Electronic and Optical Properties of Materials

MS-380
Relationship between Band Structure and Atomic bonding
for Conduction of free electrons
Electron Mobility
Electrical resistivity of metal
 Influence of Temperature

Influence of Impurities

Influence of Plastic Deformation

Free Electron Theory
❑ Outermost electrons of the atoms take part in
conduction.

❑ These electrons are assumed to be free to move through

the whole solid.
Free electron cloud / gas, Fermi gas.
❑ Potential field due to ion-cores is assumed constant.
Potential energy of electrons is not a function
of the position (constant negative potential) .

❑ The kinetic energy of the ‘free’ electron is much lower

than that of bound electrons in an isolated atom
 K =π/L, 2π/L…….

K can takes both positive and negative values

K =±π/L, ±2π/L…….
𝐴 = 𝜋𝑟 2
In general, K =±nπ/L,
where the quantum number n takes on
successively increasing integer values

ℎ2𝑛2
𝐸=
8𝑚𝐿2
For three-dimensional solid

+
ℎ2[𝑛𝑥2 + 𝑛𝑦2 𝑛𝑧2 ]
𝐸=
8𝑚𝐿2
 Probability of finding an electron:
P α A2 (square of the amplitude of the wave).
Therefore P is maximum at midpoint for λ=2L
Contradictory

Waves are considered to be travelling waves with a constant velocity, so that the time
averaged probability of finding an electron is constant throughout the solid.
 Fermi level

❑ At zero K the highest filled energy level (EF) is called the Fermi level
❑ If E F is independent of temperature (valid for usual temperatures)
► Fermi level is that level which has 50% probability of occupation
by an electron (finite T)
n= 1028 m-3, e = 1.6 x 10-19C
Ʈ = 10-14 s, m = 9.1 x 10-31 kg
Diffraction Phenomenon
Energy Gap in Solids
➢ In the model of free electrons, the potential field is assumed to be
constant.

➢ In reality, potential energy of an electron will be undoubtedly a

function of its position.

➢ This fact combined with the diffracting properties of electrons has

an important effect on the electron energy calculations.

➢ Consider the motion of electrons along only one axis.

➢ Electrons moving to the right or to the left are scattered by the

atoms in the path
➢ If, the spacing d between neighboring atoms along the axis is such
that the Bragg equation nλ = 2d sin Ф

➢ is exactly satisfied, the electrons are totally reflected.

➢ For the unidirectional motion, the atoms along the axis can be
visualized as successive ‘planes’ perpendicular to the direction of
electron motion so that sin Ф = 1.

➢ Then, from above Eq. , the wavelength λ of the electron takes on

critical values of 2d, d, 2d/3, and

➢ If Expressed in terms of the wave number k (k = 2Π/ λ), we get the

➢ critical conditions at k = ± Π /d, ± 2Π /d, 3 ± Π /d,…..
➢ Wave form of the electrons under such critical conditions comes out
to be two standing waves rather than the travelling wave.

➢ Standing waves can be obtained from linear combinations of two

travelling waves moving in opposite directions.

➢ Two possible combinations (the sum and the difference) of the

travelling waves give respectively a cosine wave and a sine wave.

➢ These waves have the maximum

amplitude at fixed points in space.

➢ Probability of finding an electron

at a point is proportional to the
square of the amplitude of the
wave at that point.

➢ Electron is localized here.

➢ The E–k relationship is replotted in, taking into account the
deviations from the average potential energy

➢ . At a critical condition, electron is described by a

standing wave and is therefore localized

➢ Deviations from the average potential energy appear as a break in

the E–k curve
➢ Slope is zero at critical values
➢ In the three-dimensional crystal, the electrons can move in any
direction.

➢ The Bragg angle Ф can have any value from 0 to 90°.

➢ Critical values of k will then correspond to n k = ±n Π /d sin Ф and not

±n Π /d.
➢ Ranges of k that lie between the forbidden gaps are called Brillouin
zones.

➢ The first Brillouin zone contains all the energy levels up to the first
E–k discontinuity,

➢ Second zone contains all levels between the first and the second
discontinuities and so on
Intrinsic Semiconductors

➢ A very large field is required for electronic transition

➢ The other possibility is by thermal excitation.

➢ Conduction is due to the intrinsic processes.

➢ A pure crystal of silicon or germanium is an intrinsic

semiconductor
➢ The number of electrons excited across the gap can be calculated
from the Fermi–Dirac probability distribution.
➢ Probability P(E) of an electron occupying energy level E

➢ Number n of electrons promoted across the gap

➢ Number holes and electrons are equal. Ie

➢ Under an external applied field both electrons and holes
move in the opposite directions.

