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1.9 THE CRYSTALLINE STATE

1.9.1 TYPES OF CRYSTALS

What is Crystalline Solid? Or What do you understand by Crystalline solid?

What are the properties of crystalline solids?
 A crystalline solid is a solid in which the atoms bond with each other in a regular
Pattern to form a periodic collection (array) of atoms shown in the following figure.
 Here, the local bonding geometry is repeated many times at regular intervals, to produce a periodic
array of atoms that constitutes the crystal structure.
 The most important property of a crystal is periodicity, which leads to what is termed long-range
order.
 The location of each atom is well-known by virtue of periodicity.

Example: Nearly all metals, many ceramics and semiconductors, and various polymers are crystalline
solids.

Example:
Nearly all metals, many ceramics and semiconductors, and various polymers are crystalline solids.

Properties of Crystalline Solids:

 The most important property of a crystal is periodicity, which leads to what is termed long-range
order.
 In a crystal, the local bonding geometry is repeated many times at regular intervals, to produce a
periodic array of atoms that constitutes the crystal structure.
 The location of each atom is well known by virtue of periodicity.
 There is therefore a long-range order, since we can always predict the atomic arrangement anywhere
in the crystal.

Explain the concept of Lattice and Basis using an example:

All crystals can be described in terms of a lattice and a basis. A lattice is an infinite periodic array of geometric
points in space, without any atoms. When we place an identical group of atoms (or molecules), called a basis, at

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each lattice point, we obtain the actual crystal structure. The crystal is thus a lattice plus a basis at each lattice
point. In the copper crystal each lattice point has one Cu atom and the basis is a single Cu atom.

What is Unit cell? Why unit cell is defined? Write about the significance of unit cell of a crystal.
Since the crystal is essentially a periodic repetition of a small volume (or cell) of atoms in three dimensions, it is
useful to identify the repeating unit so that the crystal properties can be described through this unit. The unit
cell is the most convenient small cell in the crystal structure that carries the properties of the crystal. The
repetition of the unit cell in three dimensions generates the whole crystal structure.

Fig.The unit cell of the copper crystal is cubic with Cu atoms at its corners and one Cu atom at the center of each
face. The unit cell of Cu is thus said to have a face-centered cubic (FCC) structure.

Types of Crystal: Simple cubic reduced

sphere structure
1. SC (Simple cubic structure)
2. FCC (Face centered cubic structure)
3. BCC (Body centered cubic structure)
4. HCP(Hexagonal closed pack structure)
5. Diamond Structure
6. Zinc Blend Structue
7. Ionic Structures
8. Etc. FCC unit cell FCC reduced sphere

BCC Unit Cell BCC reduced sphere

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What do you understand by unit cell parameter, coordination number, number of atoms per unit
cell, atomic packing factor? Give suitable example.

Lattice Parameter:

The length of the cubic unit cell is termed the lattice parameter a of the crystal structure. For Cu, for
example, a is 0.362 nm, whereas the radius R of the Cu atom in the crystal is 0.128 nm.

Figure: Lattice parameter a shown in a FCC unit cell.

Q: What is coordination number? Give suitable example to explain the concept of

coordination number.

Coordination number:

The coordination number is the number of nearest neighbor to a particular atom in a crystal which touches that
particular atom. For example, considering a BCC unit cell one atom in the middle is in contact with eight (figure)
of its surrounding atoms. Moreover, each corner atom is shared by eight unit cells and hence each of these atoms
are in touch with eight body centered atoms. Thus the coordination number of a BCC unit cell is eight.

Fig. Coordination number for

BCC crystal

Coordination number of FCC unit cell:

In the FCC lattice each atom is in contact with 12 neighbor atoms. For, example, according to the figure, the face
centered atom in the front face is in contact with four corner atoms and four other face-centered atoms behind it
(two sides, top and bottom) and is also touching four face-centered atoms of the unit cell in front of it. Thus, FCC
coordination number is 12.

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Fig. Calculation of coordination number for FCC Crystal sturcture

Q: What is a and R ration? Give suitable example to explain the concept of a and R
ratio of a certain crystal.

a and R ratio:

The ratio between the lattice parameter and the radius of the atom is called the a and R ratio. It depends on the
types of crystal.

