ELECTRICAL PROPERTIES OF MATERIALS

Introduction: To explain the electrical properties of materials mainly 3 theories were

introduced. viz., classical free electron theory, quantum free electron theory and band
theory. Classical and quantum free electron theories tried to explain the electrical
behavior of metals only. Let us know in brief about these theories.
Classical free electron theory of metals:
1. This theory was developed by Drude and Lorentz
2. According to this theory, a metal consists of electrons which are free to move in the
crystal like molecules of a gas in a container.
3. Since the motion is completely random, average velocity in any direction is zero.
4. If a constant electric field is established inside a conductor, the electrons experience
a force F = -eE due to which they move in the direction opposite to direction of the field.
5. As a result, in addition to the random motion, the electrons are subjected to a very
slow directional motion. This motion is called drift and the average velocity of this
motion is called drift velocity vd.
6. This theory successfully verifies Ohm's law and reason for resistance of a metal
7. This theory fails to explain the temperature variation of electrical conductivity (),
specific heat and also could not explain the conductivity in semiconductors and
insulators
Quantum free electron theory:
1. This is proposed by Sommerfeld on the basis of Planck's quantum theory and
Schrodinger's wave equation.
2. According to this theory, the free electrons in a metal are assumed to be trapped in a
constant potential box as shown below.

3. Free electrons reside in discrete energy levels.

4. This theory successfully explains the temperature variation of and thermal
conductivity, but, could not explain why some materials are good conductors, some are
insulators and some are semiconductors.
Band Theory of Solids:
Band theory was framed with Bloch theorem and Kronig-Penny model. The main
postulates of this theory are
1. The electron in a solid is considered as in periodic potential created between the
neighboring atoms in the solid as shown below

In the figure, the green colored spheres represent the atoms at lattice points of the solid
and blue spheres represent the electrons in various energy levels
2. In the solid, energy bands has to be consider rather than specific energy levels to
understand the electrical properties of the solids.

Origin of Energy Bands:

1. The atoms in a solid are closely packed which vibrate about their mean position.
2. When the atoms come closer in a solid, the interaction between them disturb the
initial atomic levels. ie., the electronic states in the isolated atoms are deformed.
3. The electrons in the outer orbits which are farther away from the nucleus will get
influenced by the other neighboring nuclei in the solid as they tend to closer to them.
4. Bringing one atom close to the other results in splitting of a single sharp energy level
into two levels.
5. If there are many interacting atoms, then, each outer energy level is spread into a
continuous band of levels.
6. This is why "energy bands" rather than specific energy levels exist in solids.

Based on energy bands, materials are classified into 3 types as shown above.

Conductors:
The electronic arrangement of conductors can be considered as shown in the below
figure1. Their band structure is shown in figure2.

Figure 1

Figure 2
Basic Properties of Conductors:
1. Ohm's Law:- At constant temperature the current flowing through a conductor is
directly proportional to the potential difference across the ends of the conductor.
VI
V = IR
where, R is the proportionality constant, also named as Resistance.
2. Resistance:- The phenomenon which opposes flow of charges in the material is
called resistance. Mathematically, R = l/A,
where, is resistivity of the material, l is length of the material and A is area of crosssection of the material. The units of R are Ohms ()
3. Resistivity:- The property of the material which opposes the flow of charges through
it. It is also defined as the resistance per unit length in unit cross-sectional area of the
material. The symbol for resistivity is and units are Ohm-m (-m)
The value of R varies with dimensions of the same material, whereas, the value of is
independent of dimensions of the material, but, changes for different materials, means,
is different for different materials.
4. Conductivity:- The inverse of resistivity is called as conductivity. It specifies the
electrical character of the material. The symbol for conductivity is . Units are mho/m.

 = 1/
5. Current Density:- It is the microscopic analogy of current. Mathematically, it is the
ratio of current per unit area. Symbol is J. Units of J are Amp/m 2
J = i/A or J = E
In terms of J, Ohm's law can also be expressed as J =E

The actual path travelled by free electrons in a conductor without any applied field is
random and the average velocity is considered as zero as shown in the figure 3.

Fig.3
Now, if electric field of intensity E is applied to the material, the free electron drift in the
direction opposite to that of applied field and thus acquires an average velocity called
"drift velocity (vd)".

