MOLECULAR ORBITAL THEORY

It was proposed by Hund and Mulliken to explain the bonding and paramagnetic nature
certain molecules which remained unexplained on the basis of valence bond theory. In this
theory artomic orbitals lose their identity and form new orbitals called as molecular orbitals
having more than one center. The molecular orbital thus formed now belong to the
molecule and not associated with atom.

Main points of molecular orbital theory

• Atomic orbital which take part in the formation of molecular orbital lose their
identity.

• Molecular orbital formed are of polycentric in nature.

• The number of molecular orbitals formed are bonding molecular orbital and other
half are antibonding molecular orbitals.

• Bonding and antibonding Molecular orbitals are differentiated by asterisk or star.

• molecular orbital like atomic orbitals can have only two electrons with opposite spin.

• Like atomic orbitals molecular orbital follow same rule for filling like hund’s rule and
Aufbau’s ,pauli’s rule.

• Bonding molecular orbital has lower energy and are more stableas compared to
antibonding molecular orbitals.

• The number of molecular orbital is equal to the number of atomic orbital taken for
combination .

A.O + A.O= 2 M.O

Condition for formation of molecular orbital

• Combining atomic orbitals should be of same energy.

• Atomic orbitals must overlap to large extent.

• Atomic orbitals must carry same sign of electron density.

NOTE : Orbitals with same sign of electron density form bonding molecular orbital while
orbitals with opposite sign form antibonding molecular orbital.

Linear combination of atomic orbitals

Molecular orbitals are supposed to be formed by combination of atomic orbitals of same

atoms in molecule provided those orbitals combine linearly. Suppose two atoms A and B
having one electron each combine linearly . When these two atoms overlap ,the valence
electron will have a large space as compared to the individual atom. In such situation the
new wave function can br due to linear combination of atomic orbitals i.e wave function of
atomic orbital .
The molecular orbitals formed by attraction of wave function are called bonding molecular
orbitals and the molecular orbitals formed by subtraction or repulsion of wave unction are
called as antibonding molecular orbitals.

Graphical representation of bonding and antibonding molecular orbitals

When a graph is ploted between electron density for individual atom A and B with distance,
curve represented by dotted lines are obtained .Again a graph is plotted for bonding
molecular orbital , a curve represented by solid line is obtained.

From the graph on comparison an increase in electron density is obtained for bonding
molecular orbital than individual atomic orbital . Bonding molecular orbital has higher
probability for finding electrons than for the individual atoms.

On other hand ,from graph on comparison it is clear that molecular orbitals formed by
subtraction ,a point at the center is obtained ,where the probability of finding electron is
zero i.e a nodal plane. Antibonding molecular orbital formed when atomic orbital with
opposite sign of electron density are combined.

Molecular orbital whether bonding or antibonding does not change when rotation by 180
degrees is given or in other words orbitals are unaffected i.e there s no change in shape .
Shape of molecular orbitals are formed by

• S and s combination

• P and p combination

• P and p combination perpendicular to nuclear axis

• S and s atomic orbital: when s and s atomic orbital belonging to any energy level
combine on the same nuclear axis , these form two molecular orbitals due to a)
addition b)subtraction . These molecular orbitals formed are bonding and
antibonding.

Molecular orbitals formed by s and s combination are symmetricl as well as

cylindrical around the internuclear axis.
• P and p atomic orbitals: It is general convention that out of p orbitals, pz is
assumed to lie along the internuclear axis.
 These molecular orbitals formed have also

cylindrical symmetry around the axis .

• Lateral overlapping of p and p orbital: molecular orbitals formed by sideways

overlapping of px ,py atomic orbitals are termed as pi as shown bonding
molecular orbitals. The orbitals must carry same sign of electron density.

While antibonding molecular orbitals is formed when orbitals of different overlap

sideways.

