Crystal Growth

ANNUAL
REVIEWS Further
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Copyright 1971. All rights reserved
CRYSTAL GROWTH 8507

R. A. LAUDISE, J. R. CARRUTHERS, AND K. A. JACKSON
Access provided by 2001:d08:1203:db24:712e:255d:ca9d:7246 on 04/08/20. For personal use only.
Bell Telephone Laboratories, Inc., Murray Hill, New Jersey
I. INTRODUCTION
Annu. Rev. Mater. Sci. 1971.1:253-288. Downloaded from www.annualreviews.org
The growth of single crystals and the theory of crystal growth continues
to be an area of central importance and increasing activity in materials
science. One of the foundation stones of the electronics industry is single
crystal devices. I ndeed, the rate-limiting step in the evolution of solid-state
technology today increasingly becomes the attainment of single crystals of
the required composition and perfection. I n the search for new electronic
materials, crystal growth plays an essential part, while crystal growth theory
provides an ideal testing ground for the interplay of atomic (microscopic)
and classical (macroscopic) concepts and the most practical experimental re
alities.
In this review we will present our views of the status of crystal growth
theory and practice as of early 197 1 , together with our concepts of future
trends. We will not attempt to be encyclopedic nor to present an annotated
bibliography; we will discuss a limited set of subjects which we consider
relevant. Future reviews in this series will present other viewpoints. We be
gin by mentioning the book of Laudise ( 1970) . Our review assumes as back
ground information the material covered in this monograph. We will orga
nize the review into two theoretical sections-microscopic theory and
macroscopic theory-and two experimental crystal growth sections-crystal
growth as an exploratory materials research tool and crystal growth tech
niques. We conclude with a section devoted to characterization.
II. MICROSCOPIC THEORY

The ultimate objective of the microscopic theory of crystal growth is to
relate growth velocities to the basic atomic parameters (i.e. bond distances,
direction, and energies) of the growing crystal and to understand how the
thermodynamic driving forces influence the growth (i.e. how mass and heat
flow affect supersaturation or supercooling and hence growth) . To a large
extent the role of the driving force is more appropriately considered as a
macroscopic problem and will be discussed in Section I I I. The great water
shed in microscopic theory was the realization that a Frank- Read (Burton,
Cabrera & Frank 1951) source (screw dislocation) provided a repeatable
step for growth at low supersaturation. Parker has written a recent review
(1970) which covers many of the developments in crystal growth theory,
especially those following the B urton-Cabrera-Frank work. The next im-
253
254 LAUDISE, CARRUTHERS & JACKSON
1.0
.8 • 0' .. o.� o 0' .. 2.0
.6
.4
I
Ci
+0'-1.0
00'= I.�
x
.0'
0' �
..
3.0
5.0
.2
0
-8 7
- -6 -5 -4 -3 -2 -\ 0
L-
FIGURE 1. Roughness of a crystal surface for various values of cx. C; is the fraction of
sites in layer i which is occupied by atoms of the crystal.
portant development (Jackson 1 958) was a categorization of growth be

havior of materials based upon their entropies of transition. I n the next sec
tion we briefly review this development.
INTRINSIC GROWTH KINETICS
The intrinsic growth rate of a crystal depends on the mobility of the

species in the phase into which it is growing, on the chemical potential dif
ference between the crystal and the phase into which it is growing, and on the
structure of the interface. During some growth processes, the crystal surface
will be rough on an atomic scale; in others, it will be smooth. The degree of
roughness of the surface depends both on the growing crystal and on the
phase into which it grows. The surface roughness also depends on the
crystallographic orientation of the interface. The materials parameter which
determines the degree of roughness of a surface is the entropy change !:.S
between the two materials on either side of it. The entropy change associated
with vapor growth of, say, a metal is different from the entropy change as
sociated with the growth of the same crystal from the melt, because the
entropy of the nutrient phase is different in the two cases. The geometry of
the surface is important because the roughness of the surface depends on
the number of lateral bonds a given molecule can make parallel to the inter
face. It has been shown (Jackson 1 958) that the roughness of a surface de
pends on a factor a defined by
L N.
a=---=----
R N kT. N
where L is the latent heat associated with the transformation, k is Boltz

mann's constant, T. is the temperature of equilibrium between the two
phases, N. is the number of bonds parallel to the surface and N is the total
number of bonds. The roughness of a surface depends on a as shown in
Figure 1. For large a the surface is quite smooth, whereas for small a the
transition from liquid to solid takes place over several atomic layers .
C RYSTAL GROWTH 255
The reason for the importance of surface roughness during crystal growth
is illustrated in Figure 2. A smooth surface of a close-packed face requires
surface nucleation, or defects, for growth. A rough surface of the same plane
does not, because molecules can readily be added to many sites on the sur
face. A low-index surface provides many growth sites, independent of
whether it is rough or smooth. A crystal with rough surfaces therefore grows
rapidly and the growth rate is more or less isotropic. Growth occurs slowly
on the close-packed faces of a crystal with smooth surfaces. Growth is rapid
on the high-index faces. A crystal with smooth surfaces grows slowly, and
the growth rate is anisotropic.
The entropy changes associated with various growth processes are listed
in Table 1 . These numbers have been divided by Boltzmann's constant to
make the entropy dimensionless. The metals growing from the melt have low
entropies of fusion. Their intrinsic growth rate is rapid, and so crystal growth
in metals is usually controlled by diffusion, either of heat or of matter. Some
ionic crystals and some organic compounds also have low entropies of fusion.
Many ionic crystals, organic compounds, and elements such as Si, Ge, Sb,
Ga, and Bi have normalized entropies of fusion in the range 2-4. Most organic
TWO DIMENSIONAL CRYSTAL
(10) FACE (Ill FACE
LOW
ENTROPY
CHANGE
HIGH
ENTROPY
CHANGE
FIGURE 2. Schematic drawing of rough and smooth interfaces: on the left, a low
index (10) edge of a crystal ; on the right, an (11) edge. The two edges at the top are
for small .:lS; the two at the bottom, for l arge .:lS.
TABLE 1. ENTROPY CHANGE ON CRYSTALLIZATION FOR VARIOUS MATERIALS
kT.
1 Metals from melt
) I
Si, Ge, Sb, Bi, Ga from melt
3 Ionic materials
6 Most organic compounds from melt

