Crystal Physics

Crystalline Amorphous
A crystalline solid possesses rigid and long-range order. In a crystalline solid,
atoms, molecules or ions occupy specific (predictable) positions.
An amorphous solid does not possess a well-defined arrangement and long-
range molecular order.
Crystallinity: Repeating or periodic array over large atomic distances. 3-D
pattern in which each atom is bonded to its nearest neighbors
Crystal structure: the manner in which atoms, ions, or molecules are spatially
arranged.

Crystallization: The formation and growth of a crystal is called crystallization.

Space Lattice A lattice is also called a Space Lattice

An array of points in space such that every point has identical surroundings

Lattices ‘have translational periodicity’

or
Translationally periodic arrangement of points in space is called a lattice
2D Lattices

B P
r

o A

b
a
Two distances: a, b
b
a There are three lattice parameters which describe this lattice
One angle:
Two basis vectors generate the lattice = 90 in the current example
Unit cell: small repeating entity of the atomic structure.
The basic building block of the crystal structure. It defines the entire crystal
structure with the atom positions within.

lattice
point

Unit Cell Unit cells in 3 dimensions

 Nonprimitive cell

Primitive
cell

Primitive
cell
 How is a crystal formed?
Crystal = Lattice + Motif
Motif or basis:
an atom or a group of atoms associated with each lattice point

Lattice Crystal

Translationally periodic arrangement of Translationally periodic arrangement

points of motifs

Lattice the underlying periodicity of the crystal Lattice how to repeat

Basis atom or group of atoms associated with each lattice points Motif what to repeat
Lattice Crystal

Motif
+ =
Lattice Parameters 6 lattice parameters
3 distances (a, b, c)
3 angles ( , , )
Bravais Lattice: various viewpoints
Bravais concluded that there are only 14 possible Space Lattices (with Unit Cells to represent them).
These belong to 7 Crystal systems.

Crystal System Lattice Parameters

Cubic (a = b = c, = = = 90 )
Tetragonal (a = b c, = = = 90 )
Orthorhombic (a b c, = = = 90 )
Hexagonal (a = b c, = = 90 , = 120 )
Trigonal (a = b = c, = = 90 )
Monoclinic (a b c, = = 90 )
Triclinic (a b c, )
Bravais lattices and their crystal systems

Crystal System Bravais Lattices P Primitive

P I F C I Body Centred
1 Cubic F Face Centred
2 Tetragonal C A/B/C- Centred
3 Orthorhombic
4 Hexagonal
5 Trigonal
6 Monoclinic
7 Triclinic
Arrangement of lattice points in the Unit Cell
& No. of Lattice points / Cell

Position of lattice points Effective number of Lattice points / cell

1 P 8 Corners = [8 (1/8)] = 1

8 Corners
2 I + = [1 (for corners)] + [1 (BC)] = 2
1 body centre
8 Corners
3 F + = [1 (for corners)] + [6 (1/2)] = 4
6 face centres
A/ 8 corners
4 B/ + = [1 (for corners)] + [2 (1/2)] = 2
C 2 centres of opposite faces
 P I F C
1 Cubic Cube

I
P

a b c 90

F
Lattice point
 P I F C
2 Tetragonal Square Prism (general height)

I
P

a b c
90
 P I F C
3 Orthorhombic Rectangular Prism (general height)

One convention
a b c
I
P

a b c
90

F C
 P I F C
4 Hexagonal 120 Rhombic Prism

a b c
90 , 120
 P I F C
5 Trigonal Parallelepiped (Equilateral, Equiangular)
Rhombohedral

a b c
90
 P I F C
6 Monoclinic Parallogramic Prism

One convention
a b c a b c
90
 P I F C
7 Triclinic Parallelepiped (general)

a b c
Simple crystal structures
 Simple Cubic (SC) structure

Packing Factor a a
Volume of atoms in unit cell Coordination Number (N) = 6
PF =
Volume of unit cell
volume a
atoms atom
4 3
R=0.5a
unit cell 1 p (0.5a)
3
APF = close-packed directions
a3 volume contains 8 x 1/8 =
1 atom/unit cell
unit cell
PF for a simple cubic structure = 0.52
 Body Centered Cubic (BCC) Structure

2 atoms/unit cell: 1 center + 8 corners x 1/8

Coordination Number (N) = 8
atoms volume
4 3
unit cell 2 p ( 3a/4) atom 3a
3
PF =
volume
a3 a
unit cell

R 2a
a
PF for a body-centered cubic structure = 0.68 Close-packed directions:
length = 4R = 3 a
Face Centered Cubic (FCC) Structure

