Material Science

Prof. Satish V. Kailas

Associate Professor
Dept. of Mechanical Engineering,
Indian Institute of Science,
Bangalore – 560012
India

Chapter 14. Electrical properties

What is electrical conduction?

What is electrical resistivity?
What is electrical conductivity?
How the engineering materials are classified based on the electrical properties?
What are the conduction losses?
How to control the conductivity of a metal?
What are charge carriers in different conductors?
What are the factors that influence the conductivity?
What is energy band model? How does it explain the conductivity?
What is semi-conductivity?
Do the ceramics and polymers conduct electricity?
What is dielectric behavior?
How a dielectric material can be used to store electrical energy?
What is ferro-electricity and piezoelectricity?
Want to know how good you are in the subject?

What is electrical conduction?

Electrical conductivity of a material is defined in terms of ease with which a material

transmits an electrical current. Electrical current (I) is flow of electrons, and driving force
for the flow of electrons is called voltage (V). Ohm’s law relates these parameters as
follows:

VαI

V = IR……………………………….………..(1)

where R – is the materials resistance to flow of electrons through it.

V, I, and R respectively have units as volts, amperes, and ohms (Ω).

What is electrical resistivity?

Electrical resistance of a material is influenced by its geometric configuration; hence a

new parameter called electrical resistivity (ρ) is defined such as it is independent of the
geometry.

RA
ρ= ……………………………..……….(2)
l

where A – cross-sectional area perpendicular to the direction of the current, and l – the
distance between points between which the voltage is applied. Units for ρ are ohm-meters
(Ω-m).

What is electrical conductivity?

Reciprocal of the electrical resistivity, known as electrical conductivity (σ), is used to

express the electrical behavior of a material, which is indicative of the ease with which a
material allows of flow of electrons.

1 l
σ= = …………………………..……..(3)
ρ RA

Electrical conductivity has the following units: (Ω-m)-1 or mho/meter.

How the engineering materials are classified based on the electrical properties?

Solid engineering materials exhibit very wide range of electrical conductivity

(about 27 orders of variation). Hence the materials for electrical applications are
classified according to their electrical conductivity as: conductors, semiconductors and
insulators/dielectrics. Metals are conductors having conductivities in range of 107 (Ω-m)-
1
, while semiconductors have conductivities in range from 10-6 to 104 (Ω-m)-1, and
materials with conductivity lower than 10-10(Ω-m)-1 are termed as insulators.

What are the conduction losses?

In components designed to conduct electrical energy, minimizing losses is important to

conserve energy as well as minimize heating. The electric power (P) lost when a current
flows through a material is given by:

P = VI = I2R………………………………….. (4)

Electrical losses are also known as Joule heating losses.

How to control the conductivity of a metal?

Second form of Ohm’s law can be obtained by combining the equations (3) and
(4) to give:

I V
= σ ⇒ J = σE ………………………… (5)
A l

where J – current density (A/cm2), E – electric field strength (V/cm).

Current density can be defined in different terms as

J = n.q.v …………………………….………. (6)

where n – number of charge carriers (1/cm3), q – charge on each carrier (1.6x10-19C), v -

average drift velocity (cm/s), which occurs as a result of an applied electric or magnetic
field.

The term ‘ v /E’ is called mobility, μ (cm2/V.s) of the carriers, thus

σ = n.q.μ ……………………………………. (7)

From the above equation, the following can be concluded: electrical conductivity of a
material can be controlled by (i) controlling number of charge carriers, n or (ii)
controlling the mobility of the carriers, μ. Mobility is important for metals or electrical
conductors, whereas number of carriers is important for semi-conductors and insulators.

What are charge carriers in different conductors?

Electrons are charge carriers in metals. In ionic materials (for example ionic ceramics),
conduction is result of net movement of charged particles (cations and anions) in addition
to any electron motion. However, both electrons and holes are charge carriers in
semiconductors and in doped conductive polymers. Thus equation 7 can be written as
follows:

for metals : σ = ne .q e .μ e …………………………(8)

for semiconductors : σ = n.q.μ n + n.q.μ p …………………..(9)

for ionic materials : σ total = σ electronic + σ ionic …………….(10)

What are the factors that influence the conductivity?

