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1.1 INTRODUCTION
There are three major stages involved in this research. The first is the
production of pure materials and improved equipment associated with the
preparation of these materials. The second is the production of single crystals first
in the laboratory and then extending it to commercial production. The third is the
characterization and utilization of these crystals in devices.
Atomic arrays that are periodic in three dimensions, with repeated distances
are called single crystals. It is clearly more difficult to prepare single crystal than
poly-crystalline material and extra effort is justified because of the outstanding of
the outstanding advantages of single crystals. The reason for growing single crystals
is. Many physical properties of solids are obscured or complicated by the effect of
grain boundaries. The chief advantages are the anisotropy, uniformity of
composition and the absence of boundaries between individual grains, which are
inevitably present in polycrystalline materials.
1
1.2 TYPES OF SEVEN CRYSTALS:
1. triclinic
(none)
simple base-centered
2. monoclinic
(1 diad)
3. orthorhombic
(3 perpendicular diads)
4. rhombohedral
(aka, trigonal)
(1 triad)
simple body-centered
5. tetragonal
(1 tetrad)
6. hexagonal
(1 hexad)
7. cubic
(4 triads)
2
1.2.1 CLASSIFICATION OF CRYSTALS:
There are four main categories of crystals, as grouped by their chemical and
physical properties:
3
1. COVALENT CRYSTALS
A covalent crystal has true covalent bonds between all of the atoms in the
crystal. You can think of a covalent crystal as one big molecule. Many covalent
crystals have extremely high melting points. Examples of covalent crystals include
diamond and zinc sulfide crystals.
2. METALLIC CRYSTALS
Individual metal atoms of metallic crystals sit on lattice sites. This leaves the
outer electrons of these atoms free to float around the lattice. Metallic crystals tend
to be very dense and have high melting points.
3. IONIC CRYSTALS
The atoms of ionic crystals are held together by electrostatic forces (ionic
bonds). Ionic crystals are hard and have relatively high melting points. Table salt
(NaCl) is an example of this type of crystal.
4. MOLECULAR CRYSTALS
4
- Liquid to solid phase transformation
In the above mentioned categories liquid growth includes both melt and
solution growth. A survey of the methods of growth suggests that almost 80% of
the single crystals are grown from the melt compared with roughly 5% from high
temperature solution, and 3% from the solid and only 2% by hydrothermal
methods.
All materials can be grown in single crystal form the melt provided they melt
congruently without decomposition at the melting pint and do not undergo any
phase transformation between the melting point and room temperature.
1. Bridgman technique
2. Czochralski technique
3. Kryopoulos technique
4. Verneuil technique
5
Fig 1.3.2 Normal freezing also called directional freezing
Fig. 1.3.3 Techniques for nucleating single crystals from the melt
(a) Conical bottom (b) Capillary (c) Necking
6
produce high vapour pressure at the melting point. This refined method of
Czochralski technique is widely adopted to grow III – V compound semiconductors.
In the zone melting technique, the feed material is taken in the form of
sintered rod and the seed is attached to one wend. A small molten zone is
maintained by surface tension between the seed and the feed. The zone is slowly
moved towards the feed. Single crystals are obtained over the seed. This method is
applied to materials having large surface tension. The main reasons for the impact
of zone refining process to modern electronic industry are the simplicity of the
process, the capability to produce a variety of organic and inorganic materials of
extreme high purity, and to produce dislocation free crystal with a low defect
density.
7
In the Verneuil technique, a fine dry powder of size 1-20 microns of the
material to be grown is shaken through the wire mesh and allowed to fall through
the oxy-hydrogen flame. The powder melts and a film of liquid is formed on the top
of the seed crystal. This freezes progressively as the seed crystal is slowly lowered.
The art of the method is to balance the rate of charge feed and the rate of
lowering of the seed to maintain a constant growth rate and diameter. By this
method ruby crystals are growth up to 90mm in diameter for use in jeweled
bearings and lasers. This technique is widely used for the growth of synthetic gems
and variety of high melting oxides.