➢ Conductivity depends on the concentration of these charge

carriers
Energy gap can be computed from the slope of straight line
between log of conductivity against the reciprocal of temperature
Extrinsic Semiconductors

➢ Doped pure semiconductor.

➢ Addition of impurities markedly increases the conductivity of a

semiconductor.

➢ Large orbit means that the fifth electron is almost free and is at an
energy level close to the conduction band.
➢ Phosphorus atom donate its electron to the semiconductor.

➢ The energy level of the fifth electron is called the donor level

➢ n –type semiconductors.

➢ Energy required to excite the fifth electron into the conduction band
is known as the ionization energy.

➢ Ionization energy of an impurity atom is very small.

➢ So, at room temperature, a large fraction of the donor level

electrons are excited into the conduction band.

➢ According to the law of mass action, the product of the number of

electrons in the conduction band and the number of holes in the
valence band must be constant
➢ The law of mass action also valid here.

➢ Positive holes become the majority charge carriers.

➢ Such an extrinsic semiconductor is called a p-type semiconductor.

The slope difference between the extrinsic and intrinsic regions
reflects the difference in magnitude between the impurity ionization
energy and the energy gap.
Junction Diode

➢ At equilibrium, there is no net current

flowing across the p-n junction.

➢ At equilibrium, the current from the n-

side to the p-side and the current in
the opposite direction, from the p-side
to the n-side, are the same, equal to I0
 Reverse Bias
Forward Bias

Forward current increases Reverse current remains constant

exponentially. at a small value I0
 Junction Transistor
➢ is a device used to amplify an electric signal.

➢ It consists of two p-n junctions in the same crystal, arranged

in the order n-p-n or p-n-p.

➢ A small change in the input voltage results in a large current

from the emitter to the base and then on to the collector.
HALL EFFECT

RH = Hall coefficient
The electrical conductivity and electron mobility for
aluminum are 3.8 X 107 (Ω - m)-1 and 0.0012 m2/V.s,
respectively. Calculate the Hall voltage for an aluminum
specimen that is 15 mm thick for a current of 25 A and a
magnetic field of 0.6 tesla

RH = -3. 16 x 10-11 V.m/A tesla

Suppose a silicon specimen is of cylindrical shape which
has the length 51 mm and diameter 5.1-mm, respectively.
Calculate the electrical conductivity of this specimen, when
a current of 0.1 A is following in the longitudinal direction
and voltage of 12.5 V is developed between two points,
which are separated by 38 mm.

σ =1/ρ = Il/VA = Il/Vπ[(d/2)]2

σ = (0.1 A)(38 × 10−3 m)/(12.5 V)(π)(5.1 × 10−3m/2)2

= 14.9 (Ω - m)-1
Suppose the Fermi energy of a metal is 4.5 eV. Calculate the
temperature at which there is a 1% probability that states
having energy of 5.0 eV will be occupied?

T = (E-EF)/ kBln{(P(E)-1-1}

T = (5 - 4.5) / 8.63 X10-5ln {(0.01-1 -1}

Hence : T = 58.5K
When a p-n diode is forward biased using 0.30 V, a current of
1 A flow through the junction. Calculate reverse current at
298K when the polarity of diode is reversed?

I0 = Iforward/ [exp eV i/kT) -1]

I0 = 1A / (exp [(0.30)/(8.63X10 -5 X(298K)] -1)

= 8.59X10-6A
Find the capacitance of a layer of Al 2O3 that is 0.5 m thick
and 2000 mm2 of square area and Ɛr =1
Calculate the polarization produced in dielectric medium of
dielectric constant 6 when it is subjected to an electric field
of 100 Vm–1.
A parallel-plate capacitor using a dielectric material having
an Ɛr of 2.5 has a plate spacing of 1 mm. If another material
having a dielectric constant of 4.0 is used and the
capacitance is to be unchanged, what must be the new
spacing between the plates?
Consider a parallel-plate capacitor having an area of 2500 mm2 and a
plate separation of 2 mm, and with a material of dielectric constant 4.0
positioned between the plates.
(a) What is the capacitance of this capacitor?
(b) Compute the electric field that must be applied for 8.0 x 10-9 C to be
stored on each plate.
Dielectric Property
Dielectric Material
: is one that is electrically insulating (nonmetallic) and exhibits or
may be made to exhibit an electric dipole structure—that is, there is a
separation of positive and negative electrically charged entities on a
molecular or atomic level.

CAPACITANCE: The capacitance C is related to the quantity of charge

stored on either plate Q by
 In the presence of
In Vacuum dielectric Material

Relative permittivity which is also as dielectric constant is given by:

FIELD VECTORS AND POLARIZATION

An electric dipole moment p is associated with each dipole as follows

where q is the magnitude of each dipole charge and d is the distance of

separation between them.