In all conductors, semiconductors, and many insulating materials, only electronic
conduction exists i.e. electrons are the only charge carriers. Ionic conduction results
because of net motion of charged ions. Movement different particles in various materials
depend on more than one parameter. These include: atomic bonding, imperfections,
microstructure, ionic compounds, diffusion rates and temperature. Because of these,
electrical conductivity of materials varies tremendously.

What is energy band model? How does it explain the conductivity?

Four different types of band structures are possible at 0 K: (1) Where one outermost band
is only partially filled with electrons. The energy corresponding to the highest filled state
at 0 K is called the Fermi energy, Ef. (2) There is overlap of an empty band and a filled
band. (3) and (4) One filled band (valence band) and an empty band (conduction band)
are separated by an energy band gap which lies between them. These are schematically
shown in the figure 14-1.

Figure 14-1: Possible electron band structures.

Band structures (1) and (2) are found in metals / conductors. Band structures (3) and (4)
are distinguished by the size of energy band gap. Narrower energy band gap i.e. size < 2
eV, is found in semiconductors, while the broader energy band gap i.e. size > 4 eV, is
found in insulators. Fermi energy for these two band structures lies within the band gap
near its center.

Metals have high conductivities because of the large number of free electrons that have
been excited into empty states above the Fermi energy. If the metal crystal lattices were
perfect and there are no lattice vibrations, the electrons would pass through the lattice un-
scattered, encountering no resistance. However, lattice vibrations and phonon scattering
play a role in disrupting the mean free path of electrons. In addition, crystalline defects
and impurity atom affect the conductivity. These scattering mechanisms act
independently on one another. Thus the effective resistivity of metals can be represented
as follows:

ρ = ρ thermal + ρ residual ……………….………..(11)

Equation 11 is some times known as Mathiessen’s rule. With increase of temperature,

thermal vibrations increase so the resistivity, and vice versa. In the same manner, with
increase of either defects or impurities, resistivity increases. Thus, in general, for pure
metals, the resistivity approaches zero at absolute zero temperature.

Some metals, however, such as Pb, lose all resistivity abruptly and completely at some
low temperatures. This phenomenon is called superconductivity, and the materials that
exhibit it are called superconductors. The temperature at which the resistivity vanishes is
called the critical transition temperature, Tc. Many elemental metals, solid-solution
alloys, some ceramics and intermetallic compounds exhibit superconductivity. For
example: Ti, V, Zn, W, Al, Hg, NbTi, Nb3Sn, MgB2, La-Sr-Cu oxide, YBa2Cu3O7-x,
carbon nanotubes, etc. BCS (Bardeen, Cooper and Schrieffer) theory explains that the
super conductivity is caused by electron-lattice interaction and that the superconducting
electrons consist of paired ordinary electrons called a Cooper pair.

What is semiconductivity?

Conductivity of semiconductors is not as high as metals / conductors but it is higher than

the insulators. However, their electrical properties are unique, in the sense that their
electrical properties are extremely sensitive to even minute concentrations of impurities.
For intrinsic semiconductors, their electrical behavior is based on inherent electronic
structure of the pure material. On the other hand, if the electrical properties are dominated
by impurities, they are called extrinsic semiconductors.

Intrinsic semiconduction: Energy band gap between the valence and conduction bands
can be used to classify materials as conductors, insulators, and semiconductors. The
magnitude of the band gap is characteristic of the lattice alone, and varies widely for
different crystals. In semiconductors, the valence and conduction bands do not overlap as
in metals, but they possess enough electrons in the valence band those can be promoted to
the conduction band at a certain temperature. Promotion of electrons leaves behind
positively charged holes in the valence band which maintain the charge neutrality. These
holes can be regarded as moving positive charges through the crystal with a charge
magnitude and ass as that of an electron. Conduction that arises from thermally / optically
excited electrons is called intrinsic semiconduction. It usually takes place at elevated
temperatures since sufficient thermal agitation is necessary to transfer a reasonable
number of electrons from the valence band to the conduction band. At still higher
temperatures, the concentration of thermally excited electrons in the conduction band
becomes so high that the semiconductor behaves more like a metal. The elements capable
of intrinsic conduction are limited, and include: Si, Ge, Sn, Pb, etc.
 Figure 14-2: Band structure and intrinsic conductivity.