Energy level diagram for molecular orbitals

Making use of postulates that molecular orbitals are formed by linear combination of atomic
orbitals. Only the atomic orbitals overlap with each other whose energies are comparable.
The order of energies of atomic orbitals is given as 1s,2s,2p,3s….
1s orbital is of lowest energy. So 1s orbital orbital of one atom overlap with 1s orbital of
another atom it gives rise to two molecular orbitals bonding and antibonding. Similarly 2s
orbital of one atom overlaps 2s orbital of another atom give rise to two molecular orbitals
one is bonding and other is antibonding.

Just after 1s and 2s ,2p orbitals take part in the formation of molecular orbitals. As a result
sigma molecular orbitals are formed , three bonding and three are antibonding molecular
orbitals is formed as a result of combination of atomic orbitals along the internuclear axis
while pi M.O is fomed due to side ways overlapping of atomic orbitals.

The order of filling M.O in an increasing order of energies given as:

There are two type of molecular orbitals energy level diagram

Type-1 the molecular orbital energy level diagram for molecule H2 to N2 is given as:
Type-2 the molecular orbital energy level diagram for molecule O2 to Ne2 given as :
Rules for filling of molecular orbital

• Molecular orbitals are filled in increasing order of energies.

• Molecular orbitals can have a maximum of two electrons with opposite spin.

• Molecular orbitals of same energy are first half filled and then pairing takes place.

In other words Molecular orbitals follow same rule for filling as followed by atomic
orbital.

Bond order and its significance

Bond order: It is half the difference between the electrons present in bonding and
antibonding Molecular orbitals.

Bond order=1/2(Nb-Na)

Na=number of electrons in antibonding Molecular orbitals.

Nb= number of electrons in bonding Molecular orbitals.

Significance of bond order

• Stability of a molecule: when for a molecule calculated bond order is

positive, the molecule is formed and is stable . higher the bond order of a
molecule more the stability.

• Dissociation energy: on the basis of bond order the magnitude of bond

dissociation energy can be predicted higher the bond order ,more the
number of covalent bond, smaller the bond distance, larger the dissociation
energy.

• Covalent bond in molecules: number of covalent bond in a molecule is

equal to bond order.

Magnetic behavior of molecules

Molecular orbital electronic configuration for molecules help in explaning

whether the given molecules show magnetic behavior or not.

When the molecules have unpaired electrons and will be attracted by

magnetic field . the molecule is paramagnetic in nature.
 When the molecules have all paired electrons and is not attracted by
magnetic field . the molecule is diamagnetic in nature.

Hence the arrangements of electron in molecular orbital ,it can be

predicted whether the molecule is paramagnetic or not. Magnetic behavior
is related with the number of unpaired electrons. More the number of
unpaired electrons , more the paramagnetic in nature.

Electronic configuration for H2 molecule = σls2

Bond order =1/2[Nb-Na]=1/2[2-0]=1

In H2 molecule the hydrogen atoms are bonded by a single covalent bond.

(ii) He2 It is not formed. The total number of electrons with He2 molecule are four. when two
atomic orbitals of He combine, two molecular orbitals σ1s and σ*1s are formed.Two
electrons add up in each of the bonding and antibonding molecular orbital i.e. σ1s2 and
σ*s2.

Molecular orbital energy level diagram 1 Electronie configuration of He2 molecule is

σ1s2,σ1s2.

Bonding order=1/2(Nb-Na)= 1/2[2-2]=0

Bonding and antibonding orbitals balanced each others effect. Thus, He2 molecule is not
formed.two electrons add up in each of the bonding and antibonding molecular orbitals i.e.,
o1s2 and o*1s2.

(iii) Lithium molecule Le2: Electronic configuration of Li(z = 3) = 1s22s1, Two atomic orbitals of
each Li atoms combines to form four molecular orbitals i.e.σ1s,σ*1s,σ2s and σ*2s. Li2
molecular orbital has Six electrons. Electronic configuration for Li2 molecule is=

σ1s2,σ*1s2 or kk σ2s2(where kk stands for σ1s2,σ*1s2

Bond order=1/2(Nb-Na)=1/2[4-2]=1
The Li2 the molecule has one covalent bond. It is of diamagnetic nature. Li2 molecule is less
stable than H2 molecule because of (a) large size of Li and (b) repulsive forces between inner
electrons i.e. electrons in 1s.

