Pauli Exclusion Principle

Electrons in a single atom occupy discrete levels of energy. No two

“energy levels” or “states” in an atom can have the same energy.
Each energy level can contain at most two electrons -- one with
“clockwise spin” and one with “counterclockwise spin”.
If two or more atoms are brought together, their outer (i.e., valence)
energy levels must shift slightly so they will be different from one another.
If many (e.g., N) atoms are brought together to form a solid, the Pauli
Exclusion Principle still requires that only two electrons in the entire solid
have the same energy. There will be N distinct, but only slightly different
valence energy levels, forming a valence band.
When a solid is formed, the different split energy levels of electrons
come together to form continuous bands of energies (electron energy
band).
The extent of splitting depends on the interatomic separation and
begins with the outer most electron shells as they are the first to be
perturbed as the atoms coalesce.
 Band Theory: Two Approaches
• There are two approaches to finding the electron energies associated with
atoms in a periodic lattice.
• Approach #1: “Bound” Electron Approach (Solve single atom energies!)
– Isolated atoms brought close together to form a solid.
• Approach #2: “Unbound” or Free Electron Approach (E = p2/2m)
– Free electrons modified by a periodic potential (i.e. lattice ions).

• Both approaches result in grouped energy levels with allowed and forbidden
energy regions.
– Energy bands overlap for metals.
– Energy bands do not overlap (or have a “gap”) for semiconductors.
 Band Theory: “Bound” Electron Approach
• For the total number N of atoms in a solid (1023 cm–3), N energy levels
split apart within a width ΔE.
– Leads to a continuous band of energies for each initial atomic
energy level (e.g. 1s energy band for 1s energy level).

Two atoms Six atoms Solid of N atoms

The electrical properties of a solid material are a consequence of its
electron band structure, that is, the arrangement of the outermost electron
bands and the way in which they are filled with electrons.
Four different types of band structure are possible at 0oK:
Outermost band is only partially filled with electrons (eg, Na, Cu) (Cu has a
single 4s valence electron, however for a solid comprised of N atoms, the 4s band is capable of
accommodating 2N electrons. Thus, only half of the 4s band is filled.)

Overlap of an empty band and a filled band (eg. Mg). (An isolated Mg atom has
2 electrons in its 3s level. When a solid is formed, the 3s and 3p energy levels overlap.)

A completely filled valence band is separated from the conduction band

by a relatively wide energy band gap (insulators).
A completely filled valence band is separated from the conduction band
by a relative narrow energy band gap (semiconductors)
Electron Energy “Freedom”
The Fermi Level corresponds to
Empty States the Highest Occupied Molecular
Ef
Energy Orbital (HOMO).
States Filled with Electrons Band
For a Li crystal with N atoms there
are 3N electrons. The 1s band is
Distance filled and the 2s band is half-filled.

The energy difference between adjacent states is infinitesimally small. The

electrons near the Fermi level can move from filled states to empty states
with no activation energy (metals).
If “valence” band is filled, no empty
“Conduction Band”
Empty space are available above the filled
states. Electrons can be promoted
Electron
Energy

Energy to the “conduction band “Lowest

“Forbidden” Gap Unoccupied Molecular Orbital –
LUMO” with an activation energy >
“Valence Band”
energy gap (band gap). Difference
Filled with Electrons
between semiconductors and
Distance insulators is due to the size of the
bandgap.
 Temperature Effect

When the temperature of the metal increases, some electrons gain energy and
are excited into the empty energy levels in a valence band. This condition
creates an equal number of empty energy levels, or holes, vacated by the
excited electrons. Only a small increase in energy is required to cause
excitation of electrons.
Both the excited electrons (free electrons) and the newly created holes
can then carry an electrical charge.
Fermi Energy is the energy corresponding to the highest filled state at 0oK.
Only electrons above the Fermi energy can be affected by an electric field
(free electrons).

Band Diagram: Fermi-Dirac “Filling” Function

The Fermi-Dirac function gives the fraction of allowed states, fFD(E), at an
energy level E, that are populated at a given temperature.
1
f FD ( E ) =
( E − EF )
e kT +1
where the Fermi Energy, EF, is defined as the energy where fFD(EF) = 1/2.
That is to say one half of the available states are occupied. T is the
temperature (in K) and kB is the Boltzman constant (kB = 8.62 x10-5 eV/K)
 Probability of electrons (fermions) to be found at various energy levels.

1
f FD ( E ) = For E – EF = 0.05 eV ⇒ f(E) = 0.12
( E − EF ) For E – EF = 7.5 eV ⇒ f(E) = 10 –129
e kT +1 Exponential dependence has HUGE effect!

Temperature dependence of Fermi-Dirac function shown as follows:

→ Step function behavior “smears” out at higher temperatures.

