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CHAPTER 1
1. I
Introduction
Crystals are the back bone of todays technological development. Present day applications require varied types of crysTals in its purest form. This led the people to concentrate on the development of new varieties of crystals, highly pure in form with almost nill defect. Urgency on the development of crystals led to the
investigation of theoretical studies on its growth process. A well developed theory is now available to help the crystal growers t o perfect the growth methods.
At
present theory and the experimental techniques have been developed to such a level that tailor made crystals for specific application can be grown. This chapter gives a general introduction to the theories and techniques of crystal growth.
1.2
The thermodynamics of crystal growth The thermodynamic equilibrium between solid and liquid phases occur when
The free energy of a system is related to the internal energy and the entropy of the system by the Gibbs [ l ] equation
G = H-TS
(1.2)
to the solid state. The driving force for crystallization comes from the lowering of the free energy of the system during this phase transformation. The free energy change associated with such a transition is
where
AH
HL-HS
AS=SL-SS AG
=
GL-Gs
=
At equilibrium AG
where
AT=T,-T
AG is positive when T,
The free energy change can also be represented a! change and super cooling AT.
Though this representation is convenient for melt growth, one may depend on concentrations rather than supercooling for solution growth and vapour growth. Thus the equation modifies to
In general
where S is the supersaturation ratio. Equation (1.4) and (1.6) explain how the free energy changes depend on the parameters like supercooling and supersahration which are decisive in the process of crystallization. The rate of growth of a crystal can be regarded as a monotonically increasing function of AG, if the other parameters remain the same.
1.3
Nucleation
Nucleation process is the conglomeration of atom! or molecules to form the
first sub-microscopic speck or nucleus of the solid crystal. Nucleation can be either
homogeneous or heterogeneous. Considering the total ii-ee energy for a group of atoms, a theory for the formation of a nucleus was put forward by Volmer and Weber [2].
Fluctuations within the supersaturdted solution give rise to small clusters of molecules known as "embryos". The probability that an embryo will grow to form
a stable nucleus depends on the change in free energy associated with its formation.
If the free energy change between the solid and liquid is AG,, the free energy of the system decreases by this amount for each unit volurne of the solid created, but increases by an amount equal to the interfacial energy o, for each unit area of the solid-liquid interface formed. Hence the change in Gibbs free energy associated with the fortnation of a spherical embryo of radius r is given by
contribution due to both surface and volume to the free energy charge are represented. The surface energy term increases with decreases with
?.
The net free energy change increases with the increase in size,
attains a maximum and decreases for the further increase in the size of the nucleus. The size of the nucleus corresponding to the maximum free energy change is known as the "critical nucleus". It is the smallest sized embryo which can grow further effecting the reduction in the free energy of the system. On the other hand if the size of the nucleus formed is below the critical dimension, no further growth is possible and it will re-dissociate into the mother system.
The minimum size of a stable, critically sized nucleus is obtained by the maximization of Equation 1.7 for r, which leads to
It may be noted that the value of r* decreases with AG, i.e., with supersaturation or supercooling. The free energy change AG* leading to the formation of the critical nucleus or, in other words, the activation energy necessary for nucleation, can be calculated by substituting r* in Equation 1.7.
AG* =
3s:
Equation 1.8 can be rearranged by introducing the Gibbs-Thomson relation and becomes 16r$@
AG*
=
3(kT 1n.s)'
where Q is the molecular volume. The rate of nucleation i.e., the number of nuclei formed per unit volume per unit time can be expressed as
Fig. I . 1
where J, is the pre-exponential factor. This equation shows that the nucleation rate is governed by the temperature, degree of supersaturation and the interfacial energy.
Rearranging Equation 1.10 and arbitrarily choosing J = 1, so that 1 n . J =0, we get the
expression for critical supersaturation as
Using the values of various parameters, the critical supersat~lrationrequired for spontaneous nucleation can be estimated.
1.4
Crystal growth theories The successive growth of the critical nuclei of microscopic size leads to the
formation of a crystal. In order to understand the mechanism and the kinetics of growth, several theories have been developed, which includes surface energy theory, diffusion theory, etc., but have been found to be unsatisfactory. Later Kossel and others analysed the atomic inhomogeneity of a crystal surface and explained the role of step and kink sites on the growth process. However, this was also not enough to provide a complete explanation for the continuous growth of a crystal surface. The
f d breakthrough came when Frank showed that crystal dislocations were capable
of providing the sources of steps required for the continuous growth of a crystal. These theories have been extensively described by a number of authors 13-71.