10 Metals from vapor Organic compounds
20 Complex molecules
J
>100 Polymers
compounds have normalized entropies of fusion in the range 4-8. Trouton's

rule states that the normalized entropy of vaporization of metals is 10.5
(21 eu) . Large molecules tend to have large normalized entropies of fusion,
in the range 8-60. Polymers have very large molecular weights and, there
fore, very large entropies of fusion.
The growth morphologies of materials with similar entropy changes are
similar, as has been illustrated by Jackson (1967) .1 Growth with a small
entropy change usually occurs with the interface within a fraction of a degree
of the melting point. For laboratory growth rates, in the mm/min range,
the interface undercooling for a normalized entropy change of 2-4 is likely
to be a few degrees, for 4-8 several degrees, and for 7-20 tens of degrees. The
intrinsic growth dominates the growth morphology for growth with large
entropy change, while diffusion processes dominate at low entropy change.
The undercooling q uoted above is approximate and applies to materials of
" usual" viscosity.
Glass-forming materials, which have great viscosity, have much slower
growth rates, because of their low molecular mobility, but their growth
morphology still depends on their entropy of fusion. This has been demon
strated by Uhlmann and co workers, who have measured the growth rate
and viscosity of glasses over a wide temperature range. The growth rate of
the low-entropy-of-fusion Si02 is linear with undercooling, after the growth
rate has been corrected for the temperature dependence of the viscosity
(Vergano & Uhlmann 1970). The growth rate of sodium disilicate, which has
a normalized entropy of fusion of 4.5, is not linear with undercooling. I t is not
slow at low undercooling and then increases rapidly at higher undercoolings
(Meiling & Uhlmann 1967). These measurements on glasses are better than
most measurements of growth rate because the intrinsic growth rate is not
masked by diffusion processes. For other materials there are often thermal
or compositional gradients in the vicinity of the crystal, so that it is difficult
1 A movie has been made illustrating several typical growth morphologies for
materials having various entropies of fusion Uackson & Miller 1969).

CRYSTAL GROWTH 257
to determine the composition and temperature at the interface. However, in
these glasses, the intrinsic growth rates are so slow that these effects are not
important.
Almost from the time of Gibbs, attempts have been made to correlate
growth rate with specific surface free energy. Estimates of this quantity
have been made by the direct correlation of the reticular density (Donnay
& Harker 1937) of the atoms in a given plane. While high-density c1ose
packed faces do have low specific surface free energy, one must take into
account the directional nature of bond formation and the details of the
spatial arrangement of atoms, particularly when bonding is not homopolar
in a compound composed of more than one element. Some improvement in

compensating for certain of these factors is obtained in the periodic bond
chain (PBC) method of Hartman & Perdok ( 1955) . In this method every
crystal is divided into periodic bond chains and growth is predicted to be
fastest in the direction of strongest chains. This approach can have limited
success at best, since the growth rates on various faces of a crystal have dif
ferent dependences on temperature or supersaturation. The morphology of
the crystal can change due to changes in the relative growth rates of the
various faces, which occur without corresponding changes in surface free
energy.
A more rigorous approach to modeling of the growth situation has been
achieved through the use of statistical mechanics. The basis for this approach
was outlined by Cahn ( 1960) . He suggested that an interface passed through
positions of lower and higher free energy during growth as a result of the
periodicity of the lattice. He showed that the height of these periodic varia
tions in surface free energy depends on the degree of roughness of the sur
face. He suggested that the growth rate at low undercoolings would depend
on surface nucleation or defects, and would depend linearly on undercooling
at undercoolings sufficiently large to overcome the barrier to the motion of
the interface. Cahn, Hillig & Sears ( 1964) applied this treatment to various
measurements of crystal growth rates by fitting adjustable parameters in the
theory to experimental data. When examined in detail (Jackson, Uhlmann &
H unt 1967) , the data cannot be fitted properly. With varying success, several
experimenters have attempted to fit their growth rate measurements to this
theory using its adjustable parameters. This scheme for calculating the
growth rate of a crystal has now been worked out in detail for various statis
tical models of the interface.
The simplest model of the interface is Jackson's two-level model ( 1958).
The two-level model using the exact solution to the I sing model presented by
B urton, Cabrera & Frank (1951) is much more complex to use, but not much
better, since it is two-level. The multilevel Bragg-Williams (Oth-order) model
was treated by Temkin ( 1966). These treatments discussed surface rough
ness and not crystal growth rates. Jackson ( 1969) presented a formalism for
calculating the growth rate from these models and applied it to the zeroth
order model (Jackson & Leamy 1971). The growth rate can be calculated
258 LAUDISE, CAR RUTHERS & JACKSON
from the free energy of the sequence of configurations which the interface
assumes during growth. The calculations confirmed Cahn's prediction that
this model would give a sudden jump in growth rate at a critical under
cooling. Jackson (1968) also calculated the growth rate based on treatments
of small repeatable areas of the crystal surface. Temkin ( 1969) presented a
different method of calculating the growth rate for the same model. This
method, i n which displacement of the interface is calculated in the computer
from the net rate of addition of atoms to each exposed layer of the crystal,
differs mathematically from J ackson's method for calculating the growth rate
of a crystal for a particular model of the interface. Leamy & Jackson ( 1971)
have presented calculations of interface roughness using a quasichemical (or

Bethe or first-order) model of the interface and also Monte Carlo calculations
of interface roughness. The zeroth- and first-order models treat clustering
differently: the zeroth-order model assumes that the sites adjacent to surface
atom have the same probability of being occupied as any other site in that
7 2
5
;1
R 4
0.2
!/
3
r- -- � I ·.
-·
2 I �l
I /� I-
/ I
EXACT TWO
I LEVEL S.OLUTION
I I I _-
I /r--
o I �/ II I I
o 0.4 0.8 1.2 1.6
1/a
FIGURE 3. Roughness of a crystal surface for various models of the interface.

