EE5508 Semiconductor Fundamentals

Department of Electrical and Computer Engineering

National University of Singapore

Prof. Wu Yihong

Room: E4-8-03; Phone: 65162139

Email: elewuyh@nus.edu.dg

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Coverage of Part I
Lattice, Reciprocal Lattice, Brillouin Zone
Energy Band Lattice vibration, Phonons

Lecture 1 & 2

Single atom Crystals

Metal

V
Semiconductor
nx=3

Insulator
nx=2
Discrete
Energy band
energy levels L
nx=1

Lecture 3 Lecture 3 Lecture 4

Duality of matter Particle in one- Bloch waves, Kronig-Penney Model,

Schrodinger equation dimensional Nearly free electron model, Direct & indirect gap,
Hydrogen model quantum wells Effective mass, Density of States
Tunneling effect
https://youtu.be/RF7dDt3tVmI

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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 Outline of Lecture 3 & 4

Hydrogen atom
Electrons in free space
Electron tunneling through a 1D potential barrier
Electrons in a quantum box, well, and wire
Density of states
Fermi-Dirac distribution
Energy band structure
Metal, semiconductor and insulator
Semiconductor band structure
Concept of holes
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
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Hydrogen atom
 The hydrogen atom has special significance in quantum mechanics as it
allows for precise comparisons of theory and experiment.
 Much of what we know about the hydrogen atom can also be extended
to other single-electron ions, or hydrogenic atoms.
 The hydrogenic atom serves as an effective model for calculating energy
levels of impurity atoms in semiconductors.

positively
charged
proton

Negatively
charged -
-

electron P

Hydrogen atom

Impurity atom in semiconductor

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
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Hydrogen atom (cont’d)
 Schrödinger equation (SE) of relative motion of electron and nucleus in a
hydrogen atom
ℏ2 2 𝑒𝑒 2
(− ∇ − )𝜓𝜓(𝑥𝑥, 𝑦𝑦, 𝑧𝑧) = 𝐸𝐸𝐸𝐸(𝑥𝑥, 𝑦𝑦, 𝑧𝑧) (𝜇𝜇: reduced mass)
2𝜇𝜇 4𝜋𝜋𝜀𝜀0 𝑟𝑟

 Due to spherical symmetry of the potential energy, SE of hydrogen atom is

best solved by converting it to a spherical coordinate system.
ℏ2 2 𝑒𝑒 2
(− ∇ − )𝜓𝜓(𝑟𝑟, 𝜃𝜃, 𝜙𝜙) = 𝐸𝐸𝐸𝐸(𝑟𝑟, 𝜃𝜃, 𝜙𝜙)
2𝑚𝑚 4𝜋𝜋𝜀𝜀0 𝑟𝑟

𝜓𝜓𝑛𝑛𝑛𝑛𝑛𝑛 (𝑟𝑟, 𝜃𝜃, 𝜙𝜙) = 𝑅𝑅𝑛𝑛𝑛𝑛 (𝑟𝑟)𝑌𝑌𝑙𝑙𝑚𝑚 (𝜃𝜃, 𝜙𝜙)

2
1 𝜕𝜕 2 𝜕𝜕 1 𝜕𝜕 𝜕𝜕 1 𝜕𝜕 2
∇ = 2 (𝑟𝑟 )+ 2 (sin 𝜃𝜃 ) + 2 2
𝑟𝑟 𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕 𝑟𝑟 sin 𝜃𝜃 𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕 𝑟𝑟 sin 𝜃𝜃 𝜕𝜕𝜙𝜙 2

 Solving the equation leads to quantized energy

levels

1 1 𝑒𝑒 2 1 o
𝐸𝐸𝑛𝑛 = − = −13.6𝑒𝑒𝑒𝑒 𝑛𝑛 = 1,2,3. . . a0 = 0.529 A Bohr radius
2 4𝜋𝜋𝜀𝜀0 𝑛𝑛2 𝑎𝑎0 𝑛𝑛2

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Electronic transition  light

 Electrons occupy lower energy

levels at the ground state.

 When they absorb sufficient

energy, they jump to a higher
energy state, known as an
excited state. Electron are excited from Recombination gives rise to light
low to high energy levels
 Electrons at excited state are
unstable, and they eventually
return to their ground state.
Light is both a wave and a particle
 During this transition, they
release energy in the form of
light (photon emission) or
heat. Frequency (ν)

 The energy of the emitted photon equals

the energy difference between the excited 𝑣𝑣 = 𝐸𝐸/ℏ
𝜆𝜆 = 𝑐𝑐/𝑣𝑣
state and the ground state. c= 3 × 108 m / s
 Wavelength, frequency and photon h =6.26 × 10 −34 j ⋅ s
Wavelength
energy are interrelated with each other. Energy (E)
(λ)
1.24 𝜆𝜆: 𝜇𝜇𝜇𝜇
𝐸𝐸 = 𝐸𝐸: eV
𝜆𝜆

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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How to make use of electrons for electrical conduction?

 One cannot make use of electrons bounded to the nucleolus to make an electronic
device (at least in cases where electrons have to flow).

1 1 e2 1
En = − = − 13.6 eV Hydrogen atom
2 4πε 0 n 2 a0 n2

 The first task for making any electronic device is to “free” the electrons so that they can move
around; this can be achieved through either releasing electrons to fee space or finding a
proper material such as metal or semiconductor which contains moveable charges.

Vacuum Semiconductor Metal

Carrier density Low Low  High Very high

Confinement Relatively Easy Difficult

& control easy
Suitability for NO YES YES
Miniaturization
Electrons in
Electrons in semiconductors
metal are like
are like water in a sponge: water in the
controllable ocean:
uncontrollable

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Vacuum  Semiconductor  ?

Si technology
(microelectronics)
Quantity (not in scale)

Boinics

Vacuum tubes Si/molucular/spin/…

(macroelectronics) Quantronics
(nanoelectronics)

Spintronics

1900 1950 2000

Topotronics
Year

Spinphotonics
Vacuum electronics

Vacuum electronics Semiconductor electronics

Spin/topology etc.

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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 Outline of Lecture 3 & 4

Hydrogen atom
Electrons in free space
Electron tunneling through a 1D potential barrier
Electrons in a quantum box, well, and wire
Density of states
Fermi-Dirac distribution
Energy band structure
Metal, semiconductor and insulator
Semiconductor band structure
Concept of holes

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Electrons in free space
 Schrodinger
h2  ∂2 ∂2 ∂2 
equation of -  2 + 2 + 2  Ψ ( x, y , z ) =E Ψ ( x, y , z ) (SE)
free electrons 2m  ∂x ∂y ∂z 
ψ ( x, y , z ) X ( x )Y ( y ) Z ( z ) → SE
=
 Separation of
variable  2 ∂2 X  2 ∂ 2Y  2 ∂2Z
− =E x X , − =E yY , − =E z Z
2m ∂x 2 2m ∂y 2 2m ∂z 2

 2 ∂2 X
− 2
= Ex X → X= A1eik x x
 Solving SE 2m ∂x
w.r.t. x, y, &z,  2 ∂ 2Y ik y y

− = E yY → Y= A2e ⇒ ψ ( x, y, z ) = Ae ik ⋅ r

respectively 2m ∂y 2
 2 ∂2Z
− = Ez Z
2
→ Z= A3eik z z E Parabolic
2m ∂z
dispersion

2mE x 2mE y 2mE z

 E-K dispersion
= kx = , ky = , kz
2 2 2
 2k 2 k
E = Ex + E y + Ez =
2m
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
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Electrons in free space (cont’d)
 Momentum   ∂ ∂ ∂ 
operator pˆ = ∇ =  , , 
i i  ∂x ∂y ∂z 

 Momentum  ∂ ∂ ∂  
pˆ ψ ( x, y, z ) =  , , ( Ae )
ik ⋅ r

operator acts on i  ∂x ∂y ∂z 
wavefunction   
  ∂ ( Aeik ⋅r ) ∂ ( Aeik ⋅r ) ∂ ( Aeik ⋅r ) 
= , ,
i  ∂x ∂y ∂z 
 
ik ⋅ r

ik ⋅ r

ik ⋅ r
= [(ik x ) Ae , (ik y ) Ae , (ik z ) Ae ]
i

= k ψ ( x , y , z )

 Momentum   
p = k (k : wavevector)

 Wavelength 2π
λ=  De Broglie wavelength
|k |

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Curvature of E-k dispersion curve
 For a function of one-variable, f = f(x), its curvature is given by

d 2 f / dx 2
Curvature of f = https://en.wikipedia.org/wiki/Curvature
[1 + ( df / dx ) 2 ]3/2

 Apply this to E-k dispersion curve, one has

 2k 2
E= The larger the
2m
curvature the
d 2 E / dk 2
Curvature of E = smaller the mass
[1 + ( dE / dk ) 2 ]3/2
2 2 / 2m
= E
[1 + (2 2k / 2m ) 2 ]3/2
m2 m1
Curvature of E|at k = 0 =  2 / m
m1 < m2
2
m= k
Curvature of E|at k = 0

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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 Outline of Lecture 3 & 4

Hydrogen atom
Electrons in free space
Electron tunneling through a 1D potential barrier
Electrons in a quantum box, well, and wire
Density of states
Fermi-Dirac distribution
Energy band structure
Metal, semiconductor and insulator
Semiconductor band structure
Concept of holes

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Electrons tunnel through a rectangular potential barrier
 The Schrödinger equation is
R
ℏ2 𝜕𝜕 2 𝜓𝜓 𝑉𝑉0 0 ≤ 𝑥𝑥 ≤ 𝐿𝐿 T
− = (𝐸𝐸 − 𝑉𝑉)𝜓𝜓, 𝑉𝑉 = �
2𝑚𝑚 𝜕𝜕𝑥𝑥 2 0 elsewhere
I II V0 III
 For electrons travelling from left to right, SE has the
0 L
following solutions: x
ψ 1 = Aeikx + Be −ikx , x ≤ 0
ψ 2 = Ce βx + De − βx , 0 < x < L
ψ 3 = Feikx , x≥L
k = 2mE / , β = 2m(V0 − E ) / 

 Apply boundary conditions at x = 0 and x = L

(wavefunction and its first derivative are continuous):
At x = 0 : A + B = C + D, ikA − ikB = βC − βD
At x = L : Ce βL + De − βL = FeikL , Cβe βL − Dβe − βL = FikeikL

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Electrons tunnel through a rectangular potential barrier
 For coherent tunneling (k remains the
same in I and III), transmission coefficient
of flux of particle is
2
F 1
T= =
A  V02 
1 +
 4 E (V − E ) sinh 2
( β L ) 
 0 
E > V0
 When E < V0 and βL >> 1,