In the presence of an electric field e, which is also a vector quantity, a

force (or torque) comes to bear on an electric dipole to orient it with
the applied field. The process of dipole alignment is termed polarization
Surface charge density D, or quantity of charge per unit area of
capacitor plate, is proportional to the electric field.
When a vacuum is present, then

An analogous expression exists for the dielectric case

D is also called the dielectric displacement

The increase in capacitance, or dielectric constant, can be explained
using a simplified model of polarization within a dielectric material

In the presence of a dielectric, the charge density between the plates,

which is equal to the surface charge density on the plates of a
capacitor, may also be represented by
where P is the polarization
P = Q/A, where A is the area of each plate
TYPES OF POLARIZATION
There are three types or sources of polarization:
Electronic, Ionic, and Orientation.
Dielectric materials typically exhibit at least one of these polarization
types, depending on the material and the manner of external field
application.

Electronic polarization
may be induced to one degree or another in all atoms.
It results from a displacement of the center of the negatively charged
electron cloud relative to the positive nucleus of an atom by the
electric field. This polarization type is found in all dielectric materials
and exists only while an electric field is present.
Ionic Polarization
Ionic polarization occurs only in materials that are ionic.
An applied field acts to displace cations in one direction and anions in
the opposite direction, which gives rise to a net dipole moment.
The magnitude of the dipole moment for each ion pair pi is equal to the
product of the relative displacement di and the charge on each ion,
Orientation Polarization

➢ The third type, orientation polarization, is found only in substances

that possess permanent dipole moments.
➢ Polarization results from a rotation of the permanent moments
➢ into the direction of the applied field, as represented in Figure.
➢ This alignment tendency is counteracted by the thermal vibrations of
the atoms, such that polarization decreases with increasing
temperature.

The total polarization P of a substance is equal to the sum of the

electronic, ionic, and orientation polarizations
FREQUENCY DEPENDENCE OF THE DIELECTRIC CONSTANT
➢ In many practical situations, the current is alternating (ac)—that is, an
applied voltage or electric field changes direction with time.
➢ Consider a dielectric material that is subject to polarization by an ac
electric field.

➢ With each direction reversal, the dipoles attempt to reorient with the field,
as illustrated in Figure, in a process requiring some finite time.

➢ For each polarization type, some minimum reorientation time exists that
depends on the ease with which the particular dipoles are capable of
realignment.

➢ The relaxation frequency is taken as the reciprocal of this minimum

reorientation time.
➢ A dipole cannot keep shifting
orientation direction when the
frequency of the applied electric
field exceeds its relaxation
frequency and, therefore, it will not
make a contribution to the dielectric
constant.

➢ The dependence of Dielectric

constant on the field frequency is
represented schematically in Figure
for a dielectric medium that exhibits
all three types of polarization.
➢ Note that the frequency axis is scaled logarithmically. As indicated
in Figure, when a polarization mechanism ceases to function, there
is an abrupt drop in the dielectric constant; otherwise, it is virtually
frequency independent.
FERROELECTRICITY
The group of dielectric materials called ferroelectrics exhibit spontaneous
polarization—that is, polarization in the absence of an electric field.
They are the dielectric analogue of ferromagnetic materials, which may display
permanent magnetic behavior.
There must exist in ferroelectric materials permanent electric dipoles, the origin of
which is explained for barium titanate, one of the most common ferroelectrics.
The spontaneous polarization is a consequence of the positioning of the Ba2+, Ti4+,
and O2- ions within the unit cell, as represented in Figure
➢ The Ba2+ions are located at the corners of the unit cell, which is of
tetragonal symmetry (a cube that has been elongated slightly in one
direction).
➢ The dipole moment results from the relative displacements of the O2-
and Ti4+ ions from their symmetrical positions, as shown in the side
view of the unit cell.
➢ The O2- ions are located near, but slightly below, the centers of each
of the six faces, whereas the Ti4+ ion is displaced upward from the
unit cell center.
➢ Thus, a permanent ionic dipole moment is associated with each unit
cell.
➢ However, when barium titanate is heated above its ferroelectric Curie
temperature 1200C , the unit cell becomes cubic, and all ions assume
symmetric positions within the cubic unit cell; the material now has a
perovskite crystal structure, and the ferroelectric behavior ceases.
PIEZOELECTRICITY
An unusual phenomenon exhibited by a few ceramic materials (as well
as some polymers) is piezoelectricity—literally, pressure electricity.
Electric polarization (i.e., an electric field or voltage) is induced in the
piezoelectric crystal as a result of a mechanical strain (dimensional
change) produced from the application of an external
force.
Reversing the sign of the force (e.g., from tension to compression)
reverses the direction of the field.
The inverse piezoelectric effect is also displayed by this group of
materials—that is, a mechanical strain results from the imposition of an
electrical field.
Optical property
ELECTROMAGNETIC RADIATION

➢ Light, heat, radar, radio waves, and x-rays are all forms of
electromagnetic radiation.