CRYSTAL GROWTH 259
0.6-- - I
"
"
"
/
/
/
/
/
0.6 I
I
/ I
/ I
/ ----ZEROTH ORDER I
1 I
I --- FIRST ORDER I
I
�O.4
+
I I
a::
I I
I I
I
I
I
L(a=4) I
I I
I f
0.2 , (a =5) 0-,
I I
I I
I I
I I
I I
I I
1
J ...
1 , ., ""I I
0.0 0.5 1.0 1.5 2.0
LAT
-
kTTe
FIGURE 4. Calculated growth rates as a function of undercooling for zeroth- and

first-order models.
layer. The first-order model introduces an ordering parameter which makes

the probability of an atom having a nearest neighbor different from the
probability of uno�cupied sites in that layer having neighbors. The Monte
Carlo computer simulation analyzes a limited area of the surface, but treats
ordering correctly. All three of these models predict similar interface pro
files, as shown in Figure 1, and similar roughness of the interface, as shown
in Figure 3. The growth rate has been calculated using both Temkin's and
Jackson's methods for the first-order model (Leamy & Jackson 197 1). The
predicted break in the growth rate curve occurs at about a factor of 3 smaller
undercooling than in the zeroth-order model, as shown in Figure 4. (The
height of the periodic free-energy variations is also lower by a factor of 3.)
The growth rate cannot be calculated from the M onte Carlo model because
of statistical uncertainties in the position of the interface.
There are three principal conclusions to be drawn from this work: First,
the roughness of a crystal surface depends on the entropy change between
the crystal and the phase around it. The calculated roughness is independent
of the model used, which gives some confidence in the calculations. Second,
all the models predict that the growth rate should be linear with under
cooling for smal l entropy change where the interface is rough (e.g. for the
metals) , and so again we have some confidence in the result. Third, the posi
tion of the break from linear g rowth rate depends strongly on the models for
high entropy change, and so the growth rate cannot be calculated by these
schemes. The reason for this is that calculating the growth rate by assuming
that the interface moves parallel to itself is fine, so long as there is no barrier,
as is the case in low entropy change. When there is a barrier, the interface
will not move parallel to itself to go over the barrier, but will nucleate part
of a new layer and so go around the barrier. This nucleation process can be
treated, using these models and methods, but this has not yet been at
tempted. Until this is done, we will not have a meaningful prediction of the
growth rates for high entropy change.
INTERFACE STABILITY AND CELLULAR GROWTH
In the theoretical work discussed thus far it has been tacitly assumed
that the interface will remain stable in the presence of imposed temperature
and composition gradients. However, interface breakdown often occurs
under particular external driving forces. There has been much work on the
stability of interfaces during crystal growth. The pioneering work in this
area was done by Rutter & Chalmers (1953) . They studied the conditions
for the occurrence of cells during the growth of slightly impure metals. The
onset of cellular growth was related quantitatively to the onset of consti
tutional supercooling by Tiller et al (1953) . Subsequent experimental work
confirmed this correlation for several metals containing various dopants
(Walton et al 195 5 , Holmes et al 195 7) . Constitutional supercooling results
from the boundary layer of impurity or dopant which occurs at the surface
of a growing crystal. The growing crystal tends to reject those species which
lower its melting point, and so these accumulate at the crystal surface. They
can be carried away by diffusion or convection. This results in a higher
liquidus temperature in the material far from the crystal surface than in
that near the surface, where the rejected species are present. If there is no
temperature gradient in the system, then the undercooling (or supersatura
tion) increases with distance from the crystal. I t tends to level off far from
the crystal. Even if there is a temperature gradient, as in Bridgman or
Czochralski growth where the liquid is hotter than the crystal, there can be
a region near the crystal where the liquid is supercooled. I t has been argued
that a bump on a crystal reaches out towards this supercooled region and
tends to grow, thus leading to instability of the interface and to cellular
CRYSTAL GROWTH 261
growth. The onset of constitutional supercooling corresponds well with the
occurrence of cells in metallic systems, but it is well known that many
crystals grow with stable flat faces into supercooled solutions. These faces
are not unstable even though the supercooling (or supersaturation) is great.
This difficulty was resolved by the application of stability theory.
Mullins & Sekerka (1963, 1964) made the first stability analysis of a growing
interface and showed that, indeed, a sinusoidal perturbation of the interface
would grow or shrink depending on a condition which was quite similar to
the constitutional supercooling condition. I n addition, their treatment was