Materials, which have high solubility and have variation in solubility with
temperature can be grown easily by solution method, there are two methods in
solute. They are
In the solution growth, crystals can be grown from solution if the solution is
supersaturated i.e., it contains more than it can be in equilibrium with the solid.
Three principal methods are used to produce the required supersaturtion:
8
In the high temperature solution growth a solid is used as the solvent instead
of liquid and the growth takes place well below the melting temperature and is know
as flux method.
The high temperature crystal growth can be divided into two major categories. They
are
1. Growth from single component system.
2. Growth from multi component system.
This method is widely used for the growth of oxide crystals. The procedure
is to heat the container having flux and the solute to a temperature so that all the
solute materials dissolve. This temperature is maintained fro a ‘soak’ period of
several hours and then the temperature is lowered very slowly.
The growth of single crystal material from the vapour phase is probably the
most versatile of all crystal growth processes. Crystals of high purity can be grown
from vapour phase by sublimation, condensation and sputtering of elemental
materials. To obtain single crystals of high melting point materials this method is
used. Molecular beam techniques have also been applied recently to crystal growth
problems.
The most frequently used method for the growth of bulk crystal utilizes
chemical transport reaction in which a reversible reaction is used to transport the
source materials as a volatile species to the crystallization region. Finding a suitable
transporting agent is formidable, problem in this technique. It is rarely possible to
grow large crystals because of multi-nucleation.
9
compounds of dopant elements into the reaction region. The thickness of the doped
layer can be controlled.
Growth is usually carries out in the steel autoclaves with gold or silver linings.
Depending on the pressure the autoclaves are grouped into low, medium and high
pressure autoclaves. The concentration gradient required to produce growth is
provided by a temperature difference between the nutrient and growth areas.
10
The requirement of high pressure presents practical difficulties and there are
only a few crystals of good quality and large dimensions are grown by this
technique. Quartz is the outstanding example of industrial hydrothermal
crystallization. One serious disadvantage of this technique is the frequent
incorporation of OH ions into the crystal, which makes them unsuitable for many
applications.
1.4.4 ELECTROCRYSTALLISATION
CHAPTER – 2
11
Non-linear optical (NLO) effects are analyzed by considering the response of
the dielectric material at the atomic level to the electric fields of an intense light
beam. The propagation of a wave through a material produces changes in the
spatial and temporal distribution of electrical charges as the electrons and atoms
interact by the filed on the charged particles is displacement of the valence
electrons from their normal orbits. This perturbation creates electric dipoles whose
macroscopic manifestation is the polarization (Narisimhamurty 1981).
12
of application to the limitations are significantly slowing the development of require
optical devices.
One of the obvious requirements for a non-linear crystal is that it should have
excellent optical quality. This means that for new materials, for which single crystal
specimens are not available. It is necessary to grow single crystal specimens of
optical quality. Thus in many cases the search for new and better non-linear
materials is very largely a crystal growing effort.
For a device to succeed it is vital that it meets a number of other criteria and
these other criteria should receive greater emphasis. The relevant issues include
reliable crystal growth techniques, ready availability, optical non-linearity,
birefringence, moderate to high transparency and optical homogeneity for high
conversion efficiency, mechanical strength, chemical stability, polishing and coating
technology for case of fabrication, low absorption properties for high average power,
damage threshold, non-linear absorption and brittleness index for lifetime and
system capability.
The explanation of non-linear effects lies in the way in which a beam of light
propagates through a solid. The nuclei and associated electrons of the atoms in the
solid from an electric dipole.
The electromagnetic radiation interacts with these diploles causing them to
oscillate which, by the classical laws of electromagnetism, results in the dipoles
themselves acting sources of electromagnetic radiation.
13
non-linear resulting in the generation of harmonic in the frequency of radiation
emitted by the oscillating dipoles.
P= ε0 χ
(1)
E (2.1)
Where,
14
P(ω0)= ε0 { χ(1) ( −ω0 ; ω1). E ( ω0) + χ(2) (ω0; ω1, ω2). E ω1.ω2 +
Where,
χ(1) is the linear term responsible for material’s linear optical properties like,
refractive index, dispersion, birefringence and absorption.