 Fermi-Dirac Function
Metals and Semiconductors

f(E) as determined
experimentally for
Ru metal (note the
energy scale)

f(E) for a
semiconductor
Velocity of the electrons
In metals, the Fermi energy gives us information about the velocities of the
electrons which participate in ordinary electrical conduction. The amount of
energy which can be given to an electron in such conduction processes is
on the order of micro-electron volts (see copper wire example), so only
those electrons very close to the Fermi energy can participate. The Fermi
velocity of these conduction electrons can be calculated from the Fermi
energy.

Speed of light: 3x108m.s-1

Fermi Energies, Fermi Temperatures, and Fermi Velocities

Element Fermi Energy eV Fermi Temperature x10^4 K Fermi Velocity 10^6 m/s

Li 4.74 5.51 1.29

Na 3.24 3.77 1.07
K 2.12 2.46 0.86
Rb 1.85 2.15 0.81
Cs 1.59 1.84 0.75
Cu 7.00 8.16 1.57
Ag 5.49 6.38 1.39
Au 5.53 6.42 1.40
Be 14.3 16.6 2.25
Mg 7.08 8.23 1.58
from N. W. Ashcroft and N. D. Mermin,

The Fermi temperature is the temperature associated with the Fermi energy by
solving
EF = kB TF
for , where m is the particle mass and kB is Boltzmann's constant.
Electrical Conductivity (σ) σ=
1
(Ω − m ) −1

ρ
Conductivity is the “ease of conduction”. Ranges
over 27 orders of magnitude!
Metals 107 (Ω.cm)-1
Semiconductors 10-6 - 104 (Ω.cm)-1
Insulators 10-10 -10-20 (Ω.cm)-1
(a) Charge carriers, such as electrons, are deflected by atoms
or defects and take an irregular path through a conductor.
(b) Valence electrons in the metallic bond move easily.
(c) Covalent bonds must be broken in semiconductors and
insulators for an electron to be able to move.
(d) Entire ions must diffuse to carry charge in many ionically
bonded materials.
• Electronic conduction:
– Flow of electrons, e- and electron holes, h+
• Ionic conduction
– Flow of charged ions, Ag+
 Microscopic Conductivity
We can relate the conductivity of a material to microscopic parameters that
describe the motion of the electrons (or other charge carrying particles such
as holes or ions). From the equations
RA V I
V = IR and ρ= ⇒ = ρ
L L A
If J=Current density (I/A) Ampere/m2; and ξ=electric field intensity (V/L) then
σ = (Ω − m )−1
1
J = σξ
ρ
We can also determine that the current density is
J = nqν
Where n is the number of charge carriers (carriers/cm3); q is the charge on
each carrier (1.6x10-19C); and ν is the average drift velocity (cm/s) at which
the charge carriers move.
Therefore
 ν
J = nq ν = σξ then σ = nq
ξ
ν ⎛ cm ⎞ 2
= μ = mobility ⎜⎜ ⎟⎟
ξ ⎝ V.s ⎠
σ = nq μ
The charge q is a constant.
Electrons are the charge carriers in metals.
Electrons and holes are both carriers of electricity in semiconductors.
Electrons that “hop” from one defect to another or the movement of
ions are both the carriers of electricity in ceramics.
 Conduction in Terms of Band
Metals
An energy band is a range of allowed electron energies.
The energy band in a metal is only partially filled with electrons.
Metals have overlapping valence and conduction bands
Drude Model of Electrical Conduction in Metals

Conduction of electrons in metals – A Classical Approach:

In the absence of an applied electric field (ξ) the electrons move in random directions colliding
with random impurities and/or lattice imperfections in the crystal arising from thermal motion of
ions about their equilibrium positions.
The frequency of electron-lattice imperfection collisions can be described by a mean free path
λ -- the average distance an electron travels between collisions.
When an electric field is applied the electron drift (on average) in the direction opposite to that
of the field with drift velocity v
The drift velocity is much less than the effective instantaneous speed (v) of the random
motion
 −2 −1 −1 1 3
In copper v ≈ 10 cm.s while v ≈ 10 cm.s mev = k BT
8 2
where
2 2
The drift speed can be calculated in terms of the applied electric field ξ and of v and λ
When an electric field is applied to an electron in the metal it experiences a force qξ
resulting in acceleration (a) qξ
a=
me
λ
Then the electron collides with a lattice imperfection and changes its direction τ=
randomly. The mean time between collisions is v
q ⋅ ξ ⋅τ q ⋅ ξ ⋅ λ
The drift velocity is v = a ⋅τ = =
me me ⋅ v
If n is the number of conduction electrons per unit volume and J is the current density

