18 April 2023 23:24

Crystal defects occur as points, along lines, or in the form of a surface,

and they are called point, line, or plane defects
Point Defects are of three types:
1. Stoichiometric Defects
2. Impurity Defects
3. Non-Stoichiometric Defects

Stoichiometric Defects

Stoichiometric Defects are basically the point defects that don’t disturb the stoichiometry of
the given solid.
Stoichiometric Defects are also called intrinsic or thermodynamic defects.
• Vacancy Defect
In the crystals, when some lattice sites are left vacant, the crystal is said to have a vacancy
defect. This causes a decrease in the density of the given substance. This defect can also
form when the substance is heated.

• Interstitial Defect
In the crystals, when some constituent particles occupy an interstitial site, the crystal is
said to have an interstitial defect. Contrary to vacancy defect, this causes an increase in
the density of the given substance.
 Note: Vacancy and Interstitial Defects are observed in non-ionic solids. Ionic solids need to
maintain electric neutrality. Thus, they do not have simple Vacancy and Interstitial defects
but have Frenkel and Schottky Defects.

• Frenkel Defect
This defect is present in ionic solids. The smaller ion (mostly the cation) gets dislocated from
its normal site and gets moved to an interstitial site. This shift in ion creates a vacancy defect
at the original site and an interstitial defect at the new location. Due to this, the Frenkel
defect is also called the dislocation defect. It doesn’t affect the density of the solid as the ion
is still present in the structure. This defect is found mostly in ionic substances where there is a
large difference between the size of the ions. For example, ZnS, AgCl, AgBr, and AgI show
Frenkel defects as Zn2+ and Ag+ ions are small in size.
Characteristic of Frenkel Defect
1. This defect occurs exclusively when the cations are smaller than the anions. There are no
changes in chemically.
2. The Frenkel defect also has no effect on the density of the solid, hence both the volume and
mass of the solid are conserved.
3. Substances retain their electrical neutrality in such instances.
4. As the like charge ions get closer together, the dielectric constant rises.
5. Because of the presence of unoccupied lattice sites, materials with Frenkel defects exhibit
conductivity and diffusion in the solid state.
6. The Frenkel flaw reduces the lattice energy and stability of crystalline solids.
7. The solid’s entropy rises.
• Schottky Defect
The Schottky defect is like a vacancy defect in the ionic solids. The number of missing
cations and anions are always constant in this defect to uphold electric neutrality. The
Schottky defect decreases the density of the substance. This defect can be observed in
ionic solids having cations and anions of similar sizes. For example, KCL, NaCl, CsCl, and
AgBr.
Characteristics of Schottky Defect
1. The size difference between cation and anion is negligible.
2. Both cation and anion depart the solid crystal.
3. Atoms are also permanently ejected from the crystal.
4. In most cases, two positions are created.
5. The density of the solid decreases significantly.

Impurity Defects

In impurity defects, foreign components or impurities replace the position of existing ions.
For example, if molten NaCl is crystallized in the presence of SrCl2, some of the sites of
 Na+ ions can be occupied by Sr2+ ions. To maintain electric neutrality, each Sr2+ ion will
replace two Na+ ions. Sr2+ ion occupies the site of one Na+ ion and the other Na+ ion site
remains vacant. Thus, the number of vacancies created is also equal to the number of Sr2
+ ions present.
Other examples of impurity defects are CdCl2 and AgCl.

Non-Stoichiometric Defects

The constituent elements in a non-stoichiometric ratio due to defects in their crystal

structures. These defects are of two types:

1. Metal excess defect

2. Metal deficiency defect

• Metal Excess Defect

Metal excess defect due to anionic vacancies – this defect is observed in alkali halides like
NaCl and KCl. In this defect, crystals have an excess of cation because the anion present
combines with an external ion to form another compound. For example, when NaCl crystals
are heated in presence of sodium vapors, the Cl– ions diffuse and form NaCl with the sodium
vapor. Thus, the crystals now have an extra Na+ ion present. This anionic site is occupied by
an unpaired electron. We call this site an F-center. This word is derived from the German
word Farbenzenter for color center). This gives off a yellow color to the NaCl crystals. The
color appears from the excitation of these electrons when they absorb energy from the
visible light falling on the crystals. Just like the above cases, excess Lithium makes LiCl
crystals pink and excess Potassium makes KCl crystals violet (or lilac).
Consequences of metal excess defect
The existence of free electrons in crystals them to be coloured. Because of the presence of
free electrons, conduct electricity and are semiconductors. Because the electric transport is
mostly accomplished by “excess” electrons, these are referred to as n-type (n for negative)
semiconductors. Because of the existence of unpaired electrons at lattice sites are
paramagnetic. When the crystal is exposed to white light, the trapped electron absorbs
 ○ Electrons revolve around the nucleus of the atom
○ Electrons also spin on their own axis, spins in opposite sides are labelled with + and – signs.

Paramagnetic
These substances are weakly magnetized in an external magnetic field. The direction is the same direction
of the magnetic field. So they gain a net magnetization When we remove paramagnetic substance from
the field, the alignment of electrons is interrupted and the substance will lose its magnetic property hence
non magnetic without external magnetic field. Paramagnetic substances are not permanent magnets.

Paramagnetism is due to at least one pair of unpaired electrons in its orbit shell which get magnetized in
the magnetic field.
Diamagnetic
In diamagnetism , substances are magnetized in an external magnetic field. But diamagnetic solids
are repelled in the field. The magnetic property effected in them is in the opposite direction of the
magnetic fields and thus they have a repulsive force.

In diamagnetic substances, all electrons in their last shell are paired, there are no valence electrons.
This is the reason that the magnetic moment of their atoms is nearly zero. Examples are substances
like Sodium Chloride, Benzene etc. Being such bad conductors, we use them as insulators.

Ferromagnetic
These solids are strongly magnetized when we place them in an external magnetic field. Besides
the very strong attraction forces, these solids can actually be magnetized permanently. This means
that even when the external magnetic fields are removed the solids will retain their magnetic
properties.

They have domains" which is a special grouping of metal ions. Each domain is similar to a small
 magnet. In an electromagnetic field, these domains rearrange themselves and align themselves
with the magnetic field. In a non-magnetized metal, these domains are randomly arranged and it
revoke out their magnetic properties.

The examples of ferromagnetic solids include Cobalt, Nickel, Chromium Oxide etc. And they have
widespread industrial and every day uses.

Antiferromagnetic
In antiferromagnetism, the domain structures of the solid are very similar to those of ferromagnetic
solids. But here the domains are oppositely oriented. This means they revoke out each other’s
magnetism.

BiFeO3

Ferrimagnetic
These substances occur when magnetic moments are aligned in both directions (parallel as well as
anti-parallel) but in unequal numbers. These are weakly attracted to magnetic fields. Also on heating,
these substances will lose their ferrimagnetism . Examples are magnetite and ferrites of Zinc and
Magnesium.
 19 April 2023 00:20

Crystal defects occur as points, along lines, or in the form of a surface,

and they are called point, line, or plane defects respectively .

Point Defects are of three types:

1. Stoichiometric Defects
2. Impurity Defects
3. Non-Stoichiometric Defects

Stoichiometric Defects

Stoichiometric Defects are basically the point defects that don’t disturb the stoichiometry of
the given solid.
Stoichiometric Defects are also called intrinsic or thermodynamic defects.
• Vacancy Defect
In the crystals, when some lattice sites are left vacant, the crystal is said to have a vacancy
defect. This causes a decrease in the density of the given substance. This defect can also
form when the substance is heated.

• Interstitial Defect
In the crystals, when some constituent particles occupy an interstitial site, the crystal is
said to have an interstitial defect. Contrary to vacancy defect, this causes an increase in
the density of the given substance.
 Note: Vacancy and Interstitial Defects are observed in non-ionic solids. Ionic solids need to
maintain electric neutrality. Thus, they do not have simple Vacancy and Interstitial defects
but have Frenkel and Schottky Defects.