able to include the stabilizing effect of surface tension, which was not impor
tant for the experimental conditions which had been examined in the metals
but becomes important at slow growth rates.
Several authors2 have subsequently introduced the effects of a slow
intrinsic growth rate into the calculation-all arriving at similar con
clusions but for various geometries and growth conditions. The general re
sult, perhaps elucidated best by J. W. Cahn (1967) , was that if the diffusion
process is rate limiting, then instability can occur. If, on the other hand, the
intrinsic growth rate is rate limiting, then the instability will not occur. For
example, metals grown from the melt have a small entropy change, and so
their intrinsic growth rate is rapid and isotropic. The growth rate is con
trolled primarily by diffusion, and the intrinsic part of the growth process
does not deter the onset of the instability. For crystals growing from solu
tion, on the other hand, the entropy change is usually large. The intrinsic
growth rate does, in this case, suppress the instability. A good example of
this effect is found in the hydrothermal growth of quartz, where the fastest
growing faces are unstable, while the more slowly growing faces are stable.
Hardy & Coriell (1969, 1970) have applied stability theory to the growth
of a cylinder of ice in undercooled water, both pure and with small amounts
of impurity added. The observed growth rates of the instability and its
axial wavelength agree well with the theory for a variety of conditions and a
reasonable value of the surface free energy of the ice-water interface.
Sekerka ( 1967) has extended the original analysis, which was limited to
small amplitude perturbations, to follow the growth of the perturbation.
Woodruff & Forty ( 1967) and Chen & Jackson (197 1) have examined the
stability of a melting interface and found it to be more stable than a freezing
interface. On melting, the onset of constitutional superheating of the solid
does not coincide with the onset of instability. I nstability theory correctly
predicts both the onset and the wavelength of the instability, which occurs
long after a considerable volume of the solid has been superheated.
DENDRITIC GROWTH
When the undercooling is large, dendritic growth can occur. I n fact,

there is a continuous range of structures from cells to dendrites, as has been
2 See the papers on pages 681-739 in Crystal Growth, ed. H. S. Peiser, Suppl. to
J. Phys. Chem. Solids (196 7) .
illustrated by Jackson (1967). More impurity, or lower bath temperature,

leads to longer cells with a s maller radius of curvature at the tip. Continuing
in this direction, we find cells which are far enough apart so that instabilities
can occur on their lateral surfaces. These instabilities grow into side branches,
and we have dendrites. Just as for cells, the dendrites occur only when the
growth process is diffusion limited. The intrinsic growth process, if it is rate
limiting, will suppress the instabilities which result in dendritic growth.
Thus dendrites are usually found only under conditions where the entropy
change on growth is small, so that the intrinsic growth rate is rapid, and
therefore not rate limiting. Dendrites are common, for example, in metal
castings.
A simple-minded way to think of the dendritic growth process is to think
that the bath undercooling, which can be eliminated only slowly by diffusion,
can be eliminated much more rapidly, if the growth rate is rapid enough, by
the growth process itself. The growing crystal subdivides itself so that all of
the remaining bath material can have its supercooling removed by diffu
sion. Wherever the supercooling has been removed, the dendrites will not
grow. However dendrites will continue to grow into isolated corners of the
bath which are still supercooled. Once they grow, .dendrites coarsen by
ripening processes.
There are several diffusional analyses of dendritic growth, none of which
treat the instability which results in branching. Papatetrou (1936) argued
many years ago that the dendrite tip should be paraboloidal, and Ivantsov
( 1947) invented an elegant mathematical method to prove it. The diffusion
around a dendrite tip is a difficult mathematical problem. The shape of the
crystal surface is one of the things to be determined from the calculation.
The moving surface is a heat or impurity SOurce for the diffusion problem.
M oving-source problems are difficult even when the source shape is known.
Ivantsov determined the surface which satisfied the heat-flow equation and
did not change shape in time, while moving at a uniform velocity. A parabo
loid of revolution moving along its axis satisfies these conditions. Unfor
tunately, for a given undercooling, only the Pec1et n umber of the dendrite is
specified by the mathematical solution. The Pec1et number contains a pro
duct of the dendrite tip radius and the growth rate. A fat dendrite growing
slowly is a solution, as is a narrow dendrite growing rapidly. B ut under given
growth conditions, only one dendrite growth rate is observed so that the
diffusion solution alone does not solve the problem. The observed growth
rate increases roughly with the square of the undercooling (Rosenberg &
Winegard 1954). Horvay & Cahn (1961) subsequently extended Ivantsov's
analysis to show that a parabaloid with an elIipticai cross section was also a
satisfactory solution.
The solution to the dendrite problem lies again in the application of
stability theory. That is, a big dendrite wiII develop a bump which grows
faster; a too-thin dendrite runs into surface energy and intrinsic growth rate
CRYSTAL GROWTH 263
problems which are not taken into account in the diffusion analysis. The
stability analysis has not yet been done.
Several approximate solutions have been made. Most of these argue that
the dendrite which will be observed is the one which grows fastest. Temkin
(1960) applied this condition to Rosenberg & Winegard's (1954) results on
tin dendrites and obtained reasonable agreement. Bolling & Tiller (1961)
presented a similar analysis. Glicksman & Schaefer (1968) used this method
to analyze their measurements of the growth rate of phosphorus. Kotler &
Tarshis (1969) developed a different (but also approximate) method of

calculating the maximum growth rate.
Dendritic growth is understood in principle from these studies. The ap