(iv) Beryllium molecule Be2: Electronic configuration of Be (z = 4) = 1s22s2

Two atomic orbitals of each Be atom ie, Is and 2s in all four atomic orbitals combine to

form four molecular orbitals ie. σ1s, σ*1s,σ2s,σ*2s,Be2 the molecule has eight electrons, so

electronic configuration of Be2 molecule is :

=σ1s2,σ*1s2,σ2s2,σ*2s2

=1/2[Nb-Na]

=1/2[4-4]=0

Be2 molecule is not formed because bond order is zero.

(v)B2 molecule: Electronic configuration of B(z=5) is ls22s22px1. Molecular orbital energy level

diagram of B, molecule.

Electronic configuration of B2 molecule is Be molecule is not formed because bond order is

σ1s2, σ*1s2, σ2s2, σ*2s2,π2px1=π2py1

Bond order=1/2[Nb-Na]

=1/2[6-4]=1

Bond order is one and B2 molecule is of paramagetic nature due to presence of two unpaired
electrons and to justify energy level diagram upto N2 is used.

(vi)C2 Molecule: Electronic configuration of C(z=6) is 1s2, 2s2, 2px12py1.Molecular orbital

energy level diagram for C2 molecule is given below:

Electronic configuration for C2 molecule is σ1s2,σ*1s2,σ2s2,σ*2s2,π2px2=π2py2

Bond order = 1/2[Nb-Na]

=1/2[8-4]=2

Bond order is 2 and C2 molecule is of daimagnetic nature again it is justified by using energy
level diagram upto N2 molecule.
(ii)Nitrogen molecule N2:Each nitrogen atom has seven electron(z=7)

Electronic configuration of nitrogen is:1s22s22px12py12pz1

and N2 molecule has 14 electon which are accomodated in molecular orbital given below in

molecular orbital energy level diagram:

Electronic configuration for N2 molecule is:

σ1s2, σ*1s2, σ2s2, σ*2s2,πpx2=π2py2,σ2pz2

Bond order = 1/2[Nb-Na]

=1/2[10-4]=3

Bond order is 3 and N2 molecule is of diamagnetic nature since all elctrons are paired

and has high value of bond energy.

(viii)Oxygen molecule O2:Electronic configuration of oxygen(z = 8) is 1s2,2s2,2px22py12pz1 and

O2 molecule has 16 electrons.

The electronic configuration of O2 molecule is:

σ1s2 ,σ*1s2,σ2s2,σ*2s2,σ2pz2,π2px2 = π2py2,π*2px1 = π*2py1

Bond order = 1/2[Nb-Na]

=1/2[10-6]

=2
 In O2 molecule oxygen atoms are held by a double covalent bond and it is of

paramagnetic nature due to the presence of two unpaired electrons in antibonding molecule

orditals.

Molecular orbital energy level diagram for O2- - molecule :

(ix)F2 molecule:Electronic configuration of F(z=9)1s2,2s2,2px2,2py2,2pz1

F2 molecule has 18 electrons, which are distributed in molecule is

σ1s2,σ*1s2,σ2s2,σ*2s2,σ2pz2,π2px2-2py2,π*2px2=π*2py2

Bond order=1/2[Nb-Na]

=1/2[10-8]=1

F2 molecule has a single covalent bond and because of the presence of all bonded pair of

electrons, F2 molecule is of diamagnetic nature.

The molecule orbital diagram of F2 given as

(x) Neon (Ne2):This molecule has 20 electrons and are placed in five bonding and five

antibonding molecular orbitals.