16 E  E  − 2 βL E < V0
T≈ 1 −  e
V0  V0 

 When E > V0, β is a complex number and

we let β = iα,
1
T=
 V02 
1 +
 4E(E − V ) sin 2
(α L ) 
 0 

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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 Outline of Lecture 3 & 4
Hydrogen atom
Electrons in free space
Electron tunneling through a 1D potential barrier
Electrons in a quantum box, well, and wire
Density of states
Fermi-Dirac distribution
Energy band structure
Metal, semiconductor and insulator
Semiconductor band structure
Concept of holes

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Electrons in a quantum well (V = ∞)
 Schrödinger equation is
E V =∞
ℏ2 𝜕𝜕 2 𝜕𝜕 2 𝜕𝜕 2
− + + 𝜓𝜓(𝑥𝑥, 𝑦𝑦, 𝑧𝑧) = (𝐸𝐸 − 𝑉𝑉)𝜓𝜓(𝑥𝑥, 𝑦𝑦, 𝑧𝑧)
2𝑚𝑚 𝜕𝜕𝑥𝑥 2 𝜕𝜕𝑦𝑦 2 𝜕𝜕𝑧𝑧 2

0 0 ≤ 𝑥𝑥 ≤ 𝐿𝐿
𝑉𝑉 = �
∞ elsewhere

 As V = ∞, electron wavefunction is zero outside the well. x

L
 SE can be solved using the separation of variable technique:
Ψ(𝑥𝑥, 𝑦𝑦, 𝑧𝑧) = 𝑋𝑋(𝑥𝑥)𝑌𝑌(𝑦𝑦)𝑍𝑍(𝑧𝑧)
 As there is no confinement in y and z direction, Y and Z should z
be in the form of L
𝑌𝑌 = 𝐶𝐶𝑒𝑒 𝑖𝑖𝑘𝑘𝑦𝑦 𝑦𝑦 , 𝑍𝑍 = 𝐷𝐷𝑒𝑒 𝑖𝑖𝑘𝑘𝑧𝑧 𝑧𝑧

 In x-direction, due to the confinement, wavefunction has the

form of a standing wave: y

𝑋𝑋 𝑥𝑥 = 𝐴𝐴 cos 𝑘𝑘𝑥𝑥 𝑥𝑥 + 𝐵𝐵 sin 𝑘𝑘𝑥𝑥 𝑥𝑥 x

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Electrons in a quantum well (V = ∞)
Ψ ( x, y , z ) =
X ( x )Y ( y ) Z ( z )
 Apply boundary condition: =
X ( x ) A cos k x x + B sin k x x E
0, Ψ ( L, y , z ) =
Ψ ( 0, y , z ) = 0

one obtains V =∞

A=0
E3
sin k x L = 0 nx=3
⇓ E2
n xπ nx=2
k x L = nπ ⇒ k x = E1
L
n x = 1, 2, 3... nx=1
L k//
2
( k // ) 2
  n xπ 
2
=E +  
2m 2m  L  Energy is quantized in kx
direction, but is still continuous
 in ky and kz direction
k // = ( k y , k z )

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Electrons in a quantum well (V = ∞)
2
 Quantized energy in
= En
 2  n xπ 
= 0.377 * 2
1 n 2x
eV
x-direction 2m  L  m L x

𝑚𝑚 = 𝑚𝑚∗ 𝑚𝑚𝑒𝑒
m*:dimensionless effective mass 𝑚𝑚𝑒𝑒 = 9.10956 × 10−31 kg
L: well width in unit of nm

 Normalized wave L a 2
∫ | X n | dx = ∫ | Bn sin( nxπx / L) |2 dx ⇒ Bn =
2
fucntion in x- 0 0 L
direction
L
2 πx V =∞
X 1 ( x) = sin
L L
2 2πx nx=3
X 2 ( x) = sin
L L
2 3πx
X 3 ( x) = sin
L L
nx=2

nx=1 𝑥𝑥
𝑥𝑥 = 0 𝑥𝑥 = 𝐿𝐿
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
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Electrons in a finite quantum well
E
 Schrödinger equation is

ℏ2 𝜕𝜕 2 𝜕𝜕 2 𝜕𝜕 2 V0
− + + 𝜓𝜓
2𝑚𝑚 𝜕𝜕𝑥𝑥 2 𝜕𝜕𝑦𝑦 2 𝜕𝜕𝑧𝑧 2
= (𝐸𝐸 − 𝑉𝑉)𝜓𝜓 nx=2

0 |𝑥𝑥| ≤ 𝐿𝐿/2
𝑉𝑉 = � nx=1
𝑉𝑉0 elsewhere x
-L/2 L/2

 As V is finite, electron wavefunction is non-zero in the barrier region.

 SE can be solved using the separation of variable technique:
Ψ ( x, y , z ) =
X ( x )Y ( y ) Z ( z )
 As there are no confinement in y and z direction, Y and Z should be in
the form of
ik y
=Y Ce
= y
, Z Deik z z

 In x-direction, SE in the well and barrier regions will be different due to

the difference in potential energy.

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Electrons in a finite quantum well (cont’d)

ℏ2 𝜕𝜕 2 𝜕𝜕 2 𝜕𝜕 2
− + + 𝑋𝑋 = 𝐸𝐸𝐸𝐸 (−𝐿𝐿/2 ≤ 𝑥𝑥 ≤ 𝐿𝐿/2)
 SE in well region  2𝑚𝑚 𝜕𝜕𝑥𝑥 2 𝜕𝜕𝑦𝑦 2 𝜕𝜕𝑧𝑧 2

ℏ2 𝜕𝜕 2 𝜕𝜕 2 𝜕𝜕 2
 SE in barrier region  − + +
2𝑚𝑚 𝜕𝜕𝑥𝑥 2 𝜕𝜕𝑦𝑦 2 𝜕𝜕𝑧𝑧 2
𝑋𝑋 = (𝐸𝐸 − 𝑉𝑉0 )𝑋𝑋 ( 𝑥𝑥 ≥ 𝐿𝐿/2)

𝑋𝑋 = 𝐴𝐴 cos 𝑘𝑘𝑥𝑥 𝑥𝑥 + 𝐵𝐵 sin 𝑘𝑘𝑥𝑥 𝑥𝑥 (|𝑥𝑥| ≤ 𝐿𝐿/2) E

 X in well region 
V0

𝛼𝛼𝛼𝛼
𝑋𝑋 = 𝐶𝐶𝑒𝑒 (𝑥𝑥 ≤ −𝐿𝐿/2) nx=2

 X in barrier regions  𝑋𝑋 = 𝐷𝐷𝑒𝑒 −𝛼𝛼𝛼𝛼 (𝑥𝑥 ≥ 𝐿𝐿/2) -L/2

nx=1

L/2
x

𝑘𝑘𝑥𝑥 = (2𝑚𝑚𝑚𝑚)1/2 /ℏ, 𝛼𝛼 = [2𝑚𝑚(𝑉𝑉0 − 𝐸𝐸)]1/2 /ℏ

𝛼𝛼 2 = 2𝑚𝑚𝑉𝑉0 /ℏ2 − 𝑘𝑘𝑥𝑥2

 Boundary conditions: X and
dX/dx are continuous at x = [𝛼𝛼 tan( 𝑘𝑘𝑥𝑥 𝐿𝐿/2) + 𝑘𝑘𝑥𝑥 ][𝑘𝑘𝑥𝑥 tan( 𝑘𝑘𝑥𝑥 𝐿𝐿/2) − 𝛼𝛼) = 0
±L/2 
𝛼𝛼 = −𝑘𝑘𝑥𝑥 cotan𝑘𝑘𝑥𝑥 𝐿𝐿/2 𝛼𝛼 = 𝑘𝑘𝑥𝑥 tan 𝑘𝑘𝑥𝑥 𝐿𝐿/2
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
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Electrons in a finite quantum well (cont’d)

α 2 = 2mV0 /  2 − k x2
α = k x tan k x L / 2
α

α = −k x cotan k x L / 2

Solve the equation

graphically to obtain
eigenvalues of kx and
energy:
ℏ2 𝑘𝑘𝑥𝑥𝑥𝑥 2
𝐸𝐸𝑥𝑥𝑥𝑥 =
2𝑚𝑚

𝑘𝑘𝑥𝑥𝑥 𝑘𝑘𝑥𝑥𝑥 𝑘𝑘𝑥𝑥𝑥 𝑘𝑘𝑥𝑥𝑥 𝑘𝑘𝑥𝑥𝑥 𝑘𝑘𝑥𝑥𝑥 𝑘𝑘𝑥𝑥𝑥 𝑘𝑘𝑥𝑥𝑥 kx 𝑛𝑛 = 1, 2, 3 … .

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Electrons in a finite quantum well (cont’d)

 Penetration depth in 𝛼𝛼 = 2𝑚𝑚(𝑉𝑉0 − 𝐸𝐸) 1/2

/ℏ E
the barrier layer:
𝑉𝑉0

nx=2
1  𝛼𝛼𝛼𝛼 𝑋𝑋 = 𝐶𝐶𝑒𝑒 −𝛼𝛼𝛼𝛼
δ= = 𝑋𝑋 = 𝐶𝐶𝑒𝑒
α 2m(V0 − E ) nx=1 x
-L/2 L/2
0.195
=
V0 − E
𝑉𝑉0
Uncertainty principle: ∆𝑥𝑥∆𝑝𝑝 > ℏ/2 𝑉𝑉0 − 𝐸𝐸
𝑬𝑬

Unit of δ: nm Electrons at barrier/well boundary

experience kinetic energy uncertainty: ∆𝐸𝐸~ 𝑉𝑉0 − 𝐸𝐸
Unit of E and V0: eV
𝑝𝑝2 ∆𝑝𝑝2
𝐸𝐸 = → ∆𝐸𝐸 = → ∆𝑝𝑝 = 2𝑚𝑚∆𝐸𝐸 = 2𝑚𝑚(𝑉𝑉0 − 𝐸𝐸)
When V0-E = 1 eV, the 2𝑚𝑚 2𝑚𝑚
penetration depth is ℏ ℏ
only 0.195 nm ∆𝑥𝑥 > =
2∆𝑝𝑝 2 2𝑚𝑚(𝑉𝑉0 − 𝐸𝐸)
Similar to penetration depth obtained from solving SE.

