Types of bonding:

Different charge distribution in the atoms give rise to different types of bonding:
They classified into five classes:

1. Ionic bonding
2. Covalent bonding
3. Metallic bonding
4. Hydrogen bonding
5. Vander-Walls bonding

Based on the bond strength atomic can be grouped into “primary” and “secondary”
bonding.
Primary bonding:

• Primary bonding has energies in the range of 1-10ev.

• Ionic, covalent and metallic bonds are examples of primary bonding among
these ionic and covalent bonds are generally stronger than the metallic bonds.

Secondary bonding:

• Secondary bonding has energies in the range 0.01-0.5ev/ bond.

• Hydrogen bonding and Vander Walls bonding are examples of secondary
bonding. Generally, Vander Walls bonding is the weakest of all.

Covalent bonding (or) Homo-Polar bonds:

1. Covalent bond is also called “Homo-Polar bonds”.
2. In this bonding the valence electrons are not transferred from one atom to
another atom as ionic crystal, because the energy required to removing all the
valence electrons is too large.
3. The covalent bonds are formed by sharing of valence electrons in the
incomplete outer shell of the atoms.
4. Such sharing results in a lowering of the potential energy of the system. The
elements of group 3rd, 4th and 5th of the periodic table show covalent bonding.
5. In silicon, germanium and diamond materials the bonds are covalent in
nature. Organic compounds such as CH4 is also having covalent bonding.
6. Polar covalent bonds: A polar bond is covalent bond in which there is
separation of charge between one end and the other in other words in which
one end is slightly positive and the other slightly negative. Example the
hydrogen – chlorine bond in HCl or the hydrogen – oxygen bonds in water are
typical.

7. Coordinate covalent bonds: A covalent bond in which both shared electrons

are donated by the same atom;

8. The simplest case of covalent bonding is hydrogen molecule (H2), in which two
hydrogen atoms contribute their 1s1 electron to form covalent bond. In the
molecule orbital of H2 the two electrons are equally shared betwwen the
nuclei and cannot be specifically identified with either nucleus. A covalent
 bond is also known as “electron - pair bond”.

9. Thus, in this example, two atoms are involved in the bond formation process
and they share a single pair of electrons. Hence the resultant bond is known
as a single covalent bond.
10.When the two coordinating atoms share two (or) three pairs of electrons
it results in a double (or) a triple bond. In oxygen double covalent is formed
while in nitrogen triple covalent bond is formed. A covalent bond may also be
formed when two (or) more atom of different non-metals share one (or)
more pairs of valence electron.
Ex- H2O, CO2, HCl and NH3.

Properties of covalent bonding-

1. Covalent bond crystals are usually hard and brittle.

2. Bonding energy is high so that their melting and boiling points are high
but low compared to ionic crystals.
3. Covalent bonds are highly directional in character.
4. These materials are soluble in non-polar solvents like benzene.
5. Pure covalent solids are good insulators of electricity at low
temperature. Conductivity increases with increase in temperature,
6. Covalent substances are insoluble in water.
Metallic Bonding

1. The metallic bonding is an electrostatic attraction between positive metal

ions which are fixed in a metal to the electron cloud which are moving
freely in between the metal ions.

2. The bonding in a metal must be considered in terms of all the atoms of the
solid taken together. No valence electron is associated with a specific atom.

3. The valence electrons from all the atoms belonging to the crystal are free
to move throughout the crystal.

4. Materials bound in this manner are good conductors of electricity and heat.
The metallic bonding can be considered as a limiting case of the ionic
bonding in which the negative ions are just electrons. For example, sodium
chloride contains equal number of Na and Cr. While metallic sodium
contains equal number of Na’ and e.

5. The crucial difference is that the mass of an electron is very small as

compared to the mass of Cl ions. As a result of this, its zero-point motion is
large so that it is not localized on a lattice. They are held together by the
resulting electrostatic interaction between the positively charged metal
ions and the cloud of negative electrons.
 6. The unsaturated nature of metallic bonding accounts for the alloying
properties of metals. If the atoms have more loosely held valence
electrons, the more metallic is the bonding.

7. For example, Sodium. Copper, Silver has high electrical and thermal
conductivities because their valence electrons are very mobile. They are
opaque because the free electrons absorb energy from light and they have
high reflectivity, because these free electrons re-emit this energy as they
fall back to lower energy.

Properties of metallic bond materials:

1. They have high electrical and thermal conductivities.

2. The metals are opaque to all electromagnetic radiations.
3. The metals have high optical reflection and absorption co-efficient.
4. The metallic bond is comparatively weaker than the ionic and covalent
bond.
5. Metallic solids have crystalline structure.
6. Metallic crystals possess a high degree of crystal symmetry due to
symmetrical arrangement of positive ions.

Origin of energy band formation in solids

The band theory solid explain the formation of energy bands and determines
whether a solid is a conductor, semiconductor or insulator.

The existence of continuous bands of allowed energies can be understood

starting with the atomic scale. The electron of a single isolated atom occupies
atomic orbital’s, which form a discrete set of energy levels.
When two identical atoms are brought closer, then the outermost orbits of these
atoms overlap and interact. When the wave functions of the electrons of
different atoms begins to overlap considerably. The energy level corresponding to
those wave functions splits.

