UNIT – V ELEMENT OF MATERIAL SCIENCE SHAILESH KAPUR

ASST. PROF.
B.TECH. ( I –II SEMESTER ) ACERC, JAIPUR
ENGINEERING PHYSICS

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B.TECH, APPLIED SCIENCE 1 YR. DEPT.
UNIT – V ELEMENT OF MATERIAL SCIENCE SHAILESH KAPUR
ASST. PROF.
B.TECH. ( I –II SEMESTER ) ACERC, JAIPUR
ENGINEERING PHYSICS

SYLLABUS
UNIT 5

ELEMENT OF MATERIAL SCIENCE

 INTRODUCTION
 BONDING IN SOLIDS
 IONIC BOND
 COVALENT BONDS
 METALLIC BONDS
 HYDROGEN BOND
 VANDER WAAL BONDS OR MOLECULAR BOND
 ENERGY BAND IN SOLIDS
 CLASSIFICATION OF SOLIDS ON THE BASIS OF ENERGY BAND GAP
 INSULATORS
 CONDUCTOR
 SEMICONDUCTOR
 INTRINSIC SEMICONDUCTORS
 CONDUCTIVITY IN INTRINSIC SEMICONDUCTOR
 EXTRINSIC SEMICONDUCTORS
 N- TYPE SEMICONDUCTORS
 P- TYPE SEMICONDUCTORS
 HALL EFFECT
 HALL COEFFICIENT

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B.TECH, APPLIED SCIENCE 1 YR. DEPT.
UNIT – V ELEMENT OF MATERIAL SCIENCE SHAILESH KAPUR
ASST. PROF.
B.TECH. ( I –II SEMESTER ) ACERC, JAIPUR
ENGINEERING PHYSICS

INTRODUCTION
A solid contains number of atoms packed closely together. When N atoms of the solid are well
separated, then these atoms lead to N-fold degenerate levels of the solid. As the atom
approach one another to form a solid. This causes each of the levels to split into N distinct
levels. It is the separation distance which specifies the amount of overlap that causes the
splitting. The amount of splitting is different for different energy levels. It means the lowest
levels remain almost unsplit. The reason is that the electrons in lower levels are the ones which
are in inner subshells of the atoms. So they are not significantly influenced by the presence of
nearby atoms. Since the potential barriers between the atoms are for them relatively high and
wide, these electrons are localized in particular atoms, even when separation distance is very
small. However, the electrons in the higher levels are the valence electrons and are not
localized at all for small separation distance but they become part of the whole system.

BONDING IN SOLIDS:
There are various types of bonds existing between the atoms constituting a solid. These are
produced by the forces between the atoms, ions and molecules. In a solid these atoms are in
close proximity to one another. The interatomic separation is of the order of few angstroms (Å)
and the radius of an atom is also of the same order of magnitude.

There are five types of bonds :

1. Ionic bond : (NaCl, CsCl, MgO) 2. Covalent Bond : (C, Si, Ge)

3. Metallic Bond: (Na, Al, Cu, Ag, Zn) 4. Hydrogen Bond: (H2O, HF)

5. Vander Waals Bond:

IONIC BOND:
An ionic bond is formed between two different atoms, one electropositive and the other
electronegative.

OR

In an ionic bond between two atoms one or more electrons are transferred from one atom to
the other with the result that one of the atoms becomes positively charged ion and the other
negatively charged ion.

The electrostatic attraction between these ions binds them to form a molecules.

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B.TECH, APPLIED SCIENCE 1 YR. DEPT.
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ENGINEERING PHYSICS

E.g. Let us consider a case of NaCl. When Na and Cl atoms are brought together, the outer
valence electron of the Na atom is transferred to the Cl atom which has seven valence
electrons. This makes both these atoms to achieve more stable electronic configuration
lowering the overall energy.

PROPERTIES
Ionic crystals have large cohesive energies and hence these crystals have cohesive energies and
hence these crystals have higher melting points.

E.g. NaCl is 180 K cal./mol. and its melting point is about 800˚C. In general their melting points
vary from 700K to 300K.

