ECE 340: Semiconductor Electronics

Chapter 3: Energy bands and

charge carriers in semiconductors
(part I)

Wenjuan Zhu

Assistant Professor
Department of Electrical and Computer Engineering
Office: MNTL 3258, Email: [email protected]
© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 1
 Outline

• Bonding force and energy band

 Bonding forces in solids
 Energy bands
 Metals, semiconductors, and insulators
 Direct and indirect semiconductors
• Charge carriers in semiconductors
 Electrons and holes
 Effective mass
 Intrinsic material
 Extrinsic material

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 2

 Ionic bonding of NaCl (insulator)

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 3

 Metallic Bonding

• Outer shell is only partially filled.

• Screening by other charges makes the valence electron very loosely bound.
• Outer electron contributed to crystal as a whole.
• Bonding can be very complex depending on the compound involved.

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 4

 Covalence bonding in silicon crystal

Si

electron

Two electrons per bond

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 5

 Outline

• Bonding force and energy band

 Bonding forces in solids
 Energy bands
 Metals, semiconductors, and insulators
 Direct and indirect semiconductors
• Charge carriers in semiconductors
 Electrons and holes
 Effective mass
 Intrinsic material
 Extrinsic material

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 6

 * FYI
Hydrogen atom emission spectrum
Lyman Balmer Paschen

1 1
Lyman: 𝑣 = 𝐶𝑅 −
12 𝑛2
1 1
Balmer: 𝑣 = 𝐶𝑅 2 −
2 𝑛2
1 1
Balmer: 𝑣 = 𝐶𝑅 32
− 𝑛2

• Light emission spectrum of hydrogen contains a series of discrete lines instead of a

continuous distribution.
© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 7
 * FYI
Quantum mechanics and Schrödinger equation
 Each particle in the system is
defined by a wavefunction.
 The normal classical quantities are
expressed with the new quantum
mechanical operators.

Classical equation for the energy of a particle:

Kinetic energy + potential energy = total energy
𝑷𝟐
+ V = E
𝟐𝒎
The time-independent Schrödinger equation is:
2 2
    V  E
2m
© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 8
 * FYI
Hydrogen Atom
Energy levels
Columbic potential

1 𝑞2
𝑉=−
4𝜋𝜖0 𝑟

Electron acted by the Coulomb potential of an atomic nucleus can have only certain
allowed energies:

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 9

 Energy Levels vs Energy Bands
• Isolated atoms: no overlap of electronic wave functions, only has original
discrete energy levels;
• Interacting atoms: overlaps of electronic wave functions, many new
energy levels are created through hybridization. If you have too many
levels, you get a band!

Multitudes of
Single atom 4 atoms in close
atoms in close
proximity
proximity

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 10

 * FYI
Quantum number selection rule
• The wavefunction of an electron in hydrogen are
quantized:
Ψ𝑛𝑙𝑚 𝑟, 𝜃, 𝜙 = 𝑅𝑛 𝑟 Θ𝑙 𝜃 Φ𝑚 𝜙

where the quantum numbers are restricted by following selection rules:

𝒏 = 𝟏, 𝟐, 𝟑 … …

𝒍 = 𝟎, 𝟏, 𝟐, … … (𝒏 − 𝟏)

𝒎 = −𝒍, … − 𝟏, 𝟎, 𝟏, … 𝒍

• The electron spin gives the fourth quantum number. The

intrinsic angular momentum of an electron is:
ℏ
𝑠=±
2

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 11

 * FYI
Pauli exclusion principle and allowed states
• Pauli exclusion principle: no two electrons in an interacting
system can have the same set of quantum number n, l, m, and s.
• Quantum numbers and allowed states:

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 12

 Electronic Configuration of Elements
ℓ=0, 1, 2, 3, 4 …
s, p, d, f, g …

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 13

 Electronic structure and energy levels in a silicon atom
Orbital model of a Si atom Energy levels in the Coulomb potential

3p

3s

Si: 1s22s22p63s23p2
• There are 4 valence electrons of Si (two in 3s states and two in 3p states).
• A Coulomb potential varies as 1/r as a function of distance from the nucleus.
Similar to “particle in a box”, the energy level is discrete.