Combining with the definition of resistivity gives J = nq ν = σξ

n ⋅q ⋅λ 2
q ⋅ λ q ⋅τ
σ= μ= =
me ⋅ v me ⋅ v me
q=1.6x10-19C
For an electron to become free to conduct, it must be promoted into an
empty available energy state
For metals, these empty states are adjacent to the filled states
Generally, energy supplied by an electric field is enough to stimulate
electrons into an empty state

“Freedom”
Electron Energy

Empty States
Energy Band
States Filled with Electrons

Distance
 Band Diagram: Metal
T>0
EC
Fermi “filling” Energy band to
function EF be “filled”
Conduction band
(Partially Filled)
E=0

At T = 0, all levels in conduction band below the Fermi energy EF are filled
with electrons, while all levels above EF are empty.
Electrons are free to move into “empty” states of conduction band with
only a small electric field E, leading to high electrical conductivity!
At T > 0, electrons have a probability to be thermally “excited” from below
the Fermi energy to above it.
 Conduction in Materials --Classical
approach
1. Drude Model
2. Temperature‐dependent conductivity 
3. Matthissen’s Rule
4. Hall effect
5. Skin effect (HF resistance of a conductor)

1. Heat Capacity and thermal conductivity
 Classic Model (Drude Model)
electron act as a particle
• Collision: the scattering of an
electron by (and only by) an
ion core
• Between collision: electrons
do not interact with each
other or with ions
• An electron suffers a collision
with probability per unit time
τ-1, (τ-1 scattering rate).
• Electrons achieve thermal
equilibrium with their
surrounding only through
collisions
Ex
u
Δx
Vibrating Cu + ions V
(a) (b)
Fig. 2.2 (a): A conduction electron in the electron gas moves about randomly in a
metal (with a mean speed u) being frequently and randomly scattered by by
thermal vibrations of the atoms. In the absence of an applied field there is no net
drift in any direction. (b): In the presence of an applied field, Ex, there is a net
drift along the x-direction. This net drift along the force of the field is
superimposed on the random motion of the electron. After many scattering events
the electron has been displaced by a net distance, Δx, from its initial position
toward the positive terminal
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
http://Materials.Usask.Ca
 Relaxation time approximation and Mobility
Ex
Δx A

vdx
Velocity gained along x
Jx Present time
vx1- ux1
Last collision

Electron 1
time
t1 Free time t
Fig. 2.1: Drift of electrons in a conductor in the presence of an vx1-ux1
applied electric field. Electrons drift with an average velocity vdx in
the x-direction.(Ex is the electric field.)
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
http://Materials.Usask.Ca Electron 2
time
t2 t
vx1-ux1

v dx = μ E x Electron 3

J = en μ E x = σ E
time
t3 t

Fig. 2.3: Velocity gained in the x-direction at time t from the

σ = ne μ (Ohm’s law) electric field (Ex) for three electrons. There will be N electrons to
consider in the metal.
eτ
μ =
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
http://Materials.Usask.Ca

me
 Temperature dependence of Conductivity for Metal

S = π a2

=uτ a
l Conduction by free electrons
and scattered by lattice
vibration
u

Electron
Fig. 2.4: Scattering of an electron from the thermal vibrations of the
atoms. The electron travels a mean distance l = u τ between
collisions. Since the scattering cross sectional area is S, in the volume
Sl there must be at least one scatterer, Ns(Suτ) = 1.
 Resistivity (ρ) in Metals

Resistivity typically increases linearly with temperature:

ρt = ρo + αT
Phonons scatter electrons. Where ρo and α are constants for an
specific material
Impurities tend to increase resistivity: Impurities scatter electrons in
metals
Plastic Deformation tends to raise resistivity dislocations scatter
electrons
1
σ= = nqμ
ρ
The electrical conductivity is controlled by controlling the number of
charge carriers in the material (n) and the mobility or “ease of
movement” of the charge carriers (μ)
 Matthiessen’s Rule
Strained region by impurity exerts a
scattering force F = - d(PE) /dx

τI

τΤ

Fig. 2.5: Two different types of scattering processes involving scattering

from impurities alone and thermal vibrations alone.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
http://Materials.Usask.Ca
 Temperature Dependence, Metals
There are three contributions to ρ:
ρt due to phonons (thermal)
ρi due to impurities
ρd due to deformation

ρ = ρt + ρi+ ρd
The number of electrons in the
conduction band does not vary
with temperature.
All the observed temperature
dependence of σ in metals arise
from changes in μ
 2000
Inconel-825
NiCr Heating Wire
1000
Iron
Tungsten
Monel-400

Resistivity (nΩ m)
ρ∝T

Tin
100 Platinum
Copper
Nickel

Silver

10
100 1000 10000
Temperature (K)

