Solid 19 July

S O L I D S TAT E
PART IX
19 JULY 2021
LETS SUMMERIZE
1. Why NaCl acquires yellow colour when heated in Na vapours ?
2. Why does ZnO exhibit increased electrical conductivity on heating ?
3. What is an F- centre ?
4. Why FeO is non-stoichiometric with the formula Fe0.95O ?
5. What happens when an ionic solid is doped with a cation of higher
valency ?
6. Differentiate between n-type and p-type semiconductors.
7. How is electrical conductivity of a group 14 element like Si affected on
adding:
– A group 13 element like Ga to it
– A group 15 element like P to it
ELECTRICAL PROPERTIES OF SOLIDS
• Solids can be classified into three types on the basis of their
conductivities.
– Conductors: Solids with conductivities ranging between 104
to 107 ohm-1 m-1 are called conductors.
• Metals having conductivities in the order of 107 ohm-1 m-1
are good conductors.
– Insulators : These are the solids with very low
conductivities ranging between 10-20 to 10-10 ohm-1 m-1 .
– Semiconductors : These are the solids with conductivities in
the intermediate range from 10-6 to 104 ohm-1 m-1 .
•BAND THEORY OF METALS

– A conductor may conduct electricity through movement of
electrons or ions.
– Metals conduct through electrons and electrolytes through
ions.
– Metals conduct electricity in solid as well as molten state.
The conductivity of metals depend upon the number of
valence electrons available per atom.
• BAND THEORY OF METALS
– The atomic orbitals of metal atoms form molecular orbitals
which are so close in energy to each other that they form a
band. If this band is partially filled or it overlaps with a
higher energy unoccupied conduction band, then electrons
can flow easily under an applied electric field and the metal
shows conductivity.
– If the gap called FORBIDDEN GAP, between filled valence
band and the next higher unoccupied conduction band is
large, electrons cannot jump to it and such a substance has
very small conductivity and it behaves as an insulator.
SODIUM ACCORDING TO BAND THEORY
Conduction band:
empty 3s antibonding
No gap
Valence band:
full 3s bonding
C
B
C
CB B
VB
V VB
B
• In case of semiconductors, the gap between the valence band
and conduction band is small . Therefore, some electrons may
jump to conduction band and show some conductivity.
• Electrical conductivity of semiconductors increases with rise in
temperature, since more electrons can jump to the conduction
band. Substances like silicon and germanium show this type of
behaviour and are called intrinsic semiconductors.
• Their conductivity is increased by adding an appropriate
amount of suitable impurity. This process is called doping.
Impurities can be electron rich or electron deficient.
• Applications of n-type and p-type semiconductors