Fig. a-R relation for simple cubic, FCC, BCC crystal

From the figure it is evident that for simple cubic crystal a=2R.
For face centered cubic crystal a2+a2=(4R)2. So, 2a2=16R2 and then, √ a=4R
For BCC crystal, a2+( √ a)2 =(4R)2 and thus 4R= √ a

Describe or explain the FCC crystal structure.

FCC Structure:
One on the common example of FCC structure is Cu crystal. The unit cell of the copper crystal is cubic with Cu
atoms at its corners and one Cu atom at the center of each face, as indicated in Figure. The unit cell of Cu is thus
said to have a face-centered cubic (FCC) structure. The following figure (a and b) shows the closed pack structure
of the unit cell and figure c shows the reduced sphere unit cell structure.

The Cu atoms are shared with neighboring unit cells. Effectively, then, only one-eighth of a corner atom is in the
unit cell and one-half of the face-centered atom belongs to the unit cell. This means there are effectively four
atoms in the unit cell. The length of the cubic unit cell is termed the lattice parameter a of the crystal structure.

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(a) FCC Unit Cell

2R
a
a
a a
(b)
(c)

Figure (a) The crystal structure of copper which is face-centered cubic (FCC). The atoms are positioned
at well- defined sites arranged periodically, and there is a long-range order in the crystal. (b) An FCC
unit cell with close-packed spheres. (c) Reduced-sphere representation of the FCC unit cell. Examples:
Ag, Al, Au, Ca, Cu, γ-Fe (>912 °C), Ni, Pd, Pt, and Rh.

Why FCC crystal structure of Cu is known as a closed-packed crystal structure?

The FCC crystal structure of Cu is known as a close-packed crystal structure because the Cu atoms are packed as
closely as possible. The volume of the FCC unit cell is 74 percent full of atoms, which is the maximum packing
possible with identical spheres.

Explain/Describe the simple cubic structure.

Simple Cubic Structure:

Simple cubic structure has eight corner atoms. The

reduced sphere diagram of simple cubic structure is shown
below. Here the effective number of atom is one per unit
cell. As eight corner atoms each of which are one eighth of
the full atom. The coordination number is six as one single
atom is connected with six neighboring atoms. Atomic
packing factor is 0.52. That means 52% of the unit cell is
occupied by the atoms and the rest 48% is empty. No
metals (except Po) has this crystal structure.
Fig. Left side shows the actual picture of the
unit cell and the right side shows

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Explain/Describe the BCC crystal structure.

BCC Crystal Structure

Iron has a body- centered cubic (BCC) crystal

structure, and its unit cell is shown in the Figure. The
BCC unit cell has Eight Fe atoms at its corners and
one Fe atom at the center of the cell. The volume of
the BCC unit cell is 68 percent full of atoms, which
is lower than the maximum possible packing factor.
Figure a represents the closely packed hard spheres
representing the Fe atoms. The figure b represents a
reduced-sphere unit cell. Here, the effective no of
atoms are 2. One from the center atom and the other
one is consists of eight corner atoms which are one
eighth of a full atom. Here, the coordination number is
eight as we can see from figure b that the center atom
is connected with the eight corner atoms.

What is atomic packing factor? Write about the significance of APF. Calculate and compare the APF for
simple cubic, FCC, and BCC crystal.

Atomic Packing Factor of FCC, BCC, and Simple Cubic Structure:

Atomic packing factor is the ratio between the volumes occupied effectively by the atoms in a unit cell to the
volume of that unit cell. It represents about how densely the atoms are packed inside a unit cell. Also, in other way
we can know about the percentage of empty space inside the unit cell. The atomic packing factor depends on the
types of crystal as the atomic arrangement is different for various types of crystal. The calculation of atomic
packing factor is show below for simple cubic, FCC, and BCC crystals.

