Crystal Structure

4.1 Introduction

This is the story of how materials are made up from atoms. There are only about 100 kinds of
atoms in the entire Universe, and whether these atoms form trees or tyre, ashes or animals, water or
the air we breathe, depends on how they are put together. The same atoms are used again and again.
Structure determines not only the appearance of materials, but also their properties. When an
electrical insulator can become a superconductor, a pencil a diamond, a common cold a deadly virus,
we begin to understand how important it is to understand the structure of materials.

Atoms can be gathered together as an aggregate through a number of different processes,

including condensation, pressurization, chemical reaction, electrodeposition, and melting. The process
usually determines, at least initially, whether the collection of atoms will take to form of a gas, liquid
or solid. The state usually changes as its temperature or pressure is changed. Melting is the process
most often used to form an aggregate of atoms. When the temperature of a melt is lowered to a certain
point, the liquid will form either a crystalline solid or and amorphous solid. Polycrystalline solids are
an aggregate of a large number of small crystals or grains in which the structure is regular, but the
crystals or grains are arranged in a random fashion.

4.1.1 Amorphous and Crystal Solids

A solid substance with its atoms held apart at equilibrium spacing, but with no long-range
periodicity in atom location in its structure is an amorphous solid. Examples of amorphous solids are
glass and some types of plastic (figure 4.1). The physical properties of amorphous solids are identical
in all directions along any axis so they are said to have isotropic properties.

In a single crystal, the physical and mechanical properties often differ with orientation. When
the properties of a material vary with different
crystallographic orientations, the material is said to
Crystalline SiO2 Amorphous SiO2
be anisotropic.
(Quartz) (Glass)
4.2 Importance of Crystal Structure

All compounds exist as solid under certain

suitable temperature and pressure. Also, many
compounds exists as solids. Solids are immense
technological importance. Their appearance, their
mechanical, optical, electrical and magnetic
properties etc., are gretaly influenced by their crystal
strucutre. For example, graphite and diamond are
Figure 4.1 two compounds of very different physical and
chemical properties and having immense
applications in our day to day life. In spite of their
great difference in many things, it is to be noted that,
both are made of carbon alone (therfore they are called the allotropic forms of carbon). All these are
due to the difference in the spatical arrangemant of carbon atoms.

The above example shows that why the study of crystals, crystallography, is so important.
The crystallography can answer many questions like the reason behind the brilliancy of gemstones,
the nature of cement, lubricants and abrasives, the electrical properties of various substances,
superconductivity and so on.
4.2Crystal structure

Crystalline solids are a three dimensional collection of individual atoms, ions, or whole
molecules organized in repeating patterns. These atoms, ions, or molecules are called lattice points
and are typically visualized as round spheres. The two dimensional layers of a solid are created by

Square array Close packed array

Figure 4.2 Two possible arrangements for identical atoms in a 2-D structure

packing the lattice point “spheres” into square or closed packed arrays (figure 4.2).

Stacking the two dimensional layers on top of each other creates a three dimensional lattice
point arrangement represented by a unit cell. A unit cell is the smallest collection of lattice points that
can be repeated to create the crystalline solid. The solid can be envisioned as the result of the stacking
a great number of unit cells together.

All crystals comprise a fundamental, repeating block of atoms this is called the unit cell.

4.3 Crystal Lattice and Unit Cell

4.3.1 Lattice

Crystals have an ordered internal arrangement of atoms, i.e., atoms are arranged in a
symmetrical fashion on a three-dimensional network referred to as lattice

A Lattice is a regular and periodical arrangement of points in three dimensions. The term
lattice can be defined in another way. In an arrangement, if the surrounding environment looks the
same when arrangement is viewed from different lattice points, then that arrangement is said to be
lattice.

4.3.2 Basis

An ideal crystal is constructed by the infinite regular repetition in space of identical structural
units. We describe the structure of all crystals in terms of a single periodic lattice, but with a group of
atoms attached to each lattice point or situated in each elementary parallelepiped. This group of atoms
is called the basis; the basis is repeated in space to form the crystal. We now make the definitions
more precise.

To construct a crystal structure some basic arrangements is to be fixed at each and every
lattice point. This basic arrangement is said to be a basis. Therefore, it can be written as,

Crystal structure = lattice + basis

 The above equation is not a mathematical expression, but it is used to explain the formation of
crystal structure. For example the arrangement shown in figure 4.3b (basis) is to be fixed in figure
4.3a (lattice points) to get the crystal structure shown in figure 4.3c.