proximate methods give reasonable agreement with experiment. The stabil
ity analysis which would give detailed understanding remains intractable.
III. MACROSCOPIC ASPECTS OF CRYSTAL GROWTH
One major practical interest in crystal growth is its use as a technique for
controlling the properties of solids. Thus, we must control both the level and
distribution of the chemical composition and the nature and concentration
of structural imperfections during crystal growth. This is accomplished by
recognizing that crystal growth is a nonequilibrium process in which we
must control both the flow of heat and mass. Early crystal growers were
content to use heat and mass flows to constrain the growing interface and
eliminate nucleation at other points in the system. However as more strin
gent requirements were placed on the crystals and extensive characteriza
tion became more general, it was found that the crystal properties are af
fected by dynamical conditions in ways that we still do not understand com
pletely. The control of the dynamics of mass and heat flow have been found
to be crucial in the effects of thermal and constitutional supercooling on
interface stability, in the redistribution of solutes or impurities in zone re
fining, and in the importance of liquid-mass transport kinetics over surface
transport kinetics during melt growth in general. The discoveries of the im
portance of these three areas were all made within the short period of time
from 1948 to 1953. The reader should consult the books by Pfann (1966) and
Chalmers ( 1964) for a review of contributions of this period. Most of the
advances in growth dynamics since 1953 have been concerned with studying
interactions between heat and mass flow, applying earlier ideas to more
complicated compound and multiphase systems, and understanding the
nature and influence of natural convection in the presence of thermal and
concentration gradients. We shall describe some of these more recent ad
vances in crystal growth dynamics by focusing on the problem of composi
tional control in simple binary systems. The problem of the interaction of
heat and mass flow with structural imperfections will not be reviewed here
because of its complexity and relatively embryonic state of development,
but it may be expected to become of increasing concern in the growth of

nonstoichiometric compounds.
DISTRIBUTION CoEFFICIENTS
Any discussion of compositional control must recognize that, for any

component in a binary system undergoing crystallization, the compositions
in equilibrium at a fixed temperature and pressure are usually different
in the bulk solid and liquid phases as well as at the interface. An advancing
interface is no longer at equilibrium and the degree of disruption of the

composition depends on the material and its growth rate. M aterials with
Iowa factors (Section II) will reach compositional equilibrium at rates

too rapid to be influenced by normal growth velocities (for velocities up to
",10 cm/hr) . Thus mass transport kinetics in the liquid will determine the
interfacial composition and the corresponding "equilibrium" solid value.
For these materials, solutions of the solute continuity equations (such as that
given by Burton, Prim & Slichter 1953, 1958) provide adequate descriptions
of the solute distribution in the solid as it is affected by the artificial liquid
diffusion boundary layer. However, in the presence of fluctuating growth
rates it has been shown recently that the spatially averaged distribution
coefficient is not equal to that obtained in the absence of fluctuations (Hude,
Jakeman & Pike 1968) . Calculations for specific cases showed that the
average degree of solute segregation decreases in the presence of fluctuations
(Hude & Jakeman 1969), as was i nitially reported by Barthel & Eichler
( 1967). Since most growth rates are never steady but fluctuate for various
reasons, these considerations are extremely important in measuring or
assessing solute segregation.
Materials with intermediatea factors such as melt-grown semiconduc
tors and oxides are not able to completely reach compositional equilibrium,
and we observe such phenomena as the "facet effect" where the solid com
position varies with the crystallographic orientation of the interface (Dikhoff
1960, Mullin & Hulme 1960) and the "transient effect" where cyclic growth
rates produce extremely large compositional variations (Carruthers & Ben
son 1963, Carruthers 1966) . The two basic problems in such materials are
(a) the difference in equilibrium surface compositions across 'the different
regions of the growth interface on which a crystallographic facet is allowed
to develop because of thermal considerations, and (b) the long time required
to reestablish equilibrium when such facets propagate. Under normal growth
conditions, diffusion fluxes in the solid near the interface, on the surface
itself, and in the adjacent liquid all play some role in determining the re
sulting solid composition. However there is no completely satisfactory
analytical treatment of such solute incorporation because the influence of the
electronic structure at the surface is not well understood. The various models
do not account for all of the known factors. New experimental techniques,
such as the pulsed interface method developed by Witt & Gatos (1967) or
CRYSTAL GROWTH 265
the temperature dependence of the facet effect investigated by Casey,
Panish & Wolfstirn ( 1970) , are needed to understand the phenomena. The
pulsed interface experiments have clarified many unsteady growth phe
nomena such as remelting and initial interface breakdown morphologies
(Singh, Witt & Gatos 1970) . A very fundamental discovery was made with
the pulsing technique when it was observed that under fluctuating growth
conditions the nonfaceted portion of an I nSb interface exhibits cyclic be
havior of the growth rate perpendicular to the interface while the faceted
region shows uniform normal growth rates. This is very convincing support
for lateral growth behavior on faceted solid-liquid interfaces. In addition it
has been discovered that when conditions are adj usted to produce a uniform
growth rate, the facet effect in I nSb becomes much less pronounced. This
behavior is expected from the analysis of the transient effect by Carruthers
( 1966) and shows that the transient and facet effects arise from the same
growth mechanism. Further studies of intermediate and Iowa-factor ma
terials at a variety of growth rates would be useful.
Materials with low or intermediate a factors at their congruent melting
temperatures will exhibit increased a factors when grown at lower tem
peratures from either fluxes, solutions, or the vapor phase. The work of
Casey, Panish & Wolfstirn ( 1970) on the incorporation of Te in GaAs de
posited epitaxially from liquid gallium solutions is of special interest since it
reports quantitative data concerning the facet effect in solution growth.
These workers have recently demonstrated the influence of surface band
bending at the growth interface on the incorporation of fully ionized im
purities. This is the first verification of an idea proposed originally by
Longini & Greene ( 1956) and developed further by Lehovec ( 1964) .
Another factor influencing the distribution coefficient is the possibility
of complexing in the melt. Such behavior in simple systems was demon
strated by Edwards ( 1968) for boron doping of germanium melts. Edwards
postulated that the residual oxygen forms thermodynamically stable com
plexes with the boron and these complexes have different distribution coef
ficients (as well as different electrical behaviors in the solid) .
I n compound growth, an excess of one of the components in the liquid
may be treated as being equivalent to an impurity in a simple binary system.
Rurle, Jones & M ullin ( 1961) used this concept to explain constitutional
supercooling due to an excess of one component over stoichiometric com
positions in I I I-V semiconductors and Cockayne ( 1968) has summarized
results for oxide crystals. More recently, Carruthers, Peterson, Bridenbaugh
& Grasso (197 1) and Bridenbaugh (private communication 1971) have used
similar concepts in studies on the phase equilibria in the system Li20 -Nb20.
in excess region of lithium niobate. This work showed that the stoichiometric
and congruently melting compositions were not the same and consequently
that crystals grown at noncongruent melt compositions possessed spatial
variations in stoichiometry.
MAss AND HEAT TRANSPORT