 Various combinations of n-type and p-type semiconductors are used for making
electronic components.
 Diode is a combination of n-type and p-type semiconductors and is used as a
rectifier.
 Transistors are made by sandwiching a layer of one type of semiconductor
between two layers of the other type of semiconductor.
 npn and pnp type of transistors are used to detect or amplify radio or audio
signals.
 The solar cell is an efficient photo-diode used for conversion of light energy into
electrical energy.
IMPERFECTIONS / DEFECTS IN SOLIDS
• Points to remember
Metal deficiency is caused by those metals which show
variable valencies.
Impurity defect in ionic solids is caused by a foreign atom.
Doping means adding an impurity to the crystal.
N- type semiconductors have extra electrons.
P- type semiconductors are electron deficient.
Both n- and p- type semiconductors are better conductors
of electricity.
• Points to remember
Metallic conductors conduct electricity by movement of
electrons.
Electrolytic conductors conduct by flow of ions.
Forbidden gap in metals decides their electrical properties
as conductors, semiconductors or insulators.
Electrical conductivity of semiconductors can be increased
by doping them with some impurity.
MAGNETIC PROPERTIES OF SOLIDS
• Each electron in an atom behaves like a tiny magnet. Its
magnetic moment originates from two types of motions:
I. its orbital motion around the nucleus and
II. its spin around its own axis
• As electron is a charged particle, its orbital motion produces a
small magnetic field along the axis of rotation and its spinning
motion along the spin axis.
• Thus, each electron has a permanent spin and an orbital
magnetic moment associated with it.
• On the basis of their magnetic properties, substances can be classified into five
categories.
I. Paramagnetic
II. Diamagnetic
III. Ferromagnetic
IV. Antiferromagnetic
V. Ferrimagnetic
•Paramagnetic substances
– Substances which are attracted by the
external magnetic field are called
paramagnetic substances.
– Paramagnetism is shown by those
substances whose atoms, ions or
molecules contain unpaired electrons.
However they loose their magnetism in
the absence of magnetic field.
e.g. O2-, Cu2+ , Fe3+ , Cr3+
• Diamagnetic substances
– Substances which are weakly repelled by the external magnetic field
are called diamagnetic substances.
– Diamagnetism is shown by those substances which contain fully filled
orbitals and no unpaired electron is present.
– The magnetic moment possessed by an electron is cancelled by
another electron with opposite spin.
e.g. H2O, NaCl, C6H6 and TiO2
• Ferromagnetic substances
– Substances which show permanent magnetism even in the absence of
magnetic field are called ferromagnetic substances.
– Ferromagnetism is shown by those substances which have a large
number of unpaired electrons.
– In solid state, the metal ions of ferromagnetic substances are grouped
together into small regions called domains.
– Each domain acts as a tiny magnet. In an unmagnetised piece of a
ferromagnetic substance, the domains are randomly oriented and
their magnetic moments get cancelled.
• Ferromagnetic substances (contd.)
– When the substance is placed in a
magnetic field all the domains get
oriented in the direction of the magnetic
field and a strong magnetic effect is
produced.
– This ordering of domains persist even
when the magnetic field is removed and
the ferromagnetic substance becomes a
permanent magnet.
e.g. iron, cobalt, nickel, gadolinium
and CrO2
• Antiferromagnetic Substances
– Substances which are expected to
possess paramagnetism or
ferromagnetism on the basis of
magnetic moments of the domains
but actually possess zero net magnetic
moment are called antiferromagnetic
substances.
– Antiferromagnetism is due to the
presence of equal number of domains
in the opposite direction.
e.g. MnO
• Ferrimagnetic substances
– Substances which are expected to
possess large magnetism on the basis
of the magnetic moments of the
domains but actually have small net
magnetic moment are called
ferrimagnetic substances.
– This arises due to unequal number of
domains in opposite direction.
e.g. Fe3O4 (magnetite), ferrites like
MgFe2O4 and ZnFe2O4
a) Ferromagnetic
b) Antiferromagnetic
c) Ferrimagnetic
• All magnetically ordered solids like ferromagnetic and

antiferromagnetic substances change into paramagnetic at high
temperature due to randomisation of domains on heating.
• This temperature is called curie temperature.
e.g. ferrimagnetic substance, Fe3O4, becomes paramagnetic at 850 K.
•Points to remember
Electron in an atom shows spin and orbital magnetic moment and behaves like a
tiny magnet.
Paramagnetic substances have a few unpaired electrons and are weakly
attracted in external magnetic field.
 Diamagnetic substances have a no unpaired electrons and are repelled in
external magnetic field.
 Ferromagnetic substances have a large number of unpaired electrons and are
strongly attracted in external magnetic field. These can be converted to
permanent magnets.
•Points to remember
Antiferromagnetic substances are expected to show
paramagnetism but have zero magnetic moment.
Ferrimagnetic substances are expected to show large
magnetic moment but show small.
At curie temperature, all ferromagnetic and
antiferromagnetic substances change into paramagnetic.
LET’S DISCUSS
1. Which type of defect is found in KCl crystal?
2. A compound forms hcp structure. What is the total number of voids in
0.5 mol of it? How many of these are tetrahedral voids? (Td voids =
6.022 x 1023 ; Total voids = 9.033 x 1023)
3. Why is glass in window panes of old buildings slightly thickened at the
bottom?
4. If NaCl is doped with 10-3 mol % SrCl2, what is the concentration of cation
vacancies? (6.02 x 1018 mol-1)
5. Nickel oxide has the formula Ni0.98O1.00 . What fractions of Nickel exist as
Ni2+ and Ni3+ ions? (Ni2+ = 96%, Ni3+ = 4%)
6. The electrical conductivity of a metal decreases with rise in temperature
while that of a semiconductor increases. Explain.
SLIDE TITE
We are going to have a
great year learning
together!
THANK
YOU

Solid 19 July

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S O L I D S TAT E

•BAND THEORY OF METALS

• Applications of n-type and p-type semiconductors

• All magnetically ordered solids like ferromagnetic and

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