BITS Pilani

Pilani Campus

CHEM F343: Inorganic Chemistry

III
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Electronic Materials

Book:

T2: The Science and Engineering of Materials, Donald R.

Askeland, Pradeep P. Phule, Cengage learning (India edition)

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 Different kind of Materials Exhibit
Different Electronic Properties

Polymers shows
Semiconducting prop.
Ceramic materials shows
Superconducting prop.
Amorphous Si exhibits
solar cells
Cu and Al in power
transmission
Porcelain used in
electrical insulation

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Ohms Law and Electrical Conductivity

One of the most important electrical

characteristics of a solid materials is Ohms law,
V = IR
The value of R depends on the specimen
configuration. The electrical resistivity (, .cm) or
conductivity is independent of specimen geometry,
= RA/l, R = l/A (where = conductivity)
In components designed to conduct electrical energy,
minimizing power losses is important, not only to conserve
energy and to minimize heating
The electrical power lost (P, in watts),
P = VI = I2R (High resistance: larger power losses)
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 Second Form of Ohms Law
I/A = V/l,
J = E ( = electrical conductivity, ohm-1cm-1)
[J(I/A) = current density (A/cm2) and E (V/l)= electric field (V/cm)]

Other form of J = n x q x (where n = is the number of charge carriers

(carriers/cm3),
q = charge on each carrier; = average drift velocity (cm/s) at which the
charge carriers move
So, = nq(/E)
Diffusion due to temperature and concentration gradients,
Drift due to an applied electric or magnetic field.
(/E) = the mobility of the carriers
So, = nq
The conductivity can be controlled by either no of charges or mobility

Mobility is particularly important in metals whereas the number of carriers is

more important in semiconductors or insulators

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 Charge Carriers and classification

Metals: Electrons are the

charge carriers.
Semiconductors: Both es
and holes carry the charge

For semiconductors,
= nqn + pqp
n and q are the
concentrations of free
electrons and holes

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 Classification of Electronic Materials
Electronic materials can be classified depending upon the magnitude
of their electrical conductivity

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 Electronic Conduction vs Ionic conduction

I. Electronic conduction: An electric current results from

the motion of electrically charged particles in response
to forces that act on them from externally applied
electric field. Within most solid materials the current
arises from the flow of electrons.

2. Ionic conduction: For ionic materials, charged is

carried by the ions themselves

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Superconductor:

Type II are preferred over Type I for most

practical applications by virtue of their
higher critical temperatures
higher critical magnetic fields

Examples, Nb-Zr alloy; Nb-Ti alloy; Nb3Sn

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 Energy Band Structures in Solids:
What it is?

In solid-state physics, the electronic band structure of a

solid describes those ranges of energy that an electron
within the solid may have (called energy bands, allowed
bands, or simply bands), and ranges of energy that it may
not have (called band gaps or forbidden bands).

Band theory derives these bands and band gaps by

examining the allowed quantum mechanical wave functions
for an electron in a large, periodic lattice of atoms or
molecules.

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 Energy Band Structures in Solids:
Why it is required?

Band theory has been successfully used to

explain many physical properties of solids, such
as electrical resistivity and optical absorption,
and forms the foundation of the understanding
of all solid-state devices (transistors, solar
cells, etc.)

A useful way to visualize the difference

between conductors, insulators and
semiconductors is to plot the available energies
for electrons in the materials.

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Energy Band Structures in Solids: Charge Carriers

In all conductors, semiconductors and many

insulating materials only electronic conduction
exists and the magnitude of the electronic
conductivity is strongly dependent on the number
of electrons available to participate in the
conduction process.

Does all the electrons present in those materials

will accelerate in presence of electric field??
No,

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 Energy Band Structures in Solids:
What does it indicate?

The number of electrons available for electrical

conduction in a particular material is related to the
arrangement of electron states or levels with respect to
energy and then the manner in which these states are
occupied by electrons

A thorough exploration of these topics is complicated and

involves principles of quantum mechanics

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 Energy Band Structures in Solids: atomic
concept

Each individual atom there exists discrete energy levels

that may be occupied by electrons arranged into shells
and subshells;
Shells are designated by integers (1, 2, 3 etc) and
subshells by letters (s, p, d and f);
For each of s, p, d and f subshells, there exist 1, 3, 5
and 7 states, respectively;
The electrons in most atoms fill only the states having
the lowest energies, two electrons of opposite spin per
state, in accordance with the Pauli exclusion principle

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 Band Theory of Solids

spread the range of energies

covered by the molecular
orbitals

N molecular orbitals (from N

atoms) covering a band of
finite width

the lowest energy orbital of

this band is fully bonding and
the highest energy orbital is
fully anti bonding

Formation of a band of N molecular

orbitals of successive addition of N atoms
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 Band Theory of Solids
1. while the LUMO moves down in
energy; as a result energy of
transition decreases

2. The energy diff. between HOMO and

LUMO level decreases and
eventually becomes smaller than
thermal energy

3. Now, the levels are considered to be

merged to form bands.

4. In the case of the infinite ring

containing solid, the gap reduces to
zero and the top of the valence band
touches the bottom of the conduction
band; this is just like metal.

V. 5. When the gap cannot reduce zero,

we obtain semiconductors or insulators.
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 Band Theory of solids

The material is insulator at T=0 and is semiconductor at

T>0
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 Band Theory of solids

A band formed from

overlap of s orbitals is
called an s band

If the atoms have p

orbitals available, then
the same procedure
leads to a p band

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 Band Theory of solids

When N electrons occupy a band of N orbitals, it is only half full

and the electrons near the Fermi level are mobile

Fermi Level: It is the highest energy level that an electron can reach or
occupy in a material at absolute zero temperature. It is one of the energy
levels in a semiconductor above which all energy levels are vacant at absolute
temperature.

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 Band Structure of C in diamond

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Relation between drift velocity and Mean Free Path

1. Mobility: conductivity can be changed by influencing the

mobility () of the carriers.
2. Mobility is proportional to the average drift velocity, ,
which is low if the electrons collide with imperfections in the
lattice
3. The mean free path (e) wave of electrons is defined as,
e = ; = the average time between collisions
4. The mean free path defines the average distance between
collisions;
A longer mean free path permits high mobility and high
conductivity and is affected by
(a) temperature;
(b) effect of atomic level defects

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 Factors on which Conductivity
Depends:
Temperature effect: When the temperature of a metal increases, thermal
energy causes the atoms to vibrate. At any instant, the atom may not be in its
equilibrium position, and it therefore interacts with and scatters electrons. The
mean free path decreases, the mobility of electrons is reduced, conductivity
decreases/resistivity increases
The change in resistivity of a pure metal: = RT(1 + RT)
= the resistivity at any T; T = (T TRT);
RT = the resistivity at room temperature (i.e., 25C),
R = temp resistivity coefficient

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Effect of Atomic Level Defects

Imperfections in crystal structures scatter electrons,

reducing the mobility and conductivity of the metal.
For example, the increase in the resistivity due to solid
solution/defect atoms, d = b(1x)x,
x = the atomic fraction of the impurity,
b = the defect resistivity coefficient
In a similar manner, vacancies, dislocations and grain
boundaries reduce the conductivity of the metal
Each defect contributes to an increase in the resistivity of
the metal. Thus the overall resistivity is
= T + d where d equals the contributions from all the
defects. This equation is known as Matthiessens rule.

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 Please look at the class notes as well.

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