DIFFERENT TYPES OF CRYSTAL GROWTH METHODS

INTRODUCTION:

Crystals are used in semiconductor physics, engineering, as electro-optic devices etc., so

there is an increasing demand for crystal[1-5]. For years, Natural specimens were the only source
of large, well formed crystals.
The growth of crystals generally occurs by means of following sequence of process.  Diffusion
of the molecules of the crystallizing substance through the surrounding environment.
 Diffusion of these molecules over the surface of the crystal to special sites on the
surface.
Today almost all naturally occurring crystals of interest have been synthesized successfully in the
laboratory[6-9]. It is now possible only by crystal growth techniques.
The growth aspect differs from crystal depending as their physics and chemical properties such
as solubility, melting point[10-15], decomposition, phase change, etc,This chapter gives a brief
account of the methods of crystal growth.

BASICS OF CRYSTAL GROWTH:

To grow a crystal, the basic condition to be attained is the state of super saturation, followed by
the process of nucleation[16-21]. The information of super saturation and nucleation forms the
basis of crystal growth.

CONDITIONS FOR GROWING CRYSTAL:

The growth of crystals from liquid and gaseous solutions, pure liquids and pure gases can only
occur if some degree of super saturation or super cooling has been first achieved in the
system[22-27]. The attainment of the supersaturated state is essential for any crystallization
operation and the degree of super saturation or deviation from the equilibrium saturated
condition is the prime factor controlling the deposition process. Growth of crystals can be
considered to compress these steps[28-35].

1. Achievement of super saturation or super cooling.

2. Formation of crystal nucleus of microscopic size.
3. Successive growth of crystals to yield distinct factors

CRYSTAL GROWTH TECHNIQUES:

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Crystal growth is a challenging task and the technique followed for crystal growth
depends upon the characteristics of the materials under investigation[36-43], such as its melting
point, Volatile nature, solubility in water or other organic solvents and so on.

The basic growth methods available for crystal growth are broadly.

 Growth from melt.

 Growth from vapour.
 Growth from solution.
 Growth from solid.

CRYSTALS GROWTH

From Melt From Solid From Va por From Solution

With Without DVT HVT

Crucible Crucible

Low Temperature High Temperature

Slow Evaporation Slow Evaporation

Cooling Cooling

Dgman Kyropoulds Verneuil Floating Zone

Stock Czochralksi Technique Zone Movement
Barge

Figure. 1. Classification of Crystal growth methods

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GROWTH FROM THE MELT:

Melt growth is the process of crystallization of fusion and resolidification of the pure material,
crystallization from a melt on cooling the liquid below its freezing point. In this technique apart
from possible contamination from crucible materials and surrounding atmosphere[44-50], no
impurities are introduced in the growth process and the rate or growth is normally much higher
than possible by other methods. Melt growth is commercially the most important method of
crystal growth. The growth from melt can further be sub-grouped into various techniques.
a) Bridgmann method.
b) Czochralski method.
c) Vernuil method.
d) Zone melting method.
e) Kyropoulos technique.
f) Skull melting.

Bridgmann method:
This technique was named after its inventor Bridgemann in 1925, Stockbarger in1938.

Figure.2.Bridgmann method
The Bridgmann technique is a method of growing single crystal ingots or boules. The
method involves heating polycrystalline material in a container above its melting point and
slowly cooling it from one end where a seed crystal is located. Single crystal material is
progressively formed along the length of the container,the process can be carried out in a
horizontal or vertical geometry.

Advantage:
This method is technically simple.
This technique is low cost.
Selecting the appropriate container can produce crystal of pre assigned diameter.

Disadvantage:

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 The compression of the solid by the contracting container during cooling can lead to the
development of stresses high enough to nucleate dislocations in the material.

