UNIT I

CRYSTAL STRUCTURE
Solid State Physics
Solid state physics is the study of how atoms arrange themselves into solids and what
properties these solids have. The atoms arrange in particular patterns because the patterns
minimize the energy in a binding, which is typical with more than one neighbour in a solid. An
ordered (periodic) arrangement is called crystal, a disordered arrangement is called amorphous.
In the other hand, solid-state is that particular aggregation form of matter characterized by
strong interaction forces between constituent particles (atoms, ions, or molecules). As a result, a
solid state material has an independent geometric form (in contrast to liquids, which take the
form of the container) and an invariant volume (in contrast to gases/vapours) in given
temperature and pressure conditions. As temperature increases, a solid state material can evolve
into another aggregation form (liquid or gas). Solid state physics studies the structural,
mechanical, thermodynamic, colour, density, elasticity, electrical, magnetic, and optical
properties of (poly-)crystalline and non-crystalline solids (for example, amorphous materials,
such as glass) and more.
Crystal Structure
A crystal structure is made of atoms. A crystal lattice is made of points. A crystal system
is a set of axes. In other words, crystal structure is obtained by attaching atoms, groups of
atoms or molecules. This structure occurs from the intrinsic nature of the constituent particles
to produce symmetric patterns. A small group of a repeating pattern of the atomic structure is
known as the unit cell of the structure. A unit cell is the building block of the crystal structure
and it also explains in detail the entire crystal structure and symmetry with the atom positions
along with its principal axes. The length, edges of principal axes and the angle between the unit
cells are called lattice constants or lattice parameters.
We will often imagine a solid as one single crystal, a perfect lattice of atoms without any
defects whatsoever, and it may seem that such perfect crystals are not particularly relevant for
real materials. But this is not the case. Many solids are composed of small crystalline grains.
These solids are called polycrystalline, in contrast to a macroscopic single crystal, but the

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number of atoms in a perfect crystalline environment is still very large compared to the number
of atoms on the grain boundary. For instance, for a grain size on the order of 10003 atomic
distances, only about 0.1% of the atoms are at the grain boundaries. There are, however, some
solids that are not crystalline. These are called amorphous. In other words, the materials in
which atoms are arranged irregularly are known as amorphous. The amorphous materials
have no long-range order, however, there may be some short-range order between the atoms.
But, it has least their optical properties are similar to that of crystalline materials because the
wavelength of the incident photons (1 μm) is much larger than the lattice constant of crystals.
Other properties of non-crystalline materials are derived based on concepts proper to crystalline
solids and, therefore, the crystal structure is extremely important in understanding the
properties of solid state materials. The properties of crystalline solids are determined by the
symmetry of the crystalline lattice.
Lattice
We are most familiar with solid crystalline substances. The physics of solid state is to a
very great extent the physics of crystals. To begin, we need to learn how to describe the regular
geometrical arrangement of atoms in space that is the essence of crystallinity. Crystals are finite
regular arrangements of atoms in space. In practice, the atomic arrangement is never perfect,
but in crystallography, we neglect this aspect and describe crystals by reference to perfect
infinite arrays of geometrical points called lattices. A lattice is an infinite array of points in
space so arranged that every point has identical surroundings (Fig.1.1). All lattice points
are geometrically equivalent. A lattice, therefore, exhibits perfect translational symmetry
(Periodicity) and, relative to an arbitrarily chosen origin, at a lattice point, any other lattice
point has the position vector. The group of points or atoms that is associated with every
lattice point is called a basis (Fig.2). The basis is positioned in a set of mathematical/abstract
points that form the lattice (also called Bravais lattice). A crystal structure is, therefore, the
sum of two quantities: namely a lattice of points and a basis, which is a geometrical
arrangement of atoms associated with every lattice point. Our description of crystals starts with
the mathematical definition of the lattice. A lattice is a set of regularly spaced points with
positions defined as multiples of generating vectors. In two dimensions, a lattice can be defined

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as all the points that can be reached by the vectors r, created from two vectors 𝐚𝟏 and 𝐚𝟐 . In
two dimensions, all Bravais lattice points:
r1  n1a  n2 a2 (1)
We assume that there are 3 non-coplanar vectors a1; a2, and a3 that leave all the
properties of the crystal unchanged after the shift as a whole by any of those vectors. In three
dimensions, the definition is
R0  n1 a1  n2 a 2  n3 a3 (2)
where ni are integers and the lengths of the vectors 𝐚𝟏, 𝐚𝟐 and a3 are often called the lattice
constants. Such a lattice of building blocks (points) is called the Bravais lattice. The crystal
structure could be understood by the combination of the properties of the building block (basis)
and the Bravais lattice. Every point of a Bravais lattice is equivalent to every other point, i.e.
the arrangement of atoms in the crystal is the same when viewed from different lattice points.
The numbers n are necessarily integral and the vectors a, b and c are fundamental units of the
translational symmetry. On the other hand, by definition, the volume associated with a single
lattice point is unique, but since there is a choice regarding the vectors a, b and c, it may take a
variety of shapes as illustrated for a two-dimensional example in Figs 1.1 and 1.2.

Figure 1.1 Two-dimensional Bravais lattice

Fig1.2 Basis of (a) one atom and (b) two atoms

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 The volume associated with a single lattice point is called the primitive cell, and this
usually takes one of two forms. Either the lattice point is confined to the centre of the
primitive cell, which is then determined by the planes bisecting the lines joining the particular
point with its neighbours, or the primitive cell may be described as the unit of the mesh formed
by the lines connecting lattice points (Fig1.3); in the latter case points lie at the vertices of the
cell and this is the primitive cell most often used in crystallography. A special choice of the
primitive unit cell is the Wigner–Seitz cell that is also shown in (Fig. 1.4). where the lattice
point is enclosed within the primitive cell, is called a Wigner-Seitz cell. The basis (lattice point)
can consist of one or several atoms.

Fig. 1.3 The primitive cell has an arbitrary shape but a fixed area or volume.

Fig. 1.4 The Wigner-Seitz cell that surrounds each lattice point.

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Unit Cell:

Fig.1.5 Three dimensional Unit cell

Crystals use x-rays, which excite signals from the atom. The signals given by these
atoms have different strengths, and they usually depend upon the electron density distribution
in closed shells. The signals released by the atoms varies. Lighter the atoms, weaker is their
signals. The mutual arrangement of atoms is also known as crystal structures. Crystal structures
are derived from the physical density and chemical formulas of solids. The smallest group of
symmetrically aligned atoms which can be repeated in an array to make up the entire crystal is
called a unit cell( Fig.15). In other words, the structure of a crystal can be seen to be
composed of a repeated element in three dimensions. This repeated element is known as the
unit cell. It is the building block of the crystal structure. A group of atoms, ions or molecules,
which are arranged together essentially to build the crystal. The unit cells are structured in
three-dimensional space, which describes the bulk arrangement of atoms of the crystal. We
define the unit cell in terms of the lattice (set of identical points). In three dimensions the unit
cell is any parallelepiped whose vertices are lattice points, in two dimensions it is any
parallelogram whose vertices are lattice points. Of course, this definition means that there is an
infinite number of possible unit cells. So, in general, the unit cell is chosen such that it is the
smallest unit cell that reflects the symmetry of the structure. There are two distinct types of the
unit cell:
1. Primitive (or Simple): one lattice point per unit cell.
2. Non-primitive, (or Multiple) e.g. double, triple, etc.: more than one lattice point per
unit cell primitive and non-primitive.