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 14

 Energy levels in Si as a function of interatomic spacing
When N Si atoms
were brought
together

3p2

3s2

2p2
2s2

1s2
Repulsion Attraction

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 15

 Energy Band Diagram

Ec
Electron energy Eg
Ev
Position

Simplified version of energy band model, indicating:

• Bottom edge of the conduction band (Ec)
• Top edge of the valence band (Ev)
Ec and Ev are separated by the band gap energy Eg

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 16

 Outline

• Bonding force and energy band

 Bonding forces in solids
 Energy bands
 Metals, semiconductors, and insulators
 Direct and indirect semiconductors
• Charge carriers in semiconductors
 Electrons and holes
 Effective mass
 Intrinsic material
 Extrinsic material

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 17

 Metal, semiconductor and insulator

Metal Si, Semiconductor SiO2, insulator

• Metal has partially filled energy bands and are highly conductive.
• In insulators and semiconductors, the valence band is completed filled
while the conduction band is completely empty at low temperatures.
• In insulator, the band gap is greater than 5 eV, while in semiconductor,
the band gap is typically smaller than 5 eV.
© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 18
 Outline

• Bonding force and energy band

 Bonding forces in solids
 Energy bands
 Metals, semiconductors, and insulators
 Direct and indirect semiconductors (*FYI)
• Charge carriers in semiconductors
 Electrons and holes
 Effective mass (*FYI)
 Intrinsic material
 Extrinsic material

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 19

 * FYI
E-k diagram
𝑚𝑉 2 𝑃2 ℏ2 𝑘 2
For classic objects, the kinetic energy 𝐸𝑘𝐸 = = =
2 2𝑚 2𝑚
E~k curve (dispersion curve) is a “parabola”.

In quantum mechanics, free electron has the planewave

wavefunction,
𝜓𝑘 𝑥 = 𝑒 𝒋𝒌𝒙 ∙𝒙

2𝜋
Where the wavevector 𝑘𝑥 = 𝑛 n=0, 1, 2…
𝐿
𝒏𝟐 ℏ𝟐 𝝅𝟐
Energy of the electron 𝑬𝒏 = 𝟐𝒎𝑳𝟐

The E~k relationship is similar:

ℏ2 𝑘 2
𝐸=
2𝑚

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 20

 * FYI
Band structures in semiconductors

For electron in a periodic lattice, the

wavefunction is
𝝍𝒌 𝒙 = 𝑼(𝒌𝒙 , 𝐱)𝒆𝒋𝒌𝒙 ∙𝒙
called Bloch function.

Since the periodicity of most lattices is different in various directions, the (E,K)
diagram must be plotted for various crystal directions, and the full relationship
between E and k is a complex surface.

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 21

 Direct and indirect band gap * FYI

Direct band gap Indirect band gap

Direct band gap: minimum in the conduction band and maximum of valence band occurs at
the same k value.
Indirect band gap: minimum in the conduction band and maximum of valence band occurs at
the different k value

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 22

 E-K vs. E-X Diagram
E

Ec

Electron energy
Eg
Ev
k
Position

GaAs

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 23

 Outline

• Bonding force and energy band

 Bonding forces in solids
 Energy bands
 Metals, semiconductors, and insulators
 Direct and indirect semiconductors
• Charge carriers in semiconductors
 Electrons and holes
 Effective mass
 Intrinsic material
 Extrinsic material

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 24

 Electron and holes
T=0K T>0K

Empty Ec Electron
Electron-
Eg Hole pair
(EHP)
Ev Hole
Filled

No free electrons in Some electrons receive enough thermal energy

the semiconductor to be excited from valence band to conduction
band
© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 25
 Hole
• What is a hole?
 An empty state in the valence band
 Treated as a positive charge carrier in the semiconductor

