CRYSTAL GROWTH AND THIN FILMS

Unit 1: Crystal Growth Kinetics

1.1 SOLIDS AND CRYSTALS

The word "crystal" comes from Greek roots meaning "clear ice. Crystals are solid.
The three states of matter: solid, liquid, and gas. The best way to picture the difference in the
three states of matter is shown below figure. Figure (A) In the solid, atoms are close together.
They vibrate but cannot move past one another. Figure (B) In the liquid, the atoms are almost
as closely packed as in the solid, but they can move past one another. Figure (C) In the gas
the atoms are widely separated, and can move almost independently.

1.2 CRYSTALLIZATION

Crystallization is the process that happens when the materials solidify from a liquid,
or as they precipitate out of a liquid or gas. This process can be carried out by causing a
physical change, like a change in temperature, or a chemical change like acidity. The
crystallization process is carried out on the basis of the size and shapes of the molecules
involved, and their chemical properties.
The unit cell is known as the smallest unit of crystal. It is the base form of atoms or
molecules upon which more units can be attached. Crystallization goes on as if the blocks are
getting attached in all directions. Some of the materials form different shaped crystals, which
results in great variation in shape, size, and color of various crystals.

1.3 IMPORTANCE OF CRYSTAL GROWTH

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 We realize that ‘education’ is needed for the important field of crystal-growth
technology in order to achieve efficient developments in novel high technologies, in energy
saving, in solar energy generation and in future laser-fusion energy.
• Crystal growth is a vital and fundamental part of materials science and engineering.

• The ever-increasing application of semiconductor-based electronics creates an

enormous demand for high-quality crystals.

• The photonic device evolution we see today is due to III-V compound semiconductor
crystals.

• Nonlinear optical crystals are very important for laser frequency conversion.

• Quartz crystals have the ability to rotate a plane of polarization and high transparency
from UV to NIR region.

• Without crystals, there would be no electronics, no photonic industry, and no

fibre optic communications

1.4 METHODS OF CRYSTAL GROWTH

The ideal crystal is an infinite lattice of atoms arranged in patterns, which repeat in all
three dimensions with repeated distances (lattice spacing). In general, a single crystal is a
periodic array of atoms arranged in three dimensional structures with equally repeated
distance in a given direction. Natural crystals have often been formed at relatively low
temperatures by crystallization from solutions, sometimes in the course of hundreds and
thousands of years. Now days, crystals are produced artificially to satisfy the needs of science
and technology. Many attempts have been made for a long time to produce good crystals of
desired material. Presently, crystal growth specialists have moved from the periphery to the
center of the materials-based technology.

Crystal growth methods are generally classified into three categories:

i) growth from solid,

ii) growth from vapour and

iii) growth from liquid

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 The job of the crystal grower is to prepare large specimens of crystalline material such
that there is a complete crystallographic continuity across a given specimen in all directions is
achieved.

1.4.1 Growth from Solid Phase

Solid state growth technique can be considered as the conversion of a polycrystalline

material into a single crystal by causing the grain boundaries to be swept through and pushed
out of the material due to atomic diffusion. But this is very slow at ordinary temperatures and
is only rarely used.
Elevated temperature
X (Solid) X (Crystal)

1.4.2 Growth From Vapour Phase

Single crystals of high purity can be grown from the vapour by sublimation, chemical
vapour deposition and Physical vapour deposition. In these processes, the source material
which is a solid or one or two components of the phase to be crystallized is provided from the
vapour phase. The ampoule must be translated through the temperature gradient at a rate
equal to the linear growth rate of the crystal. This ensures that the supercooling conditions
remain constant so that spurious nucleation does not occur.

X (Vapour) X (Crystal)

A (Vapour) + B (Vapour) X (Crystal)

1.4.3 Growth from Liquid Phase

a. Low temperature solution growth

The method of growing crystals from solutions may be used for substances fairly
soluble in a solvent and not reactive with it. Moreover, growth of crystals from solutions is
the only method for the crystallization of substances which undergo decomposition before
melting.

(i) Slow evaporation method

(ii) Slow cooling method
(iii) Temperature gradient method

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 Low temperature
X (Solid) + Solvent X (Crystal)
Atm. pressure

Low temperature
A (Solid) +B (Solid) + Solvent C (Crystal)
Atm. pressure

b. High temperature solution growth (Melt)

Melt growth can be achieved by a variety of techniques (e.g. free melt surface of
confined configurations) depending on the specific properties of the material (e.g. contraction
or expansion during solidification) and requirements.