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The primitive unit cell of a lattice contains only one lattice point (Fig.1.6). It is also possible to
define non-primitive unit cells that contain several lattice points. These fill space without
leaving voids when translated through a subset of the Bravais lattice vectors. Possible choices
of a unit cell for a two-dimensional rectangular Bravais lattice are given in Figure 1.6. From the
figure, it is evident that a non-primitive unit cell has to be translated by a multiple of one (or
two) lattice vectors to fill space without voids and overlap.

Fig.1.6 Primitive cell

It was mentioned above that the (eight) lattice points at the corners of the unit cell
contribute only one lattice point to the cell. This is because the lattice points at the corners are
shared between eight unit cells. Each corner lattice point, therefore, is equivalent to 1/8 of a
lattice point per unit cell. Similarly, lattice points on the edge of a unit cell are shared among
four unit cells and are worth 1/4 of a lattice point per unit cell. Lattice points on the face of a
unit cell are shared between two unit cells and are worth 1/2 of a lattice point per unit cell.
Lattice points contained entirely within the unit cell are worth one lattice point per unit cell.
Crystal Systems
Crystal System refers to one of the many classes of crystals, space groups, and lattices.
In crystallography terms, lattice system and crystal, the system are associated with each other
with a slight difference. Based on their point groups crystals and space groups are divided into
seven crystal systems.
Seven Crystal Systems
The seven crystal systems are a method of classifying crystals according to their atomic
lattice or atomic structure. The atomic lattice is a three-dimensional network of atoms that are
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arranged in a symmetrical pattern. With the help of the lattice, it is possible to determine the
appearance and physical properties of the crystal. There are seven crystal systems or groups,
each of which has a distinct atomic lattice. It is possible to identify to which crystal system they
belong to. Here we have outlined the basic atomic structure of the seven systems, along with
some common examples of each system.
Triclinic System
All three axes are inclined towards each other, and they are of different length: a ≠ b ≠ c and
α≠β≠γ≠90o. In other words, All three axes are of different lengths and inclined towards each
other (Fig.1.7). Based on the three inclined angles the various forms of crystals are in the
paired faces. Some common Triclinic Systems include CuSO4, K2Cr2O7.

Fig.1.7 Triclinic System

Monoclinic System
It comprises three axes, each of different lengths. Two are at right angles to each other and the
third is inclined (Fig.1.8): a ≠ b ≠ c and α≠ 90o and β=γ=90o. Based on the inner structure the
monoclinic system includes Basal pinacoids and prisms with inclined end faces. Some
examples include Diopside, Gypsum, Vivianite.

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 Fig.1.8 Monoclinic System
Orthorhombic System
It comprises three axes and is at right angles to each other(Fig.1.9):. There are different lengths:
a ≠ b ≠ c and 𝛂 =β=γ=90o. Based on their Rhombic structure the orthorhombic system includes
various crystal shapes namely pyramids, double pyramids, rhombic pyramids, and pinacoids.
Some common orthorhombic crystals include Sulphur, Topaz, Tanzanite, Iolite, Zoisite,
Danburite.

Fig.1.9 Orthorhombic System

Trigonal System (Rhombohedral)
Angles and axis in a trigonal system are similar to Hexagonal Systems(Fig.1.10):. At the
base of a hexagonal system (cross-section of a prism), there will be six sides. In the cross-
section of a Trigonal crystal, there will be three sides. Crystal shapes in a trigonal system
include three-sided pyramids, Scalenohedral and Rhombohedra. In this system a = b = c and 𝛂
= 𝞫 = 𝝲 ≠ 90o
Some typical examples include Ruby, Quartz, Calcite, Agate, Jasper, Tiger’s Eyes and more.

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 (Fig.1.10): Trigonal System
Hexagonal System:
It comprises four axes. Among them, three axes are of the same length and are on one
plane. They intersect each other at an angle of 60 degrees. The fourth axis intersects other axes
at right angles (Fig.1.11). Based on a hexagonal (6-sided) inner structure. : a = b ≠ c and 𝛂 = 𝞫
= 90o and 𝝲 = 120o. Crystal shapes of hexagonal systems include Double Pyramids, Double-
Sided Pyramids, and Four-Sided Pyramids. Example: Quartz, Beryl, Cancrinite, Apatite,
Sugilite, etc.

Fig.1.11 Hexagonal System

Tetragonal Systems
It consists of three axes (Fig.1.12). The main axis varies in length; it can either be short
or long. The two-axis lie in the same plane and are of the same length. Three axes are
perpendicular to each other: a = b ≠ c and 𝛂 = 𝞫 = 𝝲 = 90o. Example: Indium and pyrite.

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 Fig.1.12 Tetragonal Systems
Cubic System:
Also known as the isometric system. All three axes are of equal length and intersect at right
angles. Based on a square inner structure: a = b = c and α=β=γ =90o. Crystal shapes of a cubic
system based on inner structure (square) include octahedron, cube, and Hexaciscoherdron.
Example: Silver, Garnet, Gold, and Diamond.

Fig.1.13 Cubic System

Table1 Seven Crystal systems
System Lengths Angles Example
a=b=c Silver, Garnet, Gold, Dia-
Cubic α = β = γ = 90°
mond
a =b ≠ c Indium and pyrite.
Tetragonal α = β = γ = 90°
a ≠ b ≠c Sulphur, Topaz, Tanzanite,
Orthorhombic α = β = γ = 90°
Iolite, Zoisite
Rhombohedral a=b=c Ruby, Quartz, Calcite, Agate,
α = β = γ ≠ 90°
(Trigonal) Jasper
a ≠ b ≠c Diopside, Gypsum, Vivianite
Monoclinic β = γ = 90°; α ≠90°
a≠b≠c CuSO4, K2Cr2O7
Triclinic α ≠ β ≠ γ≠90°