In intrinsic semiconductors, the number of holes equals the number of mobile electrons.
The resulting conductivity can be expressed as

σ = ne .q e .μ e + nh .q h .μ h = ne .q e .( μ e + μ h ) …..(12)

as ne = nh, and both electron and hole possess equal magnitude of charge.

The mobility of holes is always less than those of electrons i.e. μh < μe. In Si and Ge, the
ratio μe / μh is approximately three and two respectively.

Extrinsic semiconduction: The charge carrier density can also be increased by adding
impurities of either higher or lower valence. This addition of impurities is known as
doping, and impure atoms in the element are called donor atoms.

When a pentavalent substitutional atoms like P, As, or Sb are placed into a covalently
bonded tetravalent materials such as Si or Ge, only four of their five valence electrons are
required to participate in covalent bonding, while the fifth electron remains weakly bound
to the donor atom. However, this binding energy is in order of 0.01 eV, much less than
that of a covalently bonded electron. The energy state of this electron is indicated as Ed.
Energy gap between the donor and conducting bands is much smaller than that between
the valence band and conduction band, Eg. Thermal agitation, even at room temperature,
is good enough to excite this electron to the conduction band, leaving behind a positively
charged hole in the donor band. Conductivity is due to motion of negatively charged
electrons in the conduction band, and so the material is called n-type semiconductor.
Fermi level (Ef) of n-type extrinsic semiconductor is higher than that of intrinsic
semiconductor i.e. it shifted upward in the band gap, to within the vicinity of the donor
state; and its exact position is a function of both temperature and donor concentration.
 Figure 14-3: Band structure and n-type semiconductivity.

Other possibility of susbstituion involves impurity with lower valence. For example
trivalent elements like B, Al, Ga, In, Th doped to Si or Ge. Since the donor atoms are
deficient in bonding electrons, one of their bonding orbitals will contain a hole that is
capable of accepting an electron from elsewhere in the crystal. Binding energy is small,
and promotion of an electron from the valence band to the acceptor band, Ea, leaves a
positively charged hole in the valence band that can act as a charge carrier. Materials with
this p-type extrinsic semiconduction are called p-type semiconductors. Fermi level (Ef)
for p-type semiconductors is positioned within the band gap and near to the acceptor
level.

Figure 14-4: Band structure and p-type semiconductivity.

For an n-type semiconductor, electrons in the conduction band are charge carriers and
holes participate in bonding, whereas for a p-type semiconductor, the electrons
participate in bonding, and the holes are the charge carriers. Conductivity equations for
these extrinsic semiconductors are written as:

n-type semiconductor: σ ≅ n.q.μ e …….(13)

p-type semiconductor: σ ≅ n.q.μ h ……..(14)

In both types of extrinsic semiconductors, the doping elements are chosen so that both
acceptor and donor levels are located closer to the corresponding energy bands and only a
small energy gap in involved when exciting electrons. Intrinsic semiconductors are pure
to the order greater than 107, while extrinsic semiconductors are made with impurity
levels in order of 1-1000 ppm.