An extensive amount of work has been done on transport processes
during crystal growth since the developments of the early 1950s. This work
may arbitrarily be divided between the horizontal (Chalmers), Czochralski,
molten zone and vapor growth techniques.
Horizontal growth.-At one time, the solute distribution during horizontal

growth was thought to be diffusion controlled in the sense that, if natural

convection was present in the liquid, the diffusion boundary layer in the
liquid, OD, was larger than the solute diffusion distance D/R (D is the liquid
diffusion coefficient and R the growth rate) . However, careful work by Wein
berg ( 1963), using radioactive tracer techniques, showed by profiling the
longitudinal distribution of solute that partial mixing was occurring in the
liquid for most growth conditions. Abe et al (1962) similarly showed that i n
the horizontal growth o f germanium the transverse distribution o f solute was
not uniform, which indicated a nonuniform thickness of the diffusion bound
ary layer. Carruthers & Winegard ( 1966, 1967) used simulation experiments
to show that the diffusion boundary layer existed as a result of fluid flow due
to liquid density gradients arising from both composition and temperature
variations. These experiments also showed that the influence of thermal con
vection on OD could be considerably reduced by minimizing vertical tempera
ture gradients in the liquid (Carruthers 1968) . This situation also applies to
Czochralski growth, as wiII be discussed later.
Thermal convection in horizontal systems was shown independently by
Goss ( 1955) and Cole & Winegard ( 1964- 1965) to give rise to temperature
fluctuations. Such fluctuations had been observed to be the source of growth
rate fluctuations in Ge-Si alloys by Goss, Benson & Pfann ( 1956) . More
extensive work on temperature and growth rate fluctuations was reported by
M ueller & Wilhelm (1964) . However, the nature of these temperature fluc
tuations was not really understood until the pioneering work of Hurle (1966)
which showed that at low-temperature gradients, the temperature oscillated
in a simple sinusoidal mode. Hurle, Gillman & Harpe ( 1966) showed by spec
tral analysis techniques that as the temperature gradient increased, a super
position of modes occurred which gave the appearance of a complex tempera
ture fluctuation like that caused by turbulent flow. This suggested that the
fluctuations were a result of overstability. These results have subsequently
been verified by careful work showing sinusoidal temperature oscillations in
confined vertical cells for liquid gallium (Harp & Hude 1968) and for liquid
sodium nitrate (Carruthers & Pavilonis 1968) . This work showed that tem
perature fluctuations could be reduced by reducing the adverse vertical
temperature gradients, even though thermal convection will always exist for
finite nonvertical temperature gradients. Another method of reducing tem
perature fluctuations in liquid metals is by the application of a static mag
netic field, and this was shown independently by Hurle ( 1967) and Utech &
Flemings ( 1967) to be effective for metal crystal growth situations.
CRYSTAL GROWTH 267
Czochralski growth.-The early work of B urton, Prim & Slichter ( 1953)
recognized the need for crystal rotation to provide a controlled diffusion
boundary layer at the interface because of uncontrolled thermal convection
in the melt. However, the rotation itself introduced solute striations because
of the imperfect temperature distributions usually present and the resulting
changes in the instantaneous growth rate (Burton & Slichter 1958). In addi
tion the radial solute distribution was found to still be nonuniform because of
the facet effect ( Dikhoff 1960, M ullin & H ulme 1960) and the nonuniform dif
fusion boundary-layer thickness (Benson 1965, Carruthers 1967). The per

