CHAPTER-1

INTRODUCTION
1.1CRYSTALS
Crystals are minerals that have grown into regular,solid shapes.The
variety of crystals particularly those that are valued most are: diamonds,
rubies,sapphire,molten rock or magma [1]. Crystal growth is a vital and
fundamental part of materials science and engineering since crystals of
suitable size and perfection are required for fundamental data acquisition and
for practical devices such as detectors, integrated circuits etc. Behind every
new solid state device there stands a single crystal and the explosion in solid
state device development. Many new crystals had to be grown and fabricated
in order to assess their device properties.The ever increasing application of
semiconductor based electronics creates an enormous demand for high
quality semiconducting ferroelectric, piezoelectric and oxide single crystals
[2].

Fig 1.1. Structure of a crystal

1.2 FUNDAMENTAL DEFINITIONS IN
CRYSTALLOGRAPHY

1.2.1 LATTICE

Lattice is defined as an array of points which are imaginarily kept to

represent the position of atoms in the crystals such that every lattice point
has got the same environment as that of the other lattice point. A lattice is a
regular periodic arrangement of points in space.

1.2.1.1 SPACE LATTICE

A three dimensional collection of points in space are called space

lattice or crystal lattice. The environment about any particular points is in
every way the same.

1.2.1.2 LATTICE POINTS

Lattice points denote the position of atoms or molecules in the crystal.

The points in the space lattice are called lattice points [3].

1.2.2 BASIS

Basis or Motif is a unit assembly of atoms or molecules which are

identified with respect to the position of lattice point, identical in
composition, arrangement and orientation. The number of atoms in the basis
may be 1 or 2 or 3 etc and may go even above 1000. Example, A1 and Ba
has the basis of one atom. In NaCl and KCl the basis is two atoms and in
CaF₂ the basis is three atoms [4].
1.2.3 UNIT CELL

The unit cell is defined as the smallest geometric figure, the

translational repetition of which in all over the three dimensions gives the
actual crystal structure.

The unit cell may also be defined as the fundamental elementary

pattern with minimum number of atoms, molecules or groups of molecules
which represents the total characteristics of the crystal.

Fig 1.2 Unit cell

1.2.4 BRAVAIS LATTICE

There are fourteen types of lattices that are called the Bravais lattice.
A Bravais lattice is a set of all equivalent atoms in a crystal that are able to
be brought back into themselves when they are displayed by the length of a
unit vector in a direction parallel to a unit vector. Bravais lattices are not
always primitive, having one point in the unit cell, other points can be found
within the cell. These lattices are classified according to symmetry and space
rotations into the seven crystal systems.

1.3 SEVEN CRYSTAL SYSTEMS

A crystal system is a group of crystal structures that are organized

according to their axial system used to describe their lattice. The following
types are pictured and described below.

CUBIC

The cubic crystal system is also known as the isomeric system. It is

characterized by its complete symmetry. This system contains three
crystallographic axes, which are perpendicular to each other, as well as all
equal in length. These axes are all at angles 90 ° to one another. The cubic
system contains one lattice point at each of its four corners, and has six faces
[5].

HEXAGONAL

The hexagonal crystal system contains four crystallographic axes.

These consist of three equal horizontal axes at 120° of each other. It has one
vertical axis which is perpendicular to the other three, which may be shorter
or longer than the other three, horizontal axes. It is composed of eight faces.
TETRAGONAL

A tetragonal crystal is a simple cubic shape that is extended along its

vertical axis to create a rectangular prism. It consists of a square base and
top, as well as three axes. These axes have one perpendicular and two
horizontal with angles of 90° . Like the cubic system it is composed of six
faces [6].

RHOMBOHEDRAL

The rhombohedral is a trigonal system, that has a three-dimensional

shape similar to a cube, but it has been inclined to one side making it
oblique. It consists of three axes, one vertical and two horizontal all laid
perpendicular to one another. These axes are at angles of 90 ° to one another.
The rhombohedral is composed of six faces, although since the faces are not
square they are more commonly known as rhombi [7].

ORTHORHOMBIC

Orthorhombic crystal systems consist of three axes. These axes are

mutually perpendicular having all different lengths. Yet, the axes angles are
all equidistant laying at 90° to each other. The orthorhombic has six faces.

MONOCLINIC

A monoclinic system has three unequal axes. The vertical and forward
facing axes are inclined toward each other at an oblique angle, and the
horizontal axis is perpendicular to the other two axes, this is known as the
ortho axis. These angles are all arranged 90° to each other. A monoclinic
system is made up of six faces [8].
TRICLINIC

Triclinic system is made up of three unequal crystallographic axes.

The axes intersect at oblique angles. These angles are 90 ° to one another.
The triclinic system has six faces [9].