Czochralski method (or) Pulling Technique:

This method is widely used for growing semi conducting material crystal. The shape of the
crystal is free from the constraint due to the shape of the crucible. In this method the charge is
melted and maintained at a temperature slightly above the melting point.
The pulling rod is lowered to just touch the melt. Since the rod is at lower temperature of
melt occurs at the point tip of the pulling rod. The crystal is pulled slowly.
The rate of pulling upon various factors like thermal conductivity, latent heat of fusion of charge
and rate of cooling of the pulling rod. The seed is rotated to keep the grow crystal uniform and
cylindrical.

Figure. 3Czochralski method

Advantage:
 This method is used to grow large single crystals. Thus it is used extensively in the
semiconductor industry.
 There is no direct contact between the crucible walls and the crystal which helps to
produce unstressed single crystal.

Disadvantage:

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 In general this method is not suitable for incongruently melting compounds and of course
the need for a seed crystal of the same composition limits is used as tool for exploratory
synthetic research.

Vernuil method:
The basis of vernuils method is as follows. Chemically pure fine powder which emerges
through an Oxygen-hydrogen flame and falls onto the fused end of an oriented single crystal seed
fixed to a lowering mechanism. The powder charge is fed from bankeei by mean of a special
tapping mechanism. Coordinating the consumption of the charge, hydrogen and oxygen with the
rate of descent of the seed ensures crystallization at a prescribed level of the apparatus.

 Advantage:
 There is no container which eliminates the problem of physical-chemical interaction between the
melt and the container material.
 It is technically simple and the growth of crystal can be observed.
 Single crystal of ruby, sapphire etc., can be grown by this method. Single crystal in various
Shapes like plates, disc, hemi-sphere and cones can be grown by this method.
Zone Melting Method:
In this technique a liquid zone is created by melting a small amount of materials in a relatively
large or long solid charge. Zone melting techniques basically enable one to manipulate
distribution of soluble impurities or phases through a solid.

 Advantage:
 Zone melting technique is that impurities tend to be concentrated in the melted portion of the
sample.
 The process sweeps them out of the sample and concentrates them at the end of the crystal bowl,
which is then cut off and discarded.
 Thus this method is sometimes used to purify semiconductor crystals.

2.7.5 Kyropoulos Technique:

In this technique, a cooled seed to initiate single crystal growth within the melt containing
crucible. Heat removal continues by controlling the furnace temperature to grow the crystal.

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o Figure.4Kyropoulos Technique
Advantage:
 The crystal is grown in a larger diameter.
 With the large diameter crystal we can make prisms, lenses and other optical components.

Skull Melting Process:

Skull melting process is used for the growth of high melting point materials.
Cubic zirconium is made using a radio-frequency “Skull crucible” system, a specialized melt
process. This is a type of super-hot melt process used to produce the most widely accepted
diamond imitation: Cubic zirconia(cz). Zirconium oxide, the main component in cubic zirconias
has an extremely high melting point (4980’F). Conventional (low) melt crucibles cannot be used.
Therefore a crucible free technique is inevitable. The Skull melting process is used to produce
Zirconia up to 10cm long.

VAPOUR GROWTH:
Crystallization from Vapour is widely adopted to grow bulk crystal, epitaxial films, and thin
coatings. Techniques for growing crystals from vapour is divided into two types they are,
a. Chemical transport method.
b. Physical transport method.

a. Chemical transport method:

This method involves a chemical transport in which material is transported as a chemical
compound (halide), which decomposes in the growth area. In this case depending on the nature
of the reaction involved. The growth region may be either hotter or cooler than the source.

b. Physical transport method:

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This method involves in the direct transport of materials by evaporation or sublimation from a
hot source zone to a cool region II-VI compounds (Zns, Cds) are widely grown by this method
either in vaccum or with a moving gas stream. In both cases the growth can be suitable with seed
crystals, which can either be of the material being grown or some other material with similar
lattice spacing. In this case the substance evaporates and diffuses from hot end to a cooler growth
end. In then, deposits in the form of single crystals.

 Advantages:
 Films can obtain by the close spaced transport method and decomposition of compounds.
 Crystal of silicon, diamond, gas, semiconductor compounds can be grown by this method.

