ABSTRACT

High quality pure and ZnCl 2 doped KClxBr1-x crystals were grown by slow evaporation
method using water as the solvent at room temperature. The grown crystals were
characterised by Powder XRD , FTIR , UV-visible ,TG/DTA and SEM analysis.

The Powder X-ray Diffraction confirmed that the grown crystal belonged to the cubic
system.The interplannar spacing and lattice parameters were determined.The presence of
functional groups was qualitatively determined by FTIR. The optical absorption studies
revealed very low absorption over the entire visible region. The optical properties were
determined by UV-visible absorption spectra. The band gap energy was calculated from the
cut off wavelength. The fluorescence spectrum of all the grown crystals indicates the blue
light emission. The thermal stability of the grown crystals were studied from
Thermogravimetric/Differential thermal analysis. The irregular shaped non uniformly
particles of grown crystals were confirmed using SEM analysis.

1
 CHAPTER –1

INTRODUCTION

Crystals are the unacknowledged pillars of modern technology. Crystal growth is a vital
and fundamental part of material science and engineering, because crystals of suitable size
and perfection are required for fundamental data acquisition and for practical devices such as
detectors, integrated circuits and for other millions and millions of applications (Brice, J.C.,
1986, Nalwa, H.S.and Miyata, S., 1996). Behind every new solid state device there stands a
single crystal. The ever increasing application of semiconductor based electronics creates an
enormous demand for high quality semiconducting, ferroelectric, piezoelectric, oxide single
crystals. There are two principal reasons for the deliberate growth of single crystals, because
many physical properties of solids are obscured or complicated by the effects of grain
boundaries and the full range of tensor relationships between applied physical cause and
observed effect can be obtained only if the full internal symmetry of the crystal structure is
maintained through the specimen .A crystal is a solid material whose constituent atoms,
molecules, or ions are arranged in an orderly repeating pattern extending in all three spatial
dimensions.

1.1 Crystal growth

Crystal growth is a major stage in the crystallization process and consists of adding new
atoms ions, or polymer strings into the characteristic arrangement of a crystalline Bravais
lattice. If the crystal is in dynamic equilibrium with its parent phase the free energy is at a
minimum and no growth will occur. For growth to occur this equilibrium must be disturbed
by a change of the correct sign, in temperature, in pressure, chemical potential,
electrochemical potential, or strain. The system may then release energy to its surrounding to
compensate for the decrease in entropy occasioned by the ordering of atoms in the crystal and
the evolution of heat of crystallization. In a well-designed growth process just one of these
parameters is held minimally away from its equilibrium value to provide a driving force for
growth.
Crystal growth is a non-equilibrium process and thought must be given to the temperature
and concentration and other gradients. At the same time the crystal growth process must be

2
kept as near equilibrium and as near to a steady state process as possible. This is why control
of the crystal growth environment and a consideration of growth kinetics both at the
macroscopic and the atomic levels are of vital importance to the success of a crystal growth
experiment (Santhanaraghavan, P. and Ramasamy, P., 2001).

1.2 Nucleation

Nucleation is an important phenomenon in crystal growth and is the precursor of the

overall crystallization process. Nucleation is the process of generating within a metastable
motherphase, the initial fragments of a new and more stable phase capable of developing
spontaneaously into gross fragments of the stable phase. Nucleation is consequently a study
of the initial stages of the kinetics of such transformations (Santhanaraghavan and Ramasamy
2000).
Nucleation may occur spontaneously or it may be induced artificially. There are cases are
referred to as homogeneous and heterogeneous nucleation respectively. Both these nucleation
are called primary nucleation and occur in systems that do not contain crystalline matter. On
the other hand, nuclei are often generated in the vicinity of crystals present in the
supersaturated system. This phenomenon is referred to as secondary nucleation (Mullin
1972).
Growth of crystals from solutions can occur if some degree of supersaturation or
supercooling has been achieved first in the system. There are three steps involved in the
crystallization process.
i) achievement of supersaturation or supercooling
ii) formation of crystal nuclei
iii) successive growth of crystals to get distinct faces

All the above steps may occur simultaneously at different regions of a crystallization unit.
If the nuclei form homogeneously in the interior of the phase, it is called homogeneous
nucleation. If the nuclei form heterogeneously around ions, impurity molecules or on dust
particles, on surfaces or at structural singularities such as imperfections or dislocations, it is
known as heterogeneous nucleation.

3
1.3 Methods of crystal growth

Growth of crystal ranges from a small inexpensive technique to a complex sophisticated

expensive process and crystallization time ranges from minutes, hours, days and to months.
The starting points are the historical works of the inventors of several important crystal
growth techniques and their original aim. The methods of growing crystals are very wide and
mainly dictated by the characteristics of the material and its size (Santhanaraghavan, P. and
Ramasamy, P., 2001). The methods of growing single crystals may be classified according to
their phase transformation as given below.

Solid Growth - Solid-to-Solid phase transformation

Liquid Growth - Liquid to Solid phase transformation
Vapour Growth - Vapour to Solid phase transformation

Based on the phase transformation process, crystal growth techniques are classified as
solid growth, vapour growth, melt growth and solution growth (Pamplin, B.R., 1979).The
basic common principle in all these methods is that a nucleus is first formed and it grows into
a single crystal by organizing and assembling ions or molecules with specific interactions and
bonding, so that the process is slow and multiple nucleations is minimized. Crystal growth
process and size of the grown crystal differ widely and are determined by the characteristics
of the material. An efficient process is the one, which produces crystals adequate for their use
at minimum cost. The growth method is essential because it suggests the possible impurity
and other defect concentrations. Choosing the best method to grow a given material depends
on material characteristics.

1.4 Growth from solution

The crystal growth from liquid can be classified into six categories namely,

i) Melt growth
ii) High temperature solution growth (Flux growth)
iii) Hydrothermal growth
iv) Gel growth
v) Electro crystallization and
vi) Low temperature solution growth

4
1.4.1 Melt Growth

Melt growth is a method of crystal growth, in which a solid is crystallized from a molten
liquid state. There are a variety of techniques to grow suitable materials into well shaped
crystals. Some growth techniques, such as crystal pulling, zone refining, and float zone, have
been thoroughly studied for common electronic materials to not only refine but also enhance
their applicability and to apply them to new materials. Melt growth is a technique involving
crystallization through fusion and resolidification of a pure material, where a liquid becomes
a solid below its freezing point. Melt growth is further classified into various sub-techniques,
as follows:

Bridgman technique

Czochralski technique

Verneuil technique

Zone melting technique

The leading significant factors to be considered during the growth of crystals from melts are
as follows:

Volatility or dissociability

Chemical reactivity

Melting point

The advantages of this method are as follows:

No impurities found during growth process

Growth rate much greater than other methods

Commercially more familiar than ever

Has more sub techniques than ever

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1.4.2 High temperature growth

Flux and hydrothermal growths form the category of high temperature solution growth.
In the growth of crystals from high - temperature solutions, the constituents of the material to
be crystallized are dissolved in a suitable solvent and crystallization occurs as the solution
becomes critically supersaturated. The super saturation may be promoted by evaporation of
the solvent, by cooling the solution or by a transport process in which the solute is made to
flow from a hotter to a cooler region. The high temperature crystal growth can be divided into
two major categories: first one is growth from single component systems and the second one
is that from multi-components. In this method, a solid (molten salt / flux) is used as the
solvent instead of liquid and the growth takes place well below the melting point of the
solute. The success of crystal growth from high temperature solution largely depends on the
selection of the solvent system.This technique can be used for the crystallization of oxide
compounds which generally have high melting points as well as for materials which have
phase transitions below the melting point (Hubner, K.H., 1969).The crystals grown from melt
have lower concentration of equilibrium defects and lower dislocation density. One major
disadvantage of this method is the corrosive nature of the fluxes used, which attack the
common furnace materials.

1.4.3 Hydrothermal growth

The term hydrothermal means, literally, “hotwater”. Hydrothermal also implies

conditions of high pressure as well as high temperature. Loosely related to growth from
aqueous solution at ambient or near-ambient conditions is the growthfrom hydrothermal
solution. Hydrothermal growth is usually defined as the use of an aqueous solvent at elevated
temperature and pressure to dissolve a solute which would be virtuallyinsoluble at ambient
conditions. The disadvantages of the hydrothermal techniques are mainly associated with
high pressure and inability to observe growth during the process. Quartz is the crystal grown
industrially by this technique (Santhanaraghavan, P. and Ramasamy, P., 2001, Ballman, A.A
and Laudise,R.A., 1963).

1.4.4 Gel growth

The growth of variety of crystals having immense importance for their practical
consideration and theoretical interest has been achieved by gel technique. The importance of

6
the gel growth is attributed to its simplicity in technique, effectiveness in growing single
crystals of compounds that cannot easily be grown by other methods. Though the origin of
the method dates back to 1899 – the famous work of Liesegang who discovered the periodic
crystallization in gels, interest in gel technique received attention only after the work of
Henisch and his co-workers (Henisch, H.K. and Garcia-Rutz, J.M., 198); Henisch, H.K.,
1970, Henisch, H.K.,1988).Crystal growth in gels is a promising technique for growing single
crystals of substances which are slightly soluble in water and which cannot be grown
conveniently from melt or vapour. The gel method has also been applied to study the crystal
formation in urinary calculi and rheumatic diseases.

1.4.5 Electro crystallization

Electro crystallization is the basis for important fields such as corrosion, energy storage
and generation, electrodeposition, electronics material development, electro refining, electro
twinning etc. Crystallization without chemical transformation or charge transfer is the
simplest case. In certain instances, the crystallization is determined by a chemical
transformation occurring prior to or simultaneously with the crystallization process. The role
played by the chemical reaction is to supply the material, which crystallizes. Electro
crystallization is the process, which leads to the formation of a new face at the
electrode/electrolyte interface, which in turn plays a major role.

1.4.6 Low temperature solution growth

The method of growing crystals from solutions may be used for substances fairly
soluble in a solvent and not react with it. Moreover, growth of crystals from solutions is the
only method for the crystallization of substances which undergo decomposition before
melting. Growth of crystals from aqueous solution is one of the ancient methods of crystal
growth. The method of crystal growth from low temperature aqueous solutions is extremely
popular in the production of many technologically important crystals. Much attention has
been paid to understand the growth mechanism of the process.