In intrinsic semiconductors, the conductivity is dominated by the exponential relation

between temperature and band-gap. However, the conductivity of extrinsic
semiconductors is governed by competing forces: charge carrier density and charge
carrier mobility. At low temperatures, the number of charge carriers initially increases
with temperature. At intermediate temperatures, for n-type extrinsic semiconductor, most
of the donor electrons have been promoted and the number of charge carriers is nearly
independent of temperature in what is known as the exhaustion range. At higher
temperatures, the number of valence electrons excited to the conduction band greatly
exceeds the total number of electrons from the donor atoms, and extrinsic semiconductor
behaves like an intrinsic semiconductor. That is, at low temperatures the conductivity
varies with temperature as the charge carrier concentration, at higher temperatures the
charge carrier mobility dominates and the conductivity decreases with temperature, and at
still higher temperatures the extrinsic semiconductor behaves like an intrinsic
semiconductor.

Do the ceramics and polymers conduct electricity?

Yes, ceramics and polymers conduct electricity. In addition to the conduction of charge
via electrons, charge can be conducted via ions. Ions are present in most crystalline
ceramic materials such as oxides and halides. This process is called ionic conduction, and
may occur in conjunction with or separately from electronic conduction.

Several types of compounds show exceptionally high ionic conductivity. Such

phases fall into three broad categories: halide and chalcogenides of silver and copper;
oxides with β-alumina structure; and oxides of fluorite structure. Conductivity of halides
and chalcogenides is result of larger number of available sites than the number of cations.
In oxides with β-alumina structure (AM11O17) monovalent cation A (such as Na, K, Rb,
Li) is mobile. High dopant levels in the fluorite-type solid solutions leads to large defect
concentrations and vacancy ordering which results in rapid oxygen migrations. This is the
base for development of high-temperature superconductors. For example: La2CuO4 (Tc =
30 K), YBC compounds – yttrium doped perovskite structure, YBa2Cu3O7 (Tc = 92 K).

Although ceramics are insulators, by properly engineering the point defects in

ceramics, it is possible to convert them into semiconductors. For example: Indium tin
oxide (ITO) is used as a transparent conductive coating on plate glass, and also for tough
screen displays; Ytrria-stabilized zirconia (YSZ) is used as solid electrolyte in solid oxide
fuel cells; Lithium cobalt oxide is used as solid electrolyte in lithium ion batteries.

Polymers have a band structure with a large energy gap leading to low
conductivity because their valence electrons are involved in covalent boding. Hence
polymers are used frequently in applications that require electrical insulation. In some
cases however, low conductivity is undesirable. For example; static electricity can
accumulate on housing for electronic equipment making the polymer vulnerable to
electromagnetic radiation that damages the internal devices. These problems can be
solved in two approaches: (1) introducing an additive to the polymer to improve
conductivity, and (2) creating polymers with inherent conductivity.

Adding ionic compound to the polymer can reduce resistivity because the ions
migrate to the polymer surface and attract moisture, which in turn, dissipates static
charges. Introducing conductive fillers such as carbon black can also dissipate static
charges. Some polymers inherently have good conductivity as result of doping or
processing techniques. When acetal polymers are doped with agents such as arsenic
pentafluoride, electrons or holes are able to jump freely from one atom to another along
the backbone of the chain, increasing the conductivity to near that of metals. However,
unlike semiconductors, the dopant atoms or molecules do not substitute for or replace the
polymer atoms. Other polymers include polyparaphynylene, polypyrole, and polyaniline.
Some other polymers such as polyphthaocyanine can be cross-linked by special curing
processes to raise its conductivity.

What is dielectric behavior?

A dielectric is a material separating two charged bodies. For a material to be a

good dielectric, it must be an electrical insulator. Thus, any insulator is also called a
dielectric. Dielectric materials are used in capacitors, devices used to store the electric
energy.

How a dielectric material can be used to store electrical energy?