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 a=b≠c Quartz, Beryl, Cancrinite,
Hexagonal 𝛂 = 𝞫 = 90o ; 𝝲 = 120o
Bravais Lattice
The number of possible Bravais lattices that differ by symmetry is limited to 5 in two
dimensions and 14 in three dimensions. An example of a two-dimensional Bravais lattice is
given in Figure 1.1. The lengths of the vectors 𝐚𝟏 and 𝐚𝟐 are often called the lattice constants.
Having defined the Bravais lattice, we move on to the definition of the primitive unit cell. This
is any volume of space that, when translated through all the vectors of the Bravais lattice, fills
space without overlap and without leaving voids. The crystal structures that can be associated
directly with the simpler Bravais lattices. There are several ways to describe a lattice. The most
fundamental description is known as the Bravais lattice. In words, a Bravais lattice is an array
of discrete points with an arrangement and orientation that look the same from any of the
discrete points that is the lattice points are indistinguishable from one another. These lattices
are named after the French physicist Auguste Bravais. There are only fourteen different
ways of arranging identical points in three-dimensional space so that they are in every way
equivalent in their surroundings. These fourteen arrays are called the Bravais lattices; they are
listed in Table 1.2. It can be seen that the volume unit depicting the lattice is not always a
primitive cell. Note that the letters a, b, and c have been used to denote the dimensions of the
unit cells whereas the letters α, β and γ denote the corresponding angles in the unit cells.
1. Cubic Systems

In Bravais lattices with cubic systems, the following relationships can be observed: a = b
= c and α=β=γ =90o. The three possible types of cubic cells have been given below Apatite
(Fig.1.14).

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 Fig.1.14 Structure of Cubic Bravais Lattice
These three possible cubic Bravais lattices are Primitive (or Simple) Cubic Cell (P),
Body-Centered Cubic Cell (I) and Face-Centered Cubic Cell (F). Examples: Polonium has a
simple cubic structure, iron has a body-centred cubic structure, and copper has a face-centred
cubic structure.

2. Orthorhombic Systems

The Bravais lattices with orthorhombic systems obey the following equations: a ≠ b ≠ c and 𝛂
= 𝞫 = 𝝲 = 90o. The four types of orthorhombic systems (simple, base centred, body-centred
and, face-centred, orthorhombic cells) are illustrated below(Fig.1.15).

Fig.1.15 Structure of Orthorhombic Bravais Lattice

Examples of Orthorhombic Systems: Rhombic Sulphur has a simple orthorhombic structure

 Magnesium sulfate heptahydrate (MgSO4.7H2O) is made up of a base centred ortho-

rhombic structure.

 Potassium Nitrate has a structure which is body-centred orthorhombic.

 An example of a substance with a face-centred orthorhombic structure is barium sulfate.

3. Tetragonal Systems
In tetragonal Bravais lattices, the following relations are observed :a = b ≠ c and 𝛂 = 𝞫 =
𝝲 = 90o. The two types of tetragonal systems are simple tetragonal cells and body-centred te-
tragonal cells, as illustrated below (Fig.1.16):

Fig.1.16 Structure of Tetragonal Bravais Lattice

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 Examples of tetragonal Bravais lattices are stannic oxide (simple tetragonal)
and titanium dioxide (body-centred tetragonal)

4. Monoclinic Systems
Bravais lattices having monoclinic systems obey the following relations: a ≠ b ≠ c and 𝞫 = 𝝲 =
90o and 𝛂 ≠ 90o. The two possible types of monoclinic systems are primitive and base centred
monoclinic cells, as illustrated below (Fig.1.17).

Fig.1.17 Structure of Monoclinic Bravais Lattice

Examples: Monoclinic sulphur (simple monoclinic) and sodium sulfate decahydrate (base cen-
tred monoclinic)

5. Triclinic System

There exists only one type of triclinic Bravais lattice, which is a primitive cell. It obeys
the following relationship: a ≠ b ≠ c and α≠β≠γ≠90o. An illustration of a simple triclinic cell is
given below (Fig.1.18).

Fig.1.18 Structure of Triclinic Bravais Lattice

Such unit cells are found in the structure of potassium dichromate (Chemical formu-
la K2Cr2O7).

6. Rhombohedral System( Trigonal)

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 Only the primitive unit cell for a rhombohedral system exists. Its cell relation is given
by: a = b = c and 𝛂 = 𝞫 = 𝝲 ≠ 90o. An illustration of the primitive rhombohedral cell is provided
below (Fig.1.19). Calcite and sodium nitrate are made up of simple rhombohedral unit cells.

Fig.1.19 Structure of Rhombohedral Bravais Lattice

7. Hexagonal System

The only type of hexagonal Bravais lattice is the simple hexagonal cell. It has the fol-
lowing relations between cell sides and angles: a = b ≠ c and 𝛂 = 𝞫 = 90o and 𝝲 = 120o. An il-
lustration of a simple hexagonal cell is provided below(Fig.1.20). Zinc oxide
and beryllium oxide are made up of simple hexagonal unit cells.

Fig.1.20 Structure of Hexagonal Bravais Lattice

Thus, it can be noted that all 14 possible Bravais lattices differ in their cell length and angle re-
lationships. It is important to keep in mind that the Bravais lattice is not always the same as the
crystal lattice.

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Table 2 Fourteen types of Bravais lattices

Number of Structure name

System Lengths & Angles
Lattices
a=b=c Simple , Body-Centered and
Cubic 3
α = β = γ = 90° Face-Centered
a =b ≠ c Simple and Body-Centered
Tetragonal 2
α = β = γ = 90°
a ≠ b ≠c Simple , Base-Centered, Body-
Orthorhombic 4
α = β = γ = 90° Centered and Face-Centered
Rhombohedral a=b=c Simple
1
(Trigonal) α = β = γ ≠ 90°
a ≠ b ≠c Simple and Base-Centered
Monoclinic 2
β = γ = 90°; α ≠90°
a≠b≠c Simple
Triclinic 1
α ≠ β ≠ γ≠90°
a=b≠c Simple
Hexagonal 1
𝛂 = 𝞫 = 90o and 𝝲 = 120o

Crystal Planes

A Bravais lattice is an ordered three-dimensional array of points in space, but it may also
be considered as an assembly of two-dimensional arrays, i.e. planes. As Fig. 2.7 illustrates,
there is an infinite number of different families of planes associated with any Bravais lattice,
and each family of similar planes is characterized by the arrangement and density of points
within each plane and a specific interplanar spacing. Fig. 1.21 also clearly demonstrates that the
larger the interplanar spacing the greater the density of lattice points within the plane; this fol-
lows directly from the exact similarity of all points in a Bravais lattice and the unique volume
per lattice point.