4.3.3 Unit Cell

The entire lattice, structure of a crystal is found to consist of identical blocks or unit cells. The
unit cell is the smallest block or geometric figure from which the crystal is built up by repetition in
three dimensions. The unit cell is a parallelepiped by moving which in the direction of each of the
coordinate axis x, y, and z, arranged parallel to edges of the figure 4.4, the crystal lattice can be
constructed. As seen, this process resembles brick laying. It is also known as fundamental elementary
pattern because it is repeated again and again to form the lattice structure of a crystal.
In general, a unit cell may be defined as that volume of a solid from which the entire crystal
can be constructed by translational repetition in three dimensions. In fact, unit cell is the smallest part

Lattice points Basis Crystal

a b structure
c
Figure 4.3

(a) (b)
Figure 4.4 parallelepiped unit cell
of a crystal having all the structural properties of the given lattice.
The length of the side of a unit cell is the distance between atoms of the same kind. In the
case of pure metals whose crystals have simple cubic structure (figure 4.4a), it is equal to the basic
distance 'a' only. However, in the case of crystals of chemical compounds like the cubic crystal of
sodium chloride (NaCl), it is twice the distance 'd' between two adjacent atoms as shown in figure
4.4b.

4.4 Lattice Parameters of a Unit Cell

The three sides 'of a unit cell which are called the
crystallographic axes are chosen to have directions such that they
pass regularly through the lattice points associated with like-
atoms. An arbitrary arrangement of crystallographic axes, marked
X, Y and Z, defining a unit cell is shown in figure 4.5. The angles
between the three axes are called interfacial angles. The intercepts
a, b, and c define the dimensions of a unit cell and are known as
its primitives or characteristic intercepts on the axes. The
primitives and interfacial angles constitute the lattice parameters
Figure: 4.5 Unit cell
of the unit cell. These are also called the geometrical constants of a given crystal substance.

If we know the linear dimensions a, b and c and also the interfacial angles,  and , we know
the form and actual size of the unit cell. But if we do not know actual values of primitives but only
their ratio and the values of inter axial angles, and then we can only determine the form of the unit cell
and not its actual size.

4.5 The Seven Crystal Systems

As stated above, there are seven crystal systems (Table 4.1) corresponding to seven distinct
types of unit cells (or subunits). These unit cells are all parallelepipeds whose shapes are determined
by the length of the three sides a, b and c. and the values of the three interfacial angles ,  and .
4.6 The names of the seven crystal systems are:
(1) Cubic (2) Monoclinic (3) Triclinic (4) Tetragonal (4) Orthorhombic (6) Rhombohedral
(Trigonal) and (7) Hexagonal.
Now we discussed about the different structures given above.
(i) Simple cubic structure
(i) the three crystal axes are at right angles
(ii) the repetitive intervals along the three axes are equal.
(ii) Monoclinic structure
i) one of the axes is at right angles to the other two
ii) the other two axes are not at right angles to each other
iii) repetitive interval along each axis is different.
(iii) Triclinic structure
i) no two of the three axes are at right angles to each other
ii) repetitive interval along each axis is different.
(iv) Tetragonal structure
i) the three crystal axes are at right angles to each other
ii) the repetitive intervals along two of the axes are equal
iii) the interval in the third direction is different from that in the other two.
(v) Orthorhombic structure
i) the three crystal axes are at right angles
the repetitive interval along each axis is different
(vi) Rhombohedral structure
i) the three axes are equally inclined to each other at angles other than a right angle
ii) the intervals alone the three axes are different.
Table 4.1

S.N Name of Relation Interfacial Example Number of

o system between angle possible types
primitive
 4. Cubic a=b=c  =  =  NaCl, P,I,F  3
= 90 CaF2
P,C  2
2. Monoclinic abc  =  = Na2So4,
90   FeSo4 P  1

3. Triclinic abc      CuSo4, P,I  2

 90 K2Cr2O7
P,I,F,C
4. Tetragonal a=bc  =  =  NiSo4,  4
= 90 SnO2
P  1
4. Orthorhomb abc  =  =  KnO3,
ic = 90 MgSo4

7. = =  P  1
Trigonal CaSo4
a=b=c  90

2.  =  = SiO
Hexagonal a=bc 90
2

 = 120

Pprimitive, Ibody centred, FFace centered, Cbase centered

(vii) Hexagonal structure
i) there are three axes in one plane from each other and a fourth axis normal to this plane
ii) the repetition intervals along the three coplanar axes are equal but the interval along the fourth
axis is unique.
It will be seen that cubic system possesses the greatest symmetry whereas triclinic system has the
least.
4.7 Bravais Lattices
The number of ways in which points can be arranged regularly in three dimensions, such that
the stacking of unit cells fills space, is not limitless; Bravais showed in 1848 that all possible
arrangements can be represented by just fourteen lattices as shown in figure 4.6. The fourteen Bravais
lattices can be categorised into seven crystal systems (cubic, tetragonal, orthorhombic, trigonal,
hexagonal, monoclinic and triclinic); for example, the cubic system contains the cubic-P, cubic-F and
cubic-I lattices.
4.7.1 Classification of lattices