Materials having moderate to high solubility in temperature range, ambient to 100 °C

at atmospheric pressure can be grown by low temperature solution growth method. This
method is the most widely used method for the growth of single crystals, when the starting

7
materials are unstable at high temperature . This method is widely used to grow bulk crystals,
which have high solubility and have variation in solubility with temperature . Growth of
crystals from solution at room temperature has many advantages over other growth methods
though the rate of crystallization is slow. Since growth is cai-ried out at room temperature,
the structural imperfections in solution grown crystals are relatively low .
The low temperature solution growth technique also allows variety of different
morphologies and polymorphic forms of the same substance, which can be grown by
variations of growth conditions or of solvent. The proximity to ambient temperature reduces
the possibility of major thermal shock to the crystal both during growth and on removal from
the apparatus.
The low temperature solution growth technique has the merits such as
(a) Simple growth apparatus
(b) Growth of strain and dislocation free crystals
(c) Permits the growth of prismatic crystals by varying the growth conditions
(d) This is the only method which can be used for substances that undergo decomposition
before melting.
The main disadvantages of the low temperature solution growth are the slow growth rate in
many cases and the ease of solvent inclusion into the growing crystal. Under the controlled
conditions of growth, the solvent inclusion can be minimized and the high quality of the
grown crystal can compensate the disadvantage of much longer growth periods. After
undergoing so many modification and refinements, the process of solution growth now yields
good quality crystals for a variety of applications.

Low temperature solution growth can be subdivided into the following methods
(i) Slow cooling method
(ii) Slow evaporation method
(iii) Temperature gradient method

a) Slow Cooling Method

This is the most suitable method among various methods of solution growth. However,
the main disadvantage of slow cooling method is the need to use a range of temperature. The
possible range of temperature is usually low and hence much of the solute remains in the
solution at the end of the growth run. To compensate this effect, large volume of solution is

8
required. The use of wide range of temperatures may not be desirable because the properties
of the grown crystals may vary with temperature. Temperature stability may be increased by
keeping the solution in large water bath or by using a vacuum jacket. Achieving the desired
rate of cooling is a major technological hurdle. This technique needs only a vessel for the
solution in which the crystals grow. The height, radius and volume of the vessel are so chosen
as to achieve the required thermal stability. Even though this method has technical difficulty
of requiring a programmable temperature controller, it is widely used with great success. In
general, the crystals produced are small and the shapes of the crystals are unpredictable.

b) Slow Evaporation Method

In slow evaporation and slow cooling methods the apparatus are similar to each other. In
this method, the saturated solution is kept at a particular temperature and provision is made
for evaporation. If the solvent is non-toxic like water, it is permissible to allow evaporation
into the atmosphere. Typical growth conditions involve a temperature stabilization of about
0.05 °C and rate of evaporation of a few mm/h. The evaporation technique has an advantage,
viz. the crystals grow at a fixed temperature. But inadequacies of the temperature control
system still have a major effect on the growth rate. This method can effectively be used for
materials having very low temperature coefficient of solubility. But the crystals tend to be
less pure than the crystals produced by slow cooling technique because, as the size of the
crystal increases, more impurities find place in the crystal faces. Evaporation of solvent from
the surface of the solution produces high local super saturation and formation of unwanted
nuclei. Small crystals are also formed on the walls of the vessel near the surface of the liquid
from the material left after evaporation. These tiny crystals fall into the solution and hinder
the growth of the crystal. Another disadvantage lies in controlling the rate of evaporation. A
variable rate of evaporation may affect the quality of the crystal. In spite of all these
disadvantages, this is a simple and convenient method for growing single crystals of large
size.

c) Temperature Gradient Method

The temperature gradient method relies on the transport of the material from a hot region,
containing the source material to be grown, to a cooler region where the solution is
supersaturated. The main advantages of this method are as follows:

9
o Economy of solvent and solute

o Crystals grow at a fixed temperature

o Relative insensitivity to changes in temperature

1.5 Optimizing solution growth

The growth of good quality single crystals by slow evaporation and slow cooling
techniques require the optimized conditions and the same may be achieved with the help of
the following norms: (i) Material purification, (ii) Solvent selection, (iii) Solubility, (iv)
Solution preparation, (v) Seed preparation, (vi) Agitation, (vii) Crystal habit, and
(viii)Cooling rate.

1.6 Material Purification

An important prerequisite for growing good quality crystals is the availability of the
highest purity material. Solute and solvents of light purity are required, since impurity may be
incorporated into the crystal lattice resulting in the formation of flaws and defects. Sometimes
impurities may slow down the crystallization process by being absorbed on the growing face
of the crystal which changes the crystal habit. A careful repetitive use of standard purification
methods of recrystallization followed by filtration of the solution would increase the level of
purity.

1.7 Solution and Solubility

A solution is homogeneous mixture of a solute in a solvent. Solute is the component,

which is present in a smaller quantity and the one which gets dissolved in the solvent. For a
given solute, there may be different solvents. The solvent must be chosen taking into account
the following factors to grow crystals from solution. A solvent of choice is the one with
(i) a good solubility for the given solute,
(ii) a good temperature coefficient of solute solubility,
(iii) less viscosity,
(iv) less volatility,
(v) less corrosion and non-toxicity, and
(vi) cost effective.

10
 For crystal growth, high purity water is needed. Solubility of the material in a solvent
decides the amount of the material, which is available for the growth and hence defines the
total size limit. If the solubility is too high, it is difficult to grow bulk single crystals and
lower solubility restricts the size and growth rate of the crystals. Solubility gradient is another
important parameter, which dictates the growth procedure. Neither a flat nor a steep solubility
curve will enable the growth of bulk crystals from solution. If the solubility gradient is very
small, slow evaporation of the solvent is the other option for crystal growth to maintain the
supersaturation in the solution.
Low temperature solution growth is mainly a diffiision-controlled process; the mediimi
must be less viscous to enable faster transfer of the growth units from the bulk solution by
diffusion. Hence a solvent with less viscosity is preferable. Super saturation is an important
parameter for the solution growth process. The solubility data at various temperatures are
essential to determine the level of super saturation. Hence, the solubility of the solute in the
chosen solvent must be determined before starting the growth process .The solubility of the
solute can be determined by dissolving the solute in the solvent maintained at a constant
temperature with continuous stirring. On reaching saturation,equilibrium concentration of the
solute can be determined gravimetrically.
A sample of the supernatant liquid is withdrawn by means of a warmed pipette and a
weighed quantity of the sample is analyzed. By repeating the above procedure for different
temperatures, the solubility curve can be plotted. Solubility of most substances increases with
temperature .
1.8 Advantages mixed crystal
There are several advantages of crystal growth from solution. This technique makes it
possible to grow crystals that are unstable at their melting points or those exist in several
crystalline forms depending on the temperature and provide control over temperature of
growth (Tanenbaum, M., 1961). Many times there is an advantage in control of viscosity in
solution growth methods which permits crystals that tend to form glasses when cooled from
their melts to be grown. Crystals grown from solution usually have well defined faces
compared with those grown from melts. Solution growth methods are comparatively
inexpensive.
The growth from solution can be visually inspected. The method has been extensively
used for studying the growth parameters, including convection and transport. However the

11
solution growth techniques are comparatively slower, requires high purity solvents and a
good deal of designing and settings for good quality crystal growth (Galos, H.C., 1979).

1.9 Importance of crystals

Matter is composed of atoms which may or may not be joined into distinguishable
groups called molecules. The atomic aggregates are normally classified into three states of
matter, viz. the solid state, the liquid state and the gaseous state. Plasma, the fourth state is
not considered here.
A solid material with a regular and periodic atomic arrangement is said to be crystalline.
Crystals can be considered as a regular polyhedral form bounded by smooth surfaces, which
is assumed by a chemical compound, under the action of its interatomic forces, when passing
from the state of a liquid or gas to that of a solid under suitable, conditions. In the case of a
crystalline substance, the melting paint is very sharp. Crystals are incompressible and rigid.
Salt, sugar, diamonds and emeralds are all examples of crystals.
Man had admired crystals for long, as he had appreciated beauty. The gems and crystals
delivered by mother earth have always attracted our mankind. The use of gems for
ornamental purposes appears to be in practice since the birth of humankind.
Today, crystals are the pillars of modern technology. Without crystals, there would be no
electronic industry, no photonic industry, no fibre-optic communications, very little modern
optical equipment and some very important gaps in conventional production Engineering
progress in crystal growth and epitaxy technology highly demanded in view of its essential
role for the development of several important areas such as production of high efficiency
photovoltaic cells and detectors for alternative energy and medicine and the fabrication of
bright long-time light emitting diodes, for saving energy by wide use in illumination and
traffic lights.
The success of laser fusion energy depends on the timely development of high power laser
crystals and radiation resistant frequency multiplying crystals of oxide compounds. Non-
linear optical crystals are very important for laser frequency conversion. Apart from semi
conductor and crystals, there are several other materials which are technologically and
strategically important.
The increasing demand for storage and processing data has encouraged in photorefractive
crystals. This interaction of laser light with crystal such as bismuth silicate and barium
titanate produce a small change in the refractive index.

12
 Modern industry cannot do without a wide variety of crystals. Crystals are used in watches
transistorized radios, computers, lasers and many other machines. The requirements of the
electronics industry have stimulated many advances in crystal growth, both extending
existing techniques and bringing forward new ones.
Artificial crystals are grown everyday and now we scientists and researchers are more
concerned to discover new materials for the purpose of industrial and academic uses. At
present, industry, science and technology hardly make any progress without the development
of new materials of enhanced performance. Due to the increasing need of crystals in solid
state devices, scientists‟ interests have turned from pure crystals to mixed and impurity added
(doped) crystals (controlled mixing and controlled doping).

1.10 Objectives of the study

The goal of this thesis is to grow and study the structural ,optical and mechanical properties
of pure and ZnCl2 doped KClxBr1-x mixed crystals by slow evaporation method.The present
investigation is aimed at:

1) Grow bulk size pure and ZnCl2 doped KClxBr1-x mixed crystals.

2) Identify the crystal structure by powder X-ray diffraction analysis.

3)Analyse the grown crystal for its optical transmission/absorption properties.

4)Determine the thermal stability of grown crystals.

5)Find the SEM images.

13
 CHAPTER 2

REVIEW OF LITERATURE

2.1 INTRODUCTION
A Literature review is a written work that

* Compiles significant research published on a topic by accredited scholars and researchers;

*Surveys scholarly articles, books, dissertations, conference proceedings, and other sources;

* Examines contrasting perspectives, theoretical approaches, methodologies, findings, results,

conclusions.

*Reviews critically, analysis, and synthesizes existing research on a topic;

Literature reviews are important because they are usually a required step in a thesis
proposal. The proposal will not be well- supported without a literature review.

Also ,literature reviews are important because they help to learn important authors and
ideas in the field. This is ueful for our coursework and our writing. Knowing kew authors
also helps us to become acquainted with other researchers in our field.