Atomic Packing Factor (APF) for simple Cubic Crystal:

The effective number of atoms=8(corner atoms)×1/8=1
Crystal parameter a=2R,
where R=Radius of the unit cell.
Now, the APF=(1×(4/3)πR3 /a3
APF=0.52 (Putting a=2R in the equation)
Atomic Packing Factor (APF) for FCC Cubic Crystal:
The effective number of atoms=8(corner atoms)×1/8+6(Face atoms)×1/2=1+3=4
Crystal parameter √ a=4R or a=2√ R
where R=Radius of the unit cell.
Now, the APF=(4×(4/3)πR3 /a3
APF=0.74 (Putting √ a=4R in the equation)
Atomic Packing Factor (APF) for BCC Cubic Crystal:
The effective number of atoms=8(corner atoms)×1/8+1 center atom=1+1=2
Crystal parameter 4R= √ a or a= √ /4)R
where R=Radius of the unit cell.
Now, the APF=(2×(4/3)πR3 /a3
APF=0.68 (Putting a= √ /4)R in the equation)

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From the above calculation it is evident that FCC has highest packing factor and thus it is most densly
packed than the other types of crystal.
Describe the Hexagonal Closed Pack Structure

Description of Zinc structure/Description of Hexagonal Closed-Pack (HCP) structure:

In zinc, the atoms are arranged as closely as possible in a hexagonal symmetry, to form the hexagonal close-
packed (HCP) structure shown in Figure. This structure corresponds to packing spheres as closely as possible first
as one layer A, as shown in Figure. One can visualize this by arranging six pennies as closely as possible on a
table top. On top of layer A one can place an identical layer B, with the spheres taking up the voids on layer A,
as depicted in Figure. The third layer can be placed on top of B and lined up with layer A. The stacking sequence
is therefore ABAB. . . . A unit cell for the HCP structure is shown in Figure, which shows that this is not a cubic
structure.

The atomic packing density in the HCP crystal structure is 74 percent, which is the same as that in the FCC
structure.

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What is crystal direction and Plane?

Crystal Directions, Planes, and Miller indices:

Inside the crystal, there exists certain directions along which large concentration of atoms exists.
To specify a certain position of an atom or to specify a specific direction in a crystal a convention
is used which is call crystal directions. Crystal planes are defined as some imaginary planes
inside a crystal in which large concentration of atoms are present. The convention used to
identify the position or direction of the plane is called miller indices.

Why knowing of crystal direction is necessary? Or What is the significance of crystal direction?

In explaining crystal properties, we must frequently specify a direction in a crystal, or a

particular plane of atoms. Many properties, for example, the elastic modulus, electrical
resistivity, magnetic susceptibility, etc., are directional within the crystal.

How the unit cell of crystals are identified/represented?

As a convention, we generally represent the geometry of the unit cell as a parallelepiped with sides a, b,
and c and angles α, β, and γ, as depicted in the following Figure. The sides a, b, and c and angles α, β, and
γ are referred to as the lattice parameters. To establish a reference frame and to apply three-dimensional
geometry, we insert an xyz coordinate system. The x, y, and z axes follow the edges of the parallelepiped
and the origin is at the lower-left rear corner of the cell. The unit cell extends along the x axis from 0 to
a, along y from 0 to b, and along z from 0 to c.

For Cu and Fe, the unit-cell geometry has a = b = c, α = β = γ = 90°, and cubic symmetry. For Zn, the
unit cell has hexagonal geometry, with a = b ≠ c, α = β = 90°, and γ = 120°

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Explain, how to specify directions in a crystal or unit cell?

As an example, the following Figure shows a direction whose indices are to be determined. The following
steps are required to find the direction indices.
o To find the direction indices of a line inside a unit cell, first of all we need to consider the
direction moved to pass through the origin. As all
parallel vectors have the same indices.
o We need to consider a point P that passing through the
unit cell. It is generally convenient to place P where the
line cuts a surface (though this is not necessary).
o Now we need to find the coordinates xo, yo, zo where
xo, yo, and zo are projections from point P onto the x,
y, and z axes, respectively, as shown in Figure.

o We can express these coordinates in terms of the

lattice parameters a, b, and c, respectively. We then
have three coordinates, say x1, y1, and z1, (dividing xo, yo, and zo by the lattice parameters a, b,
and c respectivly). For example, if

o We then multiply or divide these numbers until we have the smallest integers (which may
include 0). If we call these integers u, v, and w, then the direction is written in square brackets
without commas as [uvw]. If any integer is a negative number, we use a bar on top of that
integer. For the particular direction in Figure, we therefore have [121].