Electronic configuration of Ne2 is

σ1s2,σ*1s2,σ2s2,σ*2s2,σ2pz2,π2px2=π2py2,π*2px2 = π*2py2, σ*2pz2

Bond order = 1/2[Nb-Na]

=1/2[10-10]
 =0

Bond order is zero, hence it is not formed or is unstable.

The molecular orbital diagram given as:

Molecular orbital energy level diagram for diatomic molecules having different

atoms (Heteronuclear diatomic molecules)

It is based on the same principle as that for diatomic molecules having similar atoms. In
molecules with different atoms due to electornegativity difference the atomic orbitals
involved

are not of same energy and are placed at different levels. Since atoms involved have
different

values of electronegativity, the bonding molecular orbitals are nearer to more

electronegative

Atom and antibonding molecalar orbitals formed are nearer to less electronegative atom.

Energy level diagram of Nitric Oxide --NO

The electronic contiguration of N and 0-atoms are:

N--1s2 2s2 2p3

O--1s2 2s2 2p4

There are five valance electrons in N-atom and six valence electrons in oxygen atom.

Thus total number of valence electrons in NO molecule is 11. Out of N and O atoms, the O

atom is more electronegative than N-atom therefore bonding M.O. close to oxygen atom

The elements configuration for NO molecule is KK2s2,σ2ps2,π2px2=π2py2,σ2pz2π*2px1

The Bond order is

B.O. =1/2[Nb-Na]

=8-3/2=2*1/2

The bond dissociation energy of NO molecule is 668KJ mol-1. The molecule of NO is

paramagnetic in nature due to presence of one unpaired electron.

COMPARISON WITH NO+

NO+ is formed by loss of e- from antibonding M.O.(π*2px)

Therefore electronic configuration of NO+ Becomes

KK2s2,*2ps2,π2px2=π2p2y,2pz2

The MO diagram given as

Bond order=8-2/2=3

The BO of NO+(3) is greater than NO(2.5) Therefore its bond dissociation energy is high and
its bond length less than that of NO.

Comparison with NO+

NO+ is formed by the gain of e- in the antibonding M.O. (2px*) so its configuration becomes

KK o2s2, o*2s2, π2p2z = π2p2z, π*2p1x, π*2p1 y

The M.O. diagram is given as

: Molecular orbital diagram for NO- molecule

Bond order = 8-4/2=2

The B.O. of NO- So it's bond dissociation energy is less and it's bond length is greater than
NO.

The decreasing order of bond order of NO, NO+, NO-.given as

NO+>NO>NO-

and decreasing order of their bond length is

NO->NO>NO+

2. Carbon Monoxide- CO: The electronic čonfiguration of C and O atoms is

C=1s2 2s2 2p2

O=1s2 2s2 2p4

There are 4 valence e-in C-atom and 6-valence e- in O-atom. Thus the total number of
valence electrons in CO is 10 out of C and O atoms, the O- atoms is more electronegative
than C- atoms. Therefore bonding M.O. close to the oxygen atom.

The electronic configuration of CO given as

KK σ2s2, σ*2s2, π2p2 x = π*2py2, π2pz2

Bond order =8-2/2 =3

This B.O. of CO molecule is three it's bond dissociation energy 1067 KJ mol- and its bond
length is 1.28 A°. In CO all the electron are in the paired state, therefore the molecules are
diamagnetic in nature.

Comparison of CO and CO+

CO + is formed by loss of an electron from antibonding M.O.(¬2s) due to its complicated

structure so its configuration becomes KK σ 2s2, π 2p2x=π 2p2y,σ2pz2,σ*2s1

Therefore its Bond order becomes

Bond order=8-1/2=3*1/2

The bond order of CO+ is greater than CO therefore the bond length of CO+(1.115A)* is less
than the bond length of CO (1.128A*)

The bond dissociation energy of CO* is greater than CO,CO+ is paramagnetic in nature due to
presence of one unpaired electron.