Fig. 2.6: The resistivity of various metals as a function of temperature

above 0 °C. Tin melts at 505 K whereas nickel and iron go through a
magnetic to non-magnetic (Curie) transformations at about 627 K and
1043 K respectively. The theoretical behavior (ρ ~ T) is shown for
reference.
[Data selectively extracted from various sources including sections in
Metals Handbook, 10th Edition, Volumes 2 and 3 (ASM, Metals
Park, Ohio, 1991)]
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
http://Materials.Usask.Ca
Scattering by Impurities and Phonons

Thermal: Phonon scattering

Proportional to temperature

ρ t = ρ o + aT
Impurity or Composition scattering
Independent of temperature
Proportional to impurity concentration

Solid Solution ρ i = Aci (1 − ci )

Two Phase ρ t = ραVα + ρ β Vβ
Deformation
ρ d = must be experimentally determined
 100
ρ∝T
10

Resistivity (nΩ m)
ρ (nΩ m)
0.1 3.5
3 ρ∝T
ρ∝ T5 2.5
0.01
2
1.5 ρ ∝ T5
0.001
1
0.5 ρ = ρR
ρ = ρR
0.0001 0
0 20 40 60 80 100
T (K)
0.00001
1 10 100 1000 10000
Temperature (K)
Fig.2.7: The resistivity of copper from lowest to highest temperatures
(near melting temperature, 1358 K) on a log-log plot. Above about
100 K, ρ ∝ T, whereas at low temperatures, ρ ∝ T 5 and at the
lowest temperatures ρ approaches the residual resistivity ρR . The
inset shows the ρ vs. T behavior below 100 K on a linear plot ( ρR
is too small on this scale).
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
http://Materials.Usask.Ca
 Electron conduction in nonmetals
Insulators Semiconductors Conductors
Many ceramics
Superconductors
Alumina
Diamond Inorganic Glasses
Mica Metals
Polypropylene
Degenerately
PVDF Soda silica glass
PET Borosilicate Pure SnO2 Doped Si Alloys
Amorphous Intrinsic Si
SiO2 Intrinsic GaAs Te Graphite NiCr Ag
As2Se3

10-18 10-15 10-12 10-9 10-6 10-3100 103 106 109 1012
Conductivity (Ωm)-1

Figure 2.24: Range of conductivites exhibited by various materials

From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
http://Materials.Usask.Ca
Control of Electrical Conductivity
By controlling the number of charge
carriers in the material (n)
By controlling the mobility or “ease of
movement” of the charge carriers (μ)

σ = nqμ
Example: Calculation of Drift velocity of electrons in copper (valence =1)
Assuming that all of the valence electrons contribute to current flow,
(a) calculate the mobility of an electron in copper and
(b) calculate the average drift velocity for electrons in a 100cm copper wire when
10V are applied.
Data: conductivity of copper = 5.98 x 105(Ω.cm)-1 ; q = 1.6x10-19C ; lattice
parameter of copper = 0.36151x10-7cm ; copper has a FCC structure

The equation that we need to apply is: σ = nqμ

n is the number of carriers. q is the charge . μ is the mobility

Number of carriers (n): The valence of copper is 1. Therefore, the number of

valence electrons equals the number of copper atoms in the material.

(atoms / cell )(electrons / atoms ) 4 ×1

n= = = 8 . 466 × 10 22
electrons / cm 3

cell _ volume (0.36151×10 −7 cm )3

 Part (a)

σ 5.98 × 105 Ω −1 .cm −1 cm 2 cm 2

μ= = −19
= 44.2 = 44.2
nq (8.466 × 10 electrons / cm )(1.6 ×10 C )
22 3
Ω.C V .s

Note : 1amp = 1Coulomb / sec ond

Part (b)
V 10V
The electric field intensity is: ξ= = = 0.1V .cm −1
L 100cm

The equation we need to use is ν = μξ

cm 2 V What does it mean?
v = ( 44.2 )(0.1 ) = 4.42cm / s
V .s cm The drift velocity is the average velocity that a particle,
such as an electron, attains, due to an electric field.

The electron moves at the Fermi speed and it has only a tiny drift velocity
superimposed by the applied electric field.
In metals, the Fermi energy gives us information about the velocity of the electrons
which participate in ordinary electrical conduction. The amount of energy which can be
given to an electron in such conduction processes is on the order of micro-electron
volts, so only those electrons very close to the Fermi energy (EF) can participate.