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

23
Electrons in a quantum wire
 Schrödinger ℏ2 𝜕𝜕 2 𝜕𝜕 2 𝜕𝜕 2
− + + Ψ(𝑥𝑥, 𝑦𝑦, 𝑧𝑧) = 𝐸𝐸𝐸(𝑥𝑥, 𝑦𝑦, 𝑧𝑧)
2𝑚𝑚 𝜕𝜕𝑥𝑥 2 𝜕𝜕𝑦𝑦 2 𝜕𝜕𝑧𝑧 2
equation:

 Wave function: Ψ𝛹𝛹( x𝑥𝑥,, y

𝑦𝑦,, 𝑧𝑧z ) =
= )Y𝑦𝑦( y𝑍𝑍) Z𝑧𝑧 ( z )(separation of variable)
𝑋𝑋 (𝑥𝑥x 𝑌𝑌
X
X𝑋𝑋( x𝑥𝑥 ) = A𝐴𝐴11cos
= cosk𝑘𝑘x𝑥𝑥x𝑥𝑥 +
+B 𝐵𝐵11 sin
sin 𝑘𝑘 k𝑥𝑥x 𝑥𝑥x z
Standing wave
YY( y𝑦𝑦) =A𝐴𝐴
= 22 cos
cosk𝑘𝑘y𝑦𝑦y𝑦𝑦++B𝐵𝐵22sin
sin k𝑘𝑘𝑦𝑦y 𝑦𝑦
y
Propagating wave ZZ( z𝑧𝑧) ==Ce ik z
𝐶𝐶𝑒𝑒 𝑖𝑖𝑘𝑘z 𝑧𝑧 𝑧𝑧
Quantum wire

 Boundary Ψ𝛹𝛹( 00,, 𝑦𝑦,

y ,𝑧𝑧z ) =
=0 ⇒ A
0⇒ 𝑋𝑋1 0=0= 0 ⟹ 𝐴𝐴1 = 0 L y
conditions Ψ𝛹𝛹( L
𝐿𝐿,,𝑦𝑦,y ,𝑧𝑧z )==
00 ⇒ 𝑋𝑋 𝐿𝐿 = 0 L
nπ 𝑛𝑛 𝜋𝜋 x
𝑥𝑥𝑛𝑛𝑥𝑥 𝜋𝜋
⟹
⇒⟹𝑘𝑘x𝑥𝑥𝑘𝑘L
k 𝐿𝐿𝑥𝑥 =𝐿𝐿=n
=𝑛𝑛π𝑥𝑥𝑛𝑛𝜋𝜋
⇒ ⟹
𝑥𝑥 𝜋𝜋k⟹ 𝑘𝑘𝑥𝑥𝑘𝑘=
x = 𝑥𝑥 =𝐿𝐿
L 𝐿𝐿

 𝑘𝑘𝑥𝑥 , 𝑘𝑘𝑦𝑦 Ψ𝛹𝛹( x𝑥𝑥,, 0

0,, 𝑧𝑧z ) =
=00⇒ A20=
⇒ 𝑌𝑌 0 0 ⟹ 𝐴𝐴2 = 0
= • Confined in
quantized Ψ𝛹𝛹( x𝑥𝑥,, 𝐿𝐿,
L,𝑧𝑧z )== 00 ⇒ 𝑌𝑌 𝐿𝐿 = 0 xy plane
• Free to move
mπ 𝑛𝑛𝑦𝑦𝑛𝑛𝜋𝜋𝑦𝑦 𝜋𝜋
⟹
⇒⟹k𝑘𝑘y𝑦𝑦𝑘𝑘L𝐿𝐿𝑦𝑦 𝐿𝐿
= =m
=𝑛𝑛π𝑦𝑦𝑛𝑛𝜋𝜋
⇒
𝑦𝑦 ⟹
𝜋𝜋 k
⟹ y 𝑘𝑘
= 𝑦𝑦 𝑦𝑦== 𝐿𝐿
𝑘𝑘 in z direction
L 𝐿𝐿

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

24
Electrons in a quantum wire
E E-k dispersion

(ℏ𝑘𝑘𝑧𝑧 )2 4ℏ2 𝜋𝜋 2
𝐸𝐸 = +
2𝑚𝑚 𝑚𝑚 𝐿𝐿
V =∞
(ℏ𝑘𝑘𝑧𝑧 )2 5ℏ2 𝜋𝜋 2

𝑋𝑋(𝑥𝑥) 𝐸𝐸 = +
2𝑚𝑚 2𝑚𝑚 𝐿𝐿
𝑛𝑛𝑥𝑥 , 𝑛𝑛𝑦𝑦 = (2, 2)
(ℏ𝑘𝑘𝑧𝑧 )2 ℏ2 𝜋𝜋 2
𝐸𝐸 = +
2𝑚𝑚 𝑚𝑚 𝐿𝐿
𝑛𝑛𝑥𝑥 , 𝑛𝑛𝑦𝑦 = (2, 1)
𝑛𝑛𝑥𝑥 , 𝑛𝑛𝑦𝑦 = (1, 2)
𝑛𝑛𝑥𝑥 , 𝑛𝑛𝑦𝑦 = (1, 1) 𝒌𝒌𝒛𝒛
𝑥𝑥 = 0 𝑥𝑥 = 𝐿𝐿

𝑌𝑌 𝑦𝑦 is the same (ℏ𝑘𝑘𝑧𝑧 )2 ℏ2 𝑛𝑛𝑥𝑥 𝜋𝜋 2 ℏ2 𝑛𝑛𝑦𝑦 𝜋𝜋 2

𝐸𝐸 = + +
2𝑚𝑚 2𝑚𝑚 𝐿𝐿 2𝑚𝑚 𝐿𝐿

Energy is quantized in kx and ky direction,

but is still continuous in kz direction

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

25
Electrons in a box (or quantum dot)
 Schrodinger 2  ∂2 ∂2 ∂2 
equation of free −  2 + 2 + 2 ψ = ( E − V )ψ
electrons  2m  ∂x ∂y ∂z 
 0 | x |≤ L / 2, | y |≤ L / 2, and | z |≤ L / 2
V =
∞ elsewhere
 Outside the box  ψ =0

ψ ( x, y, z ) = X ( x)Y ( y ) Z ( z ) → SE
 Inside the box 
2 ∂2 X 2 ∂2 X 2 ∂2 X
− = Ex X , − = E yY , − = Ez Z
2m ∂x 2 2m ∂y 2 2m ∂y 2

X = A1 cos k x x + B1 sin k x x
 General s z
solutions  Y = A2 cos k y y + B2 sin k y y Electrons are
confined in all
Z = A3 cos k z z + B3 sin k z z directions
L y
 Boundary 𝑋𝑋 0 = 𝑋𝑋 𝐿𝐿 = 0 L
𝑌𝑌 0 = 𝑌𝑌 𝐿𝐿 = 0 L
conditions  x
𝑍𝑍 0 = 𝑍𝑍 𝐿𝐿 = 0

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

26
Electrons in a box (cont’d)

 Apply boundary A1 = 0, A2 = 0, A3 = 0
conditions to X, Y, n xπ
and Z B1 sin nx L = 0 → k x =
L V =∞
n yπ
B2 sin n y L = 0 → k y =
L
n zπ
B3 sin nz L = 0 → k z =
L

2 π 2 2 2 2
 Energy  E( n x , n y , n z ) = 2
( n x + n y + n z )
2m L L

3/ 2
2 n π   n yπ   n z π 
 Wavefunction  ψ =  sin  x x  sin  y  sin  z
L  L   L   L 

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

27
Electrons in a box (cont’d)
 Unlike quantum wells and wires, in quantum boxes or dots, energy is completely
quantized.
 State of electron in the quantum box is specified by (kx, ky, kz) (and spin).
 Different combination of kx, ky, and kz can have same energy  degeneracy
 Degree of degeneracy depends on energy. The table below lists the degree of
degeneracy of the first few energy levels:

Quantum number (nx, ny, nz) Energy Degree of

(π2ħ2/2mL) degeneracy
(1,1,1) 3 Non-degenerate
(2,1,1), (1,2,1), (1,1,2) 6 3-fold
(2,2,1), (2,1,2), (1,2,2) 9 3-fold
(3,1,1), (1,3,1), (1,1,3) 11 3-fold
(2,2,2) 12 Non-degenerate
(1,2,3), (3,1,2), (2,3,1), (1,3,2), (2,1,3), (3,2,1) 14 6-fold

(3,2,2), (2,3,2), (2,2,3) 17 3-fold

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

28
Quantum well, wire, and box
(ℏ𝑘𝑘∥ )2 ℏ2 𝑛𝑛𝑥𝑥 𝜋𝜋 2
𝐸𝐸 = + E
E 2𝑚𝑚 2𝑚𝑚 𝐿𝐿
z
V =∞
3D (bulk) L
(free electron) (ℏ𝑘𝑘)2
𝐸𝐸 =
2𝑚𝑚
2D
k
y
𝑘𝑘 = (𝑘𝑘𝑥𝑥2 + 𝑘𝑘𝑦𝑦2 + 𝑘𝑘𝑧𝑧2 )1/2 Quantum well
x L k//
𝑘𝑘∥ = (𝑘𝑘𝑦𝑦2 + 𝑘𝑘𝑧𝑧2 )1/2

z E
z V =∞
V =∞

Quantum wire
L 0D y 1D
L
L L y
x
Quantum box L L 𝒌𝒌𝒛𝒛
x L
2 2
ℏ 𝜋𝜋 (ℏ𝑘𝑘𝑧𝑧 )2 ℏ2 𝑛𝑛𝑥𝑥 𝜋𝜋 2 ℏ2 𝑛𝑛𝑦𝑦 𝜋𝜋 2
𝐸𝐸 = (𝑛𝑛2 + 𝑛𝑛𝑦𝑦2 + 𝑛𝑛𝑧𝑧2 )
2𝑚𝑚𝐿𝐿2 𝑥𝑥 𝐸𝐸 =
2𝑚𝑚
+
2𝑚𝑚 𝐿𝐿
+
2𝑚𝑚 𝐿𝐿
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
29
 Outline of Lecture 3 & 4

Hydrogen atom
Electrons in free space
Electron tunneling through a 1D potential barrier
Electrons in a quantum box, well, and wire
Density of states
Fermi-Dirac distribution
Energy band structure
Metal, semiconductor and insulator
Semiconductor band structure
Concept of holes

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

30
 kz

Reciprocal
space

kx ky

But it is always the same in

reciprocal space: electrons fill up
the Fermi sphere.