When a voltage is applied between two parallel plates in a vacuum, one plate
becomes positively charged and the other negatively charged, with corresponding field
directed from the positive to the negative. Then the energy stored, Q, is given by:

Q = CV …..…………………………………. (15)

where C is the capacitance (units: coulombs per volt or farads [F]). It is dependent on the
geometry of plates as follows:

A
C = ε0 …………………………….……. (16)
l

where A – area of the plates, l – distance between them, and ε0 – permittivity of vacuum
(8.85 X 10-12 F/m). If a dielectric material is inserted between the plates,

A
C =ε ……………………………………. (17)
l
ε – permittivity of the medium, which will be greater in magnitude than ε0. The relative
permittivity εr, also called dielectric constant, is defined as

ε
εr = ……………………………………... (18)
ε0

which is greater than unity, and presents the increase in charge storing capacity by
insertion of the dielectric medium between the plates. This is result of polarization –
orientation of permanent or induced dipoles under externally applied electric field.
Polarization causes positive charge to accumulate on the bottom surface next to the
negatively charged plate, and causes negative charge to accumulate toward the positively
charged plate on the top. This tends to decrease the effective surface charge density on
either plate. The expected decrease in effective charge corresponds to the polarization, of
the material which equals the induced dipole moment per unit volume of polarizable
material. The magnitude of the charge per unit area on either plate, called the dielectric
displacement or flux density or surface charge density, D, is defined as:

D = εξ ………………………………………. (19)

where ξ – electric field strength,

ξ = V / l……………………………………….. (20)

In the presence of the dielectric, surface charge density can also be presented as

D = εξ = ε 0ξ + P …………………………… (21)

where polarization is defined as,

P = ε 0 (ε r − 1)ξ ………………………..……. (22)

the increase in charge density above that for a vacuum because of the presence of the
dielectric.
 Figure 14-5: Schematic representation of capacitor and polarization phenomenon.

The polarization may also be thought of as the total dipole moment per unit volume of the
dielectric material or as a polarization electric field within the dielectric that results from
the mutual alignment of the many a atomic or molecular dipoles. Polarization of a
dielectric material may be caused by at least one of four major types of polarization:
electronic, ionic (atomic), orientation, and space charge (interfacial).

Electronic polarization arises because the center of the electron cloud around a nucleus is
displaced under an applied electric field. Ionic polarization occurs in ionic materials
because an applied field acts to displace cations in the direction of the applied field while
displacing anions in a direction opposite to the applied field. Orientation polarization can
occur in materials that possess permanent electric dipole moments. These permanent
dipoles tend to become aligned with the applied electric field, but entropy and thermal
effects tend to counter this alignment, thus it is highly temperature dependent. Space
charge polarization results from the accumulation of charge at structural interfaces in
heterogeneous materials. Such polarization occurs when one of the phases has a much
higher resistivity than the other.

The total polarization subjected to an alternating electric field depends upon the ease with
which the permanent or induced dipoles can reverse their alignment. The time required
for dipole reversal is called the relaxation time, and its reciprocal is called the relexation
frequency. As the frequency of the applied electric field approached the relaxation
frequency, the polarization response increasingly lags behind the applied field. The
reorientation of each type of dipole is opposed by internal friction, which leads to heating
in the sample and power loss. The power loss depends on the degree to which the
polarization lags behind the electric field. This is also called dielectric loss, and a low
dielectric loss is desired at the frequency of utilization.

At high enough frequencies, the dielectric will experience electrical breakdown initiated
by the field-induced excitation of a number of electrons into the conduction band, and the
insulator become a conductor. The magnitude of the electric field required to cause
dielectric breakdown is called the dielectric strength or breakdown strength.

Many ceramics and polymers are utilized as insulators and in capacitors. For example:
glass, porcelain, stealite, mica. These have dielectric constants within the range of 6-10.
Typical applications: electrical insulation, switch bases, light receptacles. Dielectric
constant for most polymers lies in the range of 2-5, less than that for ceramics, since the
later exhibit greater dipole moments. Typical applications: insulation for wires, cables,
motors, generators, some capacitors.

What is ferro-electricity and piezoelectricity?

Two peculiar phenomena related to electric dipoles are ferro-electricity and piezo-
electricity. Ferro-electricity is defined as the spontaneous alignment of electric dipoles by
their mutual interaction in the absence of an applied electric field. This arises from the
fact that the local field increases in proportion to the polarization. Thus, ferro-electric
materials must possess permanent dipoles. Ex.: BaTiO3, Rochelle salt
(NaKC4H4O6.4H2O), potassium dihydrogen phosphate (KH2PO4), potassium niobate
(KNbO3). These materials have extremely high dielectric constants at relatively low
applied field frequencies. Thus, capacitors made from ferro-electric materials are smaller
than capacitors made of other dielectric materials.

