UNIT-I

Crystal Defects
Introduction:
Crystal is defined as regular and periodic arrangement of atoms in three
dimensions. But no crystal is perfectly regular which means crystal possesses
some defects.
The disturbance occurred in the regular arrangement of atoms or molecules
(may be at a point / along a line / in a region) is called crystal defect or
imperfection.
The concept of ideal crystal is nothing but a crystal without any defect or
imperfection. But in the real crystals this is not possible, because in every crystal
at least few imperfections are exists. Some defects are important and most
useful whereas other defects are useless.
Classification of crystal defects:
Crystal defects or imperfections can be classified on the basis of their geometry
and are four types i.e.
1. Point defects (Zero dimensional)
2. Line defects (One dimensional)
3. Surface defects (Two dimensional)
4. Volume defects (Three dimensional)
(1) Point defects:
 Point defects / imperfections are also called as Zero-dimensional
imperfections. In a crystal lattice, point defect is one which is completely
local in its effect, i.e. a vacant lattice site.
 The point defects are formed due to the missing of atoms or due to the
presence of extra /interstitial atom in the crystal.
 The point defects are again classified into four types they are
(a) Vacancy, (b) Interstitials, (c) Compositional and (d) electronic defects.
(a) Vacancy defect:
 When an atom is missing from its normal position, then the defect is called
as vacancy defect. (Or) An empty site of an atom in a crystal is called
vacancy.

Fig. Vacancy defect.

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Schottky Defect:
 The schottky defect is closely related to vacancies. It is formed when a
cation and anion are removed from a normal lattice site and replaced in
an average position on the surface of the crystal.
 A pair of one cation and one anion can be missing from an ionic crystal.
Hence ion vacancies are called as schottky defect.
 The concentration of schottky defect decreases the density of the crystal.
Crystals such as NaCl, KCl, KBr etc. show Schottky defect.

Fig.Schottky defect.

(b) Interstitial defect:

 A small sized atom occupying the void space in the parent crystal
disturbing the parent atoms from their regular sites is a interstitial impurity.

Fig.Interstitial defect.
Frenkel Defect:
 The frenkel defect is closely related to the interstitial defect. In the case of
ionic crystals, “an ion is displaced from the lattice into an interstitial site” is
called as frenkel defect.
 An atom leaves the regular site and occupies interstitial position. Such
defects are called Frenkel defects.

 A frenkel defect is the combination of interstitial defect i.e.

vacancy + interstitial = frenkel defct.

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 The concentration of frenkel defects does not change the density of the
crystal and overall electrical neutrality of the crystal. Crystals such as CaF2,
AgBr, AgI etc. shows the frenkel defect.
 Frenkel and schottky defects together are called as “intrinsic defects”.

Fig. The ion moved from lattice position to interstitial: Frenkel defect.

(c) Compositional defects:

The compositional defects are formed due to presence of unwanted impurities
or due to the doped impurities during the process of crystallization.
The presence of impurity atom in the crystal leads to the compositional defect.
Compositional defects play an important role in the semiconductors which are
specially prepared for diodes and transistors etc.
The compositional defects are again classified into two types: (i) Substitutional
impurity (ii) Interstitial impurity.

(i) Substitutional impurity:

A substitutional impurity refers to a foreign (metal) atom that replaces a
parent/regular atom in the crystal lattice.
For example, in extrinsic semiconductor either third or fifth group atoms
occupy the sites of Silicon or Germanium atoms. If the size of the
substitutional impurity is same as the parent /regular atom then the amount
of strain around will be less, otherwise it will be more.

Fig. Substitutional impurity.

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 (ii) Interstitial impurity:
An interstitial impurity refers to a small sized foreign atom lodging the void
space in the crystal without disturbing any of the parent atoms from their
sites.
The small sized atoms (lower atomic number atoms) such as hydrogen
may fit into the interstitial spaces and these atoms are known as interstitial
spaces and are responsible for the interstitial impurity.

Fig.Interstitial impurity.