Shape and size of Fermi sphere

don’t depend on the shape and
size of Cu in real space (as long
Copper can take different shapes in real space as it is approaching atomic limit)

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

31
Free electrons with periodic boundary
conditions
 Schrodinger ℏ2 𝜕𝜕 2 𝜕𝜕 2 𝜕𝜕 2
− + + 𝜓𝜓 = 𝐸𝐸𝐸𝐸
equation of free 2𝑚𝑚 𝜕𝜕𝑥𝑥 2 𝜕𝜕𝑦𝑦 2 𝜕𝜕𝑧𝑧 2
electrons 

 Boundary  ψ ( x , y , z ) = ψ ( x + L, y , z ) , ψ ( x , y , z ) = ψ ( x, y + L, z ) , ψ ( x, y , z ) = ψ ( x, y , z + L )
conditions
ψ ( x, y, z ) = X ( x)Y ( y ) Z ( z ) → SE
 Separation of
variable  2 ∂2 X 2 ∂2 X 2 ∂2 X
− = Ex X , − = E yY , − = Ez Z
2m ∂x 2 2m ∂y 2 2m ∂y 2

X ( x ) = A1eik x x + B1e − ik x x , Y ( y ) = A2 e
ik y y − ik y y
 General + B2 e
solutions  Z ( z ) = A3e ik z z + B3e −ik z z

2π 2π 2π
kx = nx , k y = ny , kz = nz (nx , n y , nz : integer )
 Apply boundary L L L
conditions   2π 
3

∆k x ∆k y ∆k z =   Volume occupied by one

 L  k-state in k-space

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

32
Density of states (DOS)
 Density of states (DOS) is a concept of great importance in dealing with
electrons in solids; it is defined as the number of available electronic states per
unit volume per unit energy around an energy E.

 From last slide, we can see that the volume occupied by one k-state in k-space
is given by
3
 2π 
∆VK =  
 L 
 Each k-state can accommodate two electrons with opposite spins; therefore,
the volume occupied by one electron is

1  2π 
3 kz
∆VK =   1  2π 
3

2 L  ∆VK = 
2 L 
 In order to find DOS, we need to determine the number of ky
k-states per unit energy interval in E-space.
kx

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

33
Density of states (cont’d)
 When L ∞, ∆Vk  0 kz
 Electrons fill up the k-space from the lowest to
the highest energy level; the latter is called
Fermi energy (EF).
ky
 Due to the quadratic dependence of energy on
k, the region of k-space occupied by electrons kx
has a spherical shape.

 2  2 L →∝
E =  ( )
 k x + k y2 + k z2 ≤ E F ∆Vk → 0
 2m 
 The surface of the sphere is called Fermi
surface.
Fermi
 DOS at (or near) the Fermi surface plays a sphere
crucial role in determining the properties of
solids.

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

34
Density of states (cont’d)
 Volume of the Fermi sphere:
4
VF = π (k F )
3
(k F = 2mE /  is the Fermi wavevector)
3
 Total number of electrons contained in the
Fermi sphere:
3 Real
4 1  2π  L
N = πk F3   space
3 2 L  L
L
 Total number of electrons in real space:
kz
N = nV = nL3
(n : electron density in real space)
 Total number of electrons is the same in both Reciprocal
space
spaces  3
4 1  2π  ky
nL3 = πk F3   kx
3 2 L 

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

35
Fermi wavevector & wavelength

Take Cu as
Total number of Total number of an example
electrons in electrons in 1 𝑚𝑚
real space reciprocal space
𝑛𝑛 = 8.49 × 1028 𝑚𝑚−3 Copper
3
4 1  2π  𝑘𝑘𝐹𝐹 = 13.57 𝑛𝑛𝑛𝑛−1
nL = πk F3
3
 
3 2 L  2𝜋𝜋 2𝜋𝜋
3 Δ𝑘𝑘𝐹𝐹 = = = 6.28 × 10−9 𝑛𝑛𝑛𝑛−1
1  2π  4 3 𝐿𝐿 1 𝑚𝑚
nL3 ⋅ ⋅   = πk F Δ𝑘𝑘𝐹𝐹 ≪ 𝑘𝑘𝐹𝐹 : Fermi surface very smooth
2  L  3
4 2𝜋𝜋
2n ⋅ 8π 3 = πk F3 𝜆𝜆𝐹𝐹 =
𝑘𝑘𝐹𝐹
= 0.46 𝑛𝑛𝑛𝑛 Very small !
3
k F3 = 3nπ 2 kz λF
(
k F = 3π 2 n )
1
3 Fermi wave vector

2π Fermi wave length

λ= Each point in k-space is
kF corresponding to a
wave in real space
kx ky

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

36
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
37
Fermi wavevector & wavelength (cont’d)

Fermi wavelength of Au: 5.2Å

Fermi wavelength of Cu: 4.6Å
Fermi wavelength of Al: 3.6Å

Atomic spacing in Cu: 2.3Å

Lattice constant of Cu: 3.61Å

Fermi wavelength of noble metals is

comparable to the lattice constant !

Difficult to see quantum

confinement effect in metal
To observe quantum confinement,
one needs atomic level structures
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
38
Density of states (cont’d)
 At Fermi surface:  Fermi energy
2
 2 k F2  2  2  N 0   3
EF =
= 3π   Total number ℏ
2m 2m   V  of electrons
𝐸𝐸𝐹𝐹 =
2𝑚𝑚
3𝜋𝜋 2 𝑛𝑛 2/3
= 36.46 × 10−2 𝑛𝑛2/3 /𝑚𝑚∗

𝑛𝑛 is electron density in 𝑛𝑛𝑛𝑛−3 and

 At energy E:
2
𝑚𝑚∗ is effective mass (dimensionless)
2k 2 2  2  N  3
Number of
=E = 3π     Fermi velocity
2m 2m   V  electrons
𝑉𝑉 2𝑚𝑚𝑚𝑚 3/2 within the ℏ𝑘𝑘𝐹𝐹
𝑁𝑁 = 2 sphere 𝑣𝑣𝐹𝐹 = = 3.58 × 107 𝑛𝑛1/3 /𝑚𝑚∗ [𝑐𝑐𝑐𝑐 𝑠𝑠 −1 ]
3𝜋𝜋 ℏ2 𝑚𝑚
defined by E
 Differentiate N w.r.t. E
E.g.: Copper
3
1 dN 1  2m  2 
= 2 2  E k 𝐸𝐸𝐹𝐹 = 36.46 × 10−2 (84.6)2/3 ≈ 7 𝑒𝑒𝑒𝑒 ~ 81000 𝐾𝐾!
V dE 2π   
dE (assume 𝑚𝑚∗ = 1)
3/ 2 E
1  2m  
D( E ) =   E 𝑣𝑣𝐹𝐹 = 0.358 𝑛𝑛1/3 = 1.57 × 108 𝑐𝑐𝑐𝑐/𝑠𝑠
2π 2   2  kF

 Use the rest mass of free electron Electron at Fermi level is very
21 “hot” & moving very fast
D( E ) = 6.812 ×10 E / eV V −1cm −3

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

39
Density of states in 2D z

 Each state can hold 2 electrons of opposite spin

(Pauli’s principle) Real
L space
 Area per state in k space:
2 y
1  2π  L
×
2  L 
 Number of states within the region with radius k: x

π k //2 k //2 E// Circular

2⋅
N= = A k// dE//
( 2π L ) 2π disk
2

Receiprocal
 Number of states within the region with radius E: space
mE// (ℏ𝑘𝑘∥ )2
𝐸𝐸 = + 𝐸𝐸𝑛𝑛𝑛𝑛
E // = (k // ) 2 / 2m N= A 2𝑚𝑚
π 2

 Number of states within interval dE// per unit area: Total density of states at E
𝑚𝑚
Density of states for dN 𝐷𝐷2𝐷𝐷 𝐸𝐸 = � Θ(𝐸𝐸 − 𝐸𝐸𝑛𝑛𝑥𝑥 )
𝜋𝜋ℏ2
dE// m 𝑛𝑛𝑥𝑥
one energy band D2 D (=
E// ) =
A π 2
1 when 𝑥𝑥 ≥ 0
Θ 𝑥𝑥 = �
0 otherwise

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

40
Density of states in 1D z

 Each state can hold 2 electrons of opposite spin

(Pauli’s principle)
y
 Length per state in k space: L
1  2π 
× Real space
2  L 
x

 Number of states within the region [-ky, ky]: dky dky

2k y 2k y ky
N= 2⋅ = L
( 2π L ) π 2kF
 Number of states within the region [-E,E]:
Reciprocal space
E y = (k y ) 2 / 2m 2 2mE y
N= L (ℏ𝑘𝑘𝑦𝑦 )2
π 𝐸𝐸 =
2𝑚𝑚
+ 𝐸𝐸𝑛𝑛𝑥𝑥 + 𝐸𝐸𝑛𝑛𝑧𝑧

 Number of states within interval dE per unit length:

dN
2𝑚𝑚 1
dE y 2m 1 𝐷𝐷1𝐷𝐷 𝐸𝐸 = � Θ(𝐸𝐸 − 𝐸𝐸𝑛𝑛𝑥𝑥 − 𝐸𝐸𝑛𝑛𝑧𝑧 )
D1 D (=
Ey ) = 𝜋𝜋ℏ 𝐸𝐸 − 𝐸𝐸𝑛𝑛𝑥𝑥 − 𝐸𝐸𝑛𝑛𝑧𝑧
L π Ey 𝑛𝑛𝑥𝑥 ,𝑛𝑛𝑧𝑧

Total density of states at E

Density of states for one energy band
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
41
Density of states in 3D, 2D, 1D
1.6E+21

1.4E+21 3D

Density of states for a

1.2E+21
3-D semiconductor
Density (cm-3eV-1)

1.0E+21 (blue curve) , a 10 nm

2D
quantum well with
8.0E+20
infinite barriers (red
6.0E+20 curve) and a 10 nm
1D by 10 nm quantum
4.0E+20
wire with infinite
2.0E+20 barriers (green
curve). m*/m0 = 0.8.
0.0E+00
0 20 40 60 80

Energy (meV)

http://ece-www.colorado.edu/~bart/book/dos.htm

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

42
Questions

1. Which of the following accurately describes the effect of quantum confinement on the
density of states (DOS) in quantum wells, quantum wires, and quantum dots?
a) In quantum wells, the DOS is a step function; in quantum wires, the DOS is inversely
proportional to the square root of energy; in quantum dots, the DOS consists of discrete
energy levels.
b) In quantum wells, the DOS is a linear function; in quantum wires, the DOS is constant; in
quantum dots, the DOS is a step function.
c) In quantum wells, the DOS is constant; in quantum wires, the DOS is a step function; in
quantum dots, the DOS is inversely proportional to the square root of energy.
d) In quantum wells, quantum wires, and quantum dots, the DOS is the same as in bulk
materials.

2. Which of the following factors primarily determines the energy level spacing in a quantum dot?
a) The shape of the quantum dot.
b) The material's band gap.
c) The size of the quantum dot.
d) The temperature of the environment.