What is family direction?

Certain directions in the crystal are equivalent because the differences between them are based only on
our arbitrary decision for labeling x, y, and z directions. For example, [100] and [010] are different
simply because of the way in which we labeled the x and y axes. Indeed, directional properties of a
material (e.g., elastic modulus, and dielectric susceptibility) along the edge of the cube [100] are
invariably the same as along the other edges, for example, [010] and [001]. All of these directions
along the edges of the cube constitute a family of directions, which is any set of directions considered to
be equivalent. We label a family of directions, for example, [100], [010], [001], . . . , by using a common

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notation, triangular brackets. Thus, <100> represents the family of six directions, [100], [010], [001],
[ ̅ 00] , [010] , and [001] in a cubic crystal. Similarly, the family of diagonal directions in the cube, shown
in Figure b, is denoted <111> which has eight members.

[ ̅ 00]

[00 ̅ ]

Fig. a Family of <100> directions Fig. b

How many direction are there in <110> plane? Show using suitable diagram
There are twelve directions in <110> plane.

The members are (110)(011)(101)( ̅ 10)( ̅ ̅ ̅ ̅ ̅ (0 ̅ 1)(01 ̅ )( ̅ ̅ )( ̅ 10 ̅ .

Figure show two members of the <110> direction.

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Crystal Plane indices or Miller indices:

Sometimes we need to describe a particular plane in a crystal. The convention used to describe a
plane inside a crystal is called Miller indices.

How to Find Miller Indices of a Crystal Plane?

For determining indices of a crystal plane we should consider the axis in a way that the plane
does not go through the origin. To find the Miller Indices we need to follow the following steps.

o We need to take the intercepts xo, yo, and zo of the plane on the x, y, and z axes,
respectively. If the plane passes through the origin, we can use another convenient
parallel plane, or simply shift the origin to another point.
o We express the intercepts xo, yo, and zo in terms of the lattice parameters a, b, and c,
respectively, to obtain x1, y1, and z1.
o We then invert these numbers. Taking the reciprocals
o Then we need to normalize the values to remove the fractions.
o The resulting number shows the Miller Indices of the plane.

Show that All planes that have been shifted by a lattice parameter have identical Miller
indices.

It can be explained from the following planes of the figure below.

From the above figure we find that all the planes have same Miller indices who are
separated by a factor of crystal parameter. In the same way we can prove that if the
plane is parallel but not separated by crystal parameter, the Miller indices will be
different. (do by yourself)

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Planner Concentration:
Planner concentration is the ratio between the effective number of atoms in a certain crystal
plane and the area enclosed by the plane. The concept of planner concentration can be described
using suitable example planner concentration of a FCC unit cell for (100), (110), and (0 ̅ 2)
planes.

(100) plane:

The area is a2 and

the effective no of atoms are (1 middle atom+4 corners× atoms)=2

Thus the planer concentration n(100)=

(110) plane:

The area is (a√ )2 and

the effective no of atoms are (2 face atoms × atoms+4 corner atoms× atoms)=1+1=2

n(110)=

(0̅2) plane:

The area is a× 2× (a2+0.5a2)1/2

Effective no of atoms are (4 corner atoms× atoms+1 middle atom)=2

̅ =2/( a× 2× (a2+0.5a2)1/2 )

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Crystal Defects
What are the origins of crystal defects? Why we need to study about crystal defects?

What happens when the crystal is grown from a liquid or vapor; do you always get a perfect crystal?
What happens when the temperature is raised? What happens when impurities are added to the solid?
There is no such thing as a perfect crystal. When the crystal is grown from liquid or vapor there mush
be some impurities. Thus we do not get perfect crystal. Moreover, when the temperature raises changes
occurs in the crystal structure. We must therefore understand the types of defects that can exist in a given
crystal structure. Quite often, key mechanical and electrical properties are controlled by these defects.