Angeli Mary et al [2001] Bis Thiourea Zinc Chloride (BTZC) a new semiorganic
nonlinear optical material has been synthesized. The solubility studies have been carried out
in the temperature range 30°- 55°C. Single crystals of BTZC have been grown by slow
evaporation of saturated aqueous solution at room temperature. The lattice parameters of the
grown crystals have been determined by single crystal X-ray diffraction technique. The UV-
Vis-NIR transmittance spectrum has been recorded in the range 200-2000 nm. The FT-IR
spectrum has been recorded in the range 400-4000 cm -1 and the spectral bands have been
compared with similar thiourea complexes.

Perumal et al (2005) have reviewed mixed and impurity-added (doped) crystals of

alkali halides are found to be harder than the end members and so they are more useful. In
view of this, it becomes necessary and useful to prepare binary- and ternary-mixed crystals
regardless of miscibility problem and characterize them by measuring their physical
properties. In the present work, we have grown (KCl)x(KBr)y−x(KI)1−y crystals for various
values of x and y by the melt method and physically characterized. Bulk composition of the

14
crystals was measured using the measured density and refractive index values. X-ray
diffraction analysis indicates the existence of two phases in the mixed crystals. Thermal
parameters were determined using the X-ray powder diffraction intensity data.

K. Jayakumar et al (2005 ) reported that the mixed crystals of NaCl, KCl and KBr were
grown by the melt method for the first time. Densities and refractive indices of all the grown
crystals were determined and also used for the estimation of the bulk composition in the
crystal. Lattice parameters and thermal parameters like Debye–Waller factor, mean square
amplitude of vibration, Debye temperature and Debye frequency were determined from the
X-ray powder diffraction data. The observed lattice parameters showed the existence of two
phases in crystals with NaCl content greater than 0.1 mole fraction. The thermal parameters
show a highly non-linear composition dependence. The results are reported.

V. Hari Babu et al(2002) studied that the physical properties of alkali halide mixed
crystals has been a subject of wide interest in the recent past. The main aim of this review is
to provide a survey of the current state of knowledge about the nature of imperfections
present and their role in understanding various properties associated with alkali halide mixed
crystals. An attempt has been made to distinguish different types of mixed crystals, the
conditions for the formation of a mixed crystal, the local strains that arise in the lattice due to
the difference in the size of the ions that constitute the mixed crystal. The results obtained
from various studies such as ionic conductivity, dielectric loss, microhardness, radiation
hardening, colour centres, thermoluminescence, optical absorption etc. on alkali halide mixed
crystals are presented. The non-linear variation of electrical conductivity, microhardness, half
widths of many colour centre bands with composition have been discussed in terms of the
concentration of various defects present in them. The aspects of the problem described
include:

a) Dislocation density and distribution studies.

b) Influence of dislocations and grain boundaries on transport properties of these crystals.

c) Role of ionic size on microhardness.

d) Lesser rate of hardening in mixed crystals due to irradiation.

e) Stability of colour centres in mixed crystals in comparison with the end products, finally
the present position and out look are summarized.

15
 Y.C. Venudhar et al (1984) determined the precision lattice parameters and the coefficients
of thermal expansion of KCl, KBr, and their solid solutions as a function of temperature by
an X-ray method using a high-temperature powder camera. From the X-ray diffractograms
obtained at room temperature the Debye-Waller factors, Debye temperatures and the root
mean square amplitudes of vibration of these mixed crystals have been evaluated. A linear
relationship is obtained between the lattice parameter and the composition of the solid
solution in accordance with Vegard's law. Both of the thermal parameters, the thermal
expansion coefficient and the root mean square amplitude of thermal vibration, vary non-
linearly with increasing mole percentage of KBr, the deviation from linearity being maximum
around equimolar concentration. The composition dependence of these parameters is
discussed in relation to a number of physical properties of these mixed crystals available in
the literature.

A. Smakula et al (1962) reported that the mixed crystals of potassium chloride and

bromide show strong internal strain evidenced by cracking. The minimum of the melting
point occurs between 63 and 65 mole % KBr. The microhardness between 25 and 65 mole %
KBr is more than twice that of either component. The lattice constant changes linearly with
composition. The macro density deviates by several percent, indicating a high concentration
of defects. The intensity of coloration by electrons shows that defects are not mainly due
to vacancies but presumably to larger aggregates of sub microscopic size or interstitials. The
broadening of exciton bands, as measured by shifts of the ultraviolet absorption edge, is
greatest at a 2:1 KCl–KBr ratio. This may indicate a certain short‐range order in KCl–KBr

mixed crystals.

Kochiro et al studied (2006) that an initial stage of heteroepitaxial growth of KCl and LiF
on a KBr substrate using RHEED, EELS and AES. Both KCl and LiF films grow heteroepitaxially on
a KBr substrate with their crystallographic axes parallel to that of substrate. In the case of KCl growth
occurs in a well ordered layer-by-layer fashion and it is found that thickness of an intermediate region
between KCl and KBr is less than 2 nm. In contrast three-dimensional island growth occurs in the
case of LiF. Differences in lattice mismatch and solid solubility seem to determine the mechanism of
heteroepitaxy of KCl and LiF on a KBr.

M. Padma et al (2007) grown multiphased mixed crystals by the melt method, using the
miscible alkali halides, namely, NaBr and KCl. X-ray powder diffraction measurements
indicate the existence of multiple phases and mostly of ternary mixed alkali halides. Density

16
and refractive index were measured and the composition was determined. Results are
reported.

  R.Baldacchini et al (1979) reported the electron –spin memory and magnetic-circular-

dichroic effects in the luminescence of F centers in KI, KBr, and KCl. They have solved the
rate equations of the optical pumping cycle of the F center in the case of two spin-mixing
parameters,ε+ and ε-.

Mishra et al (2014) synthesized the X-ray characterization of mixed KCl xKBr1-x single
crystals. The distance ‘d’ between adjacent (100) planes has been found to vary in a linear
way with the change of x different KCl xKBr1-x crystals studied through X-ray diffraction
analysis.

C.K Magadevan et al (2008) determined mixed crystals of NaBr and KBr were prepared
from melt and physically characterized. Bulk composition of the crystals was estimated using
the measured density values. X-ray diffraction analysis indicates the existence of two phases
in the mixed crystals. Thermal parameters determined from the X-ray powder diffraction data
are found to vary nonlinearly with bulk composition. DC and AC electrical measurements
were carried out at various temperatures. The results indicate that the electrical parameters
increase with the increase in temperature and vary nonlinearly with the bulk composition.

V. Hari Babu et al (1975) studied dislocations and ionic conductivity in KCl-KBr mixed
crystals. The density and distribution of dislocations in KCl-KBr mixed crystal have been
studied as a function of composition both along and normal to the growth direction
employing the etch technique.

A. esly Fathima et al (2013) studied Debye-Waller factors and Debye temperatures of

KClxBr1-x mixed crystals grown from aqueous solution. The grown crystals were
characterized by taking XRD, TG/DTA and Vickers microhardness measurement.

R.Badarayani et al (2003) have reported densities and sound velocities of glycine and
NaBr and MgCl2 at 298.15K.They observed that MgCl2 influence he apperent morel and
transparent properties of the volume and compressibilities more stronger than
1:1electolytes.The volumetric studies of amino acids in aqueous electrolyte system ,has
shown that guanidine hydrochloride is structure-beaker and interact with charged end group
of zwitterionic amino acids , causing a net decrease in electrostriction of solvent ,while
sodium sulphate is a water structure – maker.

17
 Marine et al (2008) have reviewed magneto-optic techniques the ground state spin-lattice
relaxation times (TI) of ‘F’ centers in mixed Alkali Halide crystals (KCl-KBr), was studied.
A computer assisted system to optically measure short relaxation times (approx =1ms), was
described. The technique is based on the measurements of the Magnetic Circular Dicroism
(MCD) presented by F centers. The TI magnetic field dependency at 2K (up to 65 K Guass),
was obtained as well as the MCD spectra for different relative concentration at the mixed
matrices. The theory developed by Panepucci and Mollenauer for F centers spin lattice
relaxation in pure matrices was modified to explain the behaviour of TI in mixed crystals.The
Direct Process result (T approx =2.0K) compared against that theory shows that the main
relaxation mechanism, up to 25K Guass, continues to be phonon modulation of the hiper fine
interaction between F electrons and surrounding nuclei.

Priya et al (2008) grown multiphased mixed crystals of NaCl, KCl and KI by the melt
method, for the first time. Densities and refractive indices of all the grown crystals were
determined and used for the estimation of the composition in the crystal. Atomic absorption
spectroscopic measurements were done to estimate the metal atom contents in the crystal.
Lattice parameters and thermal parameters (Debye-Waller factor, mean square amplitude of
vibration, Debye temperature and Debye frequency) were determined from the X-ray powder
diffraction data. DC and AC electrical measurements were done at various temperatures
ranging from 40 to 150°C. Activation energies were also estimated. The observed lattice
parameters showed that the system exhibits three phases each nearly corresponds to NaCl,
KCl and KI. The thermal and electrical parameters show a highly nonlinear bulk composition
dependence. Results are reported.

Sathaiah et al (1987) studied the systematic measurements of the dielectric properties of

mixed KCl KBr crystal system are carried out in the frequency range 100 Hz to 100 kHz at
room temperature to obtain composition variation of static dielectric constant (ε) and loss (tan
δ). The temperature variation is measured in the same frequency range at temperatures
ranging from room temperature to 320°C. This is the first report on detailed measurement of
dielectric properties of KCl KBr mixed crystals at room temperature as well as at elevated
temperatures. The data are used to evaluate effective ionic charge, conductivity, and
activation energy for conduction. All these properties are found to show a non-linear
composition dependence. The temperature variation of dielectric constant for KCl, KBr, and

18
the mixed crystals is analysed to obtain the unharmonic contribution to dielectric constant
and effective ionic charge.

Feridoun Samavat et al (2012) reported the growth of KClx Br1-x mixed crystals with
different composition percent and study of KBr concentration effect on optical characteristics
of mixed crystals. For their research, mixed crystals KClx Br1-x were grown by czochralski
method. Then some analysis such as chemical etching, XRD and absorbing spectrum were
established on the irradiated crystals by γ-ray.