The electrical and thermal conductivities of ionic crystals are much lower than the
conductivities of metals. Most of these are diamagnetic however in some exceptional cases
paramagnetic nature is found. These crystals are hard and brittle. These are usually transparent
for frequencies up to the fundamental absorption frequency which lies in the UV region.

COVALENT BONDS:
The covalent bond which is sometimes referred to as valence bond or homopolar bond, is an
electron-pair bond in which two atoms share two electrons. In the covalent bonding each atom
of the element effectively completes its outer electron shell by sharing electrons with its
neighbors.

E.g.

Two unpaired electrons between the two chlorine atoms forming the covalent bond, thus
belong to both and provide each atom with the stable configuration.

The number of covalent bonds that an atom of an element can form depends on how many
unpaired electrons it has. This number can be given by the so called (8-N )rule where N is the
number of the column in the periodic table containing the given element.

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B.TECH, APPLIED SCIENCE 1 YR. DEPT.
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ENGINEERING PHYSICS

PROPERTIES
The covalent bond is a strong bond and so materials having this bond have high cohesive
energy. Because of their rigid electronic structure the covalent crystals are extremely hard and
difficult to deform. Like ionic crystals the covalent crystals are transparent to radiation of longer
wavelengths. At higher frequencies the photons can excite the electrons in the valence band to
the empty levels in the conduction band. The electrical conductivity of covalent crystals varies
over a wide range. Some of these like diamond are excellent insulators, Ge and Si are
semiconductors while tin has much higher conductivity approaching that of metals. These
crystals are poor conductors of heat and are diamagnetic in nature.

METALLIC BONDS:
Metallic crystals are commonly known as metals. In the atoms of metals, the electrons in the
outermost orbits are loosely bound as the ionization energy is low in the case of metals. These
electrons are free to move around among all the atoms and are called free electrons or
conduction electrons. This way the metals have residual positive ions. The electrostatic
attraction between these positive ions and negative electrons is responsible for holding the
solid together. This type of bonding is called metallic bonding.

PROPERTIES
The metallic bond is electrostatic in nature, though partially, and do not exert directional
influence. The metallic bond is weaker in nature than the covalent bond because of the fewer
electrons bonding the nuclei. But it can be stronger for those metals in which the number of
valence electrons is greater. They are good conductors. Because of the presence of free
electrons, they have high thermal and electrical conductivities.

HYDROGEN BOND:
In certain crystals, a positive hydrogen ion (H+) attracts negative ions such F-, O-, N-, etc.
sometimes due to electrostatic
attraction, attachment between atoms
in different molecules or within a
molecule occurs in addition to bonds,
which holds atoms together to form
molecules. A hydrogen bond is formed
when a hydrogen atom makes such an
attachment or association with an
electronegative atom like oxygen,

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B.TECH, APPLIED SCIENCE 1 YR. DEPT.
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ENGINEERING PHYSICS

nitrogen, fluorine, etc. The hydrogen bond is form in H2O, HF and in many organic molecules. In
the water molecule (H2O), the hydrogen and oxygen atoms are held together by covalent
bonds. The positive dipole and i.e. hydrogen, can strongly attract the negative dipole end of
water molecule.

VANDER WAAL BONDS OR MOLECULAR BOND:

Many solids or crystals are composed of neutral atoms or molecules without any transferring or
sharing of the electrons. Hence the ionic covalent and metallic bonds are not possible between
these atoms. These substances remain bound by much weaker short range attractive forces,
which are called Vander Waals forces. These forces are weaker than the atomic bonding forces.
The Vander Waals bonds are usually found in inert gases in which outermost electron orbits are
completely filled, i.e., there are no valence electrons and hence they are incapable of forming
any bond. These bonds are formed due to electrostatic attraction between oscillating or
permanent dipoles.