Piezo-electricity, or pressure electricity, is defined as polarization induced by the

application of external force. Hence, by reversing the direction of external force,
direction of the field can be reversed i.e. the application of an external electric field alters
the net dipole length and causes a dimensional change. This property is characteristic of
materials having complicated structures with a low degree of symmetry. Thus, piezo-
electric materials can be used as transducers – devices that convert mechanical stress into
electrical energy and vice versa. Application for these materials includes microphones,
ultrasonic generators, sonar detectors, and mechanical strain gauges. Ex.: Barium titanate,
lead titanate, lead zirconate (PbZrO3), ammoinium dihydrogen phosphate (NH4H2PO4),
and quartz.

Want to know how good you are in the subject?

1. Electrical conductivity of insulators is the range _____________.

(a) 10-10(Ω-mm)-1 (b) 10-10(Ω-cm)-1 (c) 10-10(Ω-m)-1 (d) 10-8(Ω-m)-1

2. Units for electric field strength

(a) A/cm2 (b) mho/meter (c) cm2/V.s (d) V/cm

3. Energy band gap size for semiconductors is in the range ________ eV.

(a)1-2 (b) 2-3 (c) 3-4 (d) > 4

4. Energy band gap size for insulators is in the range ________ eV.

(a)1-2 (b) 2-3 (c) 3-4 (d) > 4

5. Flow of electrons is affected by the following

(a) Thermal vibrations(b) Impurity atoms (c) Crystal defects (d) all
6. Not a super conductive metallic element

(a) Fe (b) Al (c) Ti (d) W

7. Fermi energy level for intrinsic semiconductors lies

(a) At middle of the band gap (b) Close to conduction band

(c) Close to valence band (d) None

8. Fermi energy level for p-type extrinsic semiconductors lies

(a) At middle of the band gap (b) Close to conduction band

(c) Close to valence band (d) None

9. Fermi energy level for n-type extrinsic semiconductors lies

(a) At middle of the band gap (b) Close to conduction band

(c) Close to valence band (d) None

10. Not an example for intrinsic semiconductor

(a) Si (b) Al (c) Ge (d) Sn

11. In intrinsic semiconductors, number of electrons __________ number of holes.

(a) Equal (b) Greater than (c) Less than (d) Can not define

12. In n-type semiconductors, number of holes __________ number of electrons.

(a) Equal (b) Greater than (c) Less than (d) Can not define

13. In p-type semiconductors, number of holes __________ number of electrons.

(a) Equal (b) Greater than (c) Less than (d) Twice

14. Mobility of holes is ___________ mobility of electrons in intrinsic semiconductors.

(a) Equal (b) Greater than (c) Less than (d) Can not define
15. Fermi level for extrinsic semiconductor depends on

(a) Donor element (b) Impurity concentration (c) Temperature (d) All

16. Value of dielectric constant for a material __________.

(a) Equal to 1 (b) Greater than 1 (c) Less than 1 (d) Zero.

17. High dielectric constant material is must for __________.

(a) Insulation of wires (b) Generators (c) Switch bases (d) Generators.

18. Dielectric constant for most polymers lies in the range of _______.

(a) 1-3 (b) 2-5 (c) 4-7 (d) 6-10.

19. Example for piezo-electric material

(a) Rochelle salt (b) Lead zirconate (c) Potassium niobate (d) Barium Titanium
oxide

20. Example for ferro-electric material

(a) Potassium niobate (b) Lead titanate (c) Lead zirconate (d) quartz

Answers:

1. a
2. c
3. b
4. c
5. d
6. b
7. c
8. b
9. b
10. a
11. c
12. d
13. a
14. d
15. d
16. a
17. a
18. c
19. b
20. b