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

Coordination Number (N) = 12
Close-packed directions:
length = 4R = 2 a
atoms volume
2a 4 3
unit cell 4 p ( 2a/4)
3 atom
PF =
volume
a a3
unit cell
PF for a face-centered cubic structure = 0.74
Hexagonal Close-Packed Structure (HCP)
Coordination Number (N) = 12

6 atoms/unit cell
AB,AB... Stacking Sequence

A sites Top layer

c
B sites Middle layer
A sites Bottom layer
a

3D Projection 2D Projection
 𝒄
Calculation of ratio
𝒂

In Δ AA’B,
AA’
cos30° = AB
3
AA’ = AB cos30° = 𝑎
2
From Figure,
2 2
AX = 3 𝐴𝐴′ 𝑎2 𝑐 2
𝑎2 = +
AX =
2
x 𝑎
3 3 2
3
𝑎
2 𝑐2
8
AX = = = 1.633
3 𝑎2 3
 Calculation of packing factor
Area of the base = 6 X Area of equilateral triangle (ABO)
1
6 X 2 BO.AA’
3
3 X a. 𝑎
2
3 3𝑎2
2

(2r=a r=a/2)

PF for a HCP structure = 0.74

Diamond Structure
Diamond is an allotrope of carbon where the each carbon atom is bonded covalently with other surrounding four
carbon atoms and are arranged in a variation of the face centered cubic crystal structure called a diamond lattice

• Space lattice of diamond is face-centered cubic

• This structure is a combination of two interpenetrating face-
centered-cubic (FCC) sub lattices
• It is composed of two fcc lattices displaced from each other
𝟏 𝟏 𝟏
by one quarter of a body diagonal, , ,
𝟒 𝟒 𝟒
 𝟏 𝟏
Number of atoms per unit cell = 𝟖 × 𝟖 + 𝟐 × 𝟔 + 𝟒 = 𝟖
Coordination Number (N) = 4

Atomic Radius Packing Density

1 𝑁𝑜. 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑈𝑛𝑖𝑡 𝐶𝑒𝑙𝑙 × 𝑉𝑜𝑙. 𝑜𝑓 𝑜𝑛𝑒 𝑎𝑡𝑜𝑚

2𝑟 = × 𝐵𝑜𝑑𝑦 𝐷𝑖𝑎𝑔𝑜𝑛𝑎𝑙 𝑜𝑓 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑃𝐹 =
4 𝑉𝑜𝑙. 𝑜𝑓 𝑡ℎ𝑒 𝑈𝑛𝑖𝑡 𝐶𝑒𝑙𝑙
1 3
2𝑟 = × 3𝑎 Y 4 4 3
4 8 × 3 𝜋𝑟 3 8 × 3 𝜋 8 𝑎
𝑃𝐹 = =
3𝑎 𝑎3 𝑎3
∴𝑟= 3𝑎 𝑎
8
4 3𝜋
4 𝑃𝐹 = = 0.34
𝑎 Z 16
X 4 𝑎
4
𝑎 T
4
Graphite Structure
The carbon atom is arranged in regular hexagons in flat parallel
layers Such that each atom is linked by the neighboring atoms
Bond length = 1.42 Å
Bond angle = 120°
The sheets are held together in a crystal by Vander Waals force
with a spacing about 3.4 Å
Crystal planes or Lattice planes
• The periodic arrangement of atoms or ions in a natural crystal produces parallel equidistant
planes.
• These parallel and equidistant planes formed by the periodic arrangement of atoms or ions in a
natural crystal are said to be crystal planes.
Miller indices
• William Hallowes Miller introduced a method to represent a crystal planes.
• According to Miller the crystallographic planes are specified in terms of indexing schemes.
• The planes are indexed using the reciprocals of the axial intercepts.

The Miller indices are the set of numbers, used to represent a crystal plane, obtained from the
reciprocals of the intercepts made by the crystal planes.

Algorithm:
(i) The intercepts made by the plane are noted and they should
be written in terms of the lattice constants, a, b and c.
(ii) The coefficients of the intercepts are noted.
(iii)Find the inverse of these coefficients.
(iv) Find LCM and then multiply the fractions by LCM.
(v) Write the integers within the parenthesis.
(vi) The integers written within the parenthesis represent the
Miller indices of the given plane.
Crystallographic Planes
z
example a b c
1. Intercepts 1 1 c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2 c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100)
(200) a b
x
Relation between the interplanar distance (d) and interatomic distance (a):
‘d’ spacing in cubic lattice
• The distance between any two adjacent atoms of the same kind is known as interatomic distance.
• The distance between any two successive parallel planes is known as interplanar distance.