In the case of inert gases, there is a very small attraction between the atoms due to closed
outer shells. These gases condense when the temperature is reduced and hence a weak
interatomic attraction is developed due to Vander Waals forces. The Vander Waals forces are
non-directional in nature and a little energy is required to break the bonds because these are
much weaker than ionic and covalent bonds. These types of bonds are found in inert gases like
solid argon and in many organic molecules like methane.

ENERGY BAND IN SOLIDS:

As we know the electron in the atom are distributed in different orbits i.e. different allowed
energy levels. The electron first occupies that orbit in which its energy is minimum and later
higher energy orbits are filled up. The electrons in the outermost orbit, which is fully or partially
filled, are called valence electrons and that energy level is called valence level.

The valence electrons in an atom are at a larger distance from the nucleus compared to other
electrons in the inner orbits. The attractive Colombian force on the valence electron is reduced
considerably so that the valence electrons are responsible for the formation of bonds between
the atoms.

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B.TECH, APPLIED SCIENCE 1 YR. DEPT.
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B.TECH. ( I –II SEMESTER ) ACERC, JAIPUR
ENGINEERING PHYSICS

In metals particularly electron which are moves freely are called ‘free electrons’ The other
electrons in the atoms being in inner orbits
are more strongly bound with the nucleus
due to the electrostatic attractive force
and cannot move out of the orbits. These
electrons are called ‘bound electrons’.

e.g. The germanium atom has 32 electrons

which are distributed as
𝟏𝒔𝟐 , 𝟐𝒔𝟐 , 𝟐𝒑𝟔 , 𝟑𝒔𝟐 , 𝟑𝒑𝟔 , 𝟑𝒅𝟏𝟎 , 𝟒𝒔𝟐 , 𝟒𝒑𝟐 .
The first three orbits are completely filled
and the electrons in these orbits are bound
electrons. The four electrons present in
the fourth orbit are valence electrons.

In a single atom the electrons have a negative potential energy due to the attraction of the
nucleus so that the electrons remains bound in the potential field of the nucleus. These
electrons remain in the allowed energy states.

If two atoms are brought close to each other than the nucleus of one atom is in a positions to
interact with the electrons of the other atoms. Due to this interaction each energy level of both
the atoms splits into two levels. One of the levels is at a higher level than the earlier position
while the other one is at a lower level. Further due to superposition the common wall of the
potential well gets suppressed and the higher energy levels, even the valence levels become
common for both the atoms. This results in a transfer of valence electrons from one atom to
the other.

Since the interatomic distance is very small so that every atom is in a position to interact with a
number of neighboring atoms, resulting in splitting of energy levels. Each energy level is now
converted into a group of levels on both sides of the original level. The separation between
these levels in the group is so small that they almost form a continuous band, called energy
band.

The energy band in which the valence electrons are situated is

called valence band. The allowed energy band above the
valence band which is almost empty in the unexcited state is
called conduction band. In between the conduction and valence
bands there is an energy gap in which no allowed energy level is
situated, this energy gap is called forbidden energy gap.

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B.TECH, APPLIED SCIENCE 1 YR. DEPT.
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ENGINEERING PHYSICS

CLASSIFICATION OF SOLIDS ON THE BASIS OF ENERGY BAND GAP:

On the basis of energy band structure and electrical conductivity the solids can be divided into
three types:

1. INSULATOR 2. CONDUCTOR 3. SEMICONDUCTOR

1. INSULATORS: For these types of solids, the band

formation is like the forbidden gap is very wide, it is about 3eV to
6 eV. It is seen that a very few electrons from the filled band
reach the empty band, even if we thermally excite them or apply
an electrical field to them. Due to this reason, a free electron
current cannot be obtained and the solids of this type are poor
conductors of electricity. This class of solids are known as
insulators. The conductivity is very small of the order of
10−12 𝑡𝑜 10−18 𝑚ℎ𝑜/ 𝑚.

2. CONDUCTOR: In this kind of

solids the valence and conduction bands are
overlapped. Thus in these materials the forbidden
energy gap is not present i.e. ∆𝐸𝑔 = 0. Metals like
silver copper etc. have an overlapping of bands
while in sodium the valence band is only partially
filled so that the valence band itself acts as
conduction band. In conductors due to the
availability of empty allowed states the electrons
are capable of receiving energy from an applied field. As these electrons are very loosely bound
with the nuclei, these get separated from the parent atoms and move almost freely. Due to the
applied external field their random motion is affected and drift in a particular direction.