Molecular Orbital Theory of Bonding in Metals or Band Theory of Metals

Accordingly molecular orbital theroy, two atomic orbitals(each contributed by one atom)
combine, to give two molecular orbitals, one bonding molecular orbital and other
antibonding molecular orbital.If there molecular orbitals, one bonding molecular orbital,one
non-bonding molecular orbital and the third an antibonding molecular orbitals, two bonding
molecular orbitals and two antibonding molecular orbitals. In a similar way, if we have N
atoms(N is Avogadro's number,6.022x1023 atoms) each contributing one atomic orbital, we
get N molecular orbitals. Since the number of molecular orbitals is very large,
therefore,energy level of molecular orbitals are so close to each other that they form a
continous energy band. Such group of energy levels is called an energy band.

It may be noted that formation of an energy band depends upon

(i)the close proximity of large number of atoms

(ii)the energy difference between pure atomic orbitals.

As such therefore,2s-atomic orbitals give rise to energy band, 2p-atomic orbitald also
give rise to a band of closely spaced energy levels. Various energy bands from different
atomic orbitals will overlap or remain seprated from each other depending upon the relative
energies of atomic energy levels.
 Overlapping of 1s,2s, and 2p atomic orbitals of lithium metal and energy bands
formed there are shown in fig.

Let us now consider the case of Li atom whose electronic configuration is 1s2 2s1.Its
1s energy band will be completely filled.In case of 2s there are two valence electrons and
two molecular orbitals. According to Paul's exclusion principle, since two electrons can be
accomodated in each molecular orbital, therfore only bonding molecular orbital will be
completely filled. Similiarly, we can say that if there are N 2s- energy bands will be filled in
this case and other half will be empty. The electrons thus can move from half filled energy
band to the empty bands will be empty. The electrons thus can move from half filled energy
bands. This movement of electrons from one molecular orbital to another consitituents an
electric current. This explains why lithum is a good conductor of electricity.

If we heat a metal at one and, then electrons after gaining energy jump to empty
energy band. These electrons can then move easily from one part of the metal to other
thereby explaining conduction of metals.

Let us now consider the case of beryllium. It contains two valence electrons and,
therefore, N atoms of beryllium will have 2N valence electrons from 2s atomic orbitals. The
2s bands in beryllium are thus completely filled and there are no empty orbitals in 2s energy
band into which electrons can move. But 2p energy band is completely empty and overlaps
the 2s energy band. On applying the electric field, the electrons can move into an empty
band. The lowest-lying empty band is called the conduction band and the outermost filled
band 1s called conduction band and 2p band is conduction band. In beryllium, the 2s band is
the valence band and the 2p band is the conduction band. Because of Overlapping of 2s and
2p- bands, Some electrons overflow into p energy band (shown by arrow ). Because of this
overflow, some of the 2s-band is shown to be empty while some of the 2p- energy band
which was originally empty is shown to be somewhat occupied (Fig 1.16) Because of this
movement of electrons, beryllium also conducts electricity and acts like a metal. A similar
explanation can be given in case of sodium and magnesium which have one 3s and two 3s
valence electrons.

In the case of Aluminum, there are three valence electrons per atom. Therefore, in this case,
3s-band will be completely filled while 3p-band will have vacant levels because of which
aluminum also conducts electricity.

Metals, Semi-metals, and Non-metals: The difference of energy between the filled
energy band and the next empty band varies from material to material and conduction and
valance. the given material will be a metal, semi-metal or a non-metal depends upon this
energy difference. The spaces between bands represent energies forbidden to electrons in
metals and are called energy gaps.
(i) In metals the conduction and valence bands are very close to each other or overlap each
other and, therefore, the electrons can very easily go into the conduction band (Fig. 1.17 (a).
Hence metals are good conductors of heat and electricity.

(ii) In non-metals, there 1s a big energy gap between the valence band and conduction band,
and the electron can not move from valence band to conduction band (rig 1.(C)). Hence,
non-metals are non-conductors of electricity.