The surface energy theories are based on the thermodynamical treatment of equilibrium states put forward by Gibbs 111. He compared the growth of crystals with the formation of water droplets in mist and defined the equilibrium form as one with minimum total surface energy for a given volume. The thermodynamical
[81 calculated the shapes and end forms of crystals in equilibrium with solution or
vapour, consistent with Gibbs criterion. Wulff [9] gave an extension to Curie's ideas and deduced relations connecting the growth rate of different faces and the corresponding surface free energies. Marc and Ritzel [lo] further developed the concepts of Wulff, stating that different faces have different soiubilities. They
suggested that when the difference in solubility is small, growth is mainly governed by surface energy and the change in su&dce of one form is necessarily at the expense
C the growth of the different of other. Bravais [I 11 suggested that the velocities o
faces of a crystal would depend on the reticular density and the concept was modified by Donnay and Harker [12]. Soehnke [13] proposed that the faces which possess the greatest reticular densities are those with minimum surface energies and hence have minimum velocities of growth.
Berthoud [14] and Valeton [IS] disputed the surface energy theory on the basis of supersaturation. According to surface energy theory as the supersaturation increases, the growth becomes rapid in all directions. Consequently, the crystal habit ought to approximate to a spherical shape. But experimentally it has been observed that when the supemturation is high, well defined faces are developed.
1.4.2 Diffusion theory The diffusion theories, proposed by Noyes and Whimey (161 and by Nernst
( 171 is based on the following assumptions.
(a) (b)
There is a concentration gradient in the vicinity of a growing surface The growth process is a reverse process of dissolution.
According to them, the amount of solute molecules tfat will get deposited over the surface of a growing crystal in the supersaturated solution can be written as
where dm is the mass of the solute deposited over the crystal surface of area A during time dt, D is the diffusion coefficient of the solute, C and C, are the actual and equilibrium concentration of the solute and 6, the thickness of the stagnant layer adjacent to the crystal surface. experimental observations. But this theory also fails to be consistent with
The role of surface inhomogeneities on the growth process is the basis of surface nucleation model. A pure perfect crystal of a single element has-surfaces covered by steps with terraces between. These steps possess kinks and hence there are three types of sites; tenace, ledge and kink sites. This model developed by Kossel [18], Volmer [I91 and Stranski [20] presume that crystal growth is a discontinuous process taking place by the adsorption of matter layer by layer on the crystal surface. According to this theory the growth units arriving on a crystal surface do not incorporate immediately into the lattice, but become adsorbed and migrate over the surface. The migration distance xs of the adsorbed molecule is given by
where Ds is the surface diffusion coefficient and adsorbed molecule on the surface. In this model
T,
x ,
- a exp
I I
2kT
where a is the nearest neighbour distance and $J is the nearest neighbour interaction parameter. The possible lattice sites for the attachment of adsorbed atoms on crystal surface is illustrated in Figure 1.2 in which adatoms are pictured as cubes.
Fig. 1.2
An atom reaching a kink site is attracted by three out of the six nearest neighbows, while such bonds is two for a ledge and one for a terrace site. Thus the maximum binding energy between the adatom and the existing crystal surface occurs for the incorporation at a kink site. Hence the adatoms over the crystal surface migrate towards a step and moves along it to a kink site and get incorporated. Under ideal conditions this stepwise stacking will continue until the whole layer is completed. The mode of advance of a step has been extensively analysed by Burton, Cabrera and Frank 1211. A step advances by incorporating more and more adatoms at kmk sites. Assuming a diffusional flow of adatoms along the step, the rate of advance of a step can be expressed as
where y i s a frequency factor a d W is the total evaporation energy. The rate of advance is then proportional to supersaturation S and to the mean migration distance x,. Here it is assumed that the mean migration distance is much higher than the
mean distance between two adjacent kink sites on a step. When an advancing step covers the whole surface completely, further growth is possible only by the initiation of a two dimensional nucleus. According to
Volmer this is possible on account of thermal fluctuations. Assuming a circular disc-shaped nucleus of radius r and height h, the free 'znergy change associated with the formation of such a two dimensional nucleus may lie written as
Section 1.3 the activation energy necessary for the hvo dimensional nucleation can
be calculated as
AG*,
=-
*hP0
kT ins
The rate of growth of a singular face is in principle controlled by the rate of nucleation and rate of advance of a step and can be expressed as
The growth rates calculated using these equations do not agree with observed results
in many cases.
