TYPES OF CRYSTAL GROWTH

The growth technique differs from crystal to crystal depending on their physical and
chemical properties. Some of the physical properties such as solubility, melting point, decomposition,
and phase change have a vital role in determining the method of crystal growth to be carried out.
Crystal growth methods are broadly classified by the type of phase transformation occurring during
the growth process.
i.
Liquid Solid phase : Growth from solution and Melt
ii.
Vapour Solid phase : Growth from Vapour (PVD and CVD)
iii. Solid Solid phase :
Solid Phase Epitaxy methods
iv.
Precise temperature control has an effective control over the supersaturation.
v.
Crystal quality will be very good with well developed growth habits.
vi.
Real time observations of growth process can be done to evaluate the growth parameters
such as induction period, growth rate and morphology.
vii.
This is the best suited method for most of the organic and inorganic materials which
undergoes decomposition in melt or undergo structural transformation during
solidification. The major disadvantages of the solution growth method are the solvent
inclusion into the growing crystal and much longer growth periods. These problems can
be reduced effectively by suitably choosing the solvent and controlling the growth
parameters.
viii.
All the solution growth methods are sensitive to the solubility dependence parameter
of the substance such as temperature, pressure and concentration.
CRYSTAL GROWTH PARAMETERS
Growth of crystals from solution needs technical expertise and familiarity with certain
parameters called growth parameters. These are very critical parameters that require effective control
over them. The various growth parameters that controls the growth of single crystals grown from
solution are,
i Nucleation
ii Solution and Solubility
iii Saturation and Supersaturation
iv Metastable zone width
v Induction period
1.3.1
Nucleation
Nucleation is an important event in the process of crystallization. Supersaturation existing
in the system is the key parameter for nucleation which brings few atoms or molecules to join together
and hence results in a change in free energy (Volmer 1925). The joined atoms or molecules form a
cluster called nuclei. The cluster may grow further or it may disintegrate completely. If this cluster
grows, it reaches a critical size called as critical nucleus. Once the critical nucleus is attained, there is
a greater chance for the growth process to continue to form a crystal.
Nucleation takes place in a series of four stages.
i.
Attaining the supersaturation
ii.
Formation of cluster or embryo.
iii. Development of embryo into a stable critical nucleus.
iv. Relaxation process or agglomeration.
The supersaturation is attained due to chemical reactions or change in physical conditions
such as temperature, pressure, density and so on. Formation of cluster may be homogeneous or
heterogeneous. If the atoms or molecules join together spontaneously in the parent phase, it is called
homogeneous nucleation. On the other hand, if it happens artificially due to the impurity or dust
particles or scratches present on the surface of the vessels, it is termed as heterogeneous nucleation.
The cluster grows to form the critical nucleus and then reaches the relaxation process where the
texture of new phase undergoes modification.
The probability that the embryo to grow further to form a stable nucleus depends on the
change in Gibbs free energy associated with the process. For a spherical embryo of radius r, change in
the Gibbs free energy is given by,
=4
+
(1.1)

