mechanics
„ In dealing with large numbers of particles, we are interested only in the
statistical behavior of the group as a whole rather than in the behavior of
each individual particle
„ There are three distribution laws determining the distribution of particles
among available energy states

W.K. Chen Electrophysics, NCTU 61

„ Maxwell-Boltzmann distribution
‰ Particles are distinguishable
‰ No limit to the number of particles allowed in each energy state
‰ The exemplary case is low-pressure gas molecules in a container
„ Bose-Einstein distribution
‰ Particles are indistinguishable
‰ No limit to the number of particles allowed in each energy state
‰ The exemplary case is photon
„ Fermi-Dirac distribution
‰ Particles are indistinguishable
‰ Only one particle is permitted in each energy state
‰ The exemplary case is electrons in crystal

W.K. Chen Electrophysics, NCTU 62

 3.5.2 The Fermi-Dirac Probability Function
For ith energy level with gi quantum states
Only one particle is allowed in each state

First particle:
gi ways of choosing to place the particle
Second particle:
(gi -1) ways of choosing to place the particle

Ni particle:
[gi –(Ni-1)] ways of choosing to place the particle

Then the total number of ways of arranging Ni particles in the ith energy level
is
gi !
( g i )( g i − 1) L ( g i − ( N i − 1)) =
( g i − N i )!

W.K. Chen Electrophysics, NCTU 63

Since the particles are indistinguishable, the interchange of any two electrons
does not produce a new arrangement

The actual number of independent ways to distribute the Ni particles in the ith
level is

gi !
Wi =
N i !( g i − N i )!

W.K. Chen Electrophysics, NCTU 64

 N ( E )dE 1
= f E (E) = ( N ( E ) < g ( E ))
g ( E )dE ⎛ E − Ef ⎞
1 + exp⎜⎜ ⎟⎟
⎝ kT ⎠

N(E)dE (number density): Number of particles per unit volume per unit
energy (E to E+dE)
g(E)dE: number of quantum states per unit volume per unit energy

W.K. Chen Electrophysics, NCTU 65

„ Meaning of Fermi energy

„ At T=0K,
‰ The probability of a quantum state being occupied is unity for E<Ef
‰ The probability of a quantum state being occupied is zero for E>Ef

1
f E (E) =
⎛ E − Ef ⎞
1 + exp⎜⎜ ⎟⎟
⎝ kT ⎠
f E (E) = 0 for E > E f
f E (E) = 1 for E < E f

W.K. Chen Electrophysics, NCTU 66

3.5.3 Features of Fermi-Dirac Function
„ For T>0K
‰ The probability of a state being occupied at E=Ef is always ½

1 1
f E (E) = =
1 + exp(0 ) 2

W.K. Chen Electrophysics, NCTU 67

Example 3.6 3kT above the Fermi-energy

1 1 1
fE (E) = = = = 4.74%
⎛ E − Ef ⎞ ⎛ 3kT ⎞ 1 + 20.09
1 + exp⎜⎜ ⎟⎟ 1 + exp⎜ ⎟
⎝ kT ⎠ ⎝ kT ⎠

At energy above Ef, the probability of a state being occupied by an electron

become significantly less than unity

W.K. Chen Electrophysics, NCTU 68

 Example 3.7 99% probability
Assume Fermi energy is 6.25 eV, Calculate the temperature at which there
is 1 % probability that a state 0.30 below the Fermi energy level will not
contain an electron
1
1 − f E (E) = 1 −
⎛ E − Ef ⎞
1 + exp⎜⎜ ⎟⎟
⎝ kT ⎠
1
0.01 = 1 −
⎛ − 0.30 ⎞
1 + exp⎜ ⎟
⎝ kT ⎠
⇒ kT = 0.06529eV ⇒ T = 756K

k = 1.38 ×10 −23 J/K

= 8.62 ×10 −5 eV/K

W.K. Chen Electrophysics, NCTU 69

Maxwell-Boltzmann Approximation
1
f E (E) =
⎛ E − Ef ⎞
1 + exp⎜⎜ ⎟⎟
⎝ kT ⎠
When E-Ef>>kT, the exponential term in
the denominator is much greater than
the unity

⎡ E − Ef ⎤
f E ( E ) ≈ exp ⎢− ⎥ for E − E f > 3kT kT = 0.026 eV at T = 300K
⎣ kT ⎦

„ The Fermi-Dirac probability for E-Ef> 3kT can be approximated by

Boltzmann distribution
„ For E-Ef>3kT, the Boltzmann approximation is slightly larger than the Fermi-
Dirac curve with inaccuracy less than 5%

W.K. Chen Electrophysics, NCTU 70

 Example 3.8 3kT
Calculate the energy at which the difference between Boltzmann
approximation and the Fermi-Dirac function is 5%
⎛ E − Ef ⎞ 1
exp⎜⎜ − ⎟⎟ −
⎝ kT ⎠ 1 + exp⎛⎜ E − E f ⎞
⎟⎟
⎜ kT
⎝ ⎠ = 0.05
1
⎛ E − Ef ⎞
1 + exp⎜⎜ ⎟⎟
⎝ kT ⎠
⎛ E − Ef ⎞ ⎧ ⎛ E − Ef ⎞⎫
exp⎜⎜ − ⎟⎟ ⋅ ⎨1 + exp⎜⎜ ⎟⎟⎬ − 1 = 0.05
⎝ kT ⎠ ⎩ ⎝ kT ⎠⎭
⎛ E − Ef ⎞ 1
exp⎜⎜ − ⎟⎟ = 0.05 ⇒ E − E f = kT ln( ) ≈ 3kT
⎝ kT ⎠ 0.05

W.K. Chen Electrophysics, NCTU 71