controlled by the probability of two dimensional nucleation which is not appreciable until the supersaturation reaches a considerable percentage order. However, it is observed that most of the real crystals grow at supersaturation down to a value of
1 % or even lower.
The discrepancy between the observed growth rate and the theoretical prediction based on two dimensional nucleation theory points to the fact that there is some other mechanisms responsible for the continuous growth of a crystal surface. Frank 1221 proposed that dislocations having a screw component can act as a continuous source of steps on the surface of the crystal which eliminates the need for surface nucleation. A screw dislocation emerging at a point on the crystal surface provides a step on the surface with a height equal to 'a', the projection of the Burgers vector of the dislocation. Since the step provided by the screw dislocation is anchored at the emergence point of the dislocation, and since the inner parts of the steps move radially at a faster rate than the outer parts, fiuther growth takes place only by the rotation of step around the dislocation point. This mechanism is
illus~rated in Figure 1.3. Under a given condition of supersaturation these steps wind themselves up into a spiral, centred on the dislocation. Though this theory assumes the existence of dislocations in the crystal in order to enhance the growth of a surface, the growth rate does not depend on the concentration of these dislocations.
Fig. 1.3
Developm~:ntof a spiral
Based on spiral growth mechanism Burton, Cabrera and Frank could establish a
relation between the rate of growth R and the relative supersaturation which is expressed as
(1.21)
and
D, fl ,BQ
C =
x,2
where
s
S1
relative supersaturation a constant for BCF model equilibrium concentration of growth units on surface. retardation factor volume of the growth unit.
rise
B
Q
The variation of the growth rate with supersaturation thus depends on two parameters, C which determines the absolute value of growth rate and sl which determines actual growth rate.
The BCF theory therefore predicts that the growth rate 15 proportional to the square of the supersaturation for low supersaturation, changing to a linear dependence at higher supersaturations. The Frank model is currently well founded in respect of the excellent agreement between theory and observations on growth rate as well as of the direct observation of spiral pattan, characteristic of this mechanism 123-271. However, Keller [28], and Bauser [29] observed that edge dislocations can also act
as persistent sources of steps for crystal growth. Frank [30] proposed a general
explanation of nucleation at edge dislocation that the surface stresses provides the extra energy required for the formation of the growth nuclei when the dislocation component perpendicular to the surface is absent.
1.5
The process of crystal growth is a controlled change of state, or phase change, to the solid state. This transition may occur from the solid, liquid or vapour state. Depending on the phase transitions involved in the process, the crystal growth methods can generally be classified into four main categories 131-341. I)
2)
3)
4)
The growth of crystals from the liquid phase is treatetl as two categories due to the independent behaviour of melt and solution techniqu't:~. A brief description about the various techniques of growth has been presented in the following sections with an emphasis to liquid - > solid growth method.
1.5.1 Solid growth techniques In solid growth technique, single crystals are developed by the preferential growth of a polycrystalline mass. This can be achieved by straining the material and subsequent anneal'ig. Large crystals of several materials, especially metals have
been grown by this method [35]. The main advantage of solid growth method is that this technique permits the growth at low temperatures without the presence of additional component. But as the growth takes piace in the solid, density of sites for nucleation is high and it is difficult to control nucleation.
Vapour growth techniques can be adopted for the growth of materials which lack a suitable solvent and sublime before melting at normal pressure. Vapour
growth methods have been employed to produce bulk crystals and to prepare thin
layers on crystals with a high degree of purity. Growth from vapour phase may generally be subdivided in to 1) Physical vapour hamport Chemical vapour tramport.