2E F
vF =
m
 Fermi Energy Fermi Temperature Fermi Velocity
Element
eV x 10^4 K x 10^6 m/s
Li 4.74 5.51 1.29
Na 3.24 3.77 1.07
K 2.12 2.46 0.86
Rb 1.85 2.15 0.81
Cs 1.59 1.84 0.75
Cu 7.00 8.16 1.57
Ag 5.49 6.38 1.39
Au 5.53 6.42 1.40
Be 14.3 16.6 2.25
Mg 7.08 8.23 1.58
Ca 4.69 5.44 1.28
Sr 3.93 4.57 1.18
Ba 3.64 4.23 1.13
Nb 5.32 6.18 1.37
Fe 11.1 13.0 1.98
Mn 10.9 12.7 1.96
Zn 9.47 11.0 1.83
Cd 7.47 8.68 1.62
Hg 7.13 8.29 1.58
Al 11.7 13.6 2.03
Ga 10.4 12.1 1.92
In 8.63 10.0 1.74
Tl 8.15 9.46 1.69
Sn 10.2 11.8 1.90
Pb 9.47 11.0 1.83
Bi 9.90 11.5 1.87
Sb 10 9 12 7 1 96
 Insulator
The valence band and conduction band are separated by a large (> 4eV)
energy gap, which is a “forbidden” range of energies.
Electrons must be promoted across the energy gap to conduct, but the
energy gap is large. Energy gap º Eg

“Conduction Band”
Empty
Electron
Energy

“Forbidden” Energy
Gap
“Valence Band”
Filled with Electrons

Distance
 Band Diagram: Insulator
Conduction band
T>0 (Empty)
EC
Egap
EF

Valence band
EV
(Filled)

At T = 0, lower valence band is filled with electrons and upper conduction

band is empty, leading to zero conductivity.
Fermi energy EF is at midpoint of large energy gap (2-10 eV) between
conduction and valence bands.
At T > 0, electrons are usually NOT thermally “excited” from valence to
conduction band, leading to zero conductivity.
 Conduction in Ionic Materials (Insulators)
Conduction by electrons (Electronic Conduction): In a ceramic, all
the outer (valence) electrons are involved in ionic or covalent bonds and thus
they are restricted to an ambit of one or two atoms. −Eg
2 k BT
If Eg is the energy gap, the fraction of electrons in the conduction band is: e
A good insulator will have a band gap >>5eV and 2kBT~0.025eV at room temperature
As a result of thermal excitation, the fraction of electrons in the conduction band is
~e-200 or 10-80.
There are other ways of changing the electrical conductivity in the ceramic which
have a far greater effect than temperature.
•Doping with an element whose valence is different from the atom it replaces. The
doping levels in an insulator are generally greater than the ones used in
semiconductors. Turning it around, material purity is important in making a good
insulator.
•If the valence of an ion can be variable (like iron), “hoping” of conduction can
occur, also known as “polaron” conduction. Transition elements.
•Transition elements: Empty or partially filled d or f orbitals can overlap providing a
conduction network throughout the solid.
Conduction by Ions: ionic conduction
It often occurs by movement of entire ions, since the energy gap is too large
for electrons to enter the conduction band. Z .q.D
μ=
The mobility of the ions (charge carriers) is given by:
k B .T
Where q is the electronic charge ; D is the diffusion coefficient ; kB is
Boltzmann’s constant, T is the absolute temperature and Z is the valence of
the ion.
The mobility of the ions is many orders of magnitude lower than the mobility of
the electrons, hence the conductivity is very small:

Example:
σ = n.Z.q.μ
Suppose that the electrical conductivity of MgO is determined primarily by the
diffusion of Mg2+ ions. Estimate the mobility of Mg2+ ions and calculate the
electrical conductivity of MgO at 1800oC.
Data: Diffusion Constant of Mg in MgO = 0.0249cm2/s ; lattice parameter of
MgO a=0.396x10-7cm ; Activation Energy for the Diffusion of Mg2+ in MgO =
79,000cal/mol ; kB=1.987cal/K=k-mol; For MgO Z=2/ion; q=1.6x10-19C;
kB=1.38x10-23J/K-mol
 First, we need to calculate the diffusion coefficient D

⎛ − QD ⎞ cm 2 ⎛ − 79000cal / mol ⎞
D = Do exp⎜ ⎟ = 0. 0239 exp⎜
⎜ ⎟⎟
⎝ kT ⎠ s ⎝ 1.987cal / mol − Kx (1800 + 273)K ⎠
D=1.119x10-10cm2/s

Next, we need to find the mobility

Z .q .D ( 2carriers / ion )(1.6 × 10 −19 C )(1.1× 10 −10 ) C .cm 2

μ= = = 1 . 12 × 10 −9

k B .T (1.38 × 10 − 23 )(1800 + 273) J .s

C ~ Amp . sec ; J ~ Amp . sec .Volt μ=1.12x10-9 cm2/V.s

 MgO has the NaCl structure (with 4 Mg2+
and 4O2- per cell)

Thus, the Mg2+ ions per cubic cm is:

4Mg 2+ ions / cell

n= = 6 . 4 × 10 22
ions / cm 3

(0.396 ×10 −7 cm )3

σ = nZqμ = (6.4 ×10 22 )( 2)(1.6 ×10 −19 )(1.12 ×10 −9 )