χ(3) is the cubic term responsible for third harmonic generation, stimulated
Raman scatting, phase conjugation and optical bi-stability. Hence the induced
polarization is capable of multiplying the fundamental frequency to second, third
and even higher harmonics. The coefficients of χ(1), χ(2) and χ(3) give rise to certain
optical effects. These are listed in Table 2.1.
15
TABLE 2.1 OPTICAL EFFECTS OF NON-LINEAR MATERIALS
Frequency
SGH (ω + ω=2ω) doubling
Pockels effects
χ (2)
2.
(ω + 0 = ω) Electro optical
modulators
Raman Coherent
spectroscopy
4 wave mixing phase
gratings Real time
holography
16
induced by the first non-linear term is predicted to be + E2 . This contradiction can
If the same argument is used for the next higher order term, + E producers
polarization + E3 and – E and produces – E3 , so that χ(3) is the first non-zero non-
linear term in centro-symmetric media.
In second harmonic generation, the two input wavelengths are the same
During this process, a polarization wave with the second harmonic frequency
2ω1 is produced. The refractive index, n1 is defined by the phase velocity and
wavelength of the medium. The energy of the polarization wave is transferred to the
electromagnetic wave at a frequency ω2. The phase velocity and wavelength of this
electromagnetic wave are determined by n2, the refractive index of the doubled
frequency. To obtain high conversion efficiency, the vectors of input beams and
generated are to be matched.
2π
∆Κ = .................................. (2.5)
λ(n1 – n2)
Where,
the crystal length, P is the input power density and ∆Κ is the phase-mismatching.
17
In general, higher power density, longer crystal, large non-linear coefficients and
smaller phase mismatching will result in higher conversion efficiency. Also, the input
power density is to be lower than the damage threshold of the crystal. Table 2.2
lists the laser and crystal parameters for selecting a NLO crystal.
Divergence Acceptance
Many organic and inorganic materials are highly polarizable and thus ae good
candidates for study. However, the net polarization of a material depends on its
symmetry properties, with respect to the orientation of the impinging fields. It can
be shown that the odd order terms in equation (2.2) are orientation independent,
but the even terms vanish in a Centro-symmetric environment.
Thus materials for second order NLO must be orientationally noncentric to be
functional. No such restriction applies to third order materials.
18
Non-linear optical materials will be the key elements for future photonic
technologies based on the fact that photons are capable of processing information
with the speed of light. The search for new and efficient materials in which to carry
out non-linear optical process has been very active since SHG was first observed in
single crystal quartz by Franken and co-workers in 1961.
CHAPTER-3
19
LOW TEMPERATURE SOLUTION GROWTH
3.1 INTRODUCTION
If the solubility is too high, it is difficult to grow bulk single crystals and too
small a solubility restrict the size and growth rate of the crystals. Solubility gradient
20
is another parameter, which dicates the growth procedure. Neither a flat nor a steep
solubility curve will enable the growth of bulk crystal from solution; while the level
of supersaturation could not be varied by reducing the temperature in the former,
even a small fluctuation in the temperature will affect the supersaturation to a large
extent in the later disabling the growth of good quality bulk crystals in both cases. 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.
The solubility of the solute may be determined by dissolving the solute in the
solvent maintained at a constant temperature with continuous stirring. On reaching
saturation, the equilibrium concentration of the solute may be determined
gravimetrically.
The solubility curve can then be plotted in this way by repeating the above for
different temperatures.
21
The supersaturation of a system may be expressed in a number of ways. The
basic units of concentration as well as temperature must be specified.
The concentration driving force (∆C), the supersaturation ratio (S) and relative
supersaturation (σ) are related to each other as follows:
σ= S – 1
C'
CT
B" B'
C B A
Stable
BB' - Solubility curve CC' - Super solubility curve
AB"C" - Evaporation and
cooling CT- Concentration
Temperature
22
If the concentration of a solution can be measure at a given temperature and
the corresponding equilibrium saturation concentration is known, then, it is easier to
calculate the supersaturation.