If more atoms are brought together, more levels are formed and for a solid of N
atoms, each of the energy levels of an atom splits into N energy levels. These
energy levels are so close that they form an almost continuous band. The width of
the band depends upon the degree of overlap of electrons of adjacent atoms is
largest for the outermost atomic electrons.

As a result of the finite width of the energy bands. Gaps are essentially left over
between the bands called forbidden energy gap.

The electrons first occupy the lower energy levels (and are of no importance)
then the electrons in the higher energy levels are of importance so to explain
electrical properties of solids and these are called valence band and conduction
band.

Valence Band: A band occupied by valence electrons and is responsible for

electrical, thermal and optical properties of solid and it is filled at 0K.

Conduction Band: A band corresponding to outer most orbits is called conduction

band and is the highest energy band and it is completely empty at 0K.
 The forbidden energy gap between valence band and conduction band is
known as the highest energy band gap. By this, solids are classified into
conductors, semiconductors and insulators.

Classification of solids into conductors, semiconductors and

insulators

Based on the energy band diagram materials or solids are classified as follows:

CONDUCTORS: In this kind of materials, there is no forbidden gap between the

valence band and the conduction band. It is observed that the valence band
overlaps with the conduction band in metals as shown in the figure. There are
sufficient numbers of free electrons, available for electrical conduction and due
to the overlapping of the two bands there is an easy transition of electrons from
one band to another band takes place and there is no chance for the presence of
holes. Resistivity of the conductors is very small and it is very few mille-ohm
meters.

Examples: All metals (Na, Mg, Al, Cu, Ni, Ag, etc.)

SEMICONDUCTORS: In semiconductors, there is a band gap which exists between

the valence band and it is very less and it is the order of 1 to 2eV are known as
semiconductors. It will conduct electricity partially at normal conditions. The
electrical resistivity values are 0.5 to 10³ ohm-meter. Due to thermal vibrations
within the solid, some electrons gain enough energy to overcome the band gap
(or barrier) and behave as conduction electrons; conductivity exists here due to
electrons and holes.

Examples: silicon, germanium, GaAs.

INSULATORS: In insulators, the width of forbidden energy gap between the

valence band and the conduction band is very large. Due to large energy gap,
electrons cannot jump V.B. to C.B. energy gap is of the order of 10eV and higher
than semiconductors. Resistivity values of insulators are 10⁷ to 1012 ohm-meter.
Electrons are tightly bound to the nucleus, no valence electrons are available.

Example: wood, rubber, glass.

Q1. What is a semiconductor? What intrinsic and extrinsic semiconductors?

A semiconductor is substances usually a solid chemical element or compound

that can conduct electricity under some conditions but not others, making it a
medium for the control of electrical current

It has almost filled valence band, empty conduction band and very narrow energy
gap i.e., of the order of 1 eV, Energy gap or Silicon (Si) and Germanium (Ge) are
1.0 and 0.7ev respectively, and Consequently Si and Ge are semiconductors.

Effect of temperature on conductivity of semiconductors: At 0 K, all

semiconductors are insulators. At finite temperature, the electrical conductivity
of semiconductor material increases with increasing temperature. With increase
in temperature outermost electrons acquire energy and hence by acquiring
energy, outermost electrons leave the shell of the atom.

Hence with increase in temperature, number of carriers in the semiconductor

material increases and which leads to increase in conductivity of the material.

Types of semiconductors:

Intrinsic Semiconductor: An intrinsic Semiconductor is chemically Very pure

possesses poor conductivity, its equal numbers of negative carriers (electrons)
and positive carriers (holes). A silicon crystal is different from an insulator
because at any temperature above absolute zero temperature, there is a finite
probability electron in the Will behind an electron deficiency called a "hole".

The hole can travel from one atom to the adjacent atomic radius by an electron
later.

This process involves formation of new covalent bond and breaking an existing
bond by up the hole and creating new holes this the holes travel from one atom
to the adjacent in crystal lattice.

If a voltage is applied, then both the electron and the hole can contribute to a
small current.

Extrinsic Semiconductor: Extrinsic semiconductor is an improved intrinsic

semiconductor with a small amount of impurities added by a known doping,
which alters the electrical properties of the semiconductor and improves its
conductivity; impurities into the semiconductor (doping process) can control their
conductivity.

Doping process produces two groups of semiconductors: the negative Charge

conductor (It-type) and the positive charge conductor {p-type}, Semiconductors
are available as either elements or compounds. Silicon and Germanium the most
common element semiconductors, Compound Semiconductors include ln-Sb, Ln-
AS, Ga-P, Ga-Sb, Ga-AS, Si-C.

Si and Ge both have a crystalline structure called the diamond lattice. Thai is.
Each atom has its finite nearest neighbors at the comers of a regular tetrahedron
with the atom itself being at the center. In addition are the pulse element
semiconductors. Many alloys and compounds are semiconductors. The advantage
of compound semiconductor is that they provide the device engineer with wide
energy of energy gaps so that materials are available with properties that meet
specific requirements. Some of these semiconductors are called wide band gap
semiconductors.