Due to large number of free electrons the conductivity of such materials is very high or the
resistivity is very low. At room temperature electrical conductivity is of the order of
106 𝑡𝑜 108 𝑚ℎ𝑜/𝑚. .

3. SEMICONDUCTOR: For this type of

solids the forbidden gap is very narrow of about 0.1eV to 1eV.
Under this situation electrons can move easily from the highest
filled band (valence band) to the next empty band(conduction
band) when applied external energy. This can be achieved by
the thermal excitation or also by applying an electrical field.

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B.TECH, APPLIED SCIENCE 1 YR. DEPT.
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ENGINEERING PHYSICS

For this reason, a free electron current can be obtained as a few electrons are available in the
empty band. This class of solids is known as semiconductors. Silicon and Germanium are the
examples of semiconductors.

There also exists another electric current which is due to empty places left behind when the
electrons moves, which remain near the top of the uppermost filled band. These vacancies
(empty space) are called holes. The holes behave as positive electrons and can contribute to the
generation of electric current. This is possible as the electron below the hole may gain enough
energy to jump and occupy the hole due to the applied electric field. With such successive
jumps of electrons, the hole moves towards the lower energy state and contribute to the
generation of electric current.

There are two types of semiconductors

(A) INTRINSIC SEMICONDUCTORS (B) EXTRINSIC SEMICONDUCTORS

(A) INTRINSIC SEMICONDUCTORS: The pure and natural form of semiconductors are
known as intrinsic semiconductors. The transformation of electrons to the conduction band and
the generation of holes in the valence band are achieved by thermal excitation. It means this
effect is temperature dependent and produces equal numbers of electron and hole carriers.

CONDUCTIVITY IN INTRINSIC SEMICONDUCTOR: At absolute zero temperature all the

valence electrons remain tightly bound in the covalent bonds so that there is no electron in the
conduction band and the conductivity of the material is zero. Thus all semiconductors at
absolute zero behave as insulators. As the temperature increases some electrons gain sufficient
thermal energy and become free from bonding (mutual breaking of covalent bonds). As soon as

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B.TECH, APPLIED SCIENCE 1 YR. DEPT.
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ENGINEERING PHYSICS

an electron becomes free after breaking the bond it leaves behind a vacant site. This vacancy or
vacant site is called a hole.

If in an intrinsic semiconductor the number of free electrons and holes per unit volume are 𝑛𝑖
and 𝑝𝑖 then

𝑛𝑖 = 𝑝𝑖

𝑛𝑖 × 𝑝𝑖 = 𝑛𝑖 2 -----------(1)

In an intrinsic semiconductor at temperature T K

𝒏𝒊 = 𝑨 𝑻𝟑/𝟐 𝐞𝐱𝐩(−∆𝑬𝒈 / 𝟐𝒌𝑻) -----------(2)

Where A is constant and k is Boltzmann constant. It decreases exponentially with increase of

forbidden energy gap

At normal temperature the free electrons in the conduction band have a random motion like
the molecules of gas and the holes in the valence band also move randomly.

Suppose in a crystal lattice of intrinsic semiconductor an electron in covalent bond becomes

free by the external thermal energy. This creates a hole at that place. This electron with some
thermal energy breaks another covalent bond of neighboring atom and new freed electron
acquires the position of hole at previous position so that the covalent bond is completed but a
hole is created at new position. In the same way if a transition of electron takes place from one
atom to another and so on . Thus the random motion of an electron on the path results in the
random motion. Both free electrons in conduction band and holes in valence band act as charge
carriers and the electrical conduction is due to both types of charge carriers in semiconductors.