Where, 4
=
is the surface excess free energy and
is the free energy change per unit
volume. As the surface energy term increases with r2 and the volume energy term decreases with r3,
the net free energy change increases with the increase in size, attains maximum and decreases for
further increase in the size of the nucleus. The size of the nucleus corresponding to the maximum free
energy change is called critical nucleus, which can grow further if the free energy of the system
decreases. If not, the embryo will dissociate into the mother system and no growth can occur.
1.3.2
Solution and Solubility
A solution is a homogeneous mixture composed of a solute dissolved in a solvent to give
only one phase. Solute is always present in the smaller quantity. A solute can have different solvents,
but the choice of the solvent depends on various factors such as solubility, viscosity, toxicity, vapour
pressure, volatility and cost effectiveness.
Solubility of a substance is defined as the mass of solute needed to make a saturated
solution in 100 ml of the solvent at a constant temperature. The solubility of the substance in a solvent
decides the amount of the material available for the crystal growth and hence determines the crystal
size limit. Solubility of a given substance is found at various temperatures ranging from 0C to 100C
and the data are plotted on a temperature vs solubility graph and the points are connected. The curve
obtained by connecting the points is called solubility curve. Neither a flat nor a steep curve will
facilitate the bulk growth of crystals from solution. A typical solubility diagram is shown in Figure
1.1. If the solubility of a material increases with temperature, it is called positive temperature
coefficient material. If the solubility decreases with temperature, it is referred as negative temperature
coefficient material. Hence solubility of a given material must be determined prior to the crystal
growth.
1.3.3
Saturation and Supersaturation point
The state of a solution in which it is in equilibrium with the solid phase is called
saturation point. In this state, complete dissolution of solute would have been occurred. If the solution
contains more dissolved materials than that could be under normal circumstances (saturation), it is
called supersaturation. In other word, supersaturation refers to the vapour of a compound which has a
higher partial pressure than the vapour pressure of that compound. Three principal methods used to
attain the required supersaturation are,
i.
Slow evaporation of solvent (isothermal method)
ii.
Slow cooling of solution (non-isothermal method)
iii. Temperature difference method
Therefore, supersaturation depends on the solubility which in turn depends on the
temperature. Supersaturation being the key factor for nucleation, even a small fluctuation in the
temperature will seriously affect the supersaturation and hence growth of the crystal.

Figure 1.1 Solubility diagram

The solubility curve in Figure 1.1 shows three regions separated by a lower curve due to
normal solubility and an upper curve due to supersolubility. Region I is undersaturated zone which is

thermodynamically stable. No crystallization can occur in this zone. Region II is supersaturated zone
and termed as metastable zone. Crystallization is possible in this zone by introducing a seed crystal.
Region III is supersaturated zone and called as unstable or labile zone. Spontaneous crystallization is
possible in this region.
1.3.4
Metastable Zone width
Metastable zone width is a measure of stability of a growth solution in the supersaturated
region. Figure 1.2 shows a typical metastable zone width diagram (Sangwal 1994).

Figure 1.2 Metastable zone width diagram.

Larger the zone width, greater is the stability (Buckley 1951). Narrow metastable zone
widths leads to secondary nucleations which upset the growth of the main crystal. In the metastable
zone width diagram, the solution is taken from point A to A by decreasing the temperature gradually
provided the concentration remains constant. Point A is solid-solution equilibrium point. Further
decrease in temperature leads the solution to the point B where the solution becomes supersaturated.
No precipitation of solid occurs even after a long period of time. Any decrease in temperature beyond
the point B will lead to rapid crystallization. The solution remains in the metastable stable state in
between the points A and B. As the point B is reached due to reduction in temperature, this process is
termed as supercooling and is expressed as,
=( )
(1.2)
The corresponding maximum concentration difference is expressed as,
=(

)
(1.3)
The maximum supercooling and maximum concentration difference are related as,
=
(1.4)
Isothermal process can also be performed to reach the point A. This is done by increasing
the concentration of the solution from A through controlled solvent evaporation. Further slow
evaporation will take the solution from point A to the point C through the metastable zone width.
Beyond the point C, further evaporation leads to instantaneous precipitation of the solid phase.
The dashed curve separates the zone width into two regions. The region between the
dashed curve and equilibrium curve where there is no sign of nucleation. But nucleation can occur in
the region between dashed curve and the metastability boundary. So, the metastable zone width is a
critical factor for nucleation process. The metastable zone width can be affected by various factors

such as temperature, purity of the solution, thermal history of the solution, impurities or additives, rate
of cooling and mechanical disturbances. A precise control over these factors is extremely important to
control the nucleation process.
1.3.4.1
Determination of Metastable Zone width
The metastable zone width can be experimentally determined by polythermal method.
A saturated solution is prepared at the experimental temperature and sealed inside a test
tube and placed in a constant temperature bath with digital temperature control. It is then cooled
gradually from the saturation temperature or higher in a controlled manner at a particular rate until the
first speck of a particle appears. The difference in the temperatures refers to the maximum
supercooling (
). During the cooling process, the solution is left unstirred or can be stirred
continuously using a stirrer (Nyvlt et al 1970, Nyvlt 1971).
The value of
depends on the other experimental factors such as the method in
which the phase change is detected and the way of solution preparation.
1.3.5
Induction Period
The time elapsed from the moment of supersaturation and the appearance of the first
speck of particle is referred as induction period. Induction period consists of different components.
i.
Relaxation time (tr): Time required for the formation of quasi steady state cluster.
ii.
Nucleation time (tn): Time required for the formation of stable nucleus.
iii. Growth time (tg): Time required for the stable nucleus to grow to a detectable size.
Therefore the induction period is the sum of all the components. i.e.
tind = tr + tn + tg
(1.5)
The components describing the induction period can be distinguished by a graphical
representation using desupersaturation curve as shown in the Figure 1.3 (Mullin 1993).