M.Aguilar et al (1998) studied the aggregation-precipitation processes of divalent

europium ions in mixed potassium halides (Cl/Br) has been carried out. Quenched samples
lead to a single emission band at 418 nm, which compared with the emission observed in the
corresponding europium doped non-mixed alkali halide crystals, appears perturbed by the
presence of Cl or Br ions. This band has been ascribed to free europium-vacancy complexes.
The annealing at 353 K produces an emission band composed of several contributions: (1)
free dipoles, (2) an emission that might be attributed to a Suzuki type mixed phase containing
chloride as well as bromide ions and (3) a band due to a metastable mixed phase peaking at
around 450 nm. On the other hand, the annealing at 473 K induces metastable phases of the
dihalide type emitting at 430, 448 and 474 nm. The intensity of these bands changes as a
function of the content of halogen ions.

P.Easwaran et al (2009) obtained optical absorption spectra of KBr:Tl + (0.0125 mol%)

single crystals shows A, B and C bands around 258, 220 and 210 nm respectively. In
KCl0.1Br0.9 :Tl+ (0.0125 mol%) mixed crystals exhibit slightly broadening of the A-band
towards lower wavelength side. The broadening of the absorption spectra are suggested to be
due to some complex Tl+ centers involving Br- and Cl- ions formed in the mixed crystals.
When excited at A, B and C-bands of Tl + ions, PL of KBr:Tl+ showed emission band around
320 with a prominent shoulder around 365 nm. In KCl0.1Br0.9 mixed crystals the shoulder
around 365 nm is not prominent due to the perturbing influence of Cl -ions. Addition bands in
the excitation spectra are attributed to the presence of Tl + dimmers. PSL observed in X-ray
irradiated crystals resembled their respective PL emissions indicating that PSL in them is due
to Tl+ ions.
S. Pehkonen et al (2005) studied diffusion of Br- ions in KCl-KBr mixed crystals of
different compositions at temperatures from 519 to 599°C by the capacitance method. In
addition to the composition dependence of the activation energy associated with the diffusion

19
process, the dependence of the chemical diffusion coefficient on composition is determined at
different temperatures. The experimental results are in good agreement with those derived
from the diffusion theory of non-uniform thermodynamics.

M.Abtee et al (2008) studied the formation of mixed crystals in equimolar KCl-KBr

powder mixtures at temperatures from 406 to 602°C. The progress of the homogenization is
followed by measuring the change in specimen capacitance as a function of time. The results
indicate that the following three processes are involved in the mixed crystal formation: (i)
grain boundary diffusion, (ii) volume diffusion of Cl −ions, and (iii) volume diffusion of
Br− ions. The experimental results for the activation energies associated with these processes
are respectively 1 5±0 2 eV, 1 9±0 2 eV and 2 1±0 1 eV.

I.R Ananad Kumari et al (2004) reported mixed and impurity added doped crystals of
alkali halides are found to be harder than the end members and so they are more useful. In
view of this, it becomes necessary and useful to prepare binary and ternary- mixed crystals
regardless of miscibility problem and characterize them by measuring their physical
properties. In the present work we have grown (KCl)0.333 (KBr)0.333(NaI)0.333 ternary
alkali halide crystals with and without La(NO3 )3 dopant by the melt method and physically
characterized. Crystals were ã- irradiated. For the irradiated crystals, Thermoluminescence
studies have been made. Thermoluminescence glow curves were analysed as function of
irradiation strength. A thermoluminescen enhancement, relative to the pure end components
is found and mixed crystal presents a significant increase in thermoluminescence efficiency.

K.Vassiliki et al (1984) reported Ac electrical measurements for alkali halide mixed

crystals that were melt grown from NaCl, KCl and KBr starting materials. They showed a
nonlinear variation of all the electrical parameters with the bulk composition. Here, we show
that these mixed systems, depending on their major constituent, are classified into three
categories in each of which, the activation energy for the ac conductivity increases linearly
with B , where B is the isothermal bulk modulus and  the mean volume per atom.

Prasad Narayan Patil et al (2006) studied the scattering of phonons by point defects at
liquid helium temperatures studied. Single crystals of KCl-KBr solid solutions were
employed, since it is known that the Cl− and Br− ions are randomly distributed in the anion
lattice sites. A 1 mole percent addition of KBr reduced the conductivity of KCl by a factor of
three. For all the crystals measured, including pure KCl and pure KBr, the thermal
conductivity showed a maximum at the same temperature (5°K). Hence, point defects reduce
20
the conductivity on both the high- and low-temperature sides of the maximum. For the mixed
crystals the thermal conductivity was found to be related to the absolute temperature by the
empirical formula K=K0e−0.099T for the temperature interval 6°K to 16°K.

Wendell S.Williams et al (1960) studied the Thermoluminescence (TL) glow curves of X-

irradiated KCl (Pure),KBr (Pure) and KCl-KBr mixed crystals in the different dose of X-
irradiation with periods 40minutes,60 minutes& 120 minutes with temperature range 25-
300o C. A plot of the peak height against composition shows a minimum at KCl0.52: KBr
0.48 .The glow curves were analyzed & the variation of activation energy with composition
has also been studied. The variation of peak temperature and the relative intensity of the
peaks with respect to the composition the addition of Brions to the KCl lattice has been found
to be more effective in enhancing the Thermoluminescence (TL) of KCl-KBr solid solution.

V.M Anishchik et al (2008) reported the influence of X-rays of different wavelength on

the degree of structural quality of K(Cl, Br) crystals of mixed composition grown from
aqueous solutions. It is found by the methods of chemical etching, X-ray analysis,
pycnometric density, and atomic-force microscopy that X-ray irradiation leads to the
formation of crystals with a more perfect substructure and surface morphology and a decrease
of the dislocation density and concentration of pores and cavities containing the mother
liquor. It is shown that X-ray irradiation can promote preferential incorporation of less
electronegative components into the crystal lattice of a solid solution.

P.C Mehendra et al (2005) observed two thermoluminescence peaks at 90 and 150 °C in

highly pure KBr crystals (background divalent cation impurity not greater than 1 p.p.m.).
From the growth of F centres with the time of x-irradiation these two peaks have been
interpreted in terms of the two types of F centres postulated previously. The presence of Cd
impurity in KBr suppresses the formation of both the types of F centres while the presence of
Zn impurity enhances the first-stage F centres but suppresses the second-stage F centres.
Optical absorption studies of the KBr crystals doped with Cd and Zn are correlated with the
thermoluminescence data. Plastic deformation of highly pure KBr crystals considerably
increases the area under both the thermoluminescence peaks. No additional glow peak is
observed either in plastically deformed or Cd- and Zn-doped KBr crystals.

Thermoluminesence experiments performed with highly pure NaCl crystals (background

divalent cation impurity not greater than 1 p.p.m.) also show two peaks at 170 and 210 °C.
However, in analar purity NaCl crystals (background divalent cation impurity about 20

21
p.p.m.) or in NaCl crystals containing Ca and Cd, an additional Thermoluminesence
thermoluminescence peak at 80 °C is also observed.

The activation energies of both the types of F centres in KBr and NaCl and of the impurity
centres in NaCl are evaluated from the thermoluminescence results using the `initial rise
method'.

R.Bernal et al reported Thermoluminescence properties of new europium doped

KClXBr1-X:Eu2+ type phosphors were investigated as a function of the relative composition
X. We show that these phosphors exhibit better thermoluminescence properties than those
made of the alkali halides crystals with same composition, for the case of X and ultraviolet
radiation. The characterized samples were made from a mixture of KCl, KBr and Eu2O3 high
purity powders. The mixed powder were first pressed at an average pressure of 5.5 ton for 10
minutes, and then sintered five hours at 700 oC. In both cases, for X and UV radiation
exposure of the samples, the thermoluminescence response depends strongly on the
composition X, and a notorious enhancement of the thermoluminescence intensity is obtained
around X=0.3. The samples exhibit promising properties as detectors and dosimeters for X
and UV radiation.

2.3 Mixed Crystals

Many of the semiconducting materials grown have dopant ions added to produce some
desirable property. A very important situation that is special to ionic crystals arises when
these crystals are doped (or added) with impurities. The behaviour depends on the valence
state of impure ions. Whether an impure ion goes to substitutional position or interstitial
position is determined by the ionic radius of the doped (or added) ion and alsoon the
electronic configuration of the ion. If the impurity ion behaves in the same way as the lattice
ion, a wide range of solubility may be possible. To describe this effect, the term „mixed
crystal‟ is used. It should be realized, however that the impurity ions are all distributed at
random throughout the lattice so that the term „solid solution‟ is more appropriate. A solid
solution is basically a crystalline phase that can have variable composition. As with doped
crystals, simple solid solutions are one of two types, substitutional or interstitial.

22
When two substances A and B have closely similar structures (neomorphic structure) with
not much different cell dimensions, it is found that the atoms of one can replace those of the
other indiscriminately in the lattice, resulting in a mixed crystal AB or solid solution .
There are several ways in which solid solutions can form. Accordingly, they are classified
into the following three categories.

1. Substitutional solid solutions in which replacement of one atom for another takes place.
Azaroff[3] observed that substitutional solid solutions can occur only if the radius of the
larger atom does not exceed that of the smaller atom by more than 15 percent. Here, some of
the normal lattice sites in the solvent crystal are occupied by solute atoms, and structure of
the solvent remains unchanged. K eCl and KBr give solid solutions of any composition
between the two extremes.

2. Interstitical solid solution to which limited number of solute atoms occupy interstitial
position in the solvent crystal. Solid solutions CaF2 - YF3 provide examples of crystals
containing interstitial ions.

3. Defect solid solutions to which some sites in the lattice of one of the components remain
vacant. Defect solid solutions are formed typically in chemical compounds of transition
elements, as well as, sulphides, selenides and some oxides.

A mixed crystal has physical properties analogoas to those of pure crystals. The
composition dependence varies from system to system and property to property. In many
cases, the property changes monotonically with composition in a linear or nearly linear
manner. Once the trend in composition dependence is established, we have a means to have a
tailor made crystal with a desired value for a given physical property. In a few properties, the
composition dependence is highly non-linear and, in some cases, the magnitude of the
physical property for the mixed crystal even exceeds the values for the end members. In such
a case, it is as if we have a new crystal in the family. Such behaviour is shown, for instance,
in the micro hardness of alkali halide mixed crystals. In some instances, mixed crystals show
exciting behaviour. One such example is the appearance of a first order Raman spectrum in
mixed crystals of alkali halides which is absent in the pure crystal .