Temperature lowering
X (Solid) X (Crystal)

The growth from melt can be sub grouped into various techniques. The main techniques are:

i) Czochralski technique
ii) Bridgman-Stockbarger technique
iii) Vernueil technique
iv) Zone melting technique
v) Skull melting technique
vi) Shaped crystal growth technique.

c. Hydrothermal growth

The principle of hydrothermal method is that an insoluble material at ambient

temperatures could be made soluble using high temperatures and pressures. Growth occurs
from aqueous solution at high temperature and pressure. Temperatures are typically in the
range 400-600 oC 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.

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 High Temperature
X (Solid) + Solvent X (Crystal)
High pressure

d. Flux growth

In this method, the components of the desired substance are dissolved in

a solvent (flux). The method is particularly suitable for crystals needing to be free from
thermal strain. It takes place in a crucible made of highly stable, non-reactive material.

Molten state
X (Solid) + Fluxing salt X (Crystal)

e. Electro-crystallization

Electrocrystallization refers to nucleation and crystal growth occurring

on electrodes in electrochemical systems under the influence of an electric field. During
electrocrystallization, it is the intention to deposit compounds as crystals attached to
the electrode surface.

X (in solution) X (Crystal) +products

f. Gel growth

Gel growth is an alternative method to solution growth with controlled diffusion and
the growth process is free from convection. The growth of single crystals in gel is a self-
purifying process, free from thermal strains which is common in crystal grown from the melt.

Low temp.
X (In solution) + Gel medium X (Crystal)
Atm. pressure

Low Temp.
A (In solution) + B (In solution) + Gel medium X (Crystal)
Atm. pressure
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1.5 Nucleation

Nucleation is an important phenomenon in crystal growth. In a supersaturated (or

supercooled) system when a few atoms or molecules join together a change in energy takes
place in the process of formation of the clusters. The cluster consisting of such atoms or
molecules is normally termed as embryo. An embryo may grow or disintegrate and disappear
completely. If the embryo grows to a particular size, critical size known as critical nucleus,
then there is greater probability for the nucleus to grow. Thus, the birth of the critical nucleus
is an important event in crystal growth. There are four stages involved in the formation of a
stable nucleus.
a) The first stage is the development of the supersaturated stage. This may be due to a
chemical reaction, change in pressure, temperature or any other chemical or physical
conditions.
b) The second stage is the generation of embryo. The formation of an embryo may be
either homogeneous where the atoms or molecules build themselves in the interior of
the parent system or heterogeneous where the molecules build up on an impurity
atom or dust particle or on the surface of the container or on any other imperfection.
c) The third stage is the growth of the embryo from the unstable or metastable state to the
stable state or the critical size and
d) The fourth stage is the relaxation processes where the texture of the newly born
nucleus alters.
Nucleation is the process of generating within a metastable mother phase, the initial
fragments of a new and more stable phase capable of developing spontaneously into gross
fragments of the stable phase. Nucleation is consequently a study of the initial stages of the
kinetics of such transformations. Nucleation, like ordinary chemical kinetics, involves an
activation process leading to the formation of unstable intermediate stages of embryos. The
critical nucleus differs from an equal number of normal molecules or atoms in possessing an
excess of surface energy and a deficit in bulk energy due to inter-atomic or molecular
bonding, sufficient to produce the aggregate as a new phase in the presence of the mother
phase.
1.6 KINDS OF NUCLEATION

Nucleation may occur spontaneously or it may be induced artificially. These two

cases are frequently referred to homogeneous and heterogeneous nucleation respectively. At

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the present state of knowledge, there is no general agreement on nucleation nomenclature.
The term primary will be reserved for both the case of nucleations, homogeneous or
heterogeneous, 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 secondary nucleation. This classification can be represented as
follows:
Nucleation

Primary Secondary

Homogeneous Heterogeneous Fluid shear Contact nucleation

Nucleation can often be induced by external influences like agitation, mechanical

shock, friction, extreme pressures, electric and magnetic fields, spark discharge, ultraviolet,
X−rays, −rays, sonic and ultrasonic irradiation and so on.
1.6.1 Homogeneous nucleation

Nucleation generally occurs with much more difficulty in the interior of a uniform
substance, by a process called homogeneous nucleation. Supercooling brings about
supersaturation, the driving force for nucleation. When a droplet nucleus forms due to
supersaturation, certain quantity of energy is spent in the creation of a new phase. The free
energy change associated with the formation of a nucleus can be written as,

ΔG = -ΔGv +ΔGs……. (1)