Figure 1.3 Desupersaturation curve

In the Figure 1.3, A is the supersaturation point obtained at time
t=0. B is the point
where the quasi steady state cluster (not detectable) is formed. From the point B to B the
undetectable nucleus grow further to reach a detectable size. The time elapsed in this region is
(
). From B to C no significant change is noticed and this period is referred as latent period.
From the end of the latent period (point C) to the point D, rapid desupersaturation takes place. During
this period the nucleus grow bigger into a crystal. With several hours or days, the system reaches the
equilibrium E and approaches the equilibrium concentration c0. A seed crystal introduced in this
process will necessarily reduce the induction period but will not eliminate it. Induction period, latent
period and rate of desupersaturation are highly sensitive to temperature, mechanical agitation, heat of
crystallization and impurity concentration.
1.4
TYPES OF LOW TEMPERATURE SOLUTION GROWTH
Low temperature solution growth consists of the following types.
i.
Slow cooling method

ii.
Slow evaporation method
iii. Gel method
1.4.1
Crystallization by Slow Cooling Method
In this crystallization method, the required supersaturation is attained by lowering the
temperature at a particular rate. The crystallization process involves the temperature and the
concentration of the solution which moves into the metastable region along with the saturation curve
in the section of lower solubility. Since the volume of the crystallizer is finite and the amount of
substance placed in it is limited, the supersaturation requires systematic cooling. It is achieved by
using a temperature controlled water bath to control the temperature with 0.01oC accuracy. The
volume of the crystallizer is selected based on the desired size of the crystals and the temperature
dependence of the solubility of the substance. The main disadvantage of slow cooling technique is,
only the particular range of temperature is used. The possible range of temperature is usually small
and much of the solute remains in the solution at the end of the growth period.
1.4.2
Crystallization by slow evaporation of solvent
In this method, crystallization takes place due to supersaturation initiated by decrease in
volume of the solution through evaporation at constant temperature. Normally water is used as a
solvent. If the material is very much soluble or if it is insoluble, other organic solvents such as
ethanol, methanol, acetone, xylene etc., are preferred. Almost in all the 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 (Petrov 1969). In general, it
is enough to allow the vapour formed above the growth solution to get away freely into the open
atmosphere. The crystallization occurs in such a way that the point on the concentration scale moves
into the metastable region vertically in the direction of lower solubility. Unlike the slow cooling
method, the total mass of the system decreases due to evaporation of the solvent. This is achieved
when the growth solution in the crystallizer is simply left undisturbed in a fairly constant temperature
for the entire period of crystal growth. This method is highly preferred for the materials showing
small temperature coefficient of solubility and even negative temperature coefficient. Large crystals
of high quality can be grown by effectively controlling the rate of evaporation, temperature
stabilization, using ultra pure triple distilled water for solution preparation. Scratch free beakers can
be used for the growth to minimize the number of nucleations sites thereby allowing very few
nucleations to take place and grow further into large size crystals.
1.4.2.1
Selection of solvent
One of the important and very critical stages in low temperature solution growth method
is the selection of solvent. Selection of a solvent for growing a crystal depends on the physical and
chemical properties of the material to be grown. The material should have fairly good solubility in the
solvent. The solvent should not react with the material and the crystallizer. A good solvent should be
less viscous, less volatile, non toxic and have small vapour pressure.
On the part of chemical properties, there should be a chemical similarity between the
solute and solvent. Like dissolves like is the thumb rule in selecting the solvent. For example,
nonpolar organic compounds are soluble in nonpolar organic solvents. Similarly, polar compounds are
soluble in polar solvents. As the solid-liquid phase interaction always exists between the growing
crystal and the solvent, the growth habit modification can take place with respect to the nature of the
solvent used.
Many crystals are grown using water as the solvent because of its availability and easy
handling, low toxicity, low viscosity, nonreactive in its pure form. Water is more conveniently
handled during maintaining the supersaturation that exists by the change of temperature or removal of
solvent. But, water solvent may introduce water of crystallization in some of the materials which is
not desirable in anhydrous form of crystals. In such cases, other organic solvents can be used.
A solvent is suitable for crystal growth when the solute has a solubility of 10 to 60
percentages in it. If the solubility is more, i.e., more solute dissolves into the solvent, the solution
viscosity goes high and hence reduces the growth rate of the crystal. On the other hand, if the
solubility is very less, i.e., only less number of solute is available in the solution, the growth rate will
become low. This is due to the non availability of required number of solute particles to form the
crystal. In such cases, additives can be used to modify the viscosity and the solubility.
1.4.2.2
Preparation of solution