fecting of Czochralski-grown crystals by reducing striae has been greatly
aided by the studies on stirring by Singh, Witt & Gatos (1970) and Witt &
Gatos (1969). An additional problem of constitutional supercooling, which
rose during the growth of highly doped material for Esaki diodes, was shown
to be predictably affected by stirring in a series of papers from the Royal
Radar Establishment (Hude 1961 , Bardsley, Callan Chedzey & Hurle 196 1 ,
Bardsley, Boulton & Hurle 1962).
The use of large melts in semiconductor crystal growth made it necessary
to rotate the crucible to obtain uniform temperature distributions. However,
the accompanying nonuniform solute distributions in the growing crystal
pointed to the presence of some unusual convection patterns in the liquid.
These flows were studied and identified by Carruthers & Nassau (1968), who
found that differential rotation of the crystal and crucible produced non
mixing cells in the liquid through the Taylor-Proudman effect.
The heat transport problem in Czochralski growth has received sporadic
attention. I nterest centers primarily on the control of interface shape and
position, as well as on reducing temperature fluctuations from irregular
thermal convection. These two objectives are usually not compatible. I n
terface facets will exist only for materials with a> 2 which have c1osed
packed planes exposed to the liquid and where the growth interface is convex
into the liquid. Both large liquid-temperature gradients and high dislocation
densities in the crystal decrease the extent of faceting on such interfaces.
Nevertheless, solid-liquid interfaces in floating-zone configurations are quite
convex because of the nonuniform heating, and tricks such as increasing the
growth rate (and production of latent heat of fusion) are required to change
the interface shape (Ciszek 1969). I n oxide crystal growth, the lower thermal
conductivity and high radiative conductivity result in large temperature
fluctuations and highly convex interfaces, respectively. I n fact, whereas
crystal rotation produces larger growth rate fluctuations than does thermal
convection in semiconductor growth, very much the reverse situation is true
in oxide crystal growth. Also, Cockayne, Chesswas & Gasson (1969) have
shown, through a correlation of infrared transmissivity and interface shape,
that the light-pipe effect in oxide growth causes faceting.
Observations of thermal convection flow patterns on the upper surface of
oxide melts have been made in CaF2 and CaW04 by Wilcox & Fullmer (1965).
These findings showed the expected outer upward and radially inward flow
along the melt surface in the absence of crucible rotation. With the onset of
crucible rotation, the radial flows are consolidated into a small number of
rotating spirals (swirls) with larger and more regular temperature fluctua
tions. Such fluctuations cause growth rate variations when the crystal i s
unrotated and the frequencies agree reasonably with theoretical predictions
(Carruthers 1968) .
Calculations of the moving interface shape during Czochralski growth
were first reported by Wilcox & D uty ( 1966) , but the effects assumed for
radiation from the melt surface to the crystal were not applicable for most
growth situations. This work was extended by Arizumi & Kobayashi ( 1969)
for variable melt temperatures and by Kobayashi & Arizumi (1970 a, b) for
fluid motion due to both crystal and crucible rotation.
Molten zone methods . These methods include all growth from small
-
liquid zones and may be divided generally into the heteroepitaxial tech
niques originated by Nelson ( 1963) and the zone-melting techniques in
vented by Pfann (1955, 1966).
Modifications of Nelson's liquid-phase epitaxy technique involve closer
control of the deposition conditions through cooling-cycle modifications,
dipping and tipping to provide controlled liquid-solid contact, scraping to
clean the substrate, multiple doping to avoid contamination, melt-back as
well as graded composition layers to improve the perfection of the deposit,
and controlled temperature gradients and liquid volumes to avoid constitu
tional supercooling (see, for example, M inden 1970).
The zone-melting technique quickly broadened in concept to include
temperature-gradient zone melting, floating zone, traveling solvent, liquid
containment, and vapor-liquid-solid processes. Each one of these methods
involves a different arrangement of heat, mass, and sometimes external
magnetic and electromagnetic techniques to control the interface shape and
position; they will not be treated in detail here. One important advance in
the horizontal zone refining technique was reported by Pfann, Miller & Hunt
( 1966) when they eliminated the nonuniform interface shapes due to thermal
convection by slowly rotating the container about its axis. Wilcox ( 1967) has
reviewed many important aspects of heat transport in zones. In low-tem
perature solvent zones, freezing and melting interface kinetics may be rate
limiting or even unstable, and these problems have been extensively dis
cussed by Seidensticker ( 1966) and Tiller ( 1965) , among others.
Vapor transport methods.-The two common arrangements for vapor

transport are the closed and open tube methods. Both possess substantial
amounts of natural convection arising from both temperature and concen
tration gradients, particularly at higher pressures. Reed, La Fleur & Strauss
( 1968) have reviewed the roles of diffusion and convection in vapor crystal
growth. One of the fundamental concepts is that of constitutional super
saturation at the growing solid-vapor interface ( Reed & La Fleur 1964) . This
CRYSTAL GROWTH 269
phenomenon is analogous to constitutional supercooling in liquid phase
growth and has been shown to cause similar interface instability. The work
has, in fact, shown the desirability of maintaining a high temperature gradi
ent at the solid-vapor interface while simultaneously using high convection
velocities. Closed tube methods have been substantially improved by the
alternating temperature method (reported by Scholz 1967), in which the
temperature gradient is periodically reversed (See Section V). This tech
nique greatly reduces undesirable heterogeneous nucleation and thus allows
larger crystals to be grown.

IV. CRYSTAL GROWTH AS AN EXPLORATORY

MATERIALS RESEARCH TOOL
New materials are the lifeblood of solid-state research and device tech
nology. Contrary to what many believe, new materials are not usually dis
covered by device engineers, solid-state theorists, or research managers;
they are most often discovered by crystal chemists who are crystal growers.
Some physical phenomena are only exhibited in single crystals and can only
be studied and understood quantitatively in single crystals. Especially in
areas where theoretical predictive power with respect to the appearance or
magnitude of a physical property is poor, ease of growth is an important
criterion in deciding whether to pursue a given material. Thus the grower
especially if he develops a proficiency in relating structure, bonding, and
other crystal chemical considerations to properties of interest-is in a key
position in determining the direction and success of solid-state research and
ultimately electronic technology. The health of a variety of activities in our
society depends upon crystal growers realizing and cultivating this view
point. We shall try here to demonstrate the usefulness of this viewpoint by
reviewing recent materials successes catalyzed by crystal growers.
Lasers.-Progress in low-threshold optically pumped solid-state lasers

has been in large measure due to crystal chemical-crystal growth activities.
Ruby (AI203:Cra+) was the first solid-state laser (Maiman 1960). I ts thresh
old was high mainly because Cr+a is a three-level laser and population
inversion from the highly populated ground state is difficult. Nd+a is a four
level ion, so population inversion does not involve the ground state, and the
threshold of solid-state lasers where Nd+a is the active ion would be expected
to be lower. I ndeed, a survey of the spectra and selection rules of the transi
tion metal and rare-earth ions, coupled with a consideration of the case of
stabilizing their various valences, led to the conclusion that Nd+a perhaps
would provide the best hope as a low-threshold dopant. However, it soon
became apparent that the threshold of Nd+3lasers depended to a great extent
upon the host lattice. In CaW04, the first low-threshold laser obtained with
Nd+3 (Johnson & Nassau 1961) , Nd+3 occupies Ca+2 sites and for electrical
neutrality every two Nd+Ss are compensated for by one CaH vacancy. If
CaW04 is doped with Na+ and Nd+3, one Na+ at a Ca++ site charge compen
sates each Nd+3• CaW04:Nd+3, Na+ has a much lower threshold than
CaW04:Nd+3 because the resultant Nd+a spectrum is less complex since
essentially all Nd+a ions experience the same environment. Thus most of the
pump energy appears in only one transition (Johnson, Boyd, Nassau &
Soden 1962). An even lower threshold results when no charge compensation
for Nd+3 is required, as an Ya AJ,01 2 :Nd+a , where Nd+3 occupies a y+a site
(Geusic, Marcos & Van Uitert 1964). Indeed, due to a fortuitous absorption,
YaAI5012:Nd+a can be pumped with an ordinary incandescent lamp and