C .cm 2
σ = 22.94 ×10 −6 3
cm .V .s
C ~ Amp.sec ; V ~ Amp.Ω σ = 2.294 x 10-5 (Ω.cm)-1
Example:
The soda silicate glass of composition 20%Na2O-80%SiO2 and a density of
approximately 2.4g.cm-3 has a conductivity of 8.25x10-6 (Ω-m)-1 at 150oC. If the
conduction occurs by the diffusion of Na+ ions, what is their drift mobility?
Data: Atomic masses of Na, O and Si are 23, 16 and 28.1 respectively

Solution:
We can calculate the drift mobility (μ) of the Na+ ions from the conductivity
expression
σ = ni × q × μ i
Where ni is the concentration of Na+ ions in the structure.

20%Na2O-80%SiO2 can be written as M At = 0.2 × ( 2( 23) + 1(16)) + 0.8 × (1( 281.1) + 2(16))
(Na2O)0.2-(SiO2)0.8 . Its mass can be
M At = 60.48g .mol −1
calculated as:

The number of (Na2O)0.2-(SiO2)0.8 units per unit volume can be found from the
density
 ρ × NA ( 2.4g .cm −3 ) × (6.023x10 23 mol −1 )
n= =
M At 60.48g .mol −1
n = 2.39 ×10 22 (Na 2O ) 0.2 (SiO 2 ) 0.8 units − cm −3
The concentration of Na+ ions (ni) can be obtained from the concentration of
(Na2O)0.2-(SiO2)0.8 units

⎡ 0.2 × 2 ⎤ −3
ni = ⎢ ⎥ × 2. 39 × 10 22
= 3 . 18 × 10 21
cm
⎣ 0 . 2 × ( 2 + 1) + 0 . 8 × (1 + 2 ) ⎦
σ (8.25 × 10 −6 Ω −1m −1 )
And μi μi = =
q × ni (1.60 × 10 −19 C ) × (3.186 × 10 21 × 106 m −3 )
μ i = 1.62 ×10 −14 m 2V −1s −1

This is a very small mobility compared to semiconductors and metals

 Conduction in ionic crystal and glasses
Mobile charges contribute to conduction
E E 1×10-1 24%Na2O-76%SiO2
As3.0Te3.0Si1.2Ge1.0 glass
Vacancy aids the diffusion of positive ion 1×10-3
Pyrex

Conductivity 1/(Ωm)
1×10-5

1×10-7
Na+
12%Na2O-88%SiO2
1×10-9
PVAc
SiO2
1×10-11
Anion vacancy PVC
acts as a donor
Interstitial cation diffuses 1×10-13
(a) (b)
1×10-15
Fig. 2.27: Possible contributions to the conductivity of ceramic and 1.2 1.6 2 2.4 2.8 3.2 3.6 4
glass insulators (a) Possible mobile charges in a ceramic (b) A Na+
103/T (1/K)
ion in the glass structure diffuses and therefore drifts in the
direction of the field. (E is the electric field.)
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002) Fig. 2.28: Conductivity vs reciprocal temperature for various low
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conductivity solids. (PVC = Polyvinyl chloride; PVAc = Polyvinyl
acetate.) Data selectively combined from numerous sources.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)

⎛ E0 ⎞
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σ = σ 0 exp⎜ − ⎟
⎝ kT ⎠ Hopping process
Electrical Breakdown
At a certain voltage gradient (field) an insulator will break down.
There is a catastrophic flow of electrons and the insulator is fragmented.
Breakdown is microstructure controlled rather than bonding controlled.
The presence of heterogeneities in an insulator reduces its breakdown field
strength from its theoretical maximum of ~109Vm-1 to practical values of 107V.m-1
 Energy Bands in Semiconductors
Energy Levels and Energy Gap in a Pure Semiconductor.
The energy gap is < 2 eV. Energy gap º Eg

“Conduction Band” (Nearly)

Empty – Free electrons
Electron Energy

“Forbidden” Energy Gap

“Valence Band” (Nearly) Filled with

Electrons – Bonding electrons

Semiconductors have resistivities in between those of metals and insulators.