23
The evaporation of solvent from the solution may also result in
supersaturation. Line AB’C’ represents an operation carried out at constant
temperature. Penetration beyond the super solubility curve into the labile Zone
rarely happens, as the surface from which evaporation takes place is usually
supersaturated to a greater degree than the bulk of the solution.
Crystals, which appear on this surface eventually fall into the solution and
seed it. In practice, a combination of cooling and evaporation as represented by the
line AB” C” in (figure 3.1) is adopted.
Low temperature solution growth can be subdivided into the following methods,
It is the best way to grow single crystals by solution technique. The main
limitation is the need to use a range of temperature. The possible range of
temperature is usually small so that much of the solute remains in the solution at
the end of the run.
To compensate this effect, larger volumes of solution are required. The use of
a range of temperature may not be desirable because the properties of the grown
material may vary with temperature.
24
(ii) Slow evaporation method
This method is similar to the slow cooling method in view of the apparatus
requirements. The temperature is fixed constant and provision is made for
evaporation. With non – toxic solvents like water, it is permissible to allow
evaporation into atmosphere.
This method involves the transport of the material from a hot region
containing the source material to b grown to a cooler region where the solution is
supersaturated and the crystal grows. The main advantages of this method are that.
On the other hand, changes in the small temperature differences between the
source and the crystal zones have a large effect on the growth rate.
Chapter – 4
25
GROWTH AND CHARACTERISATION OF POTASSIUM DIHYDROGEN
PHOSPHATE (KDP) CRYSTAL
4.1. INTRODUCTION
They are also used as Q – switches and shutters for high – speed Photograph.
KDP is characterized by high non-linear performance, wide optical transparency
range and well – developed technology pf growth. The point group of the crystal in
42m and the space group is I4 2D (122). The structure belongs to the scalenohedral
(twelve face polyhedron) class of tetragonal system.
So, semi organic crystals which have combined properties of both inorganic
and organic species are expected to have good optical, thermal and mechanical
properties. KDP crystals have been investigated through powder XRD, FTIR,
FTRaman, UV and thermal analyses along with dielectric properties in the
microwave region.
4.2 EXPERIMENTAL
26
4.2.1 GROWTH OF THE CRYSTAL
The pure KDP crystals were grown using solution growth technique.
Recrystallised salts of KDP (99% purity) and triple-distilled water were used in the
present crystal growth experiment. Saturated solutions of KDP (each 250ml) are
separately mixed with 0.1 M solutions and stirred well using a stirrer. The well –
mixed solutions are allowed to evaporate at room temperature. Good sized crystals
were grown within two weeks and the photographs of the grown crystals are
presented in Figure 4.1.
27
Figure 4.1 Photographs of pure KDP crystals
28
CHAPTER – 5
CHARACTERIZATIONS METHOD
5.1. INTRODUTION
29
Fig.5.1.1 Schematic diagram of Bragg’s law
The diffracted beams are found when the reflections from parallel plan of
atoms interfere constructively, as in Fig.5.1.1 We treat elastic scattering, which the
energy of the x-ray is not changed on reflection. Inelastic scattering, with the
excitation of elastic waves, is discussed at the end of the chapter.
Consider parallel lattice planes spaced apart. The radiation was incident in
the plane of the paper. The path difference for rays reflective from adjacent
interference of the radiation from successive planes occurs when the path difference
is an integral number n of wavelengths λ, i.e. 2d sinθ = nλ.
This is the Bragg law. Although the reflection from each plane is specular for
only certain values of θ will the reflections from all parallel planes as up in phase to
give a strong reflected beam.
30
In each perfectly reflecting plane, only the first plane of a parallel set would
see the radiation and wavelength would be reflected. But each plane reflected 10-3
to 10-5 of the incident radiation.
The Bragg law is a consequence of the periodicity of the lattice. The law does
not refer to the arrangement of atoms in the basis associated with each lattice
point. The composition of the basis determines the relative intensity of the various
orders n of diffraction from a given set of parallel planes. Bragg reflection can occur
only wavelength λ ≤ 2d. This is why we cannot use visible light.