Crystals are anisotropic, which is to say that the physical properties (e.g. electrical resis-
tivity, magnetic susceptibility) are different when the less symmetry the crystal possesses

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measured in different crystallographic directions, the more so. We, therefore, need to describe
the different lattice planes and directions in an exact manner, and for this purpose, Miller indi-
ces are used. Since all points in a given Bravais lattice are equivalent, any choice of origin is
completely arbitrary, as is the choice of coordinate axes. We choose our origin at a particular
lattice point and whenever practicable use orthogonal axes, but the following discussion is not
dependent on the latter choice. When describing a Bravais lattice as an assembly of similar
planes it is important to remember that all the lattice points lie on the chosen assembly of
planes. It is also the case that, whatever the composition of the plane chosen, we shall find that
certain planes of the assembly (in very simple cases sometimes all of them) always intersect the
coordinate axes at lattice points. Since all planes in a given assembly are parallel, this means
that every plane in this chosen family makes intercepts on the coordinate axes that stand in a
definite rational ratio to one another. This is easily demonstrated for a two-dimensional net and
applies equally to the three-dimensional lattice. The Miller indices make use of this fact and
allow all crystallographic planes to be described within the unit cell.

Fig. 1.21 Different lattice planes

Miller indices
The Bragg condition will work not only for a special kind of lattice plane in a crystal,
such as the hexagonal planes in an hcp crystal but for all possible parallel planes in a structure.
We, therefore, come up with a more stringent definition of the term lattice plane. It can be
defined as a plane containing at least three non-collinear points of a given Bravais lattice. If it
contains three, it will contain infinitely many because of translational symmetry. Examples for

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lattice planes is shown in Fig. 1.22. In a Bravais lattice, we often need to describe a plane or a
set of planes, or a direction or a set of directions. The Miller indices are a notation for doing
this. They are also convenient in X-ray work. To denote any plane through a crystal lattice we
use a system devised by Miller in 1839, originally to describe the crystal faces. Miller indices,
group of three numbers that indicates the orientation of a plane or set of parallel planes of
atoms in a crystal. If each atom in the crystal is represented by a point and these points are
connected by lines, the resulting lattice may be divided into several identical blocks or unit
cells; the intersecting edges(cut-offs) of one of the unit cells defines a set of crystallographic
axes, and the Miller indices are determined by the intersection of the plane with these axes. The
reciprocals of these intercepts are computed, and fractions are cleared to give the three Miller
indices (hkl). The Miller indices have the advantage of eliminating all fractions from the
notation for a plane. In the hexagonal system, which has four crystallographic axes, a similar
scheme of four Bravais-Miller indices is used. The lattice planes can be characterized by a set
of three integers, the so-called Miller indices. The following is an easy way to find the values
of h, k and l. To describe a plane:
1. Find the intercepts (cut-offs) of the plane on the three axes(x, y and z ) defined by the
basis vectors (a1, a2, a3). It gives three numbers. (If the plane does not intersect an axis
this is infinity.)
2. Take the reciprocal of the three numbers.
3. Multiply each with the lowest common denominator (which yields a set of integers). The
resulting set of three numbers (h, k, l) is called the Miller indices for the plane. {h, k, l}
means all planes equivalent (by symmetry) to (h, k, l).
To find the Miller indices for a direction:
1. Find any vector in the desired direction.
2. Express this vector in terms of the basis (a1, a2, a3).
3. Divide the coefficients of (a1, a2, a3) by their greatest common divisor. The resulting set
of three integers [h, k, l ] defines a direction. 〈h, k, l 〉 means all vectors equivalent to [h,
k, l ]. Negative signs in any of the numbers are indicated by placing a bar over the

number (thus h )

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 Fig.1.22 Miller indices

Example 1 (the red plane in the above illustration):

1. Cut-offs: 2 3 1
1
1 1 /
2. Reciprocal: /2 /3
1

3. Multiply by 6: 6
/2 6
/3 6
/1 → (3,2,6)

Example 2 (the green plane):

1. Cut-offs: 4 ∞ 1
1
1 1 /
2. Reciprocal: /4 /∞
1

3. Multiply by 4: 4
/4 0 4
/1 → (1,0,4)

Miller indices of Cubic Crystal Planes

The Miller indices can be used to specify directions and planes in a crystal. The Miller
indices of a plane are defined in the following way: First, three lattice vectors have to be
defined. For cubic crystal systems, the lattice vectors are chosen along the edges of the
crystallographic unit cell (unit cube). Any crystal plane intercepts the axes in certain points.
The Miller indices are the ratios of these points and are given as a triplet of integer values (h k
l). A Miller index 0 means that the plane is parallel to the respective axis. Negative indices are
indicated with a bar written over the number. In the notation of, [h k l] with square brackets
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instead of round brackets, denotes a direction in the basis of the lattice vectors. The notation {h
k l} denotes all planes that are equivalent to (h k l) by the symmetry of the crystal. Similarly,
the notation <h k l> denotes all directions that are equivalent to,[h k l] by symmetry. For
example, a plane parallel to two axes but cutting the third axis at a length equal to one edge of a
unit cell has Miller indices of (100), (010), or (001), depending upon the axis cut; and a plane
cutting all three axes at lengths equal to the edges of a unit cell has Miller indices of (111). In
cubic crystal systems, the Miller indices of a plane are the same as those of the direction
perpendicular to the plane.

Figure 1.23: Three planes in the cubic system along with their Miller indices.
Characteristics of a unit cell
A unit cell is characterized by the following properties
1. Number of atoms per unit cell
2. Coordination number
3. Nearest neighbouring distance
4. Atomic radius
5. Packing factor
(1)Number of atoms per unit cell
It is the number of atoms possessed by a unit cell. It can be determined if the arrangement of
atoms inside the unit cell is known.
(2)Coordination number
Coordination number, the number of atoms, ions, or molecules that a central atom or ion holds
as its nearest neighbours in an in a crystal. Coordination number is the number of spheres

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(atoms, molecules or ions) directly surrounding a single sphere in a crystal. It gives the
information about the packing of atoms in the structure: Whether closely packed structure or
loosely packed structure. If the coordination is high, then the structure is more closely packed.
If it is low then the structure loosely packed structure.
(3)Nearest neighbouring distance (2r)
The nearest neighbours concept is used to find out the radius of the atom. Atomic radius
is the half of the distance between nearest neighbouring atoms in a crystal(Fig.1.24). For
example a simple cubic unit cell:

Fig.1.24 Nearest neighbouring distance

Distance between nearest neighbours (d) = AB = a
For pure elements, radius r = d/2 = a/2
Radius space of space atom space equals space an over 2
(4)Atomic radius(r)
Atomic radius, half of the nearest neighbouring distance in a Crystal
a
r
2
(5) Packing factor (PF)
It is defined as the ratio of the total volume occupied by the atoms in a unit cell to the total
volume of a unit cell.
TotalVolumeOccupiedByTheAtomsInAUnitCell(v)
PackingFactor 
TotalVolumeOfTheUnitCell (V )
Numberofatomspresentinaunitcell  Volumeofoneatom
PackingFactor 
TotalVolumeOfTheUnitCell(V )

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 It is also known as the density of the unit cell. A High packing Factor- Atoms are very
closely packed (little unoccupied space). Low packing factor-loose packing of atoms (More
unoccupied space).