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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 Outline of Lecture 3 & 4

Hydrogen atom
Electrons in free space
Electron tunneling through a 1D potential barrier
Electrons in a quantum box, well, and wire
Density of states
Fermi-Dirac distribution
Energy band structure
Metal, semiconductor and insulator
Semiconductor band structure
Concept of holes

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

44
Fermi-Dirac distribution
 Electrons are Fermions.
 Fermions are half-integer spin particles which obey the
Pauli exclusion principle.
 The Pauli exclusion principle states that only one
Fermion can occupy a single quantum state.
 As Fermions are added to a quantum system, they will fill Fermi
the available states in an energy band just like water fills sphere
a bucket, i.e., the states with the lowest energy are filled
first, followed by the next higher ones.
 At absolute zero temperature (T = 0 K), all states below T=0
Fermi energy are filled up and those above Fermi energy
are empty.
 However, at finite temperature, electrons near the Fermi Fermi
surface can always jumps forth and back between filled sphere
and empty states due to thermal agitation.
 The probability of finding an electron at an available
state obeys the Fermi-Dirac distribution. Finite temperature

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

45
Fermi-Dirac distribution
The Fermi-Dirac distribution describes the occupation of electrons in solids
and, in general, the populations of Fermions over their available states as a
function of temperature.
At absolute zero temperature, fermions
will fill up all energy levels below Fermi
The probability that level EF, obeying the Pauli exclusion
a particle will have principle. At elevated temperatures,
at energy E and some of them are “heated” up to levels
temperature T above the Fermi level.

1
f (E , T ) =
 E − EF (T ) 
1 + exp 
 k BT 
The quantum difference
that arises from the fact
that the particles are At low temperatures, those
indistinguishable. energy states below EF have a
probability of essentially 1, and
http://hyperphysics.phy-astr.gsu.edu those above EF essentially zero.

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

46
Fermi-Dirac distribution
 At T = 0, f(E) = is unity below EF and zero above EF.
 This is also true at room temperature except the region near the Fermi energy.
 For (E-EF) >> kBT, Fermi-Dirac distribution can be approximated by the Boltzmann
distribution.
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕 1/𝑘𝑘𝐵𝐵 𝑇𝑇
− = =
𝜕𝜕𝜕𝜕 𝜕𝜕𝐸𝐸𝐹𝐹 4𝑐𝑐𝑐𝑐𝑐𝑐𝑐2 𝐸𝐸 − 𝐸𝐸𝐹𝐹
1 2𝑘𝑘𝐵𝐵 𝑇𝑇
𝑇𝑇: 10, 100,
∞ 1/𝑘𝑘𝐵𝐵 𝑇𝑇
300, 500 𝐾𝐾 Since ∫−∞ 𝐸𝐸−𝐸𝐸𝐹𝐹 𝑑𝑑𝑑𝑑 = 1,
4𝑐𝑐𝑐𝑐𝑐𝑐𝑐2
2𝑘𝑘𝐵𝐵 𝑇𝑇

𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕
𝑓𝑓 0.5 we have 𝑇𝑇→0
lim −
𝜕𝜕𝜕𝜕
= lim
𝑇𝑇→0 𝜕𝜕𝐸𝐸𝐹𝐹
= 𝛿𝛿(𝐸𝐸 − 𝐸𝐸𝐹𝐹 )

𝛿𝛿(𝐸𝐸 − 𝐸𝐸𝐹𝐹 )
0
0.5 1 1.5
𝐸𝐸 − 𝐸𝐸𝐹𝐹 (𝑒𝑒𝑒𝑒) 0 0.5 1 1.5
𝐸𝐸/𝐸𝐸𝐹𝐹

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

47
 Outline of Lecture 3 & 4

Hydrogen atom
Electrons in free space
Electron tunneling through a 1D potential barrier
Electrons in a quantum box, well, and wire
Density of states
Fermi-Dirac distribution
Energy band structure
Metal, semiconductor and insulator
Semiconductor band structure
Concept of holes

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

48
 Solid

Crystalline Amorphous
Free isolated atoms

crystals

Electrons + Periodic lattice structure

Discrete energy levels

Bloch theorem Reciprocal lattice

Free electrons
Brillouin zone
Free electrons +
Periodic boundary
Bragg reflection at
Condition
BZ boundary

Quantization of k Energy band

metal semiconductor Insulator

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
49
Bloch’s theorem
 The wavefunction of electrons in a periodic potential is
   
ψ= (r )
nk
exp( ik ⋅ r ) u  (r )
nk

 
 unk ( r ) satisfies the relation

V (r)
 
  ψ (r)
u nk ( r + T ) =
 unk ( r )


Here 𝑇𝑇 is the periodicity of u(r)
the potential energy, 𝑘𝑘 is the 
ik ⋅r
wavevector, and n is the
e
index of energy band.
 The wavefunction of electrons in a periodic potential is the product
of a plane wave 𝑒𝑒 𝑖𝑖𝑘𝑘�𝑟𝑟⃗ and a function u(r) with the periodicity of the
crystal lattice.
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
50
Bloch’s theorem
 The quantity 𝑘𝑘, while still being the wavevector of the plane wave that is part
of the wave function, it has lost its simple meaning as in the case of free electrons.

 It can no longer be taken as a direct representation of the momentum 𝑝𝑝⃗ of the wave via
𝑝𝑝⃗ = ℏ𝑘𝑘 since:
ℏ ℏ ℏ
𝑝𝑝Ψ
̂ 𝑛𝑛𝑘𝑘 = ⃗ 𝑖𝑖𝑘𝑘�𝑟𝑟⃗ = ℏ𝑘𝑘Ψ𝑛𝑛𝑘𝑘 + 𝑒𝑒 𝑖𝑖𝑘𝑘�𝑟𝑟⃗ 𝛻𝛻𝑢𝑢𝑛𝑛𝑘𝑘 𝑟𝑟⃗ → 𝑝𝑝Ψ
𝛻𝛻Ψ𝑛𝑛𝑘𝑘 = 𝛻𝛻 𝑢𝑢𝑛𝑛𝑘𝑘 (𝑟𝑟)𝑒𝑒 ̂ 𝑛𝑛𝑘𝑘 ≠ ℏ𝑘𝑘Ψ𝑛𝑛𝑘𝑘
𝑖𝑖 𝑖𝑖 𝑖𝑖
 Instead of associating 𝑘𝑘 with the momentum of electrons, we may identify the quantity
ℏ𝑘𝑘 as the so‐called crystal momentum 𝑃𝑃, something like the combined momentum of
crystal and electrons.

 The crystal momentum 𝑃𝑃, while not a "true" momentum, still has many properties of the
momentum, in particular it is conserved during all kinds of scattering processes.
1 𝜕𝜕𝐸𝐸𝑛𝑛 (𝑘𝑘)
𝑉𝑉𝑛𝑛 𝑘𝑘 =
 Under external field electric field 𝐸𝐸 and magnetic field 𝐵𝐵, ℏ 𝜕𝜕𝜕𝜕
the electron dynamics is governed by Group velocity

𝑑𝑑𝑣𝑣⃗ 𝑑𝑑ℏ𝑘𝑘
𝑚𝑚 = −𝑒𝑒 𝐸𝐸 𝑟𝑟,
⃗ 𝑡𝑡 + 𝑣𝑣⃗ × 𝐵𝐵 𝑟𝑟,
⃗ 𝑡𝑡 = −𝑒𝑒 𝐸𝐸 𝑟𝑟,
⃗ 𝑡𝑡 + 𝑉𝑉𝑛𝑛 (𝑘𝑘) × 𝐵𝐵 𝑟𝑟,
⃗ 𝑡𝑡
𝑑𝑑𝑑𝑑 comparison 𝑑𝑑𝑑𝑑
(free electron) (electron in crystal)
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
51
Electrons in a periodic potential: Kronig-
Penney Model
 Kronig and Penney assumed that an electron experiences an
infinite one-dimensional array of finite potential wells & barriers.

𝑽𝑽(𝒙𝒙)
barrier
𝑽𝑽𝟎𝟎
well
𝒙𝒙
−𝒂𝒂 − 𝒃𝒃 −𝒃𝒃 0 𝒂𝒂 𝒂𝒂 + 𝒃𝒃

 Schrödinger equation is
 2 ∂ 2ψ ( x)
− = Eψ ( x) (in the well region )
2m ∂x 2
 2 ∂ 2ψ ( x)
− 2
= ( E − V0 )ψ ( x) (in the barrier region )
2m ∂x

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

52
Kronig-Penney Model (Cont’d)
 According to Bloch’s theorem:    
ψ= (r )
nk
exp(ik ⋅ r )unk ( r )
  
ψ(a + b < x < 2a + b) = ψ (0 < x < a)e ik ( a + b ) u nk ( r + T ) =
unk ( r )

ψ(a < x < a + b) = ψ (−b < x < 0)eik ( a +b ) 𝑽𝑽(𝒙𝒙) 𝑇𝑇 = 𝑎𝑎 + 𝑏𝑏

barrier
𝑽𝑽𝟎𝟎

 Solution of Schrödinger equation: well

𝒙𝒙
−𝒂𝒂 − 𝒃𝒃 −𝒃𝒃 0 𝒂𝒂 𝒂𝒂 + 𝒃𝒃

βx − βx [2m(V0 − E )]1/ 2
Ψ = Ce + De , β= -b < x < 0


iα x − iα x (2mE )1/ 2
Ψ = Ae + Be , α= 0<x<a

 Boundary conditions:

ψ is continuous at x = 0 → A+ B = C + D
dψ / dx is continuous at x = 0 → iα(A-B) = β(C-D)
ψ is continuous at x = a → Aeiαa + Be −iαa = (Ce − βb + De βb )e ik ( a +b )
dψ / dx is continuous at x = a → iα ( Aeiαa − Be −iαa ) = α (Ce − βb − De βb )eik ( a +b )
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
53
Kronig-Penney Model (Cont’d)
 These simultaneous equations will only have solutions when
𝑒𝑒 𝑥𝑥 + 𝑒𝑒 −𝑥𝑥
cosh 𝑥𝑥 =
β2 − α 2 2
sinh β b sin αa + cosh β b cos αa = cos k(a + b) 𝑒𝑒 𝑥𝑥 − 𝑒𝑒 −𝑥𝑥
2α β sinh 𝑥𝑥 =
2
5
10
1200 20 20