(iii) Semi-metals: There are certain materials in which the energy gap between the
conduction and valence band is in between those of metals and non-metals. Such materials
or called semi-metals. These are not good conductors of electricity at room temperatures.
However, With an increase of temperature, some electrons get sufficient energy to cross
over from valence band to conduction band thereby increasing the conductivity and giving
metallic properties to the materials. For example, in silicon, the energy gap is 106kI mol-1
and it, therefore acts as a semi-conductor or semimetal while in the case of carbon the
energy gap is 508 kJ mol-1 and hence it is an insulator.Germanium with an energy gap of
58kJ mol" is a semiconductor while tin, the last member of the group, with an energy gap of
8 kJ mol-1, is a metal.

1.11 SEMICONDUCTORS

All those solids which have a conductivity between those of conductors and insulators are
known as semiconductors: The conductivity of semiconductors is in the range of 10-6 ohm-1
m-1 to 104 ohm-1 m-1

The conductivity of semiconductors is either due to the presence of impurities or defects

According to band theory, the conductance of a material depends upon the energy gap
between the valence band and the conductivity band. This difference varies from material to
material. If this difference is small, then the material may be a semiconductor The energy
gaps between the valence band and conductivity, bend for some common semiconductors
are given in Table 1,2.

On cooling the crystal to absolute zero, the conductance band becomes empty and the
electrons occupy their lowest possible energy levels. In such a case, the material acts as an
insulator.-With gradual increase in temperature, the electrons start getting thermally excited
and start shifting from valence band to the conduction band and thus they can conduct
electricity at room temperature. The conductivity of a semiconductor lies.
Between that of a metal and an insulator and. depends upon the number of electrons in the
condition band.

1.11.1 Types of Semiconductors

There are mainly two types of semiconductors.

1.Intrinsic Semiconductors

2.Extrinsic Semiconductors

Let us discuss both these ones by one.

Intrinsic Semiconductors: Germanium and silicon are the most important

examples of semiconductors. The crystal structures of both are like a diamond. Atoms of Si
and

Ge both have four electrons in their, outermost shells which form four covalent bonds with
other atoms. In both Si and Ge, at very low temperatures, the valence band is filled and the
conduction band is empty. Under these conditions, Si and Ge are both, insulators and cannot
carry any. electric curren the band gaps are only 68 k mol-1 for Ge and 106 kJ mol - 1 for Si
and at room temperature a few valence electrons gain sufficient energy from the thermal
vibrations of atoms to be promoted into the conduction band. if the crystal is connected to
an electric circuit, these thermally excited electrons carry a small current and make the Si or
Ge crystals slightly conducting Alternatively, we may say that when the crystal absorbs
sufficient amount of energy, some covalent bonds are broken due to the thermal motion
and valence electrons are released. When this crystal is connected to the electric current
these electrons move leaving behind a positive charge as a positive hole at the site of a
missing electron. Now on applying electric field the electrons move in one direction and the
positive holes move in the opposite direction and the crystal, therefore, becomes electrically
conducting. The positive holes jump from one bond to another while the electrons move
through interstices (Fig 1.18) This is termed as intrinsic semiconductivity of the crystal and
the substances are called intrinsic semiconductors. The intrinsic semiconductors contain an
equal number of current-carrying holes and electrons and conduction is an intrinsic property
of the metal.
As the temperature is increased, the conductivity increases. i.e. the electrical resistance
decrease This is the opposite of the situation with metals. Above 100C, So many valence
electrons are promoted to the conduction band in Ge that the crystal lattice disintegrates.
With Silicon, the maximum working temperature is 150°C. This intrinsic semiconduction is
undesirable and precautions mist be taken to limit the working temperature of intrinsic
semiconductors.