1.3.1 CRYSTAL STRUCTURE

A crystal structure (an arrangement of atoms in a crystal) is

characterized by its unit cell, a small imaginary box containing one or more
atoms in a specific spatial arrangement. The unit cells are stacked in three-
dimensional space to form the crystal.

The scientific definition of a “crystal” is based on the microscopic

arrangement of atoms inside it, called the crystal structure. A crystal is a
solid where the atoms form a periodic arrangement [10].

The symmetry of a crystal is constrained by the requirement that the

unit cell stack perfectly with no gaps. There are 219 possible crystal
symmetries, called crystallographic space groups. These are grouped into 7
crystal systems, such as cubic crystal system (where the crystals may form
cubes or rectangular boxes) or hexagonal crystal system (where the crystals
may form hexagons). A crystal structure is composed of a pattern, a set of
atoms arranged in a particular way, and lattice exhibiting long-range order
and symmetry. Patterns are located upon the points of a lattice, which in an
array of points repeating periodically in three dimensions. The points can be
through of as forming unit cell fill the space of the lattice. The symmetry
properties of the crystals are embodied in its space group.

A crystal structure and symmetry play a role in determining many of

its physical properties, such as cleavage, electronic band structure and
optical transparency [11].
1.3.2 CRYSTALLOGRAPHY

Crystallography is the experimental science of determining the

arrangement of atoms in the crystalline solids [12]. The word
“crystallography” derives from the Greek word “crystallon”. The position in
3D space of each crystal face is plotted on a stereographic net such as a
Wolff net or Lambert net. The pole to each face is plotted on the net. Each
point is labeled with its Miller index. The final plot allows the symmetry of
the crystallography. X-ray crystallography is used to determine the structure
of large bio-molecules such as proteins.

Before the development of X-ray diffraction crystallography, the study

of crystals was based on physical measurements of their geometry. This
involved measuring the angles of crystal faces relative each other and to
theoretical reference axes (crystallographic axes), and establishing the
symmetry of the crystal. Crystallographic methods now depend on analysis
of the diffraction patterns of a sample targeted by a beam of some type. X-
rays are most commonly used; other beams used include electrons or
neutrons. This is facilitated by the wave properties of the particles.
Crystallographers often explicitly state the type of beam used, as in the
terms X-ray crystallography, neutron diffraction and electron diffraction[13].

1.4 CRYSTALLIZATION

Crystallization is the natural or artificial process of formation of solid

crystals precipitating from a solution, melts or more rarely deposited directly
from a gas. Crystallization is also a chemical solid-liquid separation
technique, in which mass transfer of a solute from the liquid solution to a
pure solid crystalline phase occurs. In chemical engineering crystallization
occurs in a crystallizer obtained through a variation of the solubility
conditions of the solute in the solvent, as compared a precipitation due to
chemical reaction [14].

1.5 AMINO ACIDS

Amino acids are biologically important organic compounds containing

amine (-NH₂) and carboxylic (COOH) functional groups, usually along with
a side-chain specific to each amino acid. The key elements of an amino acid
are carbon, hydrogen, oxygen and nitrogen, through other elements are
found in the side-chains of certain amino acids. About 500 amino acids are
known and can be classified in many ways. They can be classified according
to the core structural functional groups locations as alpha,beta, gamma or
delta amino acids; other categories relate to polarity, pH level and side-chain
group type (aliphatic, acyclic, aromatic, containing hydroxyl or sulfur etc.).
In the form of proteins, amino acids comprise the second-largest component
(water is the largest) of human muscles, cells and other tissues. Outside
proteins, amino acids perform critical roles in processes such as
neurotransmitter transport and biosynthesis.

1.6 L-PROLINE

Proline is an amino acid that is used in the biosynthesis of proteins.

The L-form is one of the 20 most common natural amino acids. L-proline is
an osmoprotectant and therefore is used in many pharmaceutical,
biotechnological applications. Proline is encoded by the codons CCU, CCC,
CCA and CCG [15].
 Fig 1.3 Molecular Structure of L-Proline

Properties

Molecular Solubility : Soluble in water

Molecular Formula : C5H9NO2

Melting Point : 221° C

Appearance : Colorless

Molar Mass : 115.13g/ml

1.7 SODIUM SULPHATE

Sodium Sulphate, also known as Sulphate of soda, is the inorganic

compound with formula Na₂SO₄ as well as several related hydrates. All
forms are white solids that are highly soluble in water. With an annual
production of 6 million tonnes, the decahydrate is a major commodity
chemical product. It is mainly used for the manufacture of detergents and in
the kraft process of paper pulping.
Properties

Molecular Solubility : Soluble in water, glycerol and hydrogen iodide

Molecular Formula : Na₂SO₄

Melting Point : 884° C

Appearance : White Crystalline Solid

Molar Mass : 142.04g/mol