lases at room temperature (Geusic, Marcos & Van Uitert 1964).
I t was recognized quite early that an attractive means of generating addi

tional coherent frequencies was by means of harmonic generation. In addi
tion, the most feasible means of impressing information (modulating) on a
coherent carrier is by means of the electro-optic effect. Efficient harmonic
generators and electro-optic materials will have large nonlinear optic effects;
that is, the polarization change will be large and nonlinear in an electric
field. If the polarization P is expressed as a power series in the electric field
E, then the proportionality constants Xi are the optical susceptibilities and
Xz should be large for modulator and harmonic generator materials and the
material should be noncentrosymmetric (see, for instance, Laudise 1968,
1969). In a harmonic generator, birefringence should exceed dispersion for
phase matching, while in a modulator negligible birefringence is a conve
nience for the device designer. A search for useful nonlinear materials in the
absence of quantitative atomic models for optical susceptibilities focused on
materials with 1 ) . great electronic polarizability-compounds with large
numbers of electrons far removed from the nucleus, e.g., elements from the
lower right side of the periodic table (Se, Te, Br, I)-or 2) . great ionic polariz
ability-compounds with large permanent dipoles, piezoelectrics with large
coupling constants, ferroelectrics with large spontaneous polarization, or
(because of the connection between P, dielectric constant, and index of
refraction) materials with large dielectric constant and/or index of refrac
tion.
Because of the qualitative nature of the above predictions, the probabil
ity of meeting the appropriate requirements if only a few materials are pre
pared is not high. Consequently, a crystal growth method capable of produc
ing single crystals of modest size and quality without an undue expenditure
of effort was required. I n addition, the method had to be capable of ulti
mately producing the high-quality large-size crystals required for those
materials which pass initial screening tests. The Czochralski technique met
these requirements. I ndeed, it is possible to use a noble metal wire as a
nucleation site, together with rf pulling from a noble metal crucible, and
grow crystals without prior knowledge of the phase diagram, while making
CRYSTAL GROWTH 271
TABLE Z . MATERIALS FOUND USING LARGE POLARIZABILITY CRITERIA
pyro-
Harmonic Electro · Acousto- Piezo-
Material eIectrIC Reference
generator optic opt'Ie electric
detection
Lithium niobate" x Boyd et al 1964.

Denton et al 1967
Lithium tantalate" x x Ballman 1965. Lenzo

et aI 1966. Warner 1965
Barium sodium niobate" x x Geusic et al 1967.

Van Uitert et al 1968,

Barium strontium niohate" x " Ballman & Brown 1967.
Glass 1968
Lead molybdate" x Pinnow H al 1969
b
lodic acid x x Bergman et al 1969
• Czochralski grown.
b Grown from aqueous solution.
e x =useful magnitude.
qualitative estimates of volatility, congruent melting, and ease of growth.

Growth experiments by A. A. B allman (1965) focused initially on high ionic
polarizability materials. Thus only those materials which "pulled easily"
were investigated further. Appropriate screening of these materials produced
most of the important present day nonlinear optical materials (see Table 2).
In addition water-soluble materials, in particular high-electron polariz
ability 103-s (Bergman et al 1969), were found to be of high interest as
nonlinear optical crystals (see Table 2) . As a byproduct of these exploratory
activities, new piezoelectric materials, new pyroelectric detector materials,
and new acousto-optic materials were discovered (Table 2) .
Semiconductor lasers.-Semiconductor lasers offer important advantages

as oscillators, mainly because they can be pumped and modulated directly.
The recombination of holes and electrons provides the luminescence upon
which lasing is based. The principal problem has been to achieve low thresh
olds and continuous lasing in the visible range. It has been shown recently
that inj ection lasers using one or two heteroj unctions can confine the recom
bination radiation so as to appreciably lower the threshold current for lasing.
Thus successful semiconductor lasers depend upon careful control of the
crystal growth process and adroit choice of the materials to be grown. Ap
propriate confinement structures combined with heat sinking have recently
resulted in threshold currents for room-temperature lasing as low as 1000
A/cm 2 (Hayashi, Panish, Fay & Sumski 1970). Figure 5 illustrates a typical
structure which confines both charge carriers and light to region 2. Light is
produced by the decay of excitons (hole-electron pairs) . Carriers are con-
ENERGY UNDER
FORWARD BIAS
k
D I STA .>o.u.lj>...>..l�-,�-�-T,:"J
I I I
GoAs
(OPTIONAL)
FIGURE 5. Schematic structure of a semiconductor confinement laser.
fined to region 2 because it is sandwiched between regions 1 and 3, both of

larger bandgap, while light is confined because regions adjacent to region
2 have a lower index of refraction. Region 4 aids in making ohmic con
tact, Regions 1 and 3 are thin to aid i n heat-si nking region 2. (Gal_zAl",)A.
solid solutions are useful because of the ease of control of index of refraction
and bandgap by control of x, without severe variations in lattice parameter.
The growth of structures like that of Figure 5 is an important crystal
growth achievement and has been done by liquid-phase epitaxy (see Section
I I I) . A typical apparatus