23
2.4 Alkali halide mixed crystals

The alkali halides constitute a family of versatile crystals. Their simple crystal structure
and bonding scheme have made them favorite candidates for testing theories. It is not as if the
alkali halides were used only for testing theories. They were also the materials of first choice
in many pioneering experiments. KCl was one of the crystals used by Laue in his famous
experiments on X-ray diffraction and NaCl was one of the first crystals which Bragg choose
for structure analysis.
Alkali halide compounds are formed by the combination of alkali atoms (Li, Na, K, Rb
and Cs) of the first group (IA) and halogens (F, Cl, Br and I) of the seventh group (VII A).
The alkali halide crystallize either in the NaCl (Sodium Chloride) structure or in the CsCl
(Cesium Chloride) structure. In ambient conditions CsCl, CsBr and CsI crystallize in the
CsCl structure and the others crystallize in the NaCl structure. All the alkali halides (except
LiF and NaF) are soluble in water and can (in principle) be crystallized from aqueous
solution. All the alkali halides have congruent melting points and therefore their crystals can
be formed from their melts.

2.5 Present work

Alkali halide crystals are compounds formed by the combination of alkali atoms of the
first group and halogens of the first group and halogens of the seventh group. The alkali
halides crystallize in either of the two structures, viz. the NaCl structure and CsCl structure.
The alkali halide crystals have always been at the centre state of solid - state physics. They
have been “model crystals” for testing many solid- state theories. In recent decades, they have
also proved useful in several applications ranging from X-ray monochromators to tunable
laser. The mixed and impurity added crystals of alkali halides are found to be harder than the
end members and so they become more useful in these applications in optical, optoelectronic
and electronic devices. So, it is necessary to prepare binary and ternary - mixed Crystals of
alkali halides. Alkali halide mixed crystals are of the completely disordered substitutional
type. Several reports are available on binary mixed crystals of alkali halides and only limited
reports are available for doped mixed crystals.
In the present study mixed crystals of kcl and kbr without and with adding Zncl have
been grown from aqueous solution by slow evaporation method and characterized. Single

24
crystals of the components, viz.KBr and KCl have also been grown from aqueous solution
and characterized for comparison purposes.
X-ray diffraction data for the powdered samples were collected and they were indexed. The
lattice parameters were determined using the standard methods. Thermal parameters like
Debye-Waller factor, mean square amplitude of vibration, Debye temperature and Debye
frequency were determined from X-ray diffraction intensity data. TG/DTA thermal analysis
respectively. Debye temperatures have also been determined from the hardness value and
melting point temperatures. Spectroscopic measurements like UV -Vis and FTIR studies have
also been carried out for all the grown crystals.

25
 CHAPTER-3

CHARACTERIZATION TECHNIQUES
In the present study the pure and and Zn ions doped crystals were subjected to various
characterizations such as X - Ray diffraction (PXRD) analysis, Fourier Transform Infra Red
(FTIR) spectroscopy, Scanning Electron Microscopy(SEM), Thermo Gravimetric/Differential
Thermal (TG/DT) analyses, UV- Visible optical analysis and Fluoresence analysis.

3.1 X-Ray Diffraction (XRD) Analysis

X- ray diffraction is a tool for the investigation of the fine structure of matter. This
technique had its beginnings in von Laue's discovery in A.D.1912 that crystals diffract X -
rays, the manner of the diffraction revealing the structure of the crystal. At first X- ray
diffraction was used only for the determination of crystal structure. Later on, however the
other uses were developed, and today the method is applied not only to structure
determination, but to such diverse problems as chemical analysis and stress measurement, to
the study of phase equilibrium and the measurement of particle size, to the determination of
the orientation of one crystal or the ensemble of orientations in a polycrystalline aggregate.
When we are focused of structure determination the single crystal and powder X- ray
diffraction techniques are used.

3.1.1 Single crystal x-ray diffraction analysis

Single crystal X-ray diffraction (X-ray crystallography) is an analytical technique in

which X-rays (wavelength range from 0.1 to 10 A) are employed to determine the actual
arrangement of atoms within a crystalline specimen. Single crystal X-ray diffraction (XRD)
is a non-destructive tool to analyze crystal structure of compounds, which can be grown as
single crystals. The molecular structure, atomic coordinates, bond lengths, bond
angles,molecular orientation and packing of molecules in single crystals can be determined
by X ray crystallography. Single crystal X-ray diffractometer (Figure 2.2) collects intensity
data required for structure determination.
Accurate measurements of intensities of reflections of all Miller indices within a
specified reciprocal radius is needed to find the structure, while unit cell parameters depend
only on direction of reflections. As die name implies, a crystalline sample is required. For
26
single-crystal work, the specimen should be smaller than cross section diameter of the beam.
Larger crystals can be cut down to proper size and smaller crystals may be suitable if they
contain strongly diffracting elements.The monochromatic X-rays incident on a plane of single
crystal at an angle theta are diffracted according to Bragg's relation
2d sind = nλ
Where, d is the interplanar spacing of the incident plane, X is the wavelength of X-rays and n
is a positive integer.
The intensity of the diffracted rays depends on the arrangement and nature of atoms in the
crystal. Collection of intensities of a full set of planes in the crystal contains the complete
structural information about the molecule. Fourier transformation techniques are used to
determine the exact coordinates of atoms in the unit cell from this data.

With the set of X-ray diffraction data collected, unit cell parameters, space
group,molecular structure, etc of the crystalline solids and Miller indexing of the different
faces of the crystal are possible. Unit cell parameter is simply the dimension of the basic
molecular brick with which the crystal is built. Space group tells us the symmetry with which
the molecules are arranged within the unit cell. All the geometrical features of molecules
(bond distance, bond angles, torsion angles between bonds, dihedral angles between planes,
etc.) may be obtained from coordinates
.
3.1.2 Powder X-ray diffraction analysis

Powder X-ray diffraction is useful for confirming the identity of a solid material and
determining crystallinity and phase purity. In general, to determine the molecular structure of
new materials, a single crystal X-ray diffractometer is used. Powder X-ray diffractometer is
used for phase identification and quantitative phase analysis.

The basic three components of an X-ray diffractometer are as follows:

 X-Ray source
 Specimen
 X-ray detector

27
 The angle between the plane of the specimen and the X-ray source is θ, the Bragg angle.
The angle between the projection of the X-ray source and the detector is 2θ. For this reason,
the X-ray diffraction patterns produced with this geometry are often known θ-2θ(theta-two
theta) scans. In the θ - 2θgeometry the X-ray source is fixed and the detector moves through a
range of angles.

The radius of the focusing circle is not constant but increases as the angle 2θdecreases.
The 2θ measurement ranges typically from 0mm to approximately 170m. In an experiment, it
is not necessary to scan the whole range of detector angles. A 2θ range from 30cm to 140cm
is an example of a typical scan. The choice of range depends on the crystal structure of the
material (if known). For an unknown specimen, a large range of angles is often used because
the positions of the reflections are not known.

The diffractometer circle is different from the focusing circle. The diffractometer circle
is centred at the specimen, and both the X-ray source and the detector lie on the
circumference of the circle; the radius of the circle is fixed. The diffractometer circle is also
referred to as the goniometer circle. The goniometer is the central component of an X-ray
diffractometer and contains the specimen holder.

3.2 Fourier Transform Infrared (FTIR) spectroscopic technique

Infrared spectroscopy is the study of the interaction of infrared light with matter. The
measurement obtained in infrared spectroscopy' is an infrared spectrum, which is a plot of
measured intensity versus wavelength (or wave number) of light. An instrument used to
obtain an infrared spectrum is called an infrared spectrometer. There are several kinds of
spectrometers in the world used to obtain infrared spectra. The most prevalent type of
spectrometer is called a Fourier Transform Infrared Spectrometer (FTIR). FTIR technique is
most useful for identifying functional groups organic and inorganic compounds. It can be
applied to the analysis of solids, liquids and gases. The term Fourier Transform Infrared
spectroscopy refers to fairly recent development in the manner in which the data is collected

28
from interference pattern to a spectrum. Today's FTIR instruments are computerized which
makes them faster and more sensitive than the older dispersive instruments.
Infrared spectroscopy deals with the study of vibrational spectra of molecules.An
infrared absorption spectrum originates from molecular vibrations (vibrations of bonds)
which cause a change in the dipole moment of the molecule. The vibrational frequencies,their
relative intensities and shapes of the infrared bands recorded in a double beam spectrometer
are used for the qualitative characterization of a sample.
FTIR spectroscopic technique is based on the principle of a Michelson Interferometer
with a sensitive infrared detector and a digital minicomputer, FTIR spectrometers provide
higher resolution, total wavelength coverage, higher accuracy in frequency and intensity
measurement. The instruments also possess greater ease and speed of operation. By
interpreting the infrared absorption spectrum, the functional groups of a compound and

29
chemical bonds in a molecule can be determined. FTIR spectra of pure compounds are
generally so unique that they are like a fingerprint. While organic compounds have very
detailed spectra, inorganic compounds are usually much simpler.Samples of FTIR can be
prepared in a number of ways. For liquids samples, the easiest is to place one drop of sample
between two plates of sodium chloride (salt), which is transparent to infrared light. The drop
forms a thin film between the plates. Solid samples can be milled with potassium bromide
(KBr) to form a very fine powder. This powder is then compressed into a thin pellet which
can be analyzed. KBr is also transparent in the IR. Alternatively solid samples can be
dissolved in a solvent such as methylene chloride and the solution placed into a single plate.
The solvent is then evaporated off leaving a thin film of the original material on the plate.
This is called a cast film and is frequently used for polymer identification .

In the present work The FTIR spectrum of the sample was recorded with a Fourier
transform infrared spectrometer in the range of 400 - 4000 cm following KBr pellet
technique.

3.3 Optical characterizations

3.3.1 UV-Visible Spectrophotometery

UV-Visible spectrophotometer allows light of a given frequency to pass through a

sample and detects the amount of transmitted light. The instrument compares the intensity of
the transmitted light with that of the incident light. The source of radiation in the UV Visible
photometer is tungsten, hydrogen or deuterium lamp. A source of radiation must be provided
with each spectral region having its own requirements. All spectrophotometers include some
way to discriminable between different radiation frequencies either they use as filters, prisms
or gratings. The polychromatic radiation is separated into its component wavelength using
monochromators which consist of a prism and a plane transmission grating. The sample
absorbs a portion of the incident radiation and the reminder is transmitted on to a detector
where it is changed into an electrical signal and displayed, usually after amplification, on a
meter, chart recorder or some type of readout device.
Automatic instruments gradually and continuously change the frequency or wavelength.
The spectrum of a compound represents a group of either wavelength or frequency,

30
continuously changing over a portion of the electromagnetic spectrum versus either percent
Transmission (%T) or absorbance (A) .

3.3.2 Fluoresence analysis

Molecular luminescence spectroscopy is the measurement of light emitted by a sample.