2)
In PVT technique the crystal is grown from its own vapours and this method does not involve any extraneous compound formation or reaction. The PVT
methods are limited to materials having an appreciable vapour pressure at attainable temperatures. There are two types of techniques employed in physical vapour The f i r s t method
involves sublimation of the charge at the high temperature end of the furnace, followed by the condensation at the colder end [36,37]. Sputtering techniques are preferred to low vapour-pressure substances and mainly this method has been used
i l m s rather than discrete crystals. The principal advantage of this to prepare thin f
technique is that film growth can be possible at lower temperature than in ordinary sublimation-condensation growth. The PVT techniques are used to prepare a variety of crystals [ 3 8 4 ] and for the production of epitaxial films [41,42].
material to be grown is melted and after that it may progressively cooled to yield the
crystalline matter. This method has been generally employed for the growth of metals, semiconductors, and laser host crystals. Single crystals with high degree of perfection and purity can be obtained by this method. Usually melt growth methods are grouped into two categories.
1)
N o d freezing method
a)
b)
2)
Zone-growth method
a)
b)
There are two versions for Bridgman's method; Horizontal Bridgman method (Chalmer's technique) and Ver&ical Bridgman method (Bridgman-Stockbarger technique). In these techniques directional solidification is obtained by slowly
The Bridgman technique is most frequently applied for the growth of But this method cannot
be used for materials having high melting point and high expansion coefficient.
Cmhralski method is the most powerful method for growing single crystals
and is basically a crystal pulling system. The advantage of this method over the
Bridgman method is that it can accommodate the volume expansion associated with the solidification. Cmhralski method has gained wide recognition particularly in growing single crystals of semiconductors like silicon [53] and other materials
154,551.
~t
may be used as a method for the growth of single c r y s ~ l s . In this method, a zone or part of the solid material is melted and this molten zone travels together with the heating elements. The advantage of zone melting is that it offers a relatively simple way of producing doped crystals containing deliberately admixed additives in a given concentration in uniform distribution 1561. Floating zone technique developed by Keck and Golay 1571 is a variant of the zone melting technique in which no crucible is used. This method is especially suitable for the preparation of high
1.5.4 Growth from solution The growth of crystals by precipitation from aqueous solution is the most simple and oldest technique. In this process, a saturated solution of the material in an appropriate solvent is used from which crystallization takes place as the solution becomes critically supersaturated. The supersaturation can be achieved either by lowering the temperature of the solution or by slow evaporation. The advantage of the method is that crystals can be prepared from a solution at temperatures well below its melting point, perhaps even at room temperature and therefore it turns out to be more applicable in many cases [58]. Solution Growth can be broadly classified into 1) High temperature solution growth. Hydrothermal method. Low temperature solution growth. Gel growth
2)
3)
4)
This reduction in
temperature is probably, the main advantage of flux growth. The materials to he crystallized are dissolved in a proper solvent at a temperature slightly above the saturation temperature and then slowly cool the crucible so that growth occurs in a spontaneously formed nucleus. The growth of crystals by the slow cooling of the flux is also effective.
Hydrothermal methods
Hydrothermal method is suited for the growth of certain class of materials which are practically insoluble in water. A number of metals and metal oxides show an appreciable increase in solubility when the temperature and pressure are increased. It can be treated as aqueous solution growth at elevated temperature and pressure. Growth is usually carried out in steel autoclaves with gold or silver
linings. A charge of crystals is dissolved in the lower part of the autoclave. The hot saturated solution is directed towards the upper (colder) part, where it cool and become supersaturated hence the growth of crystal. The spent solution returns to the other part and this process continues until the whole charge is recrystallized. The solution simply acts as a transporting agent for the solid phase. This method is extensively used for the growth of large high quality synthetic quartz crystals 1601.
It is the most effective and easy way for growing crystals. A variety of
crystals can be grown by this technique at room temperature. In this method, a saturated solution of the material is prepared in a suitable solvent and crystallization is initiated by slow cooling of the solution or by slow evaporation of the solvent. Large and perfect crystals of industrially important materials are grown by this method [61-65].
technique supersaturation is achieved either by the slow interdiffusion of solutions of two reacting species, which on mixing react to form the solute, or by the interdiffusion of a solution with a solvent in which the solute is insoluble or less soluble. Using gel technique small but highly perfect crystals of relatively insoluble materials can be grown [66]. This technique fonns the subject matter of this thesis and therefore needs further elaboration. It is given in the following chapter.
References
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