1000

15 15
800

𝑉𝑉0 = 1 𝑒𝑒𝑒𝑒 𝑉𝑉0 = 1 𝑒𝑒𝑒𝑒 𝑉𝑉0 = 100 𝑒𝑒𝑒𝑒

600
𝑎𝑎 = 5 𝑛𝑛𝑛𝑛 10
𝑎𝑎 = 5 𝑛𝑛𝑛𝑛 𝑎𝑎 = 5 𝑛𝑛𝑛𝑛
10

𝑏𝑏 = 1 𝑛𝑛𝑛𝑛 𝑏𝑏 = 0.2 𝑛𝑛𝑛𝑛 𝑏𝑏 = 0.2 𝑛𝑛𝑛𝑛

400

5 5
200

0
0 0

-200

-400 -5 -5
0 10 20 30 0 10 20 30 0 10 20 30

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

54
Kronig-Penney Model (Cont’d)
 Consider the case of a periodic 𝛿𝛿 potential in the limit:

𝑏𝑏 → 0, 𝑉𝑉0 → ∞, but 𝛽𝛽 2 𝑏𝑏𝑏𝑏/2 = 𝑃𝑃 is finite 𝑉𝑉(𝑥𝑥)

2𝑃𝑃
 In this case, 𝛽𝛽 ≫ 𝛼𝛼, 𝛽𝛽𝛽𝛽 = ≪ 1, 𝑥𝑥
𝛽𝛽𝛽𝛽 -a 0 a
the equation in the previous slide
(2𝑚𝑚𝑚𝑚)1/2 2𝑚𝑚 𝑉𝑉0 − 𝐸𝐸 1/2
can be simplified as follows: 𝛼𝛼 = ; 𝛽𝛽 =
ℏ ℏ

β2 − α 2
sinh β b sin αa + cosh β b cos αa = cos k(a + b)
2αβ

≈ 𝛽𝛽𝛽𝛽 ≈1

𝛽𝛽 2 𝛽𝛽 2 𝑏𝑏𝑏𝑏 𝑃𝑃 P
≈ = =
2𝛼𝛼𝛼𝛼 2𝛼𝛼𝛼𝛼𝛼𝛼𝛼𝛼 𝛼𝛼𝛼𝛼𝛼𝛼𝛼𝛼 sin α a + cos α a =
cos ka
αa

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

55
Kronig-Penney Model (Cont’d)
P
sin α a + cos α a =
cos ka
αa

left

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

56
Kronig-Penney Model (Cont’d)

P For allowed 𝛼𝛼, we can use this

sin αa + cos αa = cos ka equation to calculate 𝑘𝑘, and
αa then plot 𝐸𝐸 as a function 𝑘𝑘

𝑃𝑃
L.H.S. 𝑘𝑘𝑘𝑘 = 𝑐𝑐𝑐𝑐𝑐𝑐 −1 sin 𝛼𝛼𝛼𝛼 + cos 𝛼𝛼𝛼𝛼 + 𝑛𝑛𝑛𝑛
𝛼𝛼𝛼𝛼

𝐸𝐸

𝛼𝛼𝛼𝛼 𝐸𝐸 − 𝑘𝑘 dispersion is
different from that
of free electrons
Forbidden
1st allowed energy region 
band appears in bandgap
this range of 𝛼𝛼𝛼𝛼 (ℏ𝑘𝑘)2
𝐸𝐸 =
2𝑚𝑚
(2𝑚𝑚𝑚𝑚)1/2 (ℏ𝛼𝛼)2
𝛼𝛼 = 𝐸𝐸 =
ℏ 2𝑚𝑚

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

57
Kronig-Penney Model (Cont’d)
 E-K dispersion is periodic in k-space. As 𝑘𝑘 and 𝑘𝑘 + 𝑛𝑛𝐺𝐺⃗ (where 𝐺𝐺⃗ is
the translational vector of the reciprocal space) represent the
same state of the system, we can bring the E-k dispersion into the
1st BZ, leading to reduced zone representation of E-k dispersion.

'
 
Let k = k + nG
𝑮𝑮  ik' ⋅r
𝑮𝑮 ψ k' = uk' ( r )e
 inG ⋅r ik⋅r
= uk' ( r )e e
 
𝑮𝑮 = uk ( r )e ik ⋅r


𝑮𝑮 = ψ k ( r )

⃗ 𝑟𝑟⃗
Both 𝑢𝑢𝑘𝑘 , and 𝑒𝑒 𝑖𝑖𝑖𝑖𝐺𝐺� are
periodic function of 𝑇𝑇.
Extended zone Reduced zone

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

58
 How are the band and gap formed?
(ℏ𝑘𝑘)2 E E E E
𝐸𝐸 = + 𝑉𝑉
2𝑚𝑚 Ψ2 (𝑘𝑘 = 0) = 𝑢𝑢2 1 + 𝑢𝑢2 2
+ 𝑢𝑢2 3 + 𝑢𝑢2 4 …

𝑢𝑢2 (1) 𝐸𝐸2

Ψ2 (𝑘𝑘 = 𝜋𝜋/𝑎𝑎) = 𝑢𝑢2 1 − 𝑢𝑢2 2

+ 𝑢𝑢2 3 − 𝑢𝑢2 4 … 𝑢𝑢1 (1) 𝐸𝐸1
𝐸𝐸2 4

3 Bring these quantum wells

𝑢𝑢1 1 −𝑢𝑢1 2 𝑢𝑢1 3 −𝑢𝑢1 4
2 closer with each other
𝐸𝐸1 1
Ψ1 (𝑘𝑘 = 𝜋𝜋/𝑎𝑎) = 𝑢𝑢1 1
− 𝑢𝑢1 2 + 𝑢𝑢1 3 − 𝑢𝑢1 4 …
3

𝑢𝑢1 1 𝑢𝑢1 2 𝑢𝑢1 3 𝑢𝑢1 4

2
𝑢𝑢𝑖𝑖 𝑗𝑗 : wavefunction of Ψ1 (𝑘𝑘 = 0) = 𝑢𝑢1 1 + 𝑢𝑢1 2
isolated quantum well + 𝑢𝑢1 3 + 𝑢𝑢1 4 …
𝑖𝑖: index for energy level
j: index for quantum well     States 3 and 2 have the same k, but
ψ=
( r ) exp(ik ⋅ r )unk ( r )

nk different potential energy
EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010
59
 Outline of Lecture 3 & 4
Hydrogen atom
Electrons in free space
Electron tunneling through a 1D potential barrier
Electrons in a quantum box, well, and wire
Density of states
Fermi-Dirac distribution
Energy band structure
Metal, semiconductor and insulator
Semiconductor band structure
Concept of holes

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

60
Metal, semiconductor and insulator
 Electric conductivity of solid can be qualitatively understood from the
energy band structure.
 For the sake of simplicity, consider a 1D atomic chain with inter-atomic
spacing a and length L. Apply a periodic boundary condition, the k
vector will be quantized as 2𝜋𝜋 L
𝑘𝑘 = 𝑛𝑛 (n = 1, 2, . . N)
𝐿𝐿

 The BZs can be sketched below: a 𝐿𝐿

= 𝑁𝑁
Direct lattice 𝑎𝑎
G 1 st BZ

−π π 1st BZ
a a ∆𝑘𝑘 =
2𝜋𝜋
𝐿𝐿
N k-states with
− 4π − 2π 2π 4π
0 spin degeneracy
a a a a Width of 1st BZ
Reciprocal lattice

As L = Na (N is total number of atoms in period L), there are 2N 2𝜋𝜋/𝑎𝑎 2𝐿𝐿

2× = = 2𝑁𝑁
available states in the first BZ including the spin degeneracy. 2𝜋𝜋/𝐿𝐿 𝑎𝑎
spin degeneracy
∆𝑘𝑘 (width of 1 k − state)

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61
Metal, semiconductor and insulator
𝐸𝐸
 For monovalent atoms, there is only one
electron per atom; thus the 1st BZ will be
half filled up.
Total number of electrons: N

 In this case, the material will be a metal

because electrons can flow under an
applied field.

 The material can also be a metal when

there are overlapping bands and at least
Total number of
one of them is partially filled. states: 2N
𝑘𝑘
2𝜋𝜋/𝑎𝑎 2𝐿𝐿 −
π 0 π
2× = = 2𝑁𝑁 (total number of states) a a
2𝜋𝜋/𝐿𝐿 𝑎𝑎

2N available states in the 1st BZ, but only N electrons are available.

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Metal, semiconductor and insulator
𝐸𝐸
 For the case of divalent atoms, there
are 2 electrons per atom; thus the 1st
BZ will be fully filled up.
Total number of electrons: 2N

 In this case, the material can either be

a semiconductor if the forbidden gap
at the 1st BZ boundary is smaller than
4 eV, or an insulator otherwise.

 This is because when the bandgap is

small, some of the electrons can be
excited to the higher energy band
which allows electron to “flow” when 𝑘𝑘
−
π 0 π
it is partially filled. a a

2𝜋𝜋/𝑎𝑎 2𝐿𝐿
2× = = 2𝑁𝑁 (total number of states)
2𝜋𝜋/𝐿𝐿 𝑎𝑎 2N available states in the 1st BZ

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Metal, semiconductor and insulator
 A crystal can only be an insulator if the
number of valence electrons in a primitive 𝐸𝐸
cell is an even integer.
 However, if the bands overlap, then instead
of one filled band (insulator), we can have
two partially filled bands metal (e.g., Alkaline
earth metals are divalent but have
overlapping bands).
 In diamond, silicon and germanium, each of
two atoms of valence four have eight valence
electrons per primitive cell. But the bands do
not overlap so they are insulators at T = 0K.
 As the temperature is increased, electrons
are thermally excited from the valence band 𝑘𝑘
−
π 0 π
to the conduction band. The materials a a
become semi-conductive.
Thermal excitation

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Metal, semiconductor and insulator (cont’d)
Insulator Semimetal if overlap is small Metal
Metal if overlap is large
Carrier density N.A. 1019-1020 / cm3 1022 / cm3

empty Partially
Band filled
overlap.
Large gap

Filled partially
Filled
filled

Resistivity (Ωm) Resistivity (Ωm) Resistivity (Ωm)

Glass 1012 Magnesium 4.93 x 10-8 Aluminum 2.65 x 10-8

Mica 9 x 1013 Bismuth 1.29 x 10-6 Copper 1.72 x 10-8
Quartz Graphite 3-6 x 10-5 Gold 2.24 x 10-8
5 x 1016
(fused)

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Electrical properties of semiconductors
 Resistivity of a conductor decreases with decreasing temperature.
 The rate of decrease slows down at very low temperature and resistivity
eventually saturates at a nonzero resistance as T → 0.
 In contrast, the resistivity of a typical semiconductor increases
dramatically as T → 0.