Types of Unit Cell

The smallest repeating unit of the crystal lattice is the unit cell, the building block
of a crystal. The unit cells which are all identical are defined in such a way that they fill space
without overlapping. The 3D arrangement of atoms, molecules or ions inside a crystal is called
a crystal lattice. It is made up of numerous unit cells. Constituent particles like atoms,
molecules are also present. Each lattice point is occupied by one such particle. A unit cell can
either be
1. Primitive Cubic Unit Cell
2. Body-centred Cubic Unit Cell
3. Face centred cubic unit cell
In this section, we will discuss the three types of unit cell in detail.

Fig.1.25 three types of the Crystal structure

21
1. Primitive Cubic or Simple cubic structure
In the primitive cubic unit cell, the atoms are present only at the corners. Every atom at
the corner is shared among 8 adjacent unit cells. There are 4 unit cells in the same layer and 4
in the upper (or lower) layer. Therefore, a particular unit cell has the only 1/8th of an atom.
Each small sphere in the following figure represents the centre of a particle that occupies that
particular position and not its size (Fig.1.26). This structure is known as an open structure.
1. The atoms in the primitive cubic unit cell are present only at the corners
2. Every atom at the corner is shared among eight adjacent unit cells
3. Four unit cells are present in the same layer
4. Four unit cell in the upper/lower layer
5. Therefore, a particular unit cell has the only 18th of an atom
6. Each small sphere in the following figure represents the centre of a particle which
occupies that particular position and not its size

Fig. 1.26 Simple cubic unit cell

Number of atoms per unit cell
In each cubic unit cell, there are 8 atoms at the corners. Each corner atom is shared by 8
surrounding unit cells. Therefore, the total number of atoms in one unit cell is 8 × 1/8 = 1 atom.

22
Coordination number

Fig. 1.27 Coordination number of simple cubic unit cell

It has 8 corner atoms. Now consider one corner atoms ( say A). It shared by 8 adjacent
unit cells (Fig.1.27). There are 4 nearest neighbouring atoms this particular atom which is given
by b, c, d, and e in a horizontal plane. Besides there are 2 more nearest atoms, one directly
above (f) and another one directly below (atom g) to the atom [Link], there are only six
(4+2) nearest neighbours to the A atom.
Atomic radius
Consider the face of the unit cell of a simple cubic structure. The atoms touch each other along
the edges of the cube (Fig.1.28). The distance between the centres of two nearest atoms is just
equal to the cube edge a. If a is the side of the unit cell and r is the radius.
Then,

Fig. 1.28 Atomic radius of simple cubic unit cell

a  2r
a
r
2
Packing factor
The number of atoms per unit cell is 1.

23
 4
The volume of one atom is v  r 3
3
The total volume of the unit cell is V=a3
TotalVolumeOccupiedByTheAtomsInAUnitCell(v)
PackingFactor 
TotalVolumeOfTheUnitCell (V )

4 3
r
3
PackingFactor  3
a
a  2r 3
4 3 4 3 4 3 4 3
r r r r
3 3 3 3 4r 3 
PackingFactor        0.5236
2r 3 2 3 r 3 8r 3 8r 3 24r 3 6
PackingFactor  52%

Therefore, 52% of the volume is occupied by the atoms.

2. Body-centred Cubic Structure (BCC)

Fig. 1.29 Body-centered Cubic Unit Cell

24
 A BCC unit cell has atoms at each corner of the cube and an atom at the centre of the
structure. The diagram shown below is an open structure. According to this structure, the atom
at the body centre wholly belongs to the unit cell in which it is present (Fig. 1.29).
1. In BCC unit cell every corner has atoms.
2. There is one atom present at the centre of the structure
Number of Atoms in BCC Cell:
Thus, in a BCC cell, we have: 8 corners × 1/8 per corner atom = 8 × 1/8 = 1 atom
1 body centre atom = 1 × 1 = 1 atom
Therefore, the total number of atoms present per unit cell = 2 atoms.
Coordination number
In the unit cell of the BCC structure, there is one atom (Say A) at the body of the unit cell.
Further, there are ‘8’ atoms at the 8 corners of the unit cell([Link]). The corner atoms do not
touch each other. But all eight corner atoms of the unit cell touch the body-centred atom along
the body diagonal. Thus for body centre atom ‘A, there are 8 nearest neighbours which are
shown in Fig. 1.30. So, the co-ordination number of body cubic structure is 8.

Fig. 1.30 Coordination number of Body-centered Cubic Unit Cell

Atomic radius

Fig. 1.31 Atomic radius of Body-centered Cubic Unit Cell

25
The corner atoms do not touch with each other. However, each corner atom touches the central
atom (Fig. 1.31). The side of the unit cell is ‘a’. The nearest neighbouring atoms are corner
atoms C and G to the body centre atom O. Consider the atoms at C, G at the centre of the cell
‘O’. These atoms lie in one straight line along body diagonal CG of the cube. From the ΔCBA:
CA 2  CB 2  BA 2
Substituting for AB, BC value (Fig. 1.31), then we have:
CA 2  a 2  a 2

CA 2  2a 2
From Fig. 1.31.
CA 2  2a 2
CG  r  2r  r
Squaring on both sides, we have:
CG 2  4r 
2

From the ΔCAG:

CG 2  CA 2  AG 2
Substituting for CG2, CA, AG2 value is:
4r 2  2a 2  a 2  3a 2
4 2 r 2  3a 2

3a 2
r2 
42
Taking square root on both sides:
3
r a
4
Packing factor
The number of atoms per unit cell is 2.
4
The volume of 2 atoms is v  2  r 3
3
4r
Side of the unit cell is a 
3
The total volume of the unit cell is V=a3
26
 TotalVolumeOccupiedByTheAtomsInAUnitCell(v)
PackingFactor 
TotalVolumeOfTheUnitCell (V )

4
2  r 3
PackingFactor  3
a3
Substituting for a value
4 8 3 8 3 8 3
2  r 3 r r r
3 8 3 3
PackingFactor  3  3   3 3  r 3 
 4r 
3
64r 3 64r 3 64r 3 64r 3
 
 3 3 
3
3 3 3 3 3

3
PackingFactor    0.68
8
PackingFactor  68%

Thus the packing factor is 68%. Therefore, 68% of the volume is occupied by the atoms.
The remaining 32% is vacant. For instance of this kind of structure are chromium and tungsten.
3. Face-centered Cubic structure (FCC)
FCC unit cell contains atoms at all the corners of the crystal lattice and the centre of all
the faces of the cube. The atom present at the face-centre is shared between 2 adjacent unit cells
and only 1/2 of each atom belongs to an individual cell (Fig.1.32). It has repetition sequence of
ABC ABC ABC …. It is a closely packed structure because each atom has 12 nearest
neighbours. This type of structure is more common in metals.
1. In FCC unit cell atoms are present in all the corners of the crystal lattice
2. Also, there is an atom present at the centre of every face of the cube
3. This face-centre atom is shared between two adjacent unit cells
4. Only 12 of each atom belongs to a unit cell