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 26

Why hole is considered as a positively charged carrier?
The current density flowing in the conduction band can be calculated by summing the
motion of all the electrons in the conduction band:

𝐽 = ෍ −𝑞 𝑣𝑖
𝑐𝑏

The current density flowing in the valence band can be calculated by summing the motion
of all the electrons in the valence band, or the motion of all the positively charged vacant
states (holes):
𝐽 = ෍ −𝑞 𝑣𝑖 = ෍ −𝑞 𝑣𝑖 − ෍ −𝑞 𝑣𝑖
𝑣𝑏 𝐹𝑖𝑙𝑙𝑒𝑑 𝑏𝑎𝑛𝑑 𝐸𝑚𝑝𝑡𝑦 𝑠𝑡𝑎𝑡𝑒𝑠

𝐽=0− ෍ −𝑞 𝑣𝑖 = ෍ 𝑞𝑣𝑖
𝐸𝑚𝑝𝑡𝑦 𝑠𝑡𝑎𝑡𝑒𝑠 𝐸𝑚𝑝𝑡𝑦 𝑠𝑡𝑎𝑡𝑒𝑠

• Pure silicon at room temperature

 electron-hole pair density: 1010 EHP/cm3, Silicon atom density:
5x1022 atom/cm3 electrons in the conduction band are free to
move via many available empty states.
© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 27
 Electron and hole energy

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 28

 Potential energy and kinetic energy

• Hole energy increase oppositely to electron energy,

because the two carriers have opposite charge

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 29

• Let’s combine energy
bands vs. k and vs.
x:

• Note what is
potential, kinetic, and
total energy

• Note which way

energy of holes
increases

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics

 Outline

• Bonding force and energy band

 Bonding forces in solids
 Energy bands
 Metals, semiconductors, and insulators
 Direct and indirect semiconductors (FYI*)
• Charge carriers in semiconductors
 Electrons and holes
 Effective mass (FYI*)
 Intrinsic material
 Extrinsic material

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 31

 Effective Mass of electrons and holes

• Newton’s law:
𝑭𝒐𝒓𝒄𝒆 = 𝑭𝒊𝒏𝒕 + 𝑭𝒆𝒙𝒕 = 𝒎𝒂

“true” mass, same as free electron mass 𝒎𝟎

𝑭𝒊𝒏𝒕 is the collection of internal periodic crystal forces

𝑭𝒆𝒙𝒕 is the externally applied force

• If the effect of all the internal periodic crystal forces are

considered and encapsulated into the band structure.
Then electron then respond to external force with a new
mass:
𝑭𝒆𝒙𝒕 = 𝒎∗ 𝒂
where m* is the “effective mass” of the particle, which includes all the complex
influences of the crystal potential on the motion of the electron (or hole).

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 32

 * FYI
Effective Mass
• Free electron energy is:
𝑚𝑣 2 𝑃2 ℏ2 𝑘 2
𝐸= = =
2 2𝑚 2𝑚
The electron mass is inversely related to the curvature
of the (E,K) relationship:
ℏ𝟐
𝒎= 𝟐
𝒅 𝑬 Τ 𝒅𝒌𝟐
• Although electrons in solid are not free, most
energy bands are close to parabolic at their
minima or maxima. We can also approximate
effective mass near those band extrema from
the curvature of the band:
ℏ 𝟐
𝒎∗ = 𝟐
𝒅 𝑬 Τ 𝒅𝒌𝟐

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 33

 Outline

• Bonding force and energy band

 Bonding forces in solids
 Energy bands
 Metals, semiconductors, and insulators
 Direct and indirect semiconductors
• Charge carriers in semiconductors
 Electrons and holes
 Effective mass
 Intrinsic material
 Extrinsic material

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 34

 Intrinsic semiconductor

• Intrinsic semiconductor = pure, without impurities or

lattice defects

• No free charge carriers at T=0K

• What about at T=300K?
• How much energy to break a bond?
© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 35
 Generation and recombination in intrinsic semiconductor

E Generation Recombination

Electron and home generate in pairs and recombine in pairs.