SOLUTION GROWTH:
In this method, Crystals are grown from aqueous solution. This method is also widely
practiced for producing bulk crystals. The four major types are A. Low temperature solution
growth.
B. High temperature solution growth.
C. Hydro Thermal growth.
D. Gel Growth.

A. Low temperature solution growth:

This is a widely practiced method; the techniques used here are,
 Slow cooling method.
• Solvent Evaporation method.
• Temperature Gradient method.
The solvent used here are water, ethy1 alcohol, acetone, etc.,

• Slow cooling method:

A saturated solution above the room temperature is poured in a crystallizer and thermally
sealed. A seed crystal is suspended in the solution and the crystallizer is kept in a water
thermostat, whose temperature is reducing according to a pre assigned plan, which results in the
formation of large single crystals. The need to use a range of temperature is the origin of
disadvantages. The possible range is usually small so that much of the solute remains in the
solution at the end of run. To compensate for this effect, large volumes of solution are needed.

• Solvent Evaporation method:

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` In this method, an excess of a given solute is established by utilizing the difference between the
rates of evaporation of the solvent and solute. In contrast to the cooling method, in which the
total mass of the system remains constant, in the solvent evaporation method, the solution loses
particles, which are weakly bound to other components, and therefore the volume of the solution
decreases. In almost all cases, the vapour pressure of the solvent above the solution is higher than
the vapour pressure of the solute and, therefore the solvent evaporates more rapidly and the
solution becomes supersaturated(Petrov1969). Usually, it is sufficient to allow the vapour formed
above the solution to escape freely into the atmosphere. This is the oldest method of crystal
growth and technically, it is very simple. Typical growth conditions involve temperature
stabilization to about ±0.0005oC and rates of evaporation of a few mm3/hr.

• Temperature Gradient method:

The transport of material forms a hot region containing the source of the material to be grown, to
a cooler region where solution is super saturated result in the crystal growth. A smaller variation
in the temperature between the source and the crystal has larger effects on growth rate.

B. High Temperature Solution Growth:

• The solvents are considered generally effective at temperatures above room
temperature. Also the concepts of low temperature solution growth are
applicable equally well. 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 most widely used high temperature solution
growth technique is the flux growth.

C.Hydro Thermal Growth:

This is regarded as an intermediate case between growths from the vapour and solution. Growth
occurs from aqueous solution at high temperature and pressure. The liquids from which the
process starts are usually alkaline aqueous solutions. Temperatures are typically in the range 400-
600oC and the pressure involved is large (100-1000 of atmospheres). Growth is usually carried
out in steel auto claves with gold or silver linings. The concentration gradient required to produce
growth is provided by temperature difference (usually 10-100 oC) between the nutrient and
growth areas. Those materials like calcite, alumina, antimony, etc., can be grown by this
technique.

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Advantages:
 It occurs in air at a temperature much lower than the melting of the
crystallizing substance.
 Single crystals of diamond, barium titanates are to be grown by using
this method.

 Disadvantages:
 At elevated temperature of crystal growth there are some
disadvantages.

D. Gel Growth Method:

The principle used in this crystal growth techniques is very simple solution of two
suitable compounds give rise to required crystalline substance by mere chemical reactions,
crystallization takes place according to chemical reaction equation as shown below,
Atm .Pressure
X (in solution) +Gel medium X(crystal)

Various types of gels

1. Physical gel
Gel which is obtained by Physical process such as cooling is called physical gel.Eg.
Gelatin, clay.
2. Chemical gel:
Gels formed by chemical reaction such as hydrolysis (or) polymerization are called chemical
gels. E.g. Silica, Polyacryalamide.

Advantages:
1 It prevents turbulence and formation of good crystals by providing a framework of
nucleation.

2 The convection is absent in growth experiments

3 The high degree of perfection and lesser number of defects have been observed in gel
growth.

4 The Gel method has also been applied to the study of crystal formation in human system
such as cholesterol stores, Sex hormones.

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