   90    90    90

abc abc abc

  

β β β
α α α

===90 ===90 ===90 ===90

abc abc abc abc

==120 ==90 ===90 ===90

and =90 a=b=c a=bc a=bc
a=bc

===90 ===90 ===90

a=bc a=bc a=bc

Figure 4.6. Bravais’ Lattices

4.8 Space Lattices of Cubic System

The cubic system which is the simplest and also most common will be considered in detail. In
a cubic atom take positional at the comers of the cube. However, there are three types of lattices
possible in this system depending on the positions of the lattice points in the unit cell:
(i) simple cubic (SC) lattice
(ii) body-centred cubic (BCC) lattice
(iii) face-centred cubic (FCC) lattice
4.9 Unit Cell Characteristics

1. Atomic radius

The radius of atom may be defined on the assumption that they are spherical in shape. Since,
in their individual structures the atoms touch across certain dimensions, it is possible from the
measured lattice parameters to determine the atomic radius.

2. Coordination number

The coordination number of crystal lattice denotes the number of equidistant near neighbours
that an atom has in a unit cell of any crystal structure.

3. Packing factor

The packing factor is defined as the fraction of volume occupied by spherical atom as
compared to the total available volume of the structure.

4.10 Unit Cell Characteristics for Cubic system

4.10.1 Simple cubic (SC)

Perhaps the simplest cubic system is the simple cubic structure. A unit cell of this type is
shown in figure 4.7. It is clear that a simple cubic lattice containing one atom at each of the eight
corners of the cube. As each cell is surrounded on all sides by other similar cells, the atoms at its
corners are also shared by adjoining cells. The corner atom of the cell is common to seven other unit
cells adjoin to it. This means that the sphere representing a corner atom is shared equally by eight
unit cells, or only 1/8th of the sphere is contributed to each cell. The total contribution of eight lattice
points at the corners of a simple cubic cell is therefore, 1/88=1. In this way there is only one atom
per unit cell.

a=2r

a b
Figure 4.7 Simple cubic unit cell

Referring to figure 4.11a , it contains one atom at each of the eight corners of the unit cell.
Therefore, if we take the atom at one corner as the centre, it will be found to have 2 atoms along the
coordinate axis. One on either side, as its immediate neighbour. Then the coordination number CN =
23 = 6.

In a simple cubic, one atom lies on each of the eight corners as shown in figure 4.11b. Let us
consider a be the lattice parameter and r be the radius. Then

a = 2r
or r = a/2
packing factor

As shown earlier this the total number of atom in the cube is one

4 3
Volume of one atom v= r
3

= 4  a  a
3 3
Since atomic radius r=a/2, the volume of atom
3 8 6

Volume of the cube V = a3

a 3
v 6
 packing factor = V  a3

= 0.424

4.10.2 Body-Centered Cubic (BCC) Structure

The body-centered cubic unit cell has atoms at each of the eight corners of a cube (like the
cubic unit cell) plus one atom in the center of the cube (figure 4.]8). Each of the corner atoms is the
corner of another cube so the corner atoms are shared among eight unit cells. In addition to it there is
on atom per unit cell at the body centred which belongs wholly to the cell. Therefore, the total number
of atoms per unit cell is 1/88+1=2. Thus in bcc unit cell consists of a net total of two atoms.

It contains one atom at each of the eight corners of the unit cell and one atom at the body
centre. The nearest atom to the corner atom is the body centred atom and not the other corner atoms.
If we take the body centre atom as origin, it is observed that the number of nearest neighbours is eight
and their distance from body centre is half the diagonal of the unit cube. They are obviously 8 in
number. Hence the coordination number of bcc structure is 12.

If we look at the bcc unit cell closely (figure 4.8), we can see that the length of the "body
diagonal" of the cell (from one corner of the cube to the other) is equal to four times the atomic radius
(r). We can draw a right triangle the sides of which are this "body diagonal" (4r), one side of the unit
cell and diagonal line across the
"bottom" of the unit cell.