27
 Fig.1.32 Face-centered Cubic structure
Number of Atoms in FCC Cell
Thus, in a face-centred cubic unit cell, we have:
a) 8 corners × 1/8 per corner atom = 8 × 1/8 = 1 atom
b) 6 face-centred atoms × 1/2 atom per unit cell = 3 atoms
Hence, the total number of atoms in a unit cell =1+3= 4 atoms
Coordination number
In the unit cell of FCC structure, where there are ‘8’ atoms at the 8 corners of the unit
cell([Link]) and 6 atoms face centred atoms one at the centre of each face of the unit cell. To
find out the coordination number, now consider a corner atom (A) of a unit cell (Fig.1.33).

Fig. 1.33 Coordination number of Face-centered Cubic structure

28
 There are mutually perpendicular planes with common intersecting points on the atom A.
In-plane I has 4 face centred atoms (a,b,c,d)as nearest neighbours. In-plane II, it has 4 more
atoms ( e,f g, h) as nearest neighbours to the corner atom A. Likewise IIIhas 4 more face-
centred atoms (i,j,k,l) as nearest neighbours to the corner atom A. The co-ordination number of
FCC structure is 4+4+4=12.
Atomic radius

Fig.1.34 Atomic radius of Face-centered Cubic structure

The corner atoms touch with each other along the diagonal of any face of the cube. The
diagonal length of the face is 4r. In this case, the neighbouring atoms are a corner atom (D) and
an atom at the centre of the adjacent face is O (Fig.1.34). In ΔDCB:
DB 2  DC 2  CB 2
Substituting for DB2, DC2 and CB2 from [Link]:
r  2r  r 2  a 2  a 2
4r 2  2a 2
16r 2  2a 2

2a 2
r 
2

16
Taking square root on both sides:

2a 2
r2 
16

2
r2  a
4
Packing factor
The number of atoms per unit cell is 4.

29
 4
The volume of 4 atoms is v  4  r 3
3
4r
Side of the unit cell is a 
2
The total volume of the unit cell is V=a3
TotalVolumeOccupiedByTheAtomsInAUnitCell(v)
PackingFactor 
TotalVolumeOfTheUnitCell (V )

4
4  r 3
PackingFactor  3
a3
Substituting for a value
4 16 3 16 3 16 3
4  r 3 r r r
3 3 3 3 16 2 2
PackingFactor      r 3 
 4r 
3
64r 3 64r 3 64r 3
3 64r 3
 
 2 2
3
  2 2 2 2 2

2
PackingFactor    0.74
6
PackingFactor  74%

Thus the packing factor is 74%. Therefore, 74% of the volume is occupied by the atoms.
The remaining 26% is vacant. For instance of this kind of structure are Aluminium, copper and
nickel.
Hexagonal Close Packed Structure (HCP)
The hexagonal closely packed (hcp) is shown in Fig 1.35. In the hcp structure of a
unit, the cell contains three types of atoms as three layers. 12 corner atoms, one at each corner
of the hexagon. 2 base centred atoms, one at the top face of the hexagon and another at the
bottom face of the hexagon. In addition to corner and base atoms, 3 atoms are situated in
between the top and bottom face of the hexagon, in alternate vertical faces. Also, note that these
atoms are situated inside the face so that they can’t be shared by other cells (Fig .1.35)

30
 Fig. 1.35 Hexagonal Close Packed Structure
Number of atoms per unit cell
To calculate the number of atoms per unit cell, first, consider the bottom layer. The bottom
layer consists of six corner atoms and one face-centred atom. Each corner atom contributes 1/6
of its part to one unit cell. The total number of atoms contributed by the corner atoms is 1/6 x 6
= 1. The face-centred atom contributes ½ of its part to one unit cell. Therefore, the total number
of atoms contributes ½ of its part to one unit cell. Therefore, the total number of atoms present
in the case of the bottom layer is 1 + ½ = 3/2. Similarly, the number of atoms present in the
upper layer is 1 + ½ = 3/2. The number of atoms present in the middle layer = 1 x 3 = 3. The
total number of atoms present in the unit cell = 3/2 + 3/2 + 3 = 6 atoms.
Atomic Radius

Fig. 1.36 Atomic Radius of hexagonal Close Packed Structure

To find the atomic radius of the hcp structure, consider any two-corner atoms. It has to
be noted that, each corner atom touches with each other, therefore they are the nearest

31
neighbour. From figure 1.36 we can write Atomic Radius – HCP Structure, the nearest
neighbouring distance is a=2r
a
Atomicradius(r ) 
2
Coordination Number

Fig. 1.37 Coordination number of the hcp structure

The coordination number of the hcp structure can be calculated as follows. Let us consider two
unit cells as shown in Fig 1.37. The hcp structure is considered to have three layers: Bottom
Layer [B1], Top Layer [T1] and Middle Layer [M1]. In the top and bottom layers, the base
centred atom is surrounded by six corner atoms. In the middle layer, we have 3 atoms stacked
inside the unit cell as shown. Let us consider two unit cells let ‘X’ be the reference atom taken
in the bottom layer BL1 of the unit cell 1(or top layer [TL2] of the unit cell 2). This atom has 6
neighbouring atoms in its plane. Further at a distance of c/2, it has 3 atoms in the middle layer
(ML1) of unit cell -1 and 3 more atoms in the middle layer (ML2) of unit cell -2. Therefore, the
total number of neighbouring atoms is 6+3+3=12. Thus the coordination number is 12.
c/a ratio calculation
We know that ‘c’ is the height of the unit cell of the HCP structure and ‘a’ is the distance
between two neighbouring atoms. Now consider a triangle ABO in the bottom layer (Fig.1.38).
Here A, B, and O are the lattice points and exactly above these atoms at a perpendicular
distance ‘c’/2 the next layer atom lies at C.