Preparation of solution involves rapid mixing of the solute and the solvent to form a
homogeneous state. This is done by constant stirring at a controlled temperature. The amount of solid
solute material that goes into the solvent depends on the temperature of the solution. If the
temperature is maintained constant, a time will arrive when the dissolution of solute stops and the
solution becomes completely saturated. In this saturated state, by setting little higher degree of
temperature, the solution may be made to hold more solute until the next saturation point will be
reached. This method of preparing solution helps in growing large crystals, as the solute present in the
solvent may be in plenty.
1.4.2.3
Preparation of saturated solution
Saturated solutions of the chosen material can be prepared in the suitable solvent at a
fixed temperature. A know volume of solvent is taken in a beaker and the material (solute) is
dissolved gradually using a magnetic stirrer at a constant temperature until saturation point is reached.
In principle, the amount of solute in the solution decides size of the crystal. The only way to get the
solution to hold more solute is by changing the temperature until at a higher temperature another
saturation point is reached. More and more solute can be added by fixing the temperature higher and
higher upto the operating temperature.
1.4.2.4
Purification by recrystallization
Recrystallization is a procedure to purify the parent material before starting the final
crystal growth. The steps involved in this process are
i.
Finding a suitable solvent
ii.
Dissolution of material in the solvent
iii. Hot filtration
iv. Cooling
v.
Separation of crystalline material
vi. Washing and drying the product.
The solvent used for recrystallization should have positive temperature coefficient of
solubility. The material to be recrystallized should be very soluble in the hot solvent (elevated
temperature) but poor soluble in cold solvent (room temperature) provided, the cold solvent must
dissolve the impurities. Other important characteristic of solvent is its boiling point. It should be in the
range of 50 to 120C. Solvent that have boiling point less than 50C are highly volatile and evaporate
even at room temperature. If the boiling point is above 120C, it may be very difficult to remove the
solvent from the recrystallized product. Also the boiling point of the solvent should be less than the
melting point of the material.
Once the solvent is fixed, then the material to be recrystallized is gradually added and
dissolved by increasing the temperature until complete dissolution occurs. The hot solution is filtered
and allowed to cool gradually to the room temperature. Then the solution is ice cooled to enable
recrystallization. Slow crystallization results in pure crystals than the rapid cooling which tend to be
less pure. The crystalline material is separated by cold filtration and finally it is washed and dried.
This procedure can be repeated until the desired purity is reached.
Crystallization by Gel Method
All the methods of crystal growth have their own merits and demerits. The melt methods
have the disadvantage of lattice disruption due to pronounced thermal fluctuations during growth
process. In low temperature solution method, defects and lattice strains may occur at the growth
boundaries due to impurities in the growing matrix. In this perspective, different gel methods have
emerged as a convenient growth technique for growing good quality single crystals.
In many cases, gel methods are preferred for some of the reasons such as, no convection
currents and turbulence is needed, gel medium is chemically inert and acts as a three dimensional
framework for the growing crystal thereby preventing damage due to growth vessels. As the gel
medium is transparent, the growing crystal is practically visible throughout the growth period.
Moreover, the gel technique is economically cheap compared to other methods of crystal growth.
1.4.3.1
Preparation of hydrosilica gel
Sodium metasilicate powder is dissolved in the deionised water in a proper pH to obtain
the desired gel. The pH of the medium is very important, which determines the rate of polymerization
and the speed of gel setting. The desirable pH value of the gel may be between 6-8 normally and
suitably adjusted by adding the acids such as hydrochloric acid, nitric acid, tartaric acid, acetic acid