In terms of drift velocity, current flowing through the material in small interval of time 'dt'
can be expressed as
i = nevdA
where, n = number of electrons per unit volume of the material
e = charge of the electron
A = area of cross-section
Hence, J = nevd
6. Mobility:- The magnitude of drift velocity per unit applied field is called as mobility.
Symbol for it is . Mathematically, = vd/E
Or

=
neE ne

(since, vd = J/ne and = J/E)

The units of are m2/volt-s.

Electrical conductivity varies between different materials by over 27 orders of
magnitude.
Metals: > 105 (.m)-1
Semiconductors: 10-6< < 105 (.m)-1 Insulators: 10-6 (.m)-1<<10-20(.m)-1

Influence of Temperature, Impurities and plastic

deformation on the resistivity of Conductors
In general, metals are good conductors of electricity. The conductivities at room
temperature of some metals are given below as for reference.

However, metals still possess resistivity to some extent. Since crystalline defects serve
as scattering centers for conduction electrons in metals, increasing their number raises
the resistivity (or lowers the conductivity). The concentration of these imperfections
depends on temperature, composition, and the degree of cold work of a metal
specimen. In fact, it has been observed experimentally that the total resistivity of a metal
is the sum of the contributions from thermal vibrations, impurities, and plastic
deformation; that is, the scattering mechanisms act independently of one another. This
may be represented in mathematical form as follows:
total = t + i + d
in which t, i and d represent the individual thermal, impurity, and deformation
resistivity contributions, respectively.
The above equation is also named as Matthiessen's rule.
The influence of each variable on the total resistivity is demonstrated in Figure 4, a plot
of resistivity versus temperature for copper and several coppernickel alloys in
annealed and deformed states. The additive nature of the individual resistivity
contributions is demonstrated at -1000C.

Fig.4 The electrical resistivity versus temperature for copper and three copper-nickel
alloys, one of which has been deformed. Thermal, impurity and deformation
contributions to the resistivity are indicated at -100 0C.
Influence of temperature: Thermal resistivity t varies with temperature as shown in
the equation t = 0 + aT, where, 0 and a are constants for each metal. This
dependence of the thermal resistivity component on temperature is due to the increase
with temperature in thermal vibrations and other lattice irregularities (e.g., vacancies),
which serve as electron-scattering centers.

Influence of impurities: For additions of a single impurity that forms a solid solution,
the impurity resistivity i is related to the impurity concentration ci in terms of the atom
fraction (at%_100) as follows: i = A ci(1- ci)
where A is a composition-independent constant that is a function of both the impurity
and host metals.

Fig.5 Room temperature electrical resistivity versus composition for copper - nickel
alloys
Influence of Plastic Deformation: Plastic deformation also raises the electrical
resistivity as a result of increased numbers of electron-scattering dislocations. The effect
of deformation on resistivity is also represented in Figure 4. Furthermore, its influence is
much weaker than that of increasing temperature or the presence of impurities.

Semi-Conductors:
The materials whose electrical conductivity resides between good conductors and
insulators are called as semiconductors. They exhibit unique electrical properties and
they are sensitive to presence of even minute concentrations of impurities.
These are of two types. viz., intrinsic and extrinsic semiconductors.
Intrinsic semiconductors: These are pure form of semiconductors. Their band
structure is as shown below. At 0K, the conduction band is completely empty and
valence band is completely filled. The energy band gap is relatively narrow generally
less than 2 eV.

In intrinsic semi conductors, for every electron excited into the conduction band, there is
left behind a missing electron in one of the covalent bonds, or in the band structure, a
vacant electron state in the valance band as shown below.

under the influence of an electric field, the position of this missing electron within the
crystalline lattice may be thought of as moving by the motion of other valence electrons
that repeatedly fill in the incomplete bond (Figure 6).This process is expedited by
treating a missing electron from the valence band as a positively charged particle called
a hole. A hole is considered to have a charge that is of the same magnitude as that for
an electron, but of opposite sign (+1.6 X 10 -19C ). Thus, in the presence of an electric
field, excited electrons and holes move in opposite directions. Furthermore, in
semiconductors both electrons and holes are scattered by lattice imperfections.