Movable carriers decrease quickly

Movable carriers does not change much with temperature with reducing temperature

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Metal, semiconductor and insulator (cont’d)

Metal Semiconductor

High carrier density Low - high carrier density

Small length scale Good conductor Large length scale Variable conductivity

Difficult to Difficult to modulate Easy to observe Easy to modulate

quantum size carrier density quantum size carrier density
effect effect

Difficult to make Easy to make

switches and switches and
transistors transistors

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 Outline of Lecture 3 & 4

Hydrogen atom
Electrons in free space
Electron tunneling through a 1D potential barrier
Electrons in a quantum box, well, and wire
Density of states
Fermi-Dirac distribution
Energy band structure
Metal, semiconductor and insulator
Semiconductor band structure
Concept of holes
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Brillouin zone of 1D lattice
 The K-P model is powerful in the sense that it successfully explains the
origin of bandgap formation in a periodic potential.
 However, the K-P model cannot be applied directly to the calculation of
band structures of real crystals which mostly have a three-dimensional
(3D) lattice, though recently 2D crystals have also attracted the interest
due to discovery of graphene.
 To deal with the band structure of 2D and 3D crystals, we must first look
at the BZ in 2D and 3D cases. (Recap: BZ of 1D atomic chain).

Real
space
1st BZ
Reciprocal
space 2nd BZ
− 4π − 2π 2π 4π
0 3rd BZ
a a a a

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Brillouin zone of 2D lattice
 Recap: BZ of a 2D crystal

Reciprocal
lattice

1st zone

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Brillouin zone of 2D lattice (cont’d)
 Brillouin zone of a square lattice

II

III

Reciprocal lattice 1st, 2nd, 3rd BZ of a square lattice

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Brillouin zone of 3D semiconductors
 First Brillouin zone of a 3D crystal
is characterized by high symmetry
points and lines conneting its
center with these points.
 High symmetry points and lines
inside BZ are denoted by Greek
letters. K

 Points on the surfaces of the BZ

are denoted by Roman letters.
 The center of BZ is always
denoted by Γ.
 Example of FCC lattice:
[010] direction: Γ∆Χ
[111] direction: ΓΛL
[110] direction: ΓΣK

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Brillouin zone of 3D semiconductors
 The Brillouin zone of the FCC lattice is highly symmetrical which
originates from the symmetry of direct lattice.
 The operations that don’t cause any change to BZ are known as
symmetry operations of the Brillouin zone.
 If two wave vectors k and k’ in the Brillouin zone can be
transformed into each other under a symmetry operation of the
Brillouin zone, then the electronic energies at these wave vectors
must be identical.
K
 For example, in the Brillouin zone of FCC, there are eight hexagonal
faces containing the point labelled L in the centre. These eight faces
including the L points are equivalent and can be transformed into
one another through rotations by 90°.
1st BZ of FCC lattice
 Therefore, when calculating E-K dispersion curves, it is only
necessary to calculate those along high symmetry lines.

High symmetry points

and directions from Γ
point in the Brillouin
zone of the fcc lattice

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Semiconductor band structure
 The band structure of electrons in a solid may be calculated by solving the
following Schrödinger equation:
𝐻𝐻𝐻𝐻 = 𝐸𝐸𝐸𝐸

𝑝𝑝𝑖𝑖2 𝑃𝑃𝑗𝑗2 1 𝑍𝑍𝑖𝑖 𝑍𝑍𝑗𝑗 𝑒𝑒 2 𝑍𝑍𝑗𝑗 𝑒𝑒 2 1 𝑒𝑒 2

𝐻𝐻 = � +� + � −� + �
2𝑚𝑚𝑖𝑖 2𝑀𝑀𝑗𝑗 2 4𝜋𝜋𝜀𝜀0 |𝑅𝑅𝑖𝑖 − 𝑅𝑅𝑗𝑗 | 4𝜋𝜋𝜀𝜀0 |𝑟𝑟⃗𝑖𝑖 − 𝑅𝑅𝑗𝑗 | 2 4𝜋𝜋𝜀𝜀0 |𝑟𝑟⃗𝑖𝑖 − 𝑟𝑟⃗𝑗𝑗 |
𝑖𝑖 𝑗𝑗 𝑖𝑖≠𝑗𝑗 𝑖𝑖,𝑗𝑗 𝑖𝑖≠𝑗𝑗

where 𝑟𝑟⃗𝑖𝑖 , pi, m and –e denote the coordinate, momentum, mass and
charge of electrons, while 𝑅𝑅𝑗𝑗 , Pj, M and Zje are the corresponding
quantities for the nuclei.
 The above equation can only be solved with several steps of simplifications.
 The first approximation is to separate electrons into two groups: valence
electrons and core electrons. The latter can be “lumped” together with the
nuclei.
 The next approximation invoked is the Born–Oppenheimer or adiabatic
approximation, in which the motion of ions can be ignored on the time scale
of electron motion (the former is > 1000 times slower than the latter).

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Semiconductor band structure (cont’d)
 With the Born-Oppenheimer approximation the Hamiltonian can be
expressed as the sum of three terms:
    
H H ion ( R j ) + H e ( ri + R j 0 ) + H e−ion ( ri + δ R j )
=
H ion describes the ionic interaction
motion
H e describes the electronic motion
H e−ion describes the electron-ion interaction
 The electronic Hamiltonian is given by

𝑝𝑝𝑖𝑖2 1 𝑒𝑒 2 𝑍𝑍𝑗𝑗 𝑒𝑒 2
𝐻𝐻 = � + � −�
2𝑚𝑚𝑖𝑖 2 4𝜋𝜋𝜀𝜀0 |𝑟𝑟⃗𝑖𝑖 − 𝑟𝑟⃗𝑗𝑗 | 4𝜋𝜋𝜀𝜀0 |𝑟𝑟⃗𝑖𝑖 − 𝑅𝑅𝑗𝑗𝑗 |
𝑖𝑖 𝑖𝑖≠𝑗𝑗 𝑖𝑖,𝑗𝑗

 Diagonalizing this Hamiltonian to obtain the band structure is a

formidable job because there are >1023 electrons/cm3 in a typical solid.
We have to resort on a very drastic approximation known as the mean-
field approximation. This will reduce the many particle problem into a
one-electron problem.

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Semiconductor band structure (cont’d)
 In the mean-field approximation, the Hamiltonian for every electron is the
same and is given by
p2 
H=
1e + V ( r )
2m

 The next step to calculate the one-electron potential V(r) and the solve
the Schrödinger equation. Both steps are not so straightforward in real
semiconductors.
 The former has to rely on various approximations, while the latter needs
to make use of the symmetry properties of the crystals and their
corresponding reciprocal lattices.
 Commonly used methods for calculating the band structures of
semiconductors include:

- Tight-binding - k·p approximation

- Orthogonal plane-wave - Density functional theory
- Pseudopotential

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Band structure of Si, Ge and GaAs
 As an example, we show below the band structures of Ge, Si, and GaAs

 Note that, for each direction, we only show the k>0 portion as E(k) = E(-k)
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Band structure of Si, Ge and GaAs (cont’d)

 Band structures of GaAs at room temperature

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Band structure of Si, Ge and GaAs (cont’d)

 Band structures of GaAs in other directions

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Semiconductor band structure (Cont’d)
 Some key concepts and conventions:
 Conduction band: the lowest empty band at T = 0 K
 Valence band: the highest filled band at T = 0 K
 Forbidden (or energy gap): the gap between the top
edge of valence band and bottom edge of
conduction band
 Energy at bottom edge of conduction band: Ec
 Energy at top edge of valence band: Ev
 Energy gap EG = Ec-Ev
 The energy scale in band structure is often
referenced to the energy at the top edge of the
valence band.
 Direct bandgap: bottom edge of conduction band
and top edge of valence band appear at same k
 Indirect bandgap: not direct bandgap
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Semiconductor band structure (Cont’d)
 Some remarks about the conduction band:
 The conduction band is double degenerate due to electron spin.
 The conduction-band minimum is not always at k = 0.
 The conduction-band minimum of Ge occurs at right the zone
boundary in eight equaivalent <111> directions.  indirect bandgap
 For Si, the conduction-band minimum occurs at k = 0.8(2π/a) in six
equivalent <100> directions.  indirect bandgap
 In GaAs, the conduction minimum occurs at k = 0, though the L-
valley at the zone boundary is only 0.29 eV away from conduction-
band minimum.  direct bandgap

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Energy band structure (Cont’d)
 Some remarks about the valence band:
 In all cases the valence-band maximum occurs at
the zone center, at k = 0.
 The valence band consists of three sub-bands:
- heavy hole band (smaller curvature at k=0)
- light hole band (larger curvature at k=0)
- split-off band due to spin-orbit coupling
 The heavy and light hole bands are degenerate at
the zone center, though the degeneracy may be
lifted by quantum confinement or strain effect.
 All the three bands are double degenerate due to
electron spin.
 Curvature of the sub-bands in general depend on
the direction in reciprocal space.

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Effective mass
 Group velocity of electrons:

  ∂ω ∂ω ∂ω  1  ∂E ∂E ∂E  1
v g=  , , =  , , = ∇k E
 ∂k ∂k y ∂k z    ∂k x ∂k y ∂k z  
 x

 Change of vg under an applied electrical field:


d  1d 
1 d ∂E ∂E ∂E  
1 d ∂E d ∂E d ∂E dk 
vg= ∇k E =  , , =   ,  ,  
dt  dt  dt  ∂k x ∂k y ∂k z    dk ∂k x dk ∂k y dk ∂k z  dt

  2
1 ∂ E ∂ E 2
∂ E2   2 2
∂ E ∂ E ∂ E 2   2
∂ E 2
∂ E ∂ E dk2  
=  2 , ,  , , 2,  , , , 
   ∂k x ∂k y ∂k x ∂k z ∂k x   ∂k x ∂k y ∂k y ∂k z ∂k y   ∂k x ∂k z ∂k y ∂k z ∂k z   dt
     
 
1 dk  dk
= ∇k (∇k E ) = 2
 dt  / ∇k (∇k E ) dt
Compare this with free electron's case:
 
d  d  k   dk
v g=  = ⇒ m*=  2 / ∇k (∇k E ) (effective mass)
dt dt  m  m dt

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Effective mass (cont’d)
 Effective mass is a tensor. Its component is given by

1 𝜕𝜕 2 𝐸𝐸
(𝑚𝑚 ∗)−1
𝑖𝑖𝑖𝑖 = 2 (𝑖𝑖, 𝑗𝑗 = 𝑥𝑥, 𝑦𝑦, 𝑧𝑧)
ℏ 𝜕𝜕𝑘𝑘𝑖𝑖 𝜕𝜕𝑘𝑘𝑗𝑗

 In semiconductors, we are usually concerned about electrons

around certain extrema points in k space. Near these points (k0),
E can be expanded into a Taylor’s series