32
 Fig.1.38 c/a ratio
In ΔABY:
AY
cos 30 
AB

3
AY  AB cos 30  a
2
From Fig. 1.38
2
AX  AY
3
From equation AY
2 a 3 2 a 3
AX    
3 2 3 3 2
a
AX 
3
In ΔAXC:
AC 2  AX 2  CX 2
Substituting the values of AC, AX and CX in the above equation:
2
 a  c
2

a  
2
   
 3  2
a2 c2
a 
2
 2
 3 2
2

a2 c2
a2  
3 4
33
c2 a2
 a2 
4 3
c 2 3a 2  a 2

4 3
c 2 2a 2

4 3
c2 2  4

a2 3
c2 8

a2 3
Taking square root on both sides:

c2 8
2

a 3

c 8
. 
a 3
c
.  1.633
a
Packing factor
The number of atoms per unit cell is 6.
4
The volume of 6 atoms is v  6  r 3
3
Nearest neighbouring distance is a  2r
a
Atomicradius(r ) 
2
3
4 a
v  6  
3 2

24a 3
v
38
24a 3
v
24
v  .a 3
The volume of the unit cell (V)

34
Area of the base= 6×Area of Δ AOB

Area of Δ AOB 
1
BO    AY 
2

3
We have, BO  a AY  a
2

1 3
 aa
2 2

a2 3
 
2 2

a2 3

4

a2 3
Area of base  6 
4

3 3 2
 a
2
The volume of the unit cell of the HCP=Base area × height
3 3 2
V a c
2
TotalVolumeOccupiedByTheAtomsInAUnitCell(v)
PackingFactor 
TotalVolumeOfTheUnitCell (V )

Substituting for v, and V value

a 3 2  a  c 8
PackingFactor     where . 
3 3 2 3 3c a 3
a c
2
1
2  3  2
  
3 3 8
1
2 3 2
2 3 2 2
   
3 4 2 3 2 2
1
3 38 2 3 3 8


PackingFactor   0.74
3 2
PackingFactor  74%

35
 Thus the packing density is 74%, the remaining 26% is vacant. Example of the HCP
structure is. Beryllium, Zinc, and Magnesium.
SPECIAL KIND OF STRUCTURE
In addition to SC, BCC, FCC and HCP, there are some special cubic structures. It is
well known that ionic solids consist of positive and negative ions arranged in a manner to
acquire minimum potential energy. This can be achieved by decreasing the cation-anion
distance to a minimum and reducing anion-anion repulsions. The structures which these solids
adopt can be described in terms of the large anions/cations occupying one or the other type of
interstitial sites. A large number of ionic solids exhibit one of these five structures which are
discussed here: 1. Sodium Chloride Structure 2. Zinc Blende Structure 3. Wurtzite Structure 4.
Fluorite (CaF2) Structure 5. Cesium Chloride Structure.
Sodium Chloride (Rock salt) Type Structure

Fig.1.40 Sodium Chloride Structure

Sodium chloride, also known as salt or halite, is an ionic compound with the chemical formula
NaCl, representing a 1:1 ratio of sodium and chloride ions (Fig.1.40). The sodium chloride
structure is composed of Na+ and Cl- ions. The number of sodium ions is equal to that of Cl-
ions. The radii of Na+ and Cl- ions 95 pm and 181 pm giving the radius ratio of 0.524. The
radius ratio of 0.524 for NaCl suggests an octahedral void. Chloride ions are arranged in cubic
close packing. It contains chloride ions at the corners and the centre of each face of the cube.
This arrangement is also regarded as a face centred cubic arrangement (fcc). Sodium ions are
located that there are six chloride ions around it. This equivalent to saying that sodium ions
36
occupy all the octahedral sites. So that the formula of sodium chloride is NaCl i.e.
stoichiometry of NaCl is 1:1. Since there are six octahedral holes around each chloride ions,
each Cl– ion is surrounded by 6 Na+ions. Similarly, each Na+ ion is surrounded by 6 Cl– ions.
Therefore, the coordination number of Cl– as well as of Na+ ions is six. This is called 6:6
coordination. NaCl has a cubic unit cell. It is best thought of as a face-centred cubic array of
anions with an interpenetrating fcc cation lattice (or vice-versa). The cell looks the same
whether you start with anions or cations on the corners. Each ion is 6-coordinate and has a local
octahedral geometry. The sodium ions are present in all the octahedral holes. The structure of
sodium chloride consists of eight ions a unit cell, four are Na+ ions and the other four are Cl–
ions. In this structure, each corner ion is shared between eight unit cells, each ion a face of the
cell by two cells, each ion on an edge by four cells and the ion inside the cell belongs entirely
to that unit cell. So the positions of the ions are the followings (with Na at the center of axis) :
Na+ (0 0 0) (1/2 1/2 0) (1/2 0 1/2) (0 1/2 1/2), Cl– (0 1/2 0) (1/2 0 0) (0 0 1/2) (1/2 1/2 1/2).
The unit cell of sodium chloride has 4 sodium and 4 chloride ions as calculated below:
No of sodium ions = 12 (at edge centres) × 1/4 + 1 (at body centre) × 1= 4
No of chloride ions = 8(at corner) × 1/8+6(at face centres) × 1/2 = 4
Most of the alkali halides, alkaline earth oxides, and sulphides exhibit this type of
structure. Other compounds which crystallize in sodium chloride type of structure are NHCl,
NHBr, NHI, AgF, AgCl, AgBr, MgO, CaO, BaS and LiF.
Zinc Blende Structure

Fig.1.41 Zinc Blende Structure

37
 It is often referred to by the historical names "Zinc blende" from the German
“Zinkblende” = α-ZnS, a rather ubiquitous mineral. The name “Sphalerite” also comes to form
the German: “Sphalerit”, which, as was the custom of the time, stems from the Greek
“sphaleros” meaning treacherous or malicious because it is easy to confuse it with other
minerals. Of course, we see immediately that what many call Zinc blende or sphalerite is
simply an fcc lattice with two atoms in the base: atom A at (0,0,0,) and atom B at (½, ½, ½)
(Fig. 1.41). Equally, of course, we notice that we have close packing, i.e. we simply have a
case of ABCABC... stacking of the base, or an ABAB... stacking. Zinc blende is best thought of
as a face-centred cubic array of anions cations occupying one-half of the tetrahedral holes.
Each ion is 4-coordinate and has local tetrahedral geometry. A zinc blende structure has the
form of a diamond except that the two sub-lattices are occupied by different types of atoms, e.g
Zn and S.
The salient features of its structure are:
(i) The sulphur atoms are in FCC type of arrangement, i.e., sulphur atoms are at the
corners and the centre of each face of the cube. (ii) Zinc atoms are so located that there are four
sulphur atoms around it. Or it may be said that zinc atoms occupy tetrahedral sites and their
coordination number is four. (iii) As there are two tetrahedral sites available for every sulphur
atom, zinc atoms occupy only half of the tetrahedral sites. So the stoichiometry of the
compound is 1:1. Only alternate tetrahedral sites are filled by zinc atoms. (iv) Each zinc atom
is surrounded by four sulphur atoms and in turn, each sulphur atom is also surrounded by four
zinc atoms which are also disposed towards the corners of a regular tetrahedron. We may say
that cations and anions are present in equivalent positions and the coordination of zinc blende
structure is 4: 4. (v) For the arrangement of sulphur atoms to be truly close-packed and zinc
atoms to occupy tetrahedral voids, the radius ratio (rZn /rS ) should be 0.225. This value is
greater than 0.225 and so we may say that the arrangement of sulphur atoms is not close-
packed. This structure is found in a1:1 compound in which the cation is smaller than the anion.
Examples include copper halides (CuCl, CuBr, Cul), silver iodide, beryllium sulphide, ZnS,
ZnSe, SiC, and GaP. Many III-V semiconductors such as GaAs, AlsAs, InAs, or InP are of a
zinc-blende type.