The length of the remaining

side of this triangle is the length of the
diagonal line through the bottom of the
unit cell, the length of which we can
determine by using the Pythagorean
Theorem on another triangle...

The Pythagorean Theorem

states that the square of the length of Figure 48 Body centre cubic
the hypotenuse of a right triangle (c) is unit cell
equal to the sum of the squares of the lengths of the other two sides (a and b)...

c2 = a2 + b2

Thus, we can relate the length of the hypotenuse of the second triangle to the lengths of the
sides of the unit cell....

a2 + a2 = 2a2

...and the length of the remaining side of the first triangle is √2a.

Now, we use the Pythagorean Theorem once again to relate the length of one side of the unit
cell to the atomic radius (figure 4.9).

(4r)2 = a2 + (√2a)2 4r
(4r)2 = a2 + 2a2 = 3a2 a
16r2 = 3a2
a2 = (16/3) r2
r = (3/4)a 2a2
packing factor Figure 4.9

As shown earlier the total number of atom in the cube is 2

Volume of the atoms v =2 4 r 3

3

3 3
Since atomic radius r=(3/4)a, the volume of atom = 8 π ( 33a)  π 3a
3 4 8

Volume of the cube V = a3

  3a 3
v 8
 packing factor = V  a3

= 0.683

The bcc arrangement does not allow the atoms to pack together as closely as the fcc or hcp
arrangements. The bcc structure is often the high temperature form of metals that are close-packed at
lower temperatures. The volume of atoms in a cell per the total volume of a cell is called the packing
factor. The bcc unit cell has a packing factor of 0.62.

Some of the materials that have a bcc structure include lithium, sodium, potassium,
chromium, barium, vanadium, alpha-iron and tungsten. Metals which have a bcc structure are usually
harder and less malleable than close-packed metals such as gold. When the metal is deformed, the
planes of atoms must slip over each other, and this is more difficult in the bcc structure.

4.10.3 Face Centered Cubic (FCC) Structure

The face centered cubic structure has atoms located at each of the corners and the centers of
all the cubic faces. Each of the corner atoms is the corner of another cube, so, the corner atoms are
shared among eight unit cells. Additionally, each of its six face centered atoms is shared with an
adjacent cell. Thus, only half the sphere representing the atom is the share of each cell (figure 4.10).
Therefore, the total number of atoms per unit cell is1/88+1/26=4. Thus the fcc unit cell consists of
a net total of four atoms.

Figure 4.10 Face centre cubic unit

Each of the eight corners of the unit cell and one atom at the centre of each of the six faces.
The nearest atom to the corner atom, in this case, is the face centred atom and not the corner atoms. If
we take a corner atom of a unit cell as the region, it has four neighbouring atoms in its own plane, four
neighbouring atoms in a plane above it and four neighbouring atoms in a plane below it. Thus the
coordination number of FCC structure is 12.

Looking at one "face" of the fcc unit cell shows us that the length of the diagonal of the face
is equal to 4r (figure 4.11).

Using the Pythagorean Theorem...

(4r)2 = a2 + a2 = 2a2
a
16r2 = 2a2

r = (2/4)a a
Figure 4.11
packing factor
 As shown earlier this the total number of atom in the cube is 4

4 3
Volume of the atoms v = 4 r
3

= 16  ( 23a )   2 a
3 3
Since atomic radius r=(2/4)a, the volume of atom
3 4 6

Volume of the cube V = a3

 2a 3
v 6
 packing factor = 
V a3

= 0.74

In the fcc structure (and the hcp structure) the atoms can pack closer together than they can in
the bcc structure. The atoms from one layer nest themselves in the empty space between the atoms of
the adjacent layer. To picture packing arrangement, imagine a box filled with a layer of balls that are
aligned in columns and rows. When a few additional balls are tossed in the box, they will not balance
directly on top of the balls in the first layer but instead will come to rest in the pocket created between
four balls of the bottom layer. As more balls are added they will pack together to fill up all the
pockets. The packing factor (the volume of atoms in a cell per the total volume of a cell) is 0.74 for
fcc crystals. Some of the metals that have the fcc structure include aluminum, copper, gold, iridium,
lead, nickel, platinum and silver.