• Frenkel Defect
This defect is present in ionic solids. The smaller ion (mostly the cation) gets dislocated from
its normal site and gets moved to an interstitial site. This shift in ion creates a vacancy defect
at the original site and an interstitial defect at the new location. Due to this, the Frenkel
defect is also called the dislocation defect. It doesn’t affect the density of the solid as the ion
is still present in the structure. This defect is found mostly in ionic substances where there is a
large difference between the size of the ions. For example, ZnS, AgCl, AgBr, and AgI show
Frenkel defects as Zn2+ and Ag+ ions are small in size.
Characteristic of Frenkel Defect
1. This defect occurs exclusively when the cations are smaller than the anions. There are no
changes in chemically.
2. The Frenkel defect also has no effect on the density of the solid, hence both the volume and
mass of the solid are conserved.
3. Substances retain their electrical neutrality in such instances.
4. As the like charge ions get closer together, the dielectric constant rises.
5. Because of the presence of unoccupied lattice sites, materials with Frenkel defects exhibit
conductivity and diffusion in the solid state.
6. The Frenkel flaw reduces the lattice energy and stability of crystalline solids.
7. The solid’s entropy rises.
• Schottky Defect
The Schottky defect is like a vacancy defect in the ionic solids. The number of missing
cations and anions are always constant in this defect to uphold electric neutrality. The
Schottky defect decreases the density of the substance. This defect can be observed in
ionic solids having cations and anions of similar sizes. For example, KCL, NaCl, CsCl, and
AgBr.
Characteristics of Schottky Defect
1. The size difference between cation and anion is negligible.
2. Both cation and anion depart the solid crystal.
3. Atoms are also permanently ejected from the crystal.
4. In most cases, two positions are created.
5. The density of the solid decreases significantly.

Impurity Defects

In impurity defects, foreign components or impurities replace the position of existing ions.
 For example, if molten NaCl is crystallized in the presence of SrCl2, some of the sites of
Na+ ions can be occupied by Sr2+ ions. To maintain electric neutrality, each Sr2+ ion will
replace two Na+ ions. Sr2+ ion occupies the site of one Na+ ion and the other Na+ ion site
remains vacant. Thus, the number of vacancies created is also equal to the number of Sr2
+ ions present.
Other examples of impurity defects are CdCl2 and AgCl.

Non-Stoichiometric Defects

The constituent elements in a non-stoichiometric ratio due to defects in their crystal

structures. These defects are of two types:

1. Metal excess defect

2. Metal deficiency defect

• Metal Excess Defect

Metal excess defect due to anionic vacancies – this defect is observed in alkali halides like
NaCl and KCl. In this defect, crystals have an excess of cation because the anion present
combines with an external ion to form another compound. For example, when NaCl crystals
are heated in presence of sodium vapors, the Cl– ions diffuse and form NaCl with the sodium
vapor. Thus, the crystals now have an extra Na+ ion present. This anionic site is occupied by
an unpaired electron. We call this site an F-center. This word is derived from the German
word Farbenzenter for color center). This gives off a yellow color to the NaCl crystals. The
color appears from the excitation of these electrons when they absorb energy from the
visible light falling on the crystals. Just like the above cases, excess Lithium makes LiCl
crystals pink and excess Potassium makes KCl crystals violet (or lilac).
Consequences of metal excess defect
The existence of free electrons in crystals them to be coloured. Because of the presence of
free electrons, conduct electricity and are semiconductors. Because the electric transport is
mostly accomplished by “excess” electrons, these are referred to as n-type (n for negative)
semiconductors. Because of the existence of unpaired electrons at lattice sites are
 paramagnetic. When the crystal is exposed to white light, the trapped electron absorbs
some of it in order to be stimulated from the ground state to the excited state. Color is
created as a result of this transition. These are known as F-centres.

The metal excess defect is caused by the presence of extra cations at the interstitial sites at
room temperature, Zinc oxide is white. When it gets heated, it loses oxygen and turns from
white to yellow.
ZnO Zn2+ + ½O2 + 2e– (in presence of heat)
there is now an excess of Zinc in the crystal and its formula becomes Zn1+xO. The extra
Zn2+ ions get shifted to interstitial sites and the respective electrons to neighboring
interstitial sites.

• Metal Deficiency Defect

These solids have less amount of metal as compared to stoichiometric proportion.
A perfect example of this type is FeO which is mostly found with a composition of Fe0.95O. It
may range from Fe0.93O to Fe0.96O. In the crystals of FeO, there is a loss of positive charge due
to the missing Fe2+ cations. The loss of charge is covered by the presence of the Fe3+ ions to
make the substance electrically stable.