➢ Each is characterized by a specific range of wavelengths

Electromagnetic spectrum of radiation spans the wide range.

White light is simply a mixture

of all colors
LIGHT INTERACTIONS WITH SOLIDS

Radiation intensity, expressed in watts per square meter

T = Transmissivity (IT/I ), A = Absorptivity (IA/I0), and R= Reflectivity (IR/I0).

▪ Transparent Materials: Electrically insulating materials

▪ Translucent Materials
▪ Opaque Materials: Bulk metals.

▪ Semiconductors???
ATOMIC AND ELECTRONIC INTERACTIONS: Two of the
most important of these interactions are electronic polarization
and electron energy transitions.

Electronic Polarization

Two consequences of this polarization are as follows:

➢ Some of the radiation energy may be absorbed, and
➢ Light waves are decreased in velocity as they pass through
the medium
Electron Transitions ➢ Only specific ΔE exist between the energy levels

➢ All of a photon’s energy is absorbed in each excitation

event.

➢ Excited electron cannot remain in an excited state

indefinitely,

➢ As electron comes to ground state, reemission of

electromagnetic radiation.

➢ There must be a conservation of energy for absorption

and emission electron transition

The change in energy experienced by the electron, depends on the

radiation frequency as follows:
Optical Properties of Metals
➢ Metals are opaque because the incident radiation having frequencies
within the visible range excites electrons into unoccupied energy
states above the Fermi energy.
➢ Hence incident radiation is absorbed according to equation:

➢ Total absorption is within a very thin outer layer, usually less than
0.1µm

➢ Metals are opaque to all electromagnetic radiation on the low end of

the frequency spectrum.
➢ Most of the absorbed radiation is reemitted from the surface in the
form of visible light of the same wavelength, which appears as
reflected light.

➢ The reflectivity for most metals is between 0.90 and 0.95.

➢ Metals are opaque and highly reflective, the perceived color is

determined by the wavelength distribution of the radiation that is
reflected and not absorbed.

➢ A bright silvery appearance when exposed to white light indicates that

the metal is highly reflective over the entire range of the visible
spectrum.
Optical Properties of Nonmetals

REFRACTION: Bent at the interface

The index of refraction n of a material is defined as the ratio of the

velocity in a vacuum to the velocity in the medium

The magnitude of n (or the degree of bending) depends on the

wavelength of the light.
Retardation of electromagnetic radiation in a medium results from
electronic polarization

The index of refraction for a typical soda–lime glass is approximately

1.5.
REFLECTION

Just as the index of refraction of a solid depends on the wavelength of

the incident light, so does the reflectivity vary with wavelength.
ABSORPTION
➢ Light radiation is absorbed in this group of materials by two basic
mechanisms that also influence the transmission characteristics
of these nonmetals.

➢ One of these is electronic polarization

➢ The other mechanism involves valence band–conduction band
electron transitions
Excitations of electrons from VB to CB with the accompanying
absorption can take place only if the photon energy is greater than
that of the band gap Eg

The minimum wavelength for visible

light, λ(min), is about 0.4 µm, C= 3 x108
m/s and h =4.13 x 10-15 eV-s ➢ It means no visible light is absorbed by
nonmetallic materials having band gap energies
greater than about 3.1 eV;
➢ These materials, if of high purity, appear
transparent and colorless.
The maximum wavelength for visible light, λ(max), is about 0.7 µm,
C= 3 x108 m/s and h =4.13 x 10-15 eV-s

➢ This result means that all visible light is absorbed by valence band–
to–conduction band electron transitions for semiconducting materials
that have band gap energies less than about 1.8 eV;
➢ Thus, these materials are opaque.

➢ Only a portion of the visible spectrum is absorbed by materials having

band gap energies between 1.8 and 3.1 eV;
➢ Consequently, these materials appear colored.
➢ If impurities or other electrically active defects are present, electron
levels within the band gap may be introduced, such as the donor and
acceptor levels.
➢ Light radiation of specific wavelengths may be emitted as a result of
electron transitions involving these levels within the band gap.

➢ Electromagnetic energy that is absorbed by electron excitation must

be dissipated in some manner; several mechanisms are possible
TRANSMISSION

➢ Equation is derived by assuming that same

medium exists outside both front and back
faces.

➢ Thus, the fraction of incident light that is

transmitted through a transparent material
depends on the losses that are incurred by
absorption and reflection.
➢ Single-crystal material (sapphire), which is transparent;

➢ A polycrystalline and fully dense (nonporous) material, which is

translucent;

➢ and a polycrystalline material that contains approximately 5%

porosity, which is opaque.