and oxalic acid. After regulating the pH of the mixture, it is taken in the crystallization vessel for
polymerization. Commonly used crystallizers are test tubes or U-tubes depending on the methods and
materials.
1.4.3.2
Gelling mechanism
Sodium metasilicate dissolved in water gives mono-silicic acid due to the following
reversible reaction.
Na2SiO3 + 3H2O H 4SiO4 + 2NaOH
(1.6)
NaOH is formed as a by-product, which is the reason for the alkalinity of the solution.
The mono-silicic acid liberates the hydroxyl ions and polymerizes as below,
OH

OH
OH

Si

OH + OH

Si

OH

OH

Si

Si

OH + H2O

OH

OH

OH

OH

OH

OH

(1.7)
Polymerization continues until the entire molecule becomes the part of three dimensional
networks as shown in Figure 1.4.

OH

Si

Si

OH

Si

Si

OH

Si

OH

OH

OH

OH

Si

OH

Figure 1.4 Three dimensional network of Gel

In the process of gellation, the reaction releases water as a
by-product, which
accumulates at the top of the gel as it is less dense than the gel medium. This phenomenon is termed
as syneresis (Plank et al 1947).
In the due course of reaction, cross linkages are formed between the chains, which lead to
the formation of sol followed by the formation of macroscopic gel favoured by the surface energy.
The surface energy would be very high at the extreme values of pH which slows down the gellation.
The gel consists of micropores, which helps in the diffusion of ions by capillary action, and assists in
nucleation and growth of crystal.
1.4.3.3
Crystallization process in gel
The crystal growth by gel diffusion technique is classified based on the formation process
of crystal as following.
i.
Chemical reaction method
ii.
Chemical reduction method
iii. Complex decomplexion method
iv. Solubility reduction method
In chemical reaction method, reaction between the two components takes place inside the
gel. One of the components may be impregnated in the gel medium and the other may be allowed to
diffuse from the top of the test tube as shown in the Figure 1.5. The reaction mechanism can be
represented as,
AX + BY AY + BX
(1.8)

Figure 1.5 Chemical reaction method in gel (single diffusion)

AX and BY are the two reactants, which undergo reaction in the gel medium to form the
product AY and a by-product BX.
In chemical reduction method, metal sulphate is impregnated into the gel. After the
setting of gel, a reducing agent is added from the top as an outer reactant. Chemical reduction takes
place as the reducing agent diffuses into the gel and the desired metallic crystal is formed inside the
gel.
Complex decomplexion method is suitable for the materials whose solubility increases in
nonlinear manner in the presence of another soluble material with increasing concentration. Transition
metals are grown by this method.
Solubility reduction method is suitable for water soluble materials. The material to be
grown as crystal is dissolved in acidic medium and allowed to diffuse into the gel of the same pH. In
this process, the solubility of the solution reduces and hence the solution attains supersaturation.
Immediately nucleation takes place leading to the formation of crystals.
In the gel technique of crystal growth, an appreciable size of crystal can be grown,
depending on the effective control over the nucleation process. The following are some of the
commonly adopted methods for controlling the spurious nucleation in gel.
i.
Ageing of gel
ii.
Optimization of gel density
iii. Stabilized thermal conditions
iv. Concentration of nutrients
v.
Using additives
vi. Electric field utilization
Gel technique is also very effective in changing the growth habit. Face oriented crystal
can be grown, inclusion of impurities can be controlled and the morphology of the crystal can also be
varied with perfection.
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