POINT DEFECTS:
There are two types of Point defects. One is vacancy and the other one is impurity.

VACANCIES (How vacancy creats)

Above the absolute zero temperature, all crystals have atomic vacancies or atoms missing from lattice
sites in the crystal structure. The vacancies exist as a requirement of thermal equilibrium and are called
thermodynamic defects. Vacancies introduce disorder into the crystal by upsetting the perfect
periodicity of atomic arrangements.

How vacancy shifts in a crystal:

We know from the kinetic molecular theory that all the atoms in a crystal vibrate about their equilibrium
positions with a distribution of energies, a distribution that closely resembles the Boltzmann
distribution. At some instant, there may be one atom with sufficient energy to break its bonds and jump to
an adjoining site on the surface, as depicted in Figure. This leaves a vacancy behind, just below the
surface. This vacancy can then diffuse into the bulk of the crystal, because a neighboring atom can
diffuse into it. This latter process of vacancy creation has been shown to be a sequence of events in
Figure.

Vacancy formation energy:

Suppose that Ev is the average energy required to create such a vacancy. Then only a fraction,
exp(−Ev∕kT), of all the atoms in the crystal can have sufficient energy to create vacancies. If the
number of atoms per unit volume in the crystal is N, then the vacancy concentration nv is given by

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= No of atoms per unit volume × fractional percentage of vacancy

How vacancy creates distortion?

We have shown the vacancy to be the same size in the lattice as the missing
atom, which is not entirely true. The neighboring atoms around a vacancy
close in to take up some of the slack, as shown in Figure. This means that
the crystal lattice around the vacancy is distorted from the perfect
arrangement over a few atomic dimensions. The vacancy volume is therefore
smaller than the volume of the missing atom. Point defects generally involve
lattice changes or distortions of a few atomic distances.

Fig. Defects due to vacancy

Impurities: Impurities are one kind of point defect that can present in the crystal. Impurities can come
during the synthesis intentionally or unintentionally. There are two types of impurities can be present in
the crystal. i) Substitutional impurities, ii) Interstitial impurities.
Crystal defects occurs due to both types of impurities. When a host atom replaces or substitutes by any
other external atom than it is called subtitutional impurity. On the other hand any external atom comes in
the interstitial area rather than substitute then it is termed as substitutional impurities. The following
figure shows these two types of impurities. Figure (a) shows that crystal has been deformed due to the
presence of impurity atoms which size is greater than the host atom. On the other hand figure (b) show the
crystal defect due to impurity atoms which size is less than the host atom. Figure (c) show the crystal
deformation due to interstitial impurity atom.

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Point defect in Ionic crystal:

There are also defects in Ionic Crystals. These are i) Schottky Defect and ii) Frenkel defect, iii)
Substitutional impurities.

Schottky Defect:
In an ionic crystal, such as NaCl, which consists of anions (Cl−) and cations (Na+), if there is a missing of
cation–anion pair (which may have migrated to the surface), so the neutrality is maintained, as indicated
in Figure. These Schottky defects are responsible for the major optical and electrical properties of alkali
halide crystals.

Frenkel defect:
Frenkel defect occurs when a host ion is placed into an interstitial position, leaving a vacancy at its
original site. The interstitial ion and the vacancy pair constitute the Frenkel defect, as identified in
Figure.

Substitutional Imputities: Ionic crystals can also have substitutional and interstitial impurities that
become ionized in the lattice.
Overall, the ionic crystal must be
neutral. Suppose that an Mg2+ ion
substitutes for an Na+ ion in the
NaCl crystal, as depicted in Fig. b.
Since the overall crystal must be
neutral, either one Na+ ion is
missing somewhere in the crystal, or
an additional Cl− ion exists in the
crystal. Similarly, when a doubly
charged negative ion, such as O2−,
substitutes for Cl−, there must either be an additional cation (usually in an interstitial site) or a missing
Cl− somewhere in order to maintain charge neutrality in the crystal.

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