ℏ2 2
ℏ2
𝐸𝐸(𝑘𝑘) = 𝐸𝐸(𝑘𝑘0 ) + � (𝑘𝑘 − 𝑘𝑘𝑖𝑖𝑖 ) + � (𝑘𝑘 − 𝑘𝑘𝑖𝑖𝑖 )(𝑘𝑘𝑗𝑗 − 𝑘𝑘𝑗𝑗𝑗 )
2𝑚𝑚𝑖𝑖𝑖𝑖 𝑖𝑖 𝑚𝑚𝑖𝑖,𝑗𝑗 𝑖𝑖
𝑖𝑖 𝑖𝑖≠𝑗𝑗

 In most cases, however, a rotation of coordinate axis should be

able to eliminate the cross product terms of different k
components and lead to a parabolic dispersion curve:

ℏ2 𝑘𝑘𝑥𝑥2 ℏ2 𝑘𝑘𝒚𝒚2 ℏ2 𝑘𝑘𝒛𝒛2

𝐸𝐸(𝑘𝑘) = 𝐸𝐸(𝑘𝑘0 ) + + +
2𝑚𝑚𝑥𝑥𝑥𝑥 2𝑚𝑚𝑦𝑦𝑦𝑦 2𝑚𝑚𝑧𝑧𝑧𝑧

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Effective mass (cont’d)

 Effective mass can be measured using

the cyclotron resonance technique
𝑚𝑚𝑒𝑒 𝑣𝑣 2 𝑣𝑣 𝑞𝑞𝑞𝑞
= 𝑞𝑞𝑞𝑞𝑞𝑞 → 𝑓𝑓𝑐𝑐𝑐𝑐 = =
𝑟𝑟 2𝜋𝜋𝜋𝜋 2𝜋𝜋𝑚𝑚𝑒𝑒
Centripetal Lorentz force

fcr : Cyclotron resonance frequency

 Electrons strongly absorb microwaves

at resonance frequency. By
measuring fcr, me can be determined.

Si Ge GaAs InAs AlAs

me/m0 0.26 0.12 0.068 0.023 2
mh/m0 0.39 0.3 0.5 0.3 0.3

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Effective mass (cont’d)

 Effective electron mass (in units of the free-electron mass 𝑚𝑚𝑜𝑜 ) as a

function of the (low-temperature) band gap for several (direct band gap)
∗ 𝐸𝐸𝑔𝑔
semiconductors. The dashed line fulfills 𝑚𝑚 �𝑚𝑚𝑜𝑜 = 20 𝑒𝑒𝑒𝑒

Marius Grundmann
(Springer, 2021)

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86
Energy band diagram
 Once the effective masses are known at the extrema points, for practical
applications it is often sufficient to just focus on electrons near the
bottom edge of conduction band and top edge of valence band.
 If we draw two straight lines in real space at both Ec and Ev, we obtain the
so-called energy band diagram, which is very useful in designing and
understanding semiconductor devices.

Energy band diagram

Electronic band structure
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87
Constant energy surface
 From the E-k dispersion, one can construct a surface in k-space on which
all the allowed k-states will have the same energy, or constant energy
surface.
 At T = 0, the constant energy surface with highest energy for the filled-up
states is called Fermi surface.
 Fermi surface plays a crucial in understanding the electron dynamics at
the presence of an electromagnetic field.
 For free-electrons, the constant energy surface is always a spherical
surface:
kz

  2k 2  2k y2  2k 2
E (k ) = x
+ + z
= constant
2m 2m 2m

kx ky

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Constant energy surface (cont’d)

 For semiconductors, instead of

using E = 0, we use either Ec or Ev
as the reference to construct the
equal energy surface as follows:

E ( k ) − Ec (or Ev ) =
constant

 The conduction band minima of Ge are located at the L point along the <111> axis and
that the conduction band minima of Si are located at the Δ point, 15% from the X
point, along the <100> axis.
 If we take these axes as the principal axes and k = 0 at the bottom of the conduction
band, the constant-energy surfaces will be defined by
 2 2 2 2 2
= E (k ) (k x +k x ) + k z = constant
2mt 2ml
 These are ellipsoids of revolution with their long axis on <100> axes in Si and on <111>
axes in Ge. The constant-energy surface is spherical in GaAs.

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Constant energy surface (cont’d)

 Since the conduction bands consist of multiple energy

surfaces, the conduction bands are called many valleys
or many-valley structure.
 In Si there are 6 valleys, while in Ge there exist 4 valleys
(the pairs of valleys along the principal axis are apart
from the reciprocal lattice vector G and they are
equivalent).
 Recently there is an increasing interest in exploiting
valley degree of freedom for electronics applications –
a field called valleytronics, e.g.,
"Condensed-matter physics: Polarized light boosts Intersection of
valleytronics". Kamran Behnia, Nature
Nanotechnology 7, 488–489 (2012). constant energy
Jump up ^ "Valleytronics: Electrons dance in
surface by the
diamond". Christoph E. Nebel. Nature Materials 12, 1st BZ boundary
690–691 (2013). in Ge.

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 Outline of Lecture 3 & 4
Hydrogen atom
Electrons in free space
Electron tunneling through a 1D potential barrier
Electrons in a quantum box, well, and wire
Density of states
Fermi-Dirac distribution
Energy band structure
Metal, semiconductor and insulator
Semiconductor band structure
Concept of holes

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Concept of holes

 When an electric field is applied to a semiconductor, electrons in a fully

filled band don’t contribute any net current as
𝐽𝐽⃗ = � −𝑒𝑒𝑣𝑣⃗𝑔𝑔 𝑘𝑘 = 0
𝑘𝑘

 However, if there is an electron missing at 𝑘𝑘 ′ , the net current will be

𝐽𝐽⃗𝑘𝑘 ′ = � −𝑒𝑒 𝑣𝑣⃗𝑔𝑔 𝑘𝑘 − −𝑒𝑒 𝑣𝑣⃗𝑔𝑔 𝑘𝑘 ′ = +𝑒𝑒 𝑣𝑣⃗𝑔𝑔 𝑘𝑘 ′

𝑘𝑘

 Therefore, a missing electron behaves like a positively charged (+e)

particle (not a physical particle), which is called a “hole”.
 Electrons near the top of the valence band behave as if they have negative
mass as E-k curvature is negative. However, electrons in valence band
can’t move unless there is a hole. In other words, when there is a hole in
the valence band, it will behave like a positively charged particle with a
positive effective mass 𝑚𝑚ℎ∗ = 𝑚𝑚𝑒𝑒𝑒𝑒
∗
:
∗
𝑑𝑑𝑣𝑣⃗𝑔𝑔 𝑘𝑘 ∗
𝑑𝑑𝑣𝑣⃗𝑔𝑔 𝑘𝑘
− 𝑚𝑚𝑒𝑒𝑒𝑒 = −𝑒𝑒𝐸𝐸 ⇒ 𝑚𝑚𝑒𝑒𝑒𝑒 = (+𝑒𝑒)𝐸𝐸
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑

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Constant energy surface of holes
 Due to the p-like symmetry and mixing of
valence band states, the constant energy
surfaces of holes are more complicated.
 In general, the E-K dispersion may be E
written as c

E (k ) =−
2
2m {
Ak ±  B k + C ( k x k y + k y k z + k z k x )
2
 2 4 2 2 2 2 2 2 2

12
}
Here, A, B, and C are the constants that characterize
k
the valence band
 The effective masses of the valence bands
are given by hh
lh
* mo mo
mhh = , mlh*
A − B2 + C 2 / 6 A + B2 + C 2 / 6 so
m
mso* = o
A

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 Marius Grundmann
(Springer, 2021)

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

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Marius Grundmann
(Springer, 2021)
Marius Grundmann
(Springer, 2021)
Density of state of electrons and holes
 We learned that for free-electrons in 3D space, DOS is given by
3/ 2
1  2m 
D( E ) =   E
2π 2   2 
 Similarly, for electrons and holes in semiconductors with single valley and
parabolic bands, DOS is
3/2
1  2me* 
=DC ( E ) E − EC for electrons in conduction band
2π 2   2 
3/2
1  2mh* 
=DV ( E ) EV − E for holes in valence band
2π 2   2 

 For semiconductors with multiple valleys and anisotropic effective mass,

in principle, we still can use the same expression to calculate the density
of states.
 However, in this case, we have to replace the effective mass with density
of states effective mass.
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Density of state of electrons and holes
 For electrons in Si, the density of states effective mass is given by
* 2/3
=mde Z= ( ml mt2 )1/3 1.08m0
=( Z 6 is number of valleys,
= ml 0.98
= m0 , mt 0.19m0 )

 For electrons in GaAs, mde* = 0.067m0 (single valley with isotropic mass)
 For holes in valence bands,
* 32
=mdh ( mhh + mlh3 2 ) 2 3
*
Si : m=
lh 0.16m0 , mhh= 0.53m0 = 0.59m0
⇒ mdh
*
GaAs : m=
lh 0.074m0 , mhh
= 0.62m0 = 0.64m0
⇒ mdh
 Once the DOS effective mass is obtained, the density of states can be
calculated using the same formula:
3/2
1  2me* 
=DC ( E )   E − EC for electrons in conduction band
2π 2   2 
3/2
1  2mh* 
=DV ( E )   EV − E for holes in valence band
2π 2   2 
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Appendix A: density of states effective mass

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

99
Appendix A: density of states effective mass

EE5508 Semiconductor Fundamentals Lecture 3&4 Wu Yihong 09/09/2010

100
Appendix A: density of states effective mass

For multiple valleys (Z)

1/2
 m 
3

 *
de
* *
=Z ⇒ mde =Z 2/3 ( m1*m2*m3* )1/3
m
 1 m m3 2

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Appendix B: density of states effective mass

3/2 3/2 3/2

𝑚𝑚𝑑𝑑𝑑 𝑘𝑘𝐵𝐵 𝑇𝑇 𝑚𝑚𝑙𝑙ℎ 𝑘𝑘𝐵𝐵 𝑇𝑇 𝑚𝑚ℎℎ 𝑘𝑘𝐵𝐵 𝑇𝑇
𝑁𝑁𝑉𝑉 =2 =2 +2
2𝜋𝜋ℏ2 2𝜋𝜋ℏ2 2𝜋𝜋ℏ2

3/2 3/2 3/2

⇒ 𝑚𝑚𝑑𝑑𝑑 = 𝑚𝑚𝑙𝑙𝑙 + 𝑚𝑚ℎℎ

3/2 3/2
⇒ 𝑚𝑚𝑑𝑑𝑑 = (𝑚𝑚𝑙𝑙𝑙 + 𝑚𝑚ℎℎ )2/3

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