31
Fig.5.1.3 Crystal structures are determined experimentally by X-Ray
diffraction
Beams from all planes parallel to the vertical rotation axis will lie in the
horizontal plane. Planes with other orientations will reflect in layers above and below
the horizontal plane.
The intensity distribution of the radiation from a 30 keV x-ray tube with a
molybdenum target and the distribution of neutrons are emerging from a nuclear
reactor. If we reflect the beam from a monochromatic crystal, we get the
crosshatched distribution.
32
Several variations are common use. In oscillating-crystal photographs the
crystal is oscillated through a limited angular range, instead of being rotated
through 3600. The limited range reduces the possibility of overlapping reflections.
The precession camera developed by M. J. Buerger gives a picture of the various
levels of the reciprocal lattice. Modern diffractometers use scintillation counters or
proportional counter tubes to data, needed because complex structures may exhibit
10,000 diffracted rays.
Nearly all crystals with simple structures were solved by x-ray analysis long
ago. One present center of interest in x-ray structure analysis is in the
determination of the configuration of enzymes with a molecular weight between
10,000 and 100,000. The crystallization of an enzyme and the subsequent x-ray
analysis of the structure of the crystal is the most effective method for the
determination of the shape of the molecule.
The coordinate 500 to 5000 atoms in a cell are wanted, so at least this
number of x-ray reflection lines is required. Computer programs have enormously
simplified the problem of structure determination.
33
The powder method is convenient precisely because single crystals are not
required. Diffracted rays go out from individual crystallites that happen to be
oriented with planes making an incident angle θ with the beam satisfying the Bragg
equation. Diffracted rays leave the specimen along the generators of cones
concentric with the original beam. The generators make an angle of 2θ with the
direction of the original beam, where θ is the Bragg angle. The cones intercept the
film in a series of concentric rings. (Fig. 5.1.6).
34
Infra-red spectroscopy extends outside the limits we have discussed so far in
this chapter, and in particular a good deal of useful molecular information is
contained in spectra below 400cm-1, i.e. the far infra-red region, from about 400cm-1
to 20cm-1 or 10cm-1. Because sources are weak and detectors insensitive, this
region is known as ‘energy-limited’ and difficulty is experienced in obtaining good
signal-to-noise ratios by conventional means. The advent of Fourier transform
spectroscopy has made the far infra-red much more accessible, and has
considerably speeded and improved spectroscopy in the infra-red region in general.
In this region Fourier transform (FT) methods are used in absorption. The
apparatus derives from the classical attempt by Michelson to measure the ‘ether
wind’ by determining the velocity of light in two perpendicular directions. A parallel
beam of radiation is directed from the source to the interferometer, consisting of a
beam splitter B and two mirrors M1 and M2 (Fig. 5.1.7). The beam splitter is a plate
of suitable transparent material (e.g. potassium bromide) coated so as to reflect
just 50 per cent of the radiation falling on it. Thus half the radiation goes to M1 and
half to M2, returns from both these mirrors along the same path, and is then
recombined to a single beam at the beam splitter (clearly half the total radiation is
sent back to the source, but this is immaterial).
35
Taking the process further, even ‘white’ radiation emitted by the source
produces an interference pattern, which can be transformed back to the original
frequency distribution [Nakamoto, K., 1995].
36
5.1.9 UV – visible spectroscopy
The most probable position for which the transition can occur is from the
equilibrium bond distance for diatomic molecule. Since, with only zero point
vibration occurring, the vibrational wave function is a symmetric even function with
no nodes. Electronic transitions are possible for wide range of vibrational levels with
in the initial and final states.
Powder pattern XRD of KDP crystal is shown in Fig. 6.1. The XRD pattern
shows the crystalline nature of the grown KDP crystal. The table 5.2.1 gives the d
and hKl values of grown KDP crystal. It is observed that the grown KDP crystal is
monoclinic structure.
37
Table 5.2.1 INDEXED XRD DATA FOR PURE KDP CRYSTAL
The FTIR spectrum of KDP is shown in Fig. 6.2. The spectrum has shown the
various absorption frequencies of the grown KDP crystal. Table 5.2.2 gives the
absorption frequencies of various groups present in the KDP crystal and compared
with the standard values. It is observed that the growth of KDP crystal consists of
all functional groups present in the compound.