𝑂𝑁 𝑑 𝑑ℎ
cos 𝛼 ′ = =𝑎 =
𝑂𝐴 ℎ 𝑎
𝑂𝑁 𝑑 𝑑𝑘
cos 𝛽 ′ = =𝑎 =
𝑂𝐵 𝑘 𝑎
𝑂𝑁 𝑑 𝑑𝑙
cos 𝛾 ′ = =𝑎 =
𝑂𝐶 𝑙 𝑎
From the properties of the direction cosines, we have

𝑐𝑜𝑠 2 𝛼 ′ + 𝑐𝑜𝑠 2 𝛽 ′ + 𝑐𝑜𝑠 2 𝛾 ′ = 1

𝑑ℎ 2 𝑑𝑘 2 𝑑𝑙 2
+ + =1
𝑎 𝑎 𝑎
𝑑2
𝒂
𝑎2
ℎ2 + 𝑘 2 + 𝑙 2 = 1 𝒅=
𝒉𝟐 + 𝒌𝟐 + 𝒍𝟐
CRYSTAL DEFECTS
A defect or an imperfection is any deviation from the perfect periodic
arrangement of atoms observed in real crystals.

Classification of defects:
The defects found in real crystals are classified into four main categories.
1. Point defects (Zero dimensional defects)
2. Line defects or dislocations (One dimensional defects)
3. Planar defects (Two dimensional defects)
4. Volume defects (Three dimensional defects)
1. POINT DEFECTS
A point defect is a localized interruption in the regularity of the crystal lattice.

• The point defects can be divided into four types, namely

(i) Vacancies or Schottky defects,
(ii) Interstitials, or Frenkel defects,
(iii) Impurities and
(iv) Electronic defects.

 It produces strain in a small volume of the crystal surrounding the defect,

but does not affect the perfection of distant parts of the crystal.
(i) VACANCIES
A vacancy is the absence of an atom from a site normally occupied in the lattice.
● A vacancy is an atomic site from which the
atom is missing.
● Vacancies form in close packed metallic
structures.
● The concentration of vacancies in a crystal
depends on the temperature.
SCHOTTKY DEFECT
• In case of ionic crystals, the formation of a vacancy requires a local readjustment of
charge such that charge neutrality is maintained in the crystal as a whole.
• Therefore, a pair of vacancies arises due to missing of one cation and one anion from the
structure. Such a pair of vacant sites is called a Schottky defect.

 Schottky defects are ion vacancies.

 A Schottky defect is the combination of one cation
vacancy and one anion vacancy.
 This type of point defect forms in ionic crystals.
 The concentration of Schottky defects decreases
the density of the crystal.
(ii) INTERSTITIALS
• An interstitial is an atom on a non-lattice site,

 An interstitial defect arises when an atom

occupies a position in the lattice that is not
normally occupied in the perfect crystal.

 Interstitial atom produces lattice strain

because it tends to push the surrounding
atoms further apart.
FRENKEL DEFECT

 In case of ionic crystals, an ion displaced

from the lattice site into an interstitial site is
called a Frenkel defect.
 A Frenkel defect is the combination of one
cation vacancy and one cation interstitial
defect.
(iii) IMPURITIES
• An impurity is the substitution of a regular lattice atom with an atom
that does not normally occupy that site.
 (a) An impurity atom may replace an atom of the parent lattice site.
Such impurities are known as substitutional impurity or substitutional
defect.
 (b) Or an impurity may occupy an interstitial position which is a
non-atomic site. These impurities are known as interstitial impurities.
(a) Substitutional impurity
• A substitutional impurity arises when a host atom in the lattice is
replaced by a foreign atom. The substitutional atom remains in at the
regular lattice site.
 (b) Interstitial impurity

• An interstitial impurity is a small sized

atom occupying the void space in the
parent crystal, without dislodging any of
the host atoms from its site.
 (iv) ELECTRONIC DEFECTS
• Errors in charge distribution in solids
are called electronic defects.
• These defects are produced when
the composition of an ionic crystal
does not correspond to the exact
stoichiometric formula.
• Stoichiometry is a state for ionic
compounds where there is the exact
ratio of cations to anions as
predicted by the chemical formula.
2. Line defects or dislocations
• Line defects are one-dimensional defects and are also called dislocations.
• Dislocations are areas were the atoms are out of position in the crystal
structure.
• A dislocation is a one-dimensional defect around which some of the atoms
are misaligned.
• They may be defined as disturbed region between two perfect parts of a
crystal.
Dislocations are divided into two basic types:
(i) Edge dislocation, and
(ii)Screw dislocation.
 (i) Edge Dislocation
 Edge Dislocation arises when
one of the vertical planes does
not extend to the full length of
the crystal.