Elemental semiconductors (Si, Ge) are perfectly covalent; by symmetry electrons
shared between two atoms are to be found with equal probability in each atom.
Compound semiconductors (GaAs, CdSe) always have some degree of ionicity. In III-V
compounds, eg. Ga+3As+5, the five-valent As atoms retains slightly more charge than is
necessary to compensate for the positive As+5 charge of the ion core, while the charge of
Ga+3 is not entirely compensated. Sharing of electrons occurs still less fairly between the
ions Cd+2 and Se+6 in the II-VI compund CdSe.
Semiconductor Materials
Semiconductor Bandgap Energy EG (eV)
Carbon (Diamond) 5.47
Silicon 1.12
Germanium 0.66
Tin 0.082
Gallium Arsenide 1.42 IIIA IV A VA V IA

Indium Phosphide 1.35 10.811 12.01115 14.0067 15.9994

5 6 7 8
Silicon Carbide 3.00 B C N O
Cadmium Selenide 1.70 Bo ro n C a rb o n N itro g e n O xy g e n
26.9815 28.086 30.9738 32.064
Boron Nitride 7.50 13 14 15 16
Aluminum Nitride 6.20 Al Si P S
IIB Pho sp ho rus
Gallium Nitride 3.40 A lum inum Silic o n Sulfur
65.37 69.72 72.59 74.922 78.96
Indium Nitride 1.90 30 31 32 33 34
Zn Ga Ge As Se
Zinc G a llium G e rm a nium A rse nic Se le nium
112.40 114.82 118.69 121.75 127.60
48 49 50 51 52

Portion of the Periodic Table Including the Most Cd In Sn Sb Te

C a d m ium Ind ium Tin A ntim o ny Te llurium
Important Semiconductor Elements
200.59 204.37 207.19 208.980 (210)
80 81 82 83 84
Hg Ti Pb Bi Po
M e rc ury Tha llium Le a d Bism uth Po lo nium
 Band Diagram: Semiconductor with No Doping

T>0
Conduction band
(Partially Filled)
EC
EF
EV
Valence band
(Partially Empty)

At T = 0, lower valence band is filled with electrons and upper conduction

band is empty, leading to zero conductivity.
Fermi energy EF is at midpoint of small energy gap (<1 eV) between
conduction and valence bands.
At T > 0, electrons thermally “excited” from valence to conduction band,
leading to measurable conductivity.
 Semi-conductors (intrinsic - ideal)
Perfectly crystalline (no perturbations in the periodic lattice).
Perfectly pure – no foreign atoms and no surface effects
At higher temperatures, e.g., room temperature (T @ 300 K), some electrons are
thermally excited from the valence band into the conduction band where they
are free to move.
“Holes” are left behind in the valence band. These holes behave like mobile
positive charges.

CB electrons and VB holes can

move around (carriers).
At edges of band the kinetic energy
of the carriers is nearly zero. The
electron energy increases upwards.
The hole energy increases
downwards.
Si Si Si Si Si Si Si
positive
ion core
Si Si Si Si Si Si Si
valence
electron
Si Si Si Si Si Si Si

Si Si Si Si Si Si Si
free
electron
Si Si Si Si Si Si Si
free
hole
Si Si Si Si Si Si Si
Semiconductors in Group IV
Carbon, Silicon, Germanium, Tin
Each has 4 valence Electrons.
Covalent bond
Compound Semiconductors
(Group III and Group V)

The III-V semiconductors are prominent for applications in optoelectronics with particular
importance for areas such as wireless communications because they have a potential for
higher speed operation than silicon semiconductors.
The compound semiconductors have a crystal lattice constructed from atomic elements in
different groups of the periodic chart. Each Group III atom is bound to four Group V atoms,
and each Group
V atom is bound to four Group III atoms, giving the general arrangement shown in Figure.
The bonds are produced by sharing of electrons such that each atom has a filled (8
electron) valence band.
The bonding is largely covalent, though the shift of valence charge from the Group V atoms
to the Group III atoms induces a component of ionic bonding to the crystal (in contrast to
the elemental semiconductors which have purely covalent bonds).
Representative III-V compound semiconductors are GaP, GaAs, GaSb, InP, InAs, and InSb.
GaAs is probably the most familiar example of III-V compound semiconductors, used for both
high speed electronics and for optoelectronic devices.
Optoelectronics has taken advantage of ternary and quaternary III-V semiconductors to
establish optical wavelengths and to achieve a variety of novel device structures. The ternary
semiconductors have the general form (Ax;A’1-x)B (with two group III atoms used to filled the
group III atom positions in the lattice) or A(Bx;B’1-x) (using two group V atoms in the Group V
atomic positions in the lattice).
The quaternary semiconductors use two Group III atomic elements and two Group V atomic
elements, yielding the general form (Ax;A’1-x)(By;B’1-y). In such constructions, 0<x,y<1.
Such ternary and quaternary versions are important since the mixing factors (x and y) allow
the band gap to be adjusted to lie between the band gaps of the simple compound crystals
with only one type of Group III and one type of Group V atomic element.
The adjustment of wavelength allows the material to be tailored for particular optical
wavelengths, since the wavelength ¸ of light is related to energy (in this case the gap energy
Eg) by ¸ λ= hc/Eg, where h is Plank's constant and c is the speed of light.
Hall effect and Hall devices

q = +e q = -e
v v

B B
B
F = qv×B F = qv×B

(a) (b)