2. Extrinsic Semiconductors: pure silicon or germanium can be made semiconducting in a

controlled way by adding impurities which act as charge carriers. The introduction of a small
amount of impurities into the pure crystal to increase the conductivity of pure crystal is
called doping.Doping can be done with an impurity that is either electron-rich or electron-
deficient as compared to intrinsic semiconductors germanium or silicon (element of group
14).Two types of extrinsic semiconductors can be produced by doping. Depending upon the
nature of impurities

introduced, there are

(i) n-type semiconductors (n-stands for negative)

(ii) p-type semiconductors (p-stands jor positive)

(i) n-type semiconductors: When the extremely pure form of silicon or germanium are
dopped with elements of group 15, say arsenic with five valence electrons (donors), the
structure of the crystal lattice does not change but few of silicon or germanium atoms are
randomly replaced by arsenic atoms with five valence electrons (Fig. 1.19 (6). In the present
case, let us consider germanium as an example, At absolute zero or low temperatures, the
fifth electron is localized on the arsenic atom, But at normal temperatures, some of these
with electrons of arsenic are excited into the conduction band where they can carry current
readily. This is extrinsic conduction and it the amount of semiconduction far above that of
intrinsic conduction, Since the current is carried away by negative changes excess electrons,
it is known as the n-type condition and the semiconductor so obtained as n-type
semiconductors. Instead of arsenic, other elements of group 15 Ike P, Sb or Bi can also be
used as doping material to for N-type semiconductors.

(ii) p-type semiconductors: When the same pure germanium crystal is doped with elements
of group 13, say indium with three valence electrons, the structure of crystal lattice site
remains the same but an atom with three valence electrons occupies a site that would have
been occupied bý a germanium atom (Fig. I.19 (). Each Sodium atom uses its three valence
electrons to form three bands in the lattice, but they are unable to form four bonds to
complete the covalent structure. One bond is complete and the șite normally occupied by
the necessary electron is called a 'positive hole'. At absolute zero or low temperatures, 1he
positive holes are localized around indium atoms. However at normal temperatures, valence
electrons on an adjacent germanium atom.May gain sufficient energy to move into the hole.
This forms a new positive hole in the germanium atom. The positive hole seems to have
moved in the opposite direction to the electron. This positive hole can migrate across the
crystal, This Is equivalent to moving an electron in the opposite direction, and thus current is
carried. Since the current is carried by the migration of positive holes or centers, this is
known as p-type conduction and the semiconductors as p-type semiconductors instead of
indium, boron, aluminum galium can also be used as dopants to tom p-type semiconductors.

There is still another type of semiconductors called defeat semiconductors which are formed
due too non-stoichiometric defects in the given compound.For example, when alkali.metal
halides such as Naci, KCI, or LiCI are heated in an atmosphere- of pours of their respective
alkali metals, anion vacancies are produced. In this process, the alkali metal atoms deposited
on the surface of metal halide crystal and halide ions get diffused into the Surface and
combine metal atoms. The electrons thus produced by the ionization of metal atoms diffuşes
into the crystal and entrapped into anion vacancies. These'electrons entrapped in anion
vacancies are called F-centres. The ion of an F center can be excited thermally to a
conduction band giving rise to n-type semiconduction, There is yet another type of n-type
semiconductors in which extra cations occupy interstitial sites and to aim the electrical
neutrality, electrons occupy other interstitial sites. The whole situation is visualized as loss of
non-metal atoms that leave their electrons behind. The corresponding extra cations (metal
Ions) associated with the lattice then move to occupy interstitial sites. The common example
1s that OF Zinc oxide(ZnO). On heating, it loses Oxygen at high temperature and turns yellow
in color.The Zn2+ ions move into interstitial sites and equal number of Electron get entrapped
in the adjoining interstitial sites. These elements increase the electrical conductivity of zinc
oxide.

Yet there are compounds that are deficient of metals with the general formula A1-xB which
act as p-type semiconductors. In these compounds, the conductivity is because of the
movement of valence electrons from lower oxidation state metal ions to higher oxidation
state metal ions. FeO, Cu2O, NiO and FeS, etc are some examples of such compounds.