(d) Electronic defects:

Electronic defects occur as a result of errors in charge distribution in solids.
Non-uniformity of charge or charge distribution in the crystal is refers to as
electronic defect.
Errors in charge distribution in solids are called electronic defects.
In semiconductors, temperature variation changes the charge
concentration, so the variation of temperature leads to electronic defects.

Fig.Electronic defect.

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 Concentration of Schottky defects in metals (or covalent crystals):
(Calculation of Number of Vacancies at a given Temperature)
In real crystals, there are irregularities of the atomic array in which the atoms are
missing at some regular lattice points such a point is called as a vacancy (or)
Schottky defect.
If an atom leaves from the regular site and migrates to the surface of the
crystal. Such defects are called as schottky defects; the reason for such thing to
happen is thermal energy.

Schottky defect
In spite of lot of care taken in the preparation of crystals, vacancies are
always present in the crystals. The main cause for these defects is thermal
agitation /fluctuations and these vacancies are produced & destroyed
constantly. This defect may be produced by plucking the atoms from its regular
lattice site & shifting them to the surface of the crystal. This process requires
some energy.
In thermal equilibrium, a certain number of lattice vacancies are always present
which can be estimated as follows:
Let us consider Ev is the energy required to move an atom from the regular
lattice site inside the crystal to lattice site on the surface.
Therefore, the amount of energy required to produce ‘n’ number of isolated
vacancies can be written as
U = nEv ------------ (1)
The total number of ways to move ‘n’ number of atoms in a crystal (Let it consists
of ‘N’ atoms/cc) to its surface will be
𝑁!
P = Ncn =(𝑁−𝑛)! 𝑛!-----------------------------(2)

The increase in the entropy due to the formation of ‘n’ vacancies can be
written as S = KB log P ----------------- (3)
The change in the entropy causes change in the free energy F. [the creation of
vacancies produces not only change in the entropy but also change in the
free energy F of the crystal]
Therefore, free energy F = U – TS ----------------- (4)

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Substitute equation (1), (2), and (3) in (4) then we get,
𝑁!
F = nEv – KBT log ((𝑁−𝑛)! 𝑛!)

F = nEv – KBT [log N! – log (N-n)! – log n!]

By Stirling’s approximation, Log x! = x log x – x
F= nEv – KBT [N log N – N – {(N–n) log (N–n) – (N–n) –n log n – n}]
F = nEv – KBT [N log N – (N–n) log (N–n)– n log n]
At thermal equilibrium, the free energy is constant and minimum with respect to
∂𝐹
‘n’ hence, (∂𝑛) 𝑇 = 0
−1 1
1.Ev – KBT [0 – {(N – n).(N−n) + (–1). log (N – n)} – (n. n + 1. log n)] = 0
Ev – KBT [1 + log (N – n) – 1 – log n] = 0
N−n
Ev – KBT log ( )=0
𝑛
N−n
Ev = KBT log ( )
𝑛
𝐸𝑣 N−n
= log ( )
𝐾𝐵 𝑇 𝑛
𝐸𝑣 N−n
exp( )=
𝐾𝐵 𝑇 𝑛

If n<<N then N-n ≈ N

N 𝐸
= exp(𝐾 𝑣𝑇 )
𝑛 𝐵
𝑛 –𝐸𝑣
= exp(𝐾 𝑇 )
𝑁 𝐵
–𝑬𝒗
𝒏 = N exp( )
𝑲𝑩 𝑻

Where ‘n’ represents the number of vacancies created in the crystal.

The above equation indicates that by decreasing equilibrium temperature the
concentration of vacancies decreases.

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 Concentration of Schottky defects in ionic crystals:
In ionic crystals, the formation of pair of vacancies is most favored i.e. an equal
number of positive and negative ion vacancies are produced. The formation of
pairs makes it possible to keep the surface of the crystal electrostatically neutral.
 In ionic crystal, the number of Schottky defects are at a given
temperature can be calculated by assuming an equal number of positive
and negative ion vacancies are present.
 The number of pairs can be related to the total number of atoms present
in the crystal.
Let us consider the energy required to move an ion pair from lattice site inside
the crystal to a lattice site on the surface.
Therefore, the amount of energy required to produce ‘n’ number of isolated
vacancies will be
U = nEP ------------ (1)
The total number of ways that to move ‘n’ number of ion pairs out of ‘N’ number
of ionic molecules in a crystal on to the surface will be
𝑁! 𝑁! 𝑁!
P = [(𝑁−𝑛)! 𝑛!] x[(𝑁−𝑛)! 𝑛!] = [(𝑁−𝑛)! 𝑛!]2 -------------- (2)