Luminescence is the emission of light in the visible or ultraviolet region where the sample is
not being excited by heating. In luminescence, the light is emitted as the electronically
excited molecule returns to the ground state. The excited state can be generated by a variety
of techniques; thus luminescence is divided into categories depending on the mechanism by
which the excited state was formed. In chemiluminescence, the excited state is generated by a
chemical reaction; in photoluminescence, the transition to the excited state is the result of
absorption of electromagnetic radiation.
The usefulness of fluorescence spectroscopy stems from two main factors. First, the majority
of molecules do not exhibit fluorescence. As a result, in most samples, the background
fluorescence will be very small, and therefore the technique can detect specific molecules
with high sensitivity. Second, the spectral properties of the fluorescence emission are usually
highly sensitive to local environment. While for the study of small molecules this is not
especially useful, because it merely measures changes in the solvent, for fluorophores in
macromolecules, the local environment is generally different in different locations within the
macromolecule,and therefore fluorescence allows direct monitoring of changes in
conformation or interactions with other molecules.

3.4 Thermal characterizations

3.4 .1 Thermal Analysis

Thermal analysis is useful in both quantitative and qualitative analyses. Samples may be
identified and characterized by qualitative investigations of their thermal behaviour,
information concerning the detailed structure and composition of different phases of a given
sample is obtained from the analysis of thermal data. Thermal methods are based upon the
measurement of the dynamic relationship between temperature and some property of a
system such as mass, heat of reaction of volume. Of the various thermal methods, Thermo
Gravimetric Analysis (TGA) and Differential Thermal Analysis (DTA) are most important.

31
3.4.2 Thermogravimetric analysis

The TGA provides a quantitative measurement of any weight changes associated with
thermally induced transitions. For example, TGA can record directly the loss in weight as a
function of temperature or time (when operating under isothermal conditions) for transitions
that involve dehydration or decomposition .Thermo gravimetric curves are characteristic of a
given compound or material due to the unique sequence of physical transitions and chemical
reactions that occur over definite temperature ranges.
TGA data are useful in characterizing materials as well as in investigating the
thermodynamics and kinetics of the reaction and transitions that result from the application of
heat to these materials. In TG analysis, the mass of the sample is recorded continuously as a
function of temperature as it is heated or cooled at a controlled rate. A plot of mass as a
function of temperature provides both quantitative and qualitative information. The apparatus
required for TG analysis includes a sensitive recording analytical balance, a furnace, a
temperature controller and a recorder that provides a plot of sample mass as a function of
temperature. Often an auxiliary equipment to provide an inert atmosphere for sample is also
needed.

3.4.3 Differential thermal analysis

Change in the mass of the sample occurs as a result of the temperature formation of
various physical and chemical bonds at elevated temperature that lead to the evolution of
volatile products or formation of reaction products. Thus the TGA curve gives information
regarding the thermodynamics and kinetics of various chemical reactions, reaction
mechanisms, intermediate and final products. The DTA, the difference in temperature
between the sample and a thermally inert reference material is measured as a function of
temperature (usually the sample temperature). Any transition that the sample undergoes
results in liberation or absorption of energy by the sample with a corresponding deviation of
its temperature from that of the reference. As the temperature of both is increased at a
constant rate the corresponding deviation of the sample temperature from that of reference
(AT) versus the programmed temperature (T) is recorded and it explains whether the
transition is endothermic or exothermic. The DTA studies along with TGA provide detailed

32
information regarding the dehydration, decomposition and the phase transitions of a material
during heating.
In the present study the thermal characteristics of the grown crystals were studied using
Perkin TG/DTA analyzer. The temperature range selected for the present study was from
ambient temperature to 800 c.

3.5 Scanning Electron Microscopy (SEM)

The Scanning Electron Microscopy (SEM) tecnique is widely used for the observation of
surface morphology of different kinds of materials with high magnification and resolution, hi
this technique an image of very small area of the specimen under investigation is formed by
the secondary electrons (SE) ejected from the surface of the specimen by bombarding the
specimen with primary electron (PE) beam. The SEs are collected by a scintillator, which
transmit the signal to a photomultiplier and finally to a view cathode ray tube which scans
simultaneously with the PE beam. Apart from the SE, the PE beam results in the emission of
back scatted (or reflected) electrons from the specimen. Back scattered electrons possess
more energy than SE and have a definite direction. Back scattered electron imaging is more
useful in distinguishing one material from another, since the yield of the collected
backscattered electrons increases monotonically with the specimen's atomic number.
The scanning electron microscope is an electron microscope that images the sample
surface by scanning it with a high energy beam of electrons. Conventional light microscopes
use a series of glass lenses to bend light waves and create a magnified image while the
scanning electron microscope creates the magnified images by using electrons instead of light
waves.
When the beam of electrons strikes the surface of the specimen and interacts with the
atoms of the sample, signals in the form of secondary electrons, back scattered electrons and
characteristic X-rays are generated that contain information about the sample's surface
topography, composition, etc.

The SEM can produce very high-resolution images of a sample surface, revealing details
about 1-5 nm in size in its primary detection mode i.e. secondary electron imaging.
Characteristic X-rays are the second most common imaging mode for an SEM. These
characteristic X-rays are used to identify the elemental composition of the sample by a
technique known as energy dispersive X-ray (EDX). Back-scattered electrons (BSE) that

33
come from the sample may also be used to form an image. BSE images are often used in
analytical SEM along with the spectra made from the characteristic X-rays as clues to the
elemental composition of the sample. In a typical SEM, the beam passes through pairs of
scanning coils or pairs of deflector plates in the electron column to the final lens, which
deflect the beam horizontally and vertically so that it scans in a raster fashion over a
rectangular area of the sample surface. Electronic devices are used to detect and amplify the
signals and display them as an image on a cathode ray tube in which the raster scanning is
synchronized with that of the microscope. The image displayed is therefore a distribution
map of the intensity of the signal being emitted from the scanned area of the specimen. SEM
requires that the specimens should be conductive for the electron beam to scan the surface
and that the electrons have a path to ground for conventional imaging. Non-conductive solid
specimens are generally coated with a layer of conductive material by low vacuum sputter
coating or

high vacuum evaporation. This is done to prevent the accumulation of static electric charge
on the specimen during electron irradiation. Non-conducting specimens may also be imaged
uncoated using specialized SEM instrumentation such as the "Environmental SEM" (ESEM)
or in field emission gun (FEG) SEM operated at low voltage, high vacuum or at low vacuum,
high voltage.

34
 CHAPTER-4

RESULT AND DISCUSSION

4.1 INTRODUCTION
The alkali halide crystals have importance in past six decades. They have been “model
crystals” for testing many solid-state theories. In recent decades, they have also proved useful
in several applications ranging from X-ray mono chromators to tunable lasers.

In recent years alkali halide crystals have several applications viz, a radiation
dectectors, and also as laser host materials. But their applications are limited by their
mechanical strength. Mixed doped crystals of alkali halides are found o be harder than the
end member crystals and so they become more useful in their applications in optical,
optoelectronic and electronic devices. So it is necessary to grow mixed crystals and
characterize them by measuring physical properties.

In the present study mixed crystals of KCl and KBr and impurity zinc chloride added
KCl and KBr mixed crystals were grown by slow evaporation method and characterize them
by PXRD,FTIR, UV,TG/DTA and SEM.

4.2 SOLUTION PREPARATION

Take 100ml beaker were analytical reagent (AR) grade KCland KBr dissolved
double distilled water. Super saturated solutions of KCl xBr1-x were prepared for various
values of compositions. The KCl and KBr mixed crystals were grown by a desired molecular
ratio 0.05 mol% of ZnCl2 taken in a beaker and allowed to crystallize by slow evaporation
method. The weighted salt is poured into the beaker to make up 40ml of aqueous solution by
added distilled water. A magnetic stirrer is used to mix the salt with distilled water.

Beaker 1 :40ml supersaturated solution of pure KCl crystal.

Beaker2 :40ml supersaturated solution of pure KBr crystal.

Beaker3 :40ml supersaturated solution of KCl0.5 KBr0.5 mixed crystal.

35
 Beaker4 :40ml supersaturated solution of ZnCl2 doped KCl0.5KBr0.5 mied crystals.

The high quality single crystals were harvested after three weeks. The grown
crystals were carefully removed from the beakers. The crystals are dried using filter paper.

The grown crystals are characterized by powder XRD, FTIR ,UV, Fluoresence,
TG/DTA, and SEM analysis.

(a) (b)

(c) (d)

Figure 4.1: Photograph of all grown crystals

36
 a)pure KCl crystal

b)pure KBr crystal

c)KCl0.5KBr0.5 mixed crystal

d)ZnCl2 doped KCl0.5KBr0.5 mixed crystal

4.3 Powder x-ray analysis

The powder form of the specimen was subjected to powder X-ray diffraction analysis
using XPERT-PRO diffractometer with (λ=1.54060) radiation. The sample was scanned over
the range of 100c-800c at scan rate of 10/min. The diffractometer having a Cu Kα source with
the current setting at 30mA and voltage across the cathode and target being 40 KV.

The step size of 2θ and the scan step time were fixed as 10.16s respectively .From the
powder XRD studies the d-spacing values corresponding to diffraction angles were obtained.
Miller indices are identified for the diffraction peaks. The lattice parameter values have been
calculated from the powder diffraction data.

Miller indices which are related to mixed single crystals are specified according to
American Society for Testing and Materials standard with particular indices and quantities.