38
Table 5.2.2 FTIR and Frequency assignments of pure KDP crystal
KDP
Assignment FTIR
(cm-1)
(po4) 3-
γ1 (X4)
909.4(S)
Sym.bend
γ2 (E)
433.3
δd (4*4)
In plane bending
γ3 (F2) 1098.8
γd (X4)
Asym.stretching
γ4 (F2)
536.2
δd (4*4)
Bend(or) deformation
O
| 1696.1(S)
P - O – H stretch
P = O stretch 1302.1(S)
P – O stretch 1098.8(S)
P - O – H stretch 909.4(S)
O – H stretch 2500-3800
2447.9(W)
2763.0(W)
O – H bending 1330-1420
650-769
Opp – O bending 300-650
320-450
K - O stretching
2400(S)
3. UV – spectroscopy result:
39
The absorption spectrum of KDP crystal is recorded at the room temperature.
The measurement range from 200 - 1100nm. The absorption spectrum of KDP
crystal is shown in the fig. It can be seen that transparent of KDP crystal covers
234 – 1100nm and the UV cut off wavelength are at 234nm and very low
percentage of absorption in the entire visible region which is very essential property
for NLO crystal.
40
6.2 FTIR spectra of pure KDP crystal
41
.0800
42
5.3 CONCLUSION
43
The grown KDP crystals were subjected to different Characterisation
techniques. Powder XRD shows the grown KDP compound is a crystalline material.
FTIR shows the confirmation of all functional groups present in the crystal. UV –
visible spectrum shows the grown crystal may be used as a detector in UV - visible
and IR regions.
REFERENCES
44
1. J Podder J. Cryst. Growth 70-75 237 (2002)
2. J Podder, S Ramalingam and S Narayana Kalkura Cryst. Res. Technol.36
549 (2001)
3. T H Freeda and C Mahadevan Pramana J.Phys. V57 n 4 829 (2001)
4. JCPDS - International Centre for Diffraction Data, PDPDF WIN V2.02.
(1999)
5. G W Xu and X sun Cryst, Res.Technol.V37 n 193 (2002)
6. G W Lu, H R Xia, D L Sun, W Q Zheng, X Sun, S Gao and J Y Wang Phys.
Stat. Sol (a) 188 1071 (2001)
7. J J Kim, B h Choi and M N Lee J. Raman Spectrosc. 20 11 (1989).
8. Y Tominaga, M Tokunaga and I Tatzusaki Solid State Communications 54
979 (1985)
9. J J kim and B K Choi Solid State Communications 49 47 (1984).
10. Y Tomianga, H Urabe and M Tokunaga Solid State Communications 48 265
(1983).
11. E Wiener, S Levin and I Pelah J. Chem. Phys. 52 8 2882 (1979)
12. B Marchaon and A Novak J Chem. Phys. 78 2105 (1983)
13. J West Z Krist (Germany) 74 306 (1930).
14. Andrea’s Jabs Image Library of Biological Molecules (2002).
15. Andrea’s Barth Prog. Biophys. Mol. Boil. 74 141 (2002).
16. J F Pearson and M A Slifkin Spectrachim. Acta 28 A 2403 (1971).
17. Kazuo Nakamoto IR and Raman Spectra of Inorganic Compounds (New
York: Wiley Interscience).
18. Arthur R Von Hipple Dielectric Materials and Applications (Cambrigde: The
MIT Press).
19. J Grunberg, S Levin, I Pelah and D Gerlich Phys. Stat, Sol. (b) 49 857
(1972).
20. C Y She, T W Broberg and David F Edwards Phys.Rev.B4 (1971).
21. A C Chapman and L E Thiruwell Spectrachim. Acta 20 937 (1964).
22. J H Park, KS Lee and B C Choi. J. Phys. Condens. Matter 13 9411 (2001).
23. H J Jager and Linda C Prins Loo Thermochim. Acta 376 187 (2001).
24. E Ortiz, R A Vargas and B E Mellander Solid State Ionics 125 177 (1999).
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