We know that, S = KB log P ----------------- (3)

The change in the entropy causes change in the free energy (F),
F = U – TS ----------------- (4)
Substitute equation (1), (2), and (3) in (4) then we get,
𝑁!
F = nEp – KBT log ([(𝑁−𝑛)! 𝑛!]2)
𝑁!
F = nEp – KBT. 2 log ((𝑁−𝑛)! 𝑛!)

Here, Ep is the energy of formation of a pair of ion vacancies.

Using stirling’s approximation, Log x! = x log x – x; then
F = nEp – 2KBT [N log N – N – {(N–n) log (N–n) – (N–n) – n log n – n}]
F = nEp – 2KBT [N log N – (N–n) log (N–n)– n log n]
At thermal equilibrium, the free energy is constant and minimum with respect to
∂𝐹
‘n’ i.e., (∂𝑛) 𝑇 = 0
−1 1
1.Ep – 2KBT [0 – {(N – n).(N−n) + (–1). log (N – n)} – (n. n + 1. log n)] = 0
Ep – 2KBT [1 + log (N – n) – 1 – log n] = 0
N−n
Ep = 2KBT log ( )
𝑛

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 𝐸𝑝 N−n
= log ( )
2𝐾𝐵 𝑇 𝑛
N−n 𝐸
= exp(2𝐾𝑝 𝑇 )
𝑛 𝐵

If n<<N then ‘n’ can be neglected i.e. N-n ≈ N

N 𝐸
≈exp(2𝐾𝑝 𝑇 )
𝑛 𝐵
𝑛 –𝐸𝑝
≈exp(2𝐾 𝑇 )
𝑁 𝐵
–𝐸𝑝
𝒏≈ N exp( )
𝟐𝑲𝑩 𝑻

In case of NaCl crystal Ep = 0.02 eV at room temperature. Therefore, the number

of Schottky defects increase exponentially with increase of temperature.

 concentration of Frenkel defects:

Interstitial atoms are the extra atoms that are squeezed in between regular
atom sites. When an interstitial atom is formed by transferring an atom from a
regular lattice site to an interstitial position and a vacancy is created. The
vacancy associated with the interstitial atom is called frenkel defect.
As in the case of Schottky defect, now we can calculate the number of frenkel
defects present in the crystal in equilibrium at a given temperature.

The internal energy is given by, U = nEi---------------- (1)

Where, ‘Ei‘ is the energy required to displace an atom from regular lattice site to
interstitial position; and ‘n’ is the number of frenkel defects formed.
Let ‘N’ is the Total number of atoms; and ‘Ni‘ is the number of interstitial atoms.
The total number of ways in which ‘n’ frenkel defects can be formed will be
given as
𝑁! 𝑁!
P = [(𝑁−𝑛)! 𝑛!x(𝑁 −𝑛)!
𝑖
] -------------- (2)
𝑛! 𝑖

The increase in the entropy due to the creation of frenkel defects can be

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calculated based on Boltzmann law.
We know that S = KB log P ----------------- (3)
The change in the entropy causes change in the free energy and free energy
(F) is given by
F = U – TS ----------------- (4)
Substitute equation (1), (2), and (3) in (4) then we get,
𝑁! 𝑁!
F = nEi – KBT log [(𝑁−𝑛)! 𝑛!x(𝑁 −𝑛)!
𝑖
]
𝑛! 𝑖