When a battery is connected between the two ends of semiconductor then due to the electric
field the free electrons experience a force towards that positive terminal of battery and holes
towards the negative terminal. The motion of these charges carriers in a definite direction is
called drift velocity. So

The drift velocity of electrons

𝑣𝑒 = 𝜇𝑒 𝐸 ------------(1)

The drift velocity of holes

𝑣ℎ = 𝜇ℎ 𝐸 ------------(2)

Here 𝜇𝑒 = Mobility of electrons 𝜇ℎ = Mobility of holes

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ENGINEERING PHYSICS

Since the total current density in an intrinsic semiconductor is

𝐽 = 𝐽𝑒 + 𝐽ℎ ------------(3)

But 𝐽𝑒 = 𝑛 (−𝑒)(−𝑣𝑒 ) = 𝜇𝑒 𝑛 𝑒 𝐸

And 𝐽ℎ = 𝑝 (+𝑒)(+𝑣𝑒 ) = 𝜇ℎ 𝑝 𝑒 𝐸

𝑱 = 𝒆 𝑬(𝝁𝒆 𝒏 + 𝝁𝒉 𝒑)
𝑱 𝑬(𝝁𝒆 𝒏+ 𝝁𝒉 𝒑)
And CONDUCTIVITY 𝝈 = = 𝒆 = 𝒆 (𝝁𝒆 𝒏 + 𝝁𝒉 𝒑)
𝑬 𝑬

𝟏 𝟏
And RESISTIVITY 𝝆= =
𝝈 𝒆 (𝝁𝒆 𝒏+ 𝝁𝒉 𝒑)

EXTRINSIC SEMICONDUCTORS: As we know conductivity of intrinsic

semiconductors are very low. To enhance the conductivity intrinsic semiconductors are doped
with a controlled amount of an impurity elements. The obtained semiconductors are so called
as EXTRINSIC SEMICONDUCTORS. The impurity elements are taken from 3rd and 5th group of
periodic table.

There are two types of extrinsic semiconductors

1. N- type semiconductors 2. P- type semiconductors

N- TYPE SEMICONDUCTORS: If an element of 5th group (P, As, Sb) is added to

pure semiconductor, the obtained semiconductor is called as N-type semiconductor. These
added atoms of 5th group having 5 electrons in the valence orbit (Pentavalent impurity). These
impurities are known as DOPANT and the process by which these dopant are added to intrinsic
semiconductor is known as DOPING. In doping process these dopants replace an atom of
intrinsic semiconductor and 4 out of 5 electron forms covalent bonds but one electron remains
free. At room temperature this free electron is transferred to the conduction band.

The energy level of the valence electron of the pentavalent impurity element lies in the
forbidden energy gap of the intrinsic semiconductor just below the conduction band. This
energy level is called donor level. The electrons in the donor level can be easily transferred to
the conduction band. Since there are negatively charge carrier are taking part in flow of current
so the extrinsic semiconductor is called as N-type semiconductor.

P- TYPE SEMICONDUCTORS: When an element of 3rd group (B, In, Ga) is added
as impurity in pure semiconductor, the obtained semiconductor is called P-type semiconductor.
Since the 3rd group elements are trivalent. In doping process these dopants replace an atom of

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intrinsic semiconductor and all 3 electrons forms covalent bonding with neighboring pure
semiconductor atom but 4th bond is mutually formed with pure semiconductor atom. Due to
this mutual bond a deficiency of electron exists there. This deficiency or vacant site of an
electron is called HOLE and it has the capability of capturing an available electron. The impurity
of third group is called ACCEPTOR IMPURITY.

The energy level of the hole produced by the addition of 3 rd group impurities lies in the
forbidden energy gap slightly above the valence band of the semiconductor. This energy gap
slightly above the valence band of the semiconductor.

Each acceptor impurity atom generates one hole which acts as a positively charged carrier. Thus
a semiconductor doped with trivalent impurity has holes as majority charge carriers. As the
electrical conduction now is mainly by the holes which behave as positively charged carriers,
the doped semiconductor is called P-TYPE SEMICONDUCTOR.