Lattice parameters are calculated using Bragg’s equation,

nλ=2dsinθ

where,

d- interplanar spacing

h k l- miller indices

a- lattice parameter

37
Table 4.3.1: PXRD data for different 2θ peaks for pure KBr crystal

Intensity(%) Angles in d spacing Miller indices Lattice

degrees(2θ) (hkl) parameters(A0)

100 27.1796 3.28101 200

36.86 38.7385 2.32452 220

12.16 63.0777 1.47385 331

10.86 47.8801 1.89989 222

9.09 23.4932 3.78683 111 a=6.4859

7.02 55.8248 1.64687 400

6.76 69.8940 1.34587 420

4.61
45.7386 1.98375 311

Table 4.3.2: PXRD data for different 2θ peaks for pure KCl crystal

Intensity( %) Angles in d spacing Miller Lattice

degrees(2θ) indices(hkl) parameters(A0)
28.4703 3.13514 200
100

45.24 40.6369 2.22020 220

a=6.4859
15.99 420
66.4601 1.40681

10.46 50.3027 1.81392 222

58.7298
6.71 1.57215 400

38
Table 4.3.3: PXRD data for different 2θ peaks for KCl0.5 KBr0.5 mixed crystal

Intensity( %) Angles in d spacing Miller indices Lattice

degrees(2θ) (hkl) parameters(A0)
3.26242 200
100 27.3376

49.90 2.29957
39.1758 220

13.05 222
48.5539 1.87509

64.1927 1.45092 331

12.03 a=6.4119
7.38 1.32381
71.2336 420

6.72 1.62268 400

56.7317

4.63 23.5727 3.77424 111

2.21 46.3368 1.95950 311

Table 4.3.4: PXRD data for different 2θ peaks forZnCl2 doped KBr0.5 KCl0.5 crystal

Intensity Angle in d spacing Miller indices Lattice

(%) degrees(2θ) (hkl) parameters(A0)
100 200
27.4577 3.24841
35.10
39.3733 2.28849 220
7.92
48.8539 1.86427 222
a=6.3644
6.92 331
64.7295 1.44018
5.17 400
57.110 1.61281
3.95 420
71.8274 1.31432
1.57
23.6486 3.76230 111

39
 The table 4.3.1 to 4.3.4 give the diffracted X-ray intensity versus angle (2ϴ) data for
these samples. The peak positions at diffraction angle 2θ x-axis and intensity (counts) y-axis.
The peak intensity is recorded, the most intense peak is (200) plane and Miller indices
identify diffraction angle peaks. The PXRD patterns show 100% intensity for reflections
from (200) planes the inter planar spacing vary (increase) in a linear way with the different
crystals, studied through XRD. . Highly intense peaks without any additional peaks of
impurities obviously state the phase purity of material.

(a)

40
(b)

(c)

41
 (d)

Figure 4.3.1 :XRD spectrum of all grown crystals

a)pure KCl crystal

b)pure KBr crystal

c)KCl0.5KBr0.5 mixed crystal

d)ZnCl2 doped KCl0.5KBr0.5 mixed crystal

42
 The change in intensity, volume, lattice parameters suggest that the structure of ZnCl 2
doped KCl0.5KBr0.5 mixed crystals was slightly distorted when compared to pure crystal. It is
seen from the PXRD spectrum of pure and ZnCl 2 doped KCl0.5KBr0.5 mixed crystals that
there is no additional peak, but only change in the intensity of the peaks. This confirms there
is no additional phase produces due to influence of doping.

From the XRD pattern of the all grown crystals the d values corresponding to 2θ values
and the miller indices values were used to calculate the lattice parameter values. The bulk
composition of the mixed crystal is determined by Vegard’s law:

a=xa1+(1-x)a2

The bulk compositions of the mixed crystals were also verified by Retger’s rule using the
Equation:

a3=xa13+(1-x)a23

Where,

a is the lattice parameters of the mixed crystal

x is the composition of KCl

(1-x) is the composition of KBr

a1 is the lattice parameters of pure KCl

a2 is the lattice parameters of pure KBr.

The lattice parameters obtained in the present study along with those estimated from
Vegard’s law and Retger’s rule are provided in Table 4.3.5. From the pure crystals lattice
parameter through us calculate the lattice parameter of the mixed crystals.

Table 4.3.5: Lattice parameters for pure and mixed crystal

System Lattice parameter Vegard’s law Retger’s rule

KCl 6.2826 - -

KBr 6.4859 - -

KCl0.5 KBr0.5 6.3644 6.3842 6.3858

43
Table4.3.6: Interplannar spacing for mixed crystals

System Intensity (%) Miller indices(hkl) d spacing

Pure KCl crystal 3.28101

Pure KBr crystal 3.13514

100 200
KCl0.5KBr0.5 mixed 3.26242
crystals
3.24841
ZnCl2 doped
KCl0.5KBr0.5 mixed
crystals

The interplannar spacing for the grown crystals are provided in Table 4.3.5 . The PXRD
shows 100% intensity for reflections from (200) planes the inter plannar spacing values are
3.28101A0 , 3.13514A0 , 3.26242A0 , 3.24841A0 for pure KCl, KBr ,KCl0.5KBr0.5 mixed
crystal , ZnCl2 doped KCl0.5KBr0.5 mixed crystals. The interplannar spacing for KCl xKBr1-x
mixed crystal and ZnCl2 doped KClxKBr1-x mixed crystal were decreases linearly.

Table 4.3.7: Lattice parameters for all grown crystals

System Lattice parameter(A0)

Pure KCl crystal 6.2826

Pure KBr crystal 6.4859

KCl0.5KBr0.5 mixed crystals 6.4119

ZnCl2 doped KCl0.5KBr0.5 mixed crystals 6.3644

44
 The PXRD shows the lattice parameter values are a=6.2826 A 0 ,a=6.4859 A0
,a=6.4119 A0,a=6.3644 A0 for pure KCl, KBr ,KCl0.5KBr0.5 mixed crystal and, ZnCl2 doped
KCl0.5KBr0.5 mixed crystals. The Lattice parameter of all grown crystals shows cubic crystal

structure.

4.4 FTIR spectral analysis

Fourier transform infrared spectroscopy is a technique used to determine qualitative and

quantitative feature of IR active molecules inorganic and organic solid, liquid or gas samples.

Force constant of the grown crystals were determined from the FTIR transmission data
using the formula,

ν =5.3×10-12√ kf /¿ ¿ µ

Where ν is the wave number corresponding to the absorption maximum, k f is the force
constant and µ is the reduced mass.

FTIR spectra have been recorded by using IFS BRUKKER 66V spectrophotometer in the
range of 400cm-1-4000cm-1 in order to find the presence of various functional groups. The
FTIR spectrum are taken for all the grown crystals to study the spectroscopic properties .

45
(a)

(b)

46
 Transmittance [%]
-20 0 20 40 60 80

3836.83
3743. 99

3500
3375.90

3000
2923.28
2856.14
2759.61
2678. 35

2500
2356.45

2000
Wavenumber cm-1
1608.07

1500
1403.34

1000
507. 93

500

(d)

47
(c)

Page 1/1

Figure 4.4.1 :FTIR Spectrum of all grown crystals

 a)pure KCl crystal

b)pure KBr crystal

c)KCl0.5KBr0.5 mixed crystal

d)ZnCl2 doped KCl0.5KBr0.5 mixed crystal

Table 4.4.1 :Wavenumber and force constant of all grown crystals

System Wave number Absorption Force constant

(cm-1) maximum wave 102 N/cm
number (cm-1)

Pure KCl crystal 2919.98 3409.49 6.5022

Pure KBr crystal 2925.18 3395.62 6.4494

KCl0.5KBr0.5 mixed 2852.80 3371.31 6.3574
crystals
2922
ZnCl2 doped
KCl0.5KBr0.5 mixed 2855.14 3375.90 6.3852
crystals 2923.28

The ν values of the peaks correspond to chlorine and bromine are provided in Table
4.4.1. The FTIR spectrum of the crystals all the grown crystals are provided in Fig.4.4.1 for
illustration. It is found that the pure KCl and KBr has only one peak at 2919.98cm -1 and
2925.18 cm-1 .But the KCl0.5KBr0.5 and ZnCl2 doped KCl0.5KBr0.5 mixed crystals have two
peaks nearly at 2852.80 cm-1 ,2922 cm-1 and 2855.14 cm-1,2923.28 cm-1. They observed not
just a single frequency but two frequencies close to those of the pure crystals. Angress et al.,
also observed same result in the KCl RbBr system. They observed not just a single frequency
but two frequencies close to those of the pure crystals. This phenomenon is referred to as
“two mode behaviour”.

48
 In the present study, for the mixed crystals we observed not just a single frequency but
two frequencies close to those of the pure crystals. So the two mode behaviour is exhibited
for all the mixed crystals.

4.5 Optical characterizations

4.5.1 UV-Visible spectral analysis

An unknown compound can be identified with the help of UV spectroscopy. UV-
Visible spectroscopy refers to the absorption spectroscopy in the UV-Visible spectral region..
It uses light in the visible and adjacent ranges. Fluorescence deals with transitions from the
excited state to the ground state, while the absorption measures transitions from ground state
to the excited state. The wavelength of absorption peaks can be correlated with the type of
bonds in a given molecule and it is used to determine the functional groups within a
molecule. Organic compounds with a high degree of conjugation absorb light in the UV or
visible regions of the electromagnetic spectrums.
The UV-Visible spectral data also is used to measure the transparency of the crystal. The
UV radiation has sufficient energy to excite valence electrons in many atoms and molecules.
Consequently ,UV is involved with electronic excitation. Spectroscopically visible light acts
in the same way us UV light. For this reason we find that commercial UV equipment often
operates with wavelength between 800 and 200nm.

(a)

49
 (b)

(c)

(d)
Figure 4.5.1 : UV-visible spectral analysis of all grown crystals

50
 a)pure KCl crystal

b)pure KBr crystal

c)KCl0.5KBr0.5 mixed crystal

d)ZnCl2 doped KCl0.5KBr0.5 mixed crystal

The spectra were recorded in the wavelength ranging from 200-800 nm. The absorbance
and transmittance curves are opposite to each other. The absence of strong absorption in the
region between 220-800 nm in UV-Visible spectrum is useful for Opto-electronic application.
UV-Visible spectrum of absorbance and transmittance of pure and ZnCl2 doped KCl0.5KBr0.5
mixed crystals were recorded in the range of 200-600 cm-1. Figure 4.2.1 shows the UV-
Visible absorption and transmission spectrum of pure and ZnCl 2 doped KCl0.5KBr0.5 mixed
crystals. This spectrum shows the full absorption and transmission in the entire visible region.
So the pure and ZnCl2 doped KCl0.5KBr0.5 mixed crystals are very good material for electro –
optic and NLO applications (Rajesh.P,Ramaswamy.P.,2010).

The cut-off wavelengths were observed from the absorption spectra. The transmittance
absorption percentages of pure and mixed crystals are almost same.

Table 4.5.1: Optical band gap of all grown crystals

T
h System λcut (nm) Eg (eV) e

Pure KCl crystal 220

5.6471
Pure KBr crystal 225
5.5216
KCl0.5KBr0.5 mixed crystal 228
5.4490
ZnCl2 doped KCl0.5 KBr0.5 232
5.3550
crystal

optical band gap value of pure and ZnCl 2 doped KCl0.5 KBr0.5 crystals were calculated using
the Tauc’s relation,
51
 (αhν)n = A (hν – Eg)

Where ‘α’ is the absorption coefficient, ‘A’ is a constant, ‘Eg’ is the band gap energy, ‘ν’ is
the frequency of incident beam, ‘h’ is the Planck’s constant, ‘n’ is the index value depends on
nature of the transition. Assuming the indirect band gap, the plot is drawn (αhν) 2 against hν.
The intercept of the straight line on the hν axis gives the optical band gap value (Sunil Chaki
M.P,Magesh.D.,2012).