Where Gs is the surface excess free energy and Gv is the volume excess free energy.
For the spherical nucleus

…….. (2)

Since the surface energy term increases with r2 and the volume energy term
decreases with r3, the net free energy change (G) increases with the increase in size, attains

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the maximum and decreases for further increase in the size of the nucleus. Plot showsthe
dependence of surface energy change, volume energy change and the net free energy on
the size of the nucleus. The size corresponding to the maximum free energy changes is
called critical nucleus. The radius of critical nucleus is obtained by setting the

condition and the expression for critical radius from equation (2) is given by

………. (3)

Substituting the value of r* in G equation (2). The free energy change associated with the
critical nucleus is obtained as

…………..(4)

The term can be related to the equilibrium temperature, enthalpy of fusion ( ),

and the degree of undercooling ( ) as follows,

……. (5)

By evaluating this equation at the equilibrium point ( ) at the melting

temperature we achieve,

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Substitution of into the (5) equation leads to,

which by using common denominators and the definition of provides,

As the phase transformation becomes more and more favorable, the formation of a
given volume of nucleus enough energy to form an increasingly large surface, allowing
progressively smaller nuclei to become viable. Eventually, thermal activation will provide
enough energy to form stable nuclei. These can then grow until thermodynamic equilibrium
is restored.

A greater degree of supercooling favors phase transformation, and we can relate

to supercooling and find r* and as a function of by the substitution of

and

The greater the supercooling, the smaller the critical radius and the less energy
needed to form it. The spontaneous nucleation rate in, say, water changes very rapidly with
temperature, so the spontaneous nucleation temperature can be quite well defined.

1.7 THEORIES OF NUCLEATION

Gibbs was the first to realize that the formation of small embryonic
clusters with some critical size is a requirement for a macroscopic phase transformation to
take place. Owing to their increased surface-volume ratio such clusters, termed critical

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nuclei, have more energy than bulk phases of the same mass. Hence, they have a chance to
survive and to produce macroscopic entities of the new phase only within supersaturated or
undercooled systems.

CLASSICAL THEORY OF NUCLEATION

Gibbs Thomson equation for vapour

In 1806, Laplace obtained the condition for the mechanical equilibrium of a surface.
For a spherical liquid the pressure (P2) within the drop
P2- P1 = (2σ/r) ……………(a)
Where r is the radius of the drop, σ is the surface tension and P1 is the pressure in
the parent phase outside the drop.
Let  r be the chemical potential of the vapour in equilibrium with the small liquid

droplet of radius r and chemical potential of infinite radius   .

Then  r =  


If the  is varies with P as =v …………………(b)
P
where v is the volume per molecule in the liquid drop.
From equation (a),
2
r −  = v …………(c)
r
The chemical potential in terms of pressure is r = α + kT ln P

Where α is the chemical potential of the vapour when P1 is infinite. Substituting for
r and α in equ. (c), we obtain,

P2 2
kT ln = v
P1 r

The above relation is called as Gibbs-Thomson equation.

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Gibbs Thomson equation for solution

Gibbs –Thomson equation can also be applied when a crystal is formed in a

supersaturated solution. The solubility of a crystal increases as the size of the crystal
decreases. If C1 and C∞ are the concentrations of solution with a small crystal of radius r and
with a large crystal of radius ∞ respectively then

C1 2
kT ln v= v
C1 r

Gibbs Thomson equation for melt

In 1888, J.J. Thomson modified W.Thomson’s equation to show that the melting point
of a small crystal is less than that of a large crystal. Let Tm and T be the melting point of a
large crystal and a small crystal of size of radius r. Since the two phases are in equilibrium ,
their chemical potentials must be equal.  r =   .

2
From the crystal equation (c) is satisfied in melt also,  r −   = v ……(a)
r

As the crystal size changes, the melting point also changes from T to Tm.
For a variation along the coexistence line of the equilibrium,
d (r / T ) = d ( / T )

 (d (  r / T ))
At constant pressure, d (  r / T ) = dT
T
  r  2
From equ. (a), ( − )dT = d ( v)
T T T Tr

(  r −  ) H m
Since, = −( )
T T

where H m is heat of fusion per molecule.

H m 2
−( )dT = d ( v)
T Tr

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Integrating above equation between r is equal to infinite at Tm and r = r at T,

 1 1 2
H m  −  = −( v)
 Tm T  Tr

2 Tm − T
Hence, v=
rHm Tm

The above equation called as Gibbs Thomson equation for melt which
shows that the melting point of a large crystal is greater than that of a small crystal.

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