HALL EFFECT: When a semiconducting (or

conducting) plate in which current is flowing is
placed in a magnetic field perpendicular to the
direction of flow of current then a potential
difference appears between the opposite faces of
the plate i.e. a transverse electric field is
developed perpendicular to direction of current
and magnetic field. This effect is called as HALL
EFFECT.

THEORY: Consider a semiconductor bar

placed along x-z plane in which an electric current I is flowing in the x- direction by using a
⃗ is applied in the z- direction.
battery. A magnetic field 𝐵

Due to the potential due to battery charge carriers (electrons) drifted in the –x direction while
the positive charge carriers (ions or holes) will drift in +x direction.

Let q be the charge on carriers and 𝑣 be their average drift velocity. Due to the external
⃗ a force will act on the moving charge carriers. This force will be:
magnetic field 𝐵

⃗)
𝐹 = 𝑞 (𝑣 × 𝐵

For electrons 𝑞 = −𝑒 𝑣 = 𝑣(−𝑥̂) and ⃗ = 𝐵 (𝑧̂ )

𝐵

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𝐹 = −𝑒 (𝑣(−𝑥̂) × 𝐵 (𝑧̂ ))

𝐹 = 𝑒 𝑣 𝐵 (−𝑦̂) i.e. the electrons will suffer a force in the direction of y-axis.

For holes 𝑞 = +𝑒 𝑣 = 𝑣(𝑥̂) and ⃗ = 𝐵 (𝑧̂ )

𝐵

𝐹 = 𝑒 (𝑣(𝑥̂) × 𝐵 (𝑧̂ ))

𝐹 = 𝑒 𝑣 𝐵 (−𝑦̂) i.e. holes will also suffer a force in the direction of y- axis.

With electrons as a charge carriers the electrons will collected at the bottom of the
semiconductor bar and the top of the bar will become positively charged due to lack of
electrons. As a result a transverse electric field 𝐸̂𝑡 called HALL ELECTRIC FIELD will produced
which will oppose then downward movement of electrons.

In the same way with positive charge carriers, they will also be deflected downward and will
collect on the bottom of the semiconductor bar. But now the transverse electric field 𝐸̂𝑡 will be
upward (+ y direction) opposing the downward movement of positive charge carriers.

A steady state will be achieved when the force due to magnetic field will be balanced by the
force due to transverse electric field (Hall field).

In steady state

⃗ ) = −𝑞 𝐸̂𝑡 (FOR ELECTRONS)

𝑞 (𝑣 × 𝐵 ⃗ ) = 𝑞 𝐸̂𝑡
𝑞 (− 𝑣 × 𝐵 (FOR HOLES)

𝐸̂𝑡 = ( 𝑣 × 𝐵
⃗ ) 𝐸̂𝑡 = −( 𝑣 × 𝐵
⃗ )

𝐸̂𝑡 = −𝑣 𝐵 (−𝑥̂ × 𝑧̂ ) 𝐸̂𝑡 = −𝑣 𝐵 (−𝑥̂ × 𝑧̂ )

𝐸̂𝑡 = 𝑣 𝐵 (−𝑦̂) 𝐸̂𝑡 = 𝑣 𝐵 (+ 𝑦̂)

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HALL COEFFICIENT: The average drift velocity 𝑣 is related to the current density 𝐽 as

𝐽=𝑛𝑞𝑣 ∴
𝐽
𝑣 = 𝑛𝑞

𝐽 1
Since 𝐸𝑡 = 𝑣 𝐵 ∴ 𝐸𝑡 = (𝐵) = (𝐽 𝐵)
𝑛𝑞 𝑛𝑞

𝑉ℎ
If the thickness of the semiconductor bar is ‘d’ Then 𝐸𝑡 = 𝑑

𝑉ℎ 1
= (𝐽 𝐵)
𝑑 𝑛𝑞

𝒅
or 𝑽𝒉 = (𝑱 𝑩) is known as HALL VOLTAGE
𝒏𝒒

𝟏
And the factor = 𝑹𝒉 is known as HALL COEFFICIENT.
𝒏𝒒

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