Using stirling’s approximation Log x! = x log x – x; & log (ab) = log a +log b, then
F = nEi – KBT [[N log N – N – {(N–n) log (N–n) – (N–n) + n log n – n}] + [𝑁𝑖 log 𝑁𝑖 – 𝑁𝑖
– {(𝑁𝑖 –n) log (𝑁𝑖 –n) – (𝑁𝑖 –n) + n log n – n}]]
F = nEi – KBT [N log N – N – (N–n) log (N–n) + (N–n) – n log n + n + 𝑁𝑖 log 𝑁𝑖 – 𝑁𝑖 –
(𝑁𝑖 –n) log (𝑁𝑖 –n) + (𝑁𝑖 –n) – n log n + n]
F = nEi – KBT [N log N + 𝑁𝑖 log 𝑁𝑖 – (N–n) log (N–n) – (𝑁𝑖 –n) log (𝑁𝑖 –n) –2n log n]
At thermal equilibrium, the free energy is constant and minimum with respect to
‘n’. Differentiating the above equation with respect to ‘n’ at constant
∂𝐹
temperature (T), i.e., ( ) 𝑇 = 0
∂𝑛
−1 −1
1.Ei – KBT [0 – 0 – {(N – n).(N−n) + (–1). log (N – n)} – {(𝑁𝑖 – n).(𝑁 −n) + (–1). log (𝑁𝑖 –
𝑖
1
n)} – 2(n. n + 1. log n)] = 0
Ei – KBT [1+ log (N – n) + 1 +log (𝑁𝑖 – n) –2 – 2log n] = 0
Ei – KBT [log (N – n)(𝑁𝑖 – n) – log n2] = 0
(N – n)(𝑁𝑖 – n)
Ei – KBT log ( )=0
𝑛2

If n<<N and n<<𝑁𝑖 then ‘n’ can be neglected i.e. N – n ≈ N and 𝑁𝑖 – n ≈𝑁𝑖
N 𝑁𝑖
Ei = KBT log ( )
𝑛2
𝐸𝑖
= log (N 𝑁𝑖 ) – 2 log n
𝐾𝐵 𝑇
𝐸𝑖
2 log n = log (N 𝑁𝑖 ) – 𝐾𝐵 𝑇

Divide both sides by 2 and apply exponential then

–𝑬
n = (𝐍 𝑵𝒊 )𝟏/𝟐 𝐞𝐱𝐩(𝟐𝑲 𝒊𝑻)
𝑩

Therefore, ‘n’ is proportional to(N 𝑁𝑖 )1/2 . The number of frenkel defects increase
exponentially with increase of temperature.

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(2) Line defects:
 Line defects are known as one dimensional defect’s. These defects are also
known as dislocations.
 These defects appear along a line in the crystal geometry.
 These dislocations occur generally due to the presence of incomplete
atomic planes which arise due to growth accidents, thermal stress etc.
 The presence of dislocations in the crystal decreases its mechanical strength.
 A dislocation may be defined as a disturbed region between two
substantially perfect parts of a crystal.
 In general, the line defects are again classified into two categories, (a) Edge
dislocation and (b) Screw dislocation.
(a) Edge dislocation:
 An edge dislocation is created in the crystal by introducing an extra half
plane (or any extra plane that does not extend up to the base of the
crystal).
 Figure(a) shows a perfect crystal, the top sketch depicting a three
dimensional view and the bottom one showing the atoms on the front face.
 From the lower sketch of figure (b), it can be clearly seen that the atoms
above the edge of the extra plane are squeezed together and are in a
state of compression.
 The bond lengths have been compressed to smaller than the equilibrium
value just below the edge of the extra plane the atoms are pulled apart
and are in a state of tension.
 This distorted configuration extends along the edge of the crystal. There is an
extra energy due to the distortion in the region immediately surrounding the
edge of the incomplete plane.
 If one of the plane of atoms glides over another separated by an integral
multiple of interatomic distance is called slip, and slip plane is the plane in
which slip has taken place. In figure (C), XY- is the slip plane.
 If the incomplete extra plane is above the slip plane, then the edge
dislocation is positive and is represented by the symbol ‘┴’.
 If the incomplete extra plane is below the slip plane, then the edge
dislocation is negative and is represented by the symbol ’┬‘as shown in
figure (c).

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Definition of Edge Dislocation: If one of the vertical planes does not extend to
full length but ends in between within the crystal, then it is called as edge
dislocation.