Fig.6 Intrinsic semiconductor a) before excitation and b) & c) after applied field.
Since there are two types of charge carrier (free electrons and holes) in an intrinsic
semiconductor, the expression for electrical conductivity is

where p is number of holes per unit volume, n is number of electrons per unit volume, h
and e are hole and electron mobilities respectively. But, for intrinsic semiconductor,
n = p = ni. Hence, = nie (h + e), where ni is intrinsic carrier concentration.
Extrinsic Semiconductors:
The application of intrinsic semiconductors is restricted due to its low conductivity. In
electronic devices, high conducting semiconductors are more essential. The
concentration of either electrons or holes in a semiconductor should be increased
depending upon the requirements in the electronic devices.
This can be carried out simply by adding impurities (one atom in 10 7 host atoms) to the
intrinsic semiconductors. The process of adding impurity to the intrinsic semiconductors
is called doping. The doped semiconductor is called as extrinsic semiconductor. The
concentration of electrons and holes are not equal in an extrinsic semiconductor.
Usually the doping material is either pentavalent atoms (P, AS, Sb, Bi) or trivalent atoms
(B, Al, Ga, In). The pentavalent atom is called donor atom because it donates one
electron to the conduction band of pure semiconductor. The trivalent doping atom is
called acceptor atom because it accepts one electron from semiconductor atom. The
added impurity is called dopant.
In Extrinsic semiconductors, electrical conductivity is defined by impurity atoms.
Example: Si is considered to be extrinsic at room T if impurity concentration is one
impurity per 1012 lattice sites (remember our estimation of the number of electrons
promoted to the conduction band by thermal fluctuations at 300 K) unlike intrinsic
semiconductors, an extrinsic semiconductor may have different concentrations of holes
and electrons. It is called p-type if p > n and n-type if n > p.
Thus there are two types of extrinsic semiconductors depending on the type of impurity
added. viz., N-type extrinsic semiconductors, P-type extrinsic semiconductors.

N-type extrinsic semiconductors:

Excess electron carriers are produced by substituting impurities that have more valence
electron per atom than the semiconductor matrix.
Example: phosphorus (or As, Sb) with 5 valence electrons, is an electron donor in Si
since only 4 electrons are used to bond to the Si lattice when it substitutes for a Si atom.
Fifth outer electron of P atom is weakly bound in a donor state(~ 0.01 eV) and can be
easily promoted to the conduction band. Impurities which produce extra conduction
electrons are called donors. Elements in columns V and VI of the periodic table are
donors for semiconductors in the IV column, Si and Ge.
The hole created in donor state is far from the valence band and is immobile.
Conduction occurs mainly by the donated electrons thus n-type.
For these semiconductors, = nee

Fig 7 Extrinsic n-type semi conduction model (electron bonding). An impurity atom such
as phosphorus, having five valence electrons, may substitute for a silicon atom.

(a)

(b)

Fig 8 (a) Electron energy band scheme for a donor impurity level located within the
band gap and just below the bottom of the conduction band. (b) Excitation from a donor
state in which a free electron is generated in the conduction band.
P-type extrinsic semiconductors:
Excess holes are produced by substituting impurities that have fewer valence electrons
per atom than the matrix. A bond with the neighbors is incomplete and can be viewed as
a hole weakly bound to the impurity atom. Elements in columns III of the periodic table
(B, Al, Ga) are donors for semiconductors in the IV column, Si and Ge. Impurities of this
type are called acceptors.

(a)

(b)

Fig 9 (a) Energy band scheme for an acceptor impurity level located within the band gap
and just above the top of the valence band. (b) Excitation of an electron into the
acceptor level leaving behind a hole in the valence band.

Fig 10 Extrinsic p-type semi conduction model (electron bonding). An impurity atom
such as boron having three valence electrons, may substitute for a silicon atom.
The energy state that corresponds to the hole (acceptor state) is close to the top of the
valence band. An electron may easily jump from the valence band to complete the bond
leaving a hole behind. Conduction occurs mainly by the holes (thus p-type). For
extrinsic p-type semiconductors
=p|e| p

Temperature dependence of carrier concentration:

Fig 11. The variation of carrier concentration for intrinsic semiconductors as function of
temperature

Fig 12. Variations in carrier concentration of n-type semiconductor (Si doped with donor
impurity with 1021 m-3) as function of temperature.

Factors influencing carrier mobility:

Fig 13. variations in hole and electron mobilities with impurity concentration for Si.

Fig 14. Temperature dependence of a) electron and b) hole mobilities for silicon that has
been doped with various donor and acceptor impurities.