𝒏 = 𝒑 = 𝒏𝒊
n: electron concentration
p: hole concentration
ni: intrinsic carrier concentration
Mechanical analogy:

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics

 Generation and recombination rate

• Generation rate of EHP gi is determined by the

temperature and bandgap:
 High T  ____ generation rate
 Small band gap  ____ generation rate
• Recombination rate is determined by the number of
electron and hole concentration:

𝑟𝑖 = 𝛼𝑛0 𝑝0 = 𝛼𝑛𝑖2
• At equilibrium:
𝑟𝑖 = 𝑔𝑖 =𝛼𝑛𝑖2
Question: How is the intrinsic carrier concentration change with temperature
and band gap?

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 37

 Outline

• Bonding force and energy band

 Bonding forces in solids
 Energy bands
 Metals, semiconductors, and insulators
 Direct and indirect semiconductors
• Charge carriers in semiconductors
 Electrons and holes
 Effective mass
 Intrinsic material
 Extrinsic material

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 38

 Extrinsic material
• How to manipulat the carrier concentration?
• Doping = purposely introducing impurities into the crystal
• Intrinsic material = pure, undoped. Extrinsic = doped.

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 39

 N type doping
Example: Add column V elements (P, As etc) into Si or Ge crystal:

Donor level

Extra electron

• Electron concentration is much higher than holes

𝑛0 ≫ 𝑝0 𝑜𝑟 𝑛𝑖
called n type material.

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 40

 P type doping
Example: adding column III element to Si or Ge crystal:

Acceptor level

• The impurity introduce an energy level very near the

valence band. This type of impurity level “accept”
electron from valence band and are called “acceptor”
impurity.

• Hole concentration is much higher than electrons

𝑝 ≫ 𝑛0 𝑜𝑟 𝑛𝑖
called p type material.

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 41

 N type Doping
• If the impurity atoms has more
valence electrons than original
atoms in the lattice:
VI V
Use column V atom to replace IV atom
IV III
III II

extra electron will be donated

𝐸𝐹
 N type doping 𝐸𝑖

𝑛0 >𝑝0

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 42

 P type Doping

• If the impurity atoms has less

valence electrons than original
atoms in the lattice:
V VI
Use column
IV atom to replace V atom
III IV
II III
missing electron will create “holes”

 P type doping
𝐸𝑖

𝑝0 >𝑛0 𝐸𝐹

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 43

 Question
• If use Si to replace Ga in GaAs? Is Si atom server as
donor or acceptor?

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 44

 Binding energy
• Arsenic (As) dopant in Si: 4 electrons used up for bonding with
neighbors. But, how loosely bound is that 5th electron that As
brought into the Si lattice?
• Approximate binding energy using Niels Bohr’s model:

m* q 4
EB  be careful with choice
2K 2  2 of m* and K = 4πϵrϵ0

• The real numbers of donors and acceptors in Si:

Donor in Si P As Sb
Binding energy (eV) 0.045 0.054 0.039

Acceptor in Si B Al Ga In
Binding energy (eV) 0.045 0.067 0.072 0.16

• (note: binding energy = ionization energy)

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 45

 Typical Impurity Ionization Energy in Silicon

Eg Donor Ionization Energy: EI ,donor  EC  Ed

Energy

Eg/2

Acceptor Ionization Energy: EI ,acceptor  Ea  EV

E=0
Compare
to thermal energy
Typical Ionization Energy in Silicon
kT=0.0259eV

* FYI

© 2023 Wenjuan Zhu, UIUC ECE 340: Semiconductor Electronics 48