(b) Screw dislocation:

Screw dislocation is defined as a displacement of the atoms in one part of a
crystal relative to the rest of the crystal, forming a spiral ramp around the
dislocation line as shown in figure.
The plane ABCD is the slipped area, ADdislocation line. The name screw follows
the new character of atomic planes which are transferred such that as one
moves around the dislocation line in circuit. Speed of movement of a screw
dislocation is less than the edge dislocation.

Fig. Screw dislocation

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 Burger’s vector:

 Dutch physicist, Jan Burger introduced a vector, which represents the

direction and magnitude of dislocations in crystals, is called Burger’s Vector.
It is represented by ′𝑏⃗’.
 Burgers vector indicates how much and in what direction the dislocation has
been shifted. The magnitude and direction of the dislocation can be
understood from the concept of Burger’s vector.
 Burger’s vector is proportional to the square root of the elastic energy of the
dislocation.
 In most metallic materials, the magnitude of the Burgers vector is equal to the
interatomic spacing of the material, since a single dislocation will offset the
crystal lattice by one close-packed crystallographic spacing unit.
 In edge dislocations, the Burgers vector and dislocation line are at right
angles to one another. In screw dislocations, they are parallel.
Burger’s circuit:
Dislocation in a crystal is represented by a closed loop is called Burger’s circuit.
 Burger’s vector (𝒃
⃗ ) in Edge dislocation:
 As shown in figure (a), let consider a point ‘P’. From this point, we go up atom
by atom by 6 steps, then move towards right by 5 steps, and move down by
6 steps and finally move towards left by 5 steps to reach the starting point ‘P’.
Thus the circuit is closed.
 In figure (b), atoms are missing along edge, called edge dislocation. In this,
circuit is failed to close itself in the region containing edge containing
dislocation. Then the vector is necessary to close the circuit is called Burger’s
vector. Now we have to move an extra step QP to return to P in order to
close the circuit.
 Burger’s vector ⃗b = QP.
 In Edge dislocation, Burger’s Vector (b
⃗ ) is Perpendicular to dislocation line.

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 Fig. Burger’s vector in edge dislocation.
 Burger’s vector (𝒃
⃗ ) in Screw dislocation:
In figure, atoms are missing and gives dislocation in the form of screw called,
screw dislocation. In this, circuit is failed to close itself in the region containing
screw dislocation. Then the vector is necessary to close the circuit is called
Burger’s vector.
In Screw dislocation, Burger’s Vector (𝑏⃗) is Parallel to dislocation line.

Fig.Burger’s vector in Screw dislocation.

 Difference between Edge Dislocation and Screw Dislocation:-

Edge Dislocation Screw Dislocation

1.In this, an edge of atomic plane is 1. In this, only a distortion of the lattice
formed internal to the crystal. planes in the immediate vicinity is
produced.
2. Dislocation line is perpendicular to 2. Dislocation line is parallel to the
the Burger’s vector. Burger’s vector.
3. Edge dislocation moves in the 3. Screw dislocation moves in the
direction of Burger’s vector. direction perpendicular to the
Burger’s vector.
4.It has specific glide plane. 4. It doesn’t have a unique glide
plane.
5.Speed of movement of an edge 5. Speed of movement of a screw
dislocation is greater than that of dislocation is less than that of an Edge
Screw dislocation. dislocation.
6. Edge dislocation is particularly 6. Screw dislocation is especially useful
useful in explaining slip in plastic flow in explaining crystal growth as well as
during mechanical working. slip in plastic deformation.

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(3) Surface defects:
Surface defects/imperfections arise from a change in the stacking of atomic
planes on or across a boundary.
In surface defects, the crystalline irregularity extends in two dimensions. Surface
defects are also called as plane defects. The surface imperfections refer to
regions of distortions that lie about a surface having a thickness of few atomic
diameters.

(4) Volume defects:

Volume defects such as cracks may arise in crystals when they are grown or
while they are used.
 When clusters of atoms are missing, a large vacancy or void is created
which are also a volume defect /imperfection.
 Foreign particle inclusions, large voids and non-crystalline regions which
have the dimensions of the order of 1 or 3 nm are also called as volume
defects/ imperfections.

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