38
Diamond structure

Fig. 1.42 Diamond Crystal Structure

Diamond Crystal Structure
Diamond is a metastable allotrope of carbon where each carbon atom is bonded
covalently with other surrounding four carbon atoms and are arranged in a variation of the face-
centred cubic crystal structure called a diamond lattice (Fig1.42). The word “diamond” goes
back to the ancient Greek “adámas”=unbreakable. It may surprise you that diamond has not
only the highest hardness of all (natural) materials but also the highest thermal conductivity of
any bulk material. The atoms are strongly bonded to each other but not quite as strong as
carbon atoms. Silicon is quite hard but not as hard as diamond. Materials Scientists and
Engineers would love to use diamond for all kinds of application. Unfortunately, we cannot
make nice big diamond crystals. That limits technical applications to small artificial crystals in
slurries for cutting and polishing since big natural crystals do not come exactly cheap and are
thus used almost exclusively for non-technical applications.
The diamond structure is invariant not only under translations, but also under several
other symmetry operations such as reflections, rotations, or inversion. These symmetry
operations are usually denoted as point operations since they leave at least one point of the
lattice invariant, which is not the case for translations. The point group of the diamond structure
has 48 symmetry elements which are reflected in the symmetry of the first Beryllium Zones.
Lattice Vector and Basis Atoms.
39
 The structure is a combination of two identical interpenetrating fcc lattices. One of
the sub-lattices (0,0, 0) is shifted along the body diagonal of the cubic cell by one-quarter
 a0 a0 a0 
 , ,  of the length of the diagonal. We can say the diamond cubic structure is a
 4 4 4
combination of two interpenetrating FCC sublattices displaced along the body diagonal of the
cubic cell by 1/4th length of that diagonal. Thus the origins of two FCC sublattices lie at (0, 0,
0) and (1/4, 1/4,1/4) (Fig.1.43). In cubic semiconductors such as Si or Ge, the two atoms of the
basis are identical and the structure is called the diamond structure. If the two basis atoms are
different, the structure is called the zinc-blende structure.

Fig. 1.42 Diamond atomic position

The blue circles symbolize two things: The lattice points of a face-centred cubic (fcc)
lattice. Carbon atoms sitting on the lattice points. The green circles symbolize carbon atoms too
- but not lattice points. The red lines symbolize the very strong bonds between carbon atoms.
All atoms are strongly bonded to 4 neighbours and that is why it is difficult to rip them apart. In
other words: Diamond is very hard. The black lines are only there to guide the eye in seeing the
cubic lattice. A diamond emerges if one puts a dumbbell formed by two carbon atoms on any
lattice point of the fcc lattice. Semiconductors such as diamond (C), silicon (Si), germanium
Ge), and grey tin (α-Sn) crystallize in this structure. The figure shows four atoms bonded to
four others within the volume of the cell. Six atoms fall on the middle of each of the six cube
faces, showing two bonds. Out of eight cube corners, four atoms bond to an atom within the
cube. The other four bond to adjacent cubes of the crystal. The number of atoms contributed by
the corner atoms to a unit cell is 1/8 and 8 atoms in the corner of the unit cell. Therefore, the
40
number of atoms due to the corner atoms per unit cell is 1/8 ×8 =1. Each face shared by 2 unit
cells. It has 6 faces. Hence, the number of atoms contributed by the face centred atoms to the
unit cell is 1/2 × 6 = 3. atoms inside the structure =4 (Fig. 1.42). So the total number of atoms
present in a diamond cubic unit cell is 1 + 3 + 4=8. The total number of atoms per unit cell is 8.
Since each carbon atom is surrounded by four more carbon atoms. The coordination number of
the diamond is 4. The corner atoms do not touch with each other. Similarly, the face-centred
atoms also do not contact with each other. Both face and corner atoms contacted with four
atoms (1/4, 3/4, 1/4, 3/4) located on the middle of the unit cell. Let us consider two nearest
atoms which have contact with each other (X and Z atoms) which is shown in Fig. 1.41. Now
draw a perpendicular to Z atom which meets the unit cell at a point Y with the distance of a/4.
From Fig.1.43.

Fig.1.43. Atomic radius of diamond structure

XZ 2  XY 2  YZ 2
 
XZ 2  XT 2  TZ 2  YZ 2
2 2 2
a a a
XZ 2         
4 4 4
3a 2
XZ 2 
16
XZ 2  2r
3a 2
2r  2

16
3a 2
r2 
64
Taking square root on both sides, then we have:

41
 a 3
Atomicradius(r ) 
8
Packing Factor
The number of atoms per unit cell is 4.
a 3 3
The volume occupied by the atom per unit cell is v 
16
The total volume of the unit cell is V=a3
TotalVolumeOccupiedByTheAtomsInAUnitCell(v)
PackingFactor 
TotalVolumeOfTheUnitCell (V )

a 3 3
PackingFactor  16
a3

3
PackingFactor    0.34
16
PackingFactor  74%

The packing factor of the diamond is 34%. Consequently, we say that a 34% volume
of the unit cell diamond cubic structure is occupied by atoms and the remaining 66% volume is
vacant. The packing density is very low, it is termed as a very loosely packed structure.

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Similarities and differences between Zinc blende (ZnS) and Diamond (C) crystal
structure.

Zinc blende and Diamond are best thought of as a face-centred cubic (fcc) array of
atoms occupying one-half of the tetrahedral holes. There are 8 atoms in the unit cell. Each atom
is bonded covalently to 4 others equally spaced about a given atom. The zinc blende and
diamond structure both have tetrahedral coordination. In both structures, two atoms form two
interpenetrating face-centred cubic lattices. The difference between the structures is that the
two atoms that form the lattices are the same (C) for diamond while in zinc blende the two
atoms are different (Zn and S atoms). Zinc blende and diamond are the same fcc structure but
the two atoms that form the lattices are the same for diamond (C) and different for zincblende
(Zn and S).

References
[Link]
[Link]
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[Link]
[Link]
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[Link]
[Link]
center/pdfs/Miller_Indices.pdf
[Link]
[Link]
[Link]
[Link], Research Scholar, Department of Physics, Thiruvalluvar Govt Arts College,
Rasipuram, Namakkal-637401

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