4.7.4 Hexagonal Close Packed (HCP) Structure

Another common close packed structure is the hexagonal

close pack. The hexagonal structure of alternating layers is shifted so
its atoms are aligned to the gaps of the preceding layer. The atoms
from one layer nest themselves in the empty space between the atoms
of the adjacent layer just like in the fcc structure. However, instead of
being a cubic structure, the pattern is hexagonal. (figure 4.12). The
difference between the HCP and FCC structure is discussed later in
this section.

The hcp structure has three layers of atoms. In each the top Figure 4.12 Hexagonal unit cell
and bottom layer, there are six atoms that arrange themselves in the
shape of a hexagon and a seventh atom that sits in the middle of the
hexagon. The middle layer has three atoms nestle in the triangular "grooves" of the top and bottom
plane. Note that there are six of these "grooves" surrounding each atom in the hexagonal plane, but
only three of them can be filled by atoms.

As shown in the middle image above, there are six atoms in the hcp unit cell. Each of the 12
atoms in the corners of the top and bottom layers contribute 1/6 atom to the unit cell, the two atoms in
the center of the hexagon of both the top and bottom layers each contribute ½ atom and each of the
three atom in the middle layer contribute 1 atom. Therefore, the total number of atoms per unit cell
is1/612+1/22+3=7. Thus, the HCP unit cell consists of a net total of six atoms.

The coordination number of the atoms in this structure is 12. There are six nearest neighbors
in the same close packed layer, three in the layer above and three in the layer below.
Calculation of c/a ratio

Let C be the height of the unit cell and a be the

lattice parameter. Consider the triangle ABO from the
figure 4.13.

From the figure 4.13,

AC = 2 AN
3

But AN = ABcos30

a 3
=
2
So that
a
AC =
3 C/2

O
From the triangle ACM
a
A B
AM2 = AC2+CM2

CM2 = AM2-AC2 Figure 4.13

2 M
c a2
  a 
2

2 3
a C/2
O
2
c 2 2
   a
 
2 3 30
A N
C
c 8
 
a  3 B
Figure 4.14
packing factor

As shown earlier this the total number of atom in the cube is 7.

Volume of one atom v =6 4 r 3

3
= 4  a 3  a
3 3
Since atomic radius r=(a/2), the volume of atom
3 2 6

Volume of the unit cell = Area of the base  height

= Area of the base  c

Are of the base = 6Area of the triangle AOB

= 6 1 BOAN
2
 a 3
=6 1 a
2 2

3 3a 2
=
2
3 3a 2
Volume of the unit cell = c
2
a 3
 packing factor = 6
3c 3a 2
2

= 0.74

The packing factor is 0.74, which is the same as the fcc unit cell. The hcp structure is very
common for elemental metals and some examples include beryllium, cadmium, magnesium, titanium
and zinc.

Crystal structure coordination packing factor directions

Simple Cubic (SC) 6 0.42 cube edges

Body Centered Cubic (BCC) 8 0.68 body diagonal

Face Centered Cubic (FCC) 12 0.74 face diagonal

Hexagonal Close Pack (HCP) 12 0.74 hexagonal side

4.13 Miller Indices

Miller indices are used to describe crystal faces and also families of planes within solids.

In crystallography, it is convenient to characterize a Z

given crystal in terms of a set of planes. Consider a two-

dimensional plane. A number of different planes with
different orientations may be drawn, with each plane
containing some of the lattice points. Each line or plane is a
representative number of a parallel set of equally spaced
1/2
lines or planes and each lattice point must lie on one of the
lines or planes. These lattice lines and planes are labeled
using Miller Indices. 1/4
Y

Miller Indices are a symbolic vector representation 1/2

for the orientation of an atomic plane in a crystal lattice and X

(1 2 1) Figure 4.15
are defined as the reciprocals of the fractional intercepts
which the plane makes with the crystallographic axes.

If you want to describe the orientation of a crystal face or a plane of atoms within a crystal
lattice, then there are series of steps that will lead you to its notation using Miller indices.
Procedure for determining h,k and l:

1. If plane passes through origin, translate plane or choose new origin.

2. Determine intercepts of planes on each of the axes in terms of unit cell edge lengths (lattice
parameters). Note: if plane has no intercept to an axis (i.e., it is parallel to that axis), intercept is
infinity (½ ¼ ½) (figure 4.15).
3. Determine reciprocal of the three intercepts (2 4 2).
4. If necessary, multiply these three numbers by a common factor which converts all the reciprocals
to small integers (1 2 1).
5. The three indices are not separated by commas and are enclosed in curved brackets: (hkl) (121).
6. If any of the indices is negative, a bar is placed in top of that index.