Fig. 2.16 A moving charge experiences a Lorentz force in a magnetic

field. (a) A positive charge moving in the x direction experiences a
force downwards. (b) A negative charge moving in the -x direction
also experiences a force downwards.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
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 Hall effect in Semiconductor
Jy = 0 Bz
y
+ +
eEy Ey x
Jx Jx z
Ex
vhx vex
evhxBz eEy evexBz

+ + + + A
Bz

V
Fig. 2.26: Hall effect for ambipolar conduction as in a
semiconductor where there are both electrons and holes. The
magnetic field Bz is out from the plane of the paper. Both electrons
and holes are deflected toward the bottom surface of the conductor
and consequently the Hall voltage depends on the relative mobilities
and concentrations of electrons and holes.(E is the electric field.)
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
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 Thermal Conduction
δT
HOT COLD
• Metal dQ
dt A
HEAT

HEAT
HOT COLD δx

Fig. 2.19: Heat flow in a metal rod heated at one end. Consider the
rate of heat flow, dQ/dt, across a thin section δ x of the rod. The rate
of heat flow is proportional to the temperature gradient δ T/δ x and the
cross sectional area A.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
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Electron Gas Vibrating Cu+ ions

Fig. 2.18: Thermal conduction in a metal involves transferring

energy from the hot region to the cold region by conduction
electrons. More energetic electrons (shown with longer velocity
vectors) from the hotter regions arrive at cooler regions and collide
there with lattice vibrations and transfer their energy. Lengths of
arrowed lines on atoms represent the magnitudes of atomic
vibrations.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
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 The failure of Drude model

• It can explain the electric conduction, not

thermal conductivity and heat capacity
• Electronic heat capacity
– (Drude) 3
Cel = R
2
– Experimental result
CV = γT + αT 3

Need more sophisticated model (Sommerfeld or

Quantum mechanics)
 450
Ag
Thermal conductivity, κ (W K-1 m-1)

400
Ag-3Cu
50000
Cu

Thermal conductivity, κ (W K-1 m-1)

Ag-20Cu Copper
10000
300 κ
= T CWFL Au
σ
Al Aluminum
200 1000
Be
W
Mg
Mo
100 Ni Brass (Cu-30Zn) Brass (70Cu-30Zn)
100
Bronze (95Cu-5Sn)
Steel (1080) Al-14%Mg
Pd-40Ag
0 Hg
0 10 20 30 40 50 60 70 10
Electrical conductivity, σ, 106 Ω-1 m-1 1 10 100 1000
Temperature (K)
Fig. 2.20: Thermal conductivity, κ vs. electrical conductivity σ for
various metals (elements and alloys) at 20 °C. The solid line Fig. 2.21: Thermal conductivity vs. temperature for two pure metals
represents the WFL law with CWFL ≈ 2.44×108 W Ω K-2. (Cu and Al) and two alloys (brass and Al-14%Mg). Data extracted from
Thermophysical Properties of Matter, Vol. 1: Thermal Conductivity,
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
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Metallic Elements and Alloys, Y.S. Touloukian et. al (Plenum, New
York, 1970).
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
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 Phonon
• Non-metal

Diamond—Good thermal conductor

Polymer- -Bad thermal conductor

Equilibrium

Hot Cold

Energetic atomic vibrations

Fig. 2.22: Conduction of heat in insulators involves the

generation and propogation of atomic vibrations through the
bonds that couple the atoms. (An intuitive figure.)
 Q′ = ΔT/θ
Thermal
ΔT
ΔT
Hot Cold

conductivity and Q′ Q′ Q′
A
θ
L

resistance (a)

Fig. 2.23: Conduction of heat through a component in (a)

(b)

can be modeled as a thermal resistance θ shown in (b) where

Q′ = ΔT/θ.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
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Pure metal Nb Fe Zn W Al Cu Ag
κ (W m-1 K- 52 80 113 178 250 390 420
1
)
Metal alloys Stainless Steel 55Cu-45Ni 70Ni-30Cu 1080 Bronze Brass (63Cu- Dural (95Al-
Steel (95Cu- 37Zn) 4Cu-1Mg)
5Sn)
κ (W m-1 K- 12 - 16 19.5 25 50 80 125 147
1
)
Ceramics Glass- Silica-fused S3N4 Alumina Saphire Beryllia Diamond
and glasses borosilicate (SiO2) (Al2O3) (Al2O3) (BeO)

κ (W m-1 K- 0.75 1.5 20 30 37 260 ~1000

1
)
Polymers Polypropylene PVC Polycarbonate Nylon Teflon Polyethylene Polyethylene
6,6 low density high density

κ (W m-1 K- 0.12 0.17 0.22 0.24 0.25 0.3 0.5

1
)