 The plane abruptly terminates

in between, within the crystal.

 It may be viewed as an extra

half-plane inserted between a
set of parallel planes

Within the region around the edge, there is some localized distortion. This
distortion is known as edge dislocation.
 (ii) Screw dislocation
 Screw Dislocation is due to a displacement of
atoms in one part of a crystal relative to rest of
the crystal.

 In a screw dislocation, there is a line of atoms

about which the crystal planes are twisted to
give a effect similar to threads of a screw (OO’
indicates the dislocation line)

 The term screw represents that one part of

crystal is moving in spiral manner about the
dislocation line.

 If the spiral motion of one part of the crystal is

in clockwise direction then, the dislocation is
right handed, on the other hand spiral motion
is anti-clockwise direction then, the dislocation
is left handed.
 BURGER’S VECTOR
 Dislocations are described by the Burger’s vector, and it is denoted by 𝑏. It indicates
the magnitude and direction of lattice distortion associated with a dislocation in a
crystal.
 The Burger vector of an edge dislocation is perpendicular to the dislocation line and
that of a screw dislocation is parallel to the dislocation line. In case of dislocations of
mixed nature, the vector 𝑏 will be neither perpendicular nor parallel to the dislocation
line.
 The magnitude of Burgers vector is found by drawing a closed circuit, called the
Burgers circuit surrounding the dislocation line.
 Burger’s circuit - Edge dislocation Burgers vector of an edge dislocation is perpendicular to the dislocation.

 In the case of a perfect crystal,

consider a point P which moves in a
particular direction and it completes
the atomic distances in the form of
a circuit.
 In the case of a crystal containing
edge dislocation, starting from P if
we trace the Burgers circuit in a
plane normal to the dislocation line,
the circuit would not be completed
since the end point Q and the
starting point P do not coincide.
From Q, we need an extra step “b” to arrive at the starting point P. This extra step QP = b is called Burgers
vector (BV).

 The Burgers vector gives both the magnitude and direction of the displacement.
BV = QP = b
 The Burgers vector of a screw dislocation is parallel to the dislocation.
Burger’s circuit - Screw dislocation

 In the perfect crystal, starting from P, if we trace the Burgers circuit, the circuit is a closed path PMNOP.
 In case of a crystal with a screw dislocation, the circuit would not be completed and requires an extra
step b = FA, parallel to the dislocation axis, to close the circuit. This additional vector b is Burgers
vector.
3. Planar defects or Surface Defects
Defects on the surface of the material are called surface defects.

Planar defects are two dimensional defects that separate two regions of the crystal.

These defects are: (a) external surfaces, (b) grain boundaries, (c) twin boundaries, and (d) stacking faults.

(a). External surfaces

The surface of a crystal itself is a defect. The surface atoms have formed bonds with neighbours only on
one side, whereas the atoms inside the crystal formed bonds with neighbours on either side of them.
(b) Grain boundaries

A grain Boundary is a general planar defect that separates

regions of different crystalline orientation within a
polycrystalline solid.

A grain boundary is formed when two growing grain

surfaces meet. The shape of the grain is usually influenced
by the presence of surrounding grains.

This type of defects generally takes place during the

solidification of the liquid metal.
(c) Twin boundaries

If the boundaries in which the atomic arrangement

on one side of the boundary is somewhat a mirror
image of the arrangement of atoms of the other
side, the defect caused is called Twin Boundary.
(d) Stacking faults

Whenever the stacking of atoms is not in proper sequence throughout the crystal, the defect
caused is called stacking fault.

An FCC (face centered cubic) crystal is

regarded as formed by the stacking of
hexagonal close packed atomic layers, A, B
and C in the following sequence:

ABC ABC ABC …………..

If one of the layers go missing, then stacking

fault occurs in the crystal.

If the sequence changes to

ABC ABC BCA …….., then the sequence is
interrupted and a stacking fault is produced.
4. Volume defects
 Volume defects such as cracks may arise in crystals during the process of crystal
growth.
 A large vacancy may arise due to missing of clusters of atoms which is a volume
defect.
 Inclusion of foreign particles or non-crystalline regions of the size of 20 Å also
belong to the category of volume defects.