(a) (b)

(c)
(d)
Figure 4.5.2 :Tauc plot for all the grown crystals

52
 a)pure KCl crystal

b)pure KBr crystal

c)KCl0.5KBr0.5 mixed crystal

d)ZnCl2 doped KCl0.5KBr0.5 mixed crystal

Table 4.5.2 :Optical band gap from tauc plot

System Eg (eV)

Pure KCl crystal 5.5

Pure KBr crystal 4.9

KCl0.5KBr0.5 mixed crystal 5.2

ZnCl2 doped KCl0.5 KBr0.5 crystal 5

4.5.2 Fluoresence

Fluorescence is a spectrochemical method of analysis where the molecules of the

analyte are excited by irradiation at a certain wavelength and emit radiation of a different
wavelength. The emission spectrum provides information for both qualitative and
quantitative analysis. Fluorescence finds wide application in the branches of biochemical,
medical and chemical research fields for analyzing organic compounds.
The absorption of energy to produce the first excited state does not perturb the shape of
the molecule greatly and this means that the distribution of vibration levels is very similar in
both the ground and first excited states. The energy differences between the bands in the
emission spectrum will be similar to those in the absorption spectrum and frequently the
emission spectrum will be approximate to a mirror image of the absorption spectrum. Since
the emission of fluorescence always takes place from the lowest vibrational level of the first

53
excited state, the shape of the emission spectrum is always the same, despite changing the
wavelength of exciting light.
The compounds containing aromatic functionl groups of low energy π → π * transition
levels have high intense fluorescence behaviour ( Lawrance.L,Uma Devi.T.,2007). A plot of
emission against wavelength for any given excitation wavelength is known as the emission
spectrum.
The fluorescence spectrum for all grown crystals are shown in figure.

Figure4.5.3 : Fluoresence spectrum of all grown crystals

a) Pure KCl crystal

b) Pure KBr crystal

c) KCl0.5KBr0.5 mixed crystals

d) ZnCl2 doped KCl0.5KBr0.5 mixed crystals

Table 4.5.3 : Wavelength of absorbed fluorescence for all grown crystals

54
 50.00

1.40%
45.00

112uV.s/mg99.00
40.00

System Wavelength(nm) Colour of emitted light

777.2Cel
35.00 36.52uV

30.00 Pure KCl crystal 792.7Cel

98.00
blue 35.02uV
463.9
Pure KBr crystal
DTA u V

TG %
25.00
blue
55 .00
461.07
KCl0.5KBr0.5 mixed 99 .00

20.00 crystals 50 .00

blue 97.00
462.89
1.15% 98 .00

45 .00
68.1uV.s/mg
97 .00
ZnCl2 doped blue
15.00 465.07
KCl0.5KBr0.5 mixed
40 .00
crystals 741.0Cel
41.90uV
96 .00

755.4Cel
95 .00
35 .00 41.16uV
10.00 96.00
DTA u V

782.3Cel

TG %
94 .00
30 .00 13.18uV

5.00 Fluoresence
25 .00
property is used to determine the crystalline quality as well 93as.00 its
746.2Cel 92 .00
excitation fine20structure.
.00
The fluorescence emission spectra for all grown crystals
27.02uV were
3.54% 91.00
0.00 95.00
recored in the range
15 .00
from 250-700nm.The higher intensity ratio indicates purity and perfect
90 .00
100.0 200.0 300.0 400.0 500.0 600.0 700.0 800.0
crystallinity of10the
.00
grown crystals. Hence these crystals are suitable for opto elecetronic
Temp Cel
89 .00

devices.The fluorescence
5.00
result indicates that the crystals are blue light emitting materials.
10.84%
88 .00

10 0.0 20 0.0 30 0.0 40 0.0 500 .0 6 00.0 700.0 800.0

Tem p Ce l

4.6 TG/DTA Analysis

Thermal analysis is analysis of a change in a property of a sample , which is related to
an imposed change in the temperature .The sample is usually in the solid state and the
changes that occur on heating include melting phase transition , sublimation and
decomposition. The analysis of a change in the mass of a sample on heating is known as
Thermogravimetric analysis(TG).The TG measures mass changes in material as a function of
temperature or time under a controlled atmosphere.

DTA is most used thermal method of analysis. In DTA temperature of a sample is

compared with that of an inert reference material during a programmed change of
temperature. The temperature should be the same until thermal event occurs, such as
melting ,decomposition or change in the crystal structure.

55
 (a)

(a)

55.00 50.00 100.0

1.40%
50.00 99.0
45.00

45.00
40.00 (a) 84.9uV.s/mg98.0 112uV.s/mg99.00

777.2Cel
40.00 97.036.52uV
35.00 737.0Cel
41.29uV

35.00
30.00
(b) 751.3Cel
41.41uV96.0
792.7Cel
98.00
35.02uV
DTA u V

DTA u V

30.00 95.0
TG %

4.4%
TG %

25.00

25.00 94.0
20.00 97.00

20.00 93.0
15.00 741.5Cel
21.92uV
15.00 92.0
10.00 96.00
10.00
(b) 782.3Cel
91.0 13.18uV

5.00
5.00 90.0
6.0%
3.54%
0.00 95.00
100.0 200.0 300.0 400.0 500.0 600.0 700.0 800.0
100.0 200.0 Te300.0
mp Ce l 400.0 500.0 600.0 700.0 800.0
Te m p Ce l

56
 (b)
5 5.0 0

5 0.0 0 9 9.0 0

1.05%
4 5.0 0
9 8.0 0

90.7uV.s/mg
4 0.0 0
742.4Cel 9 7.0 0

3 5.0 0 (c) 40.01uV

757.4Cel
39.39uV
D TA u V

9 6.0 0

TG %
3 0.0 0

9 5.0 0
2 5.0 0

2 0.0 0 9 4.0 0
748.1Cel
22.01uV
15.00
9 3.0 0
(c)
10.00

7.02% 9 2.0 0

5.0 0
10 0.0 20 0.0 30 0.0 40 0.0 5 00 .0 6 00 .0 700 .0 800 .0
Tem p Cel

(d)

Figure 4.6.1 :TG/DTA curve of all grown crystals

a) Pure KCl crystal

b) Pure KBr crystal

c) KCl0.5KBr0.5 mixed crystals

d) ZnCl2 doped KCl0.5KBr0.5 mixed crystals

Thermal analysis of the grown crystals have been carried out by obtaining
Thermogravimetric (TG) and Differential thermal analysis(DTA) curves and are shown in
figure. From the TG/DTA curve the weight loss of the sample with temperature is obtained.

57
The Thermogravimetric analysis of KCl and KBr mixed crystal was carried out between
room temperature and 8000c in air atmosphere at a heating rate using TG/DTA analyser.

Table 4.6.1: Endothermic and decomposition of all grown crystals

Start the
Composition Endothermic decomposition
(0c) (0c)

Pure KCl crystal 782.3 772.2

Pure KBr crystal 746.3 741

KCl0.5KBr0.5 mixed 741.5 737

crystal
748.2 742.4
KCl0.5 KBr0.5 ZnCl2
crystal

In our present study, we have recorded TG thermo gram of pure as well as ZnCl 2 doped
KClxBr1-x mixed crystals, in order to understand the effect of ZnCl 2 addition on the stability of
the pure crystal. In the DTA ,the strong endothermic peaks located 782.3 , 746.3 , 741.5 ,
748.2 depict the crystallization of some of the phases of the decomposed material.

The curved portions indicate the region of thermal stability of KCl xKBr1-x mixed crystals
and the compound formed from it. The grown crystals are losing their weight gradually and
slowly upto 772.2 , 741 , 737 , 742.4 for all grown crystals.

A change in mass occurred on the TG curve which corresponds to dehydration or

decomposition and this dehydration or decomposition shows up on DTA curve as an
endotherm.

A small variation in the temperature range has been observed in the TGA curve of KCl
KBr mixed crystal samples .From the DTA curve it is clearly observed that the KCl, KBr ,
KCl0.5KBr0.5 mixed crystals loses its texture at respectively. Hence it is concluded that KCl is
thermally more stable than KBr.

58
4.7 SEM Analysis:

Scanning Electron Microscopy was performed using the JEOL Model JSM-6309V
device. The scanning Electron Microscopy uses a focused beam of high energy electrons to
generate a varity of signals at the surface of solid specimens. The signals that derive from
electron-sample interactions reveal information about the sample. Areas ranging from 1cm to
5 microns in width can be imaged in a scanning mode using convensitional SEM
techniques.The SEM is capable of performing analysis of selected point locations on the

sample.

59
(a)

60
(b)

61
(c)

62
 (d)
Figure 4.7 .1 :SEM images of all the grown crystals

a)pure KCl crystal

b)pure KBr crystal

c)KCl0.5KBr0.5 mixed crystal

d)ZnCl2 doped KCl0.5KBr0.5 mixed crystal

63
 SEM images recorded for four different magnifications revealed the morphology and size
distribution of all the grown crystals are shown in Fig . It is obvious that the size and
morphology of crystals are different. The SEM images show a uniformly developed grain
morphology of dense microstructure. The detailed examination of SEM micrograph from a
selected region of ZnCl2 doped KClxKBr1-x crystals indicates that these crystals are irregularly
shaped. The size distribution and size of the particles are not uniform.

64
 CHAPTER-5

CONCLUSION

The summary of the result of the present study and conclusions drawn are presented
below .High quality pure and ZnCl2 doped KClxBr1-x mixed crystals were grown by slow
evaporation solution growth technique at room temperature. Powder X-ray diffraction
analysis reveals that the grown crystal belongs to cubic system . The presence of functional
group was confirmed by FTIR analysis.

The optical absorption studies revealed very low absorption over the entire visible
region. The optical band gap was calculated from the cut off wavelength. All the grown
crystals had a blue fluoresence emission.The thermal stability of the grown crystals were
determined from the thermogravimetric /Differential thermal analysis. The irregular shaped
non uniformly particles of grown crystals were confirmed using SEM analysis. All of these
results confirmed that the grown crystals are suitable for opto electronic and NLO
applications.

65
5.1 Scope of future work

 In the future , attempts will be made to grow bulk size ZnCl 2 doped KClxBr1-x mixed
crystals along their growth rate ,transparency and non linear optical properties.
 Attempts will be made in future to investigate the nucleation parameters.
 Advanced microscopic techniques such as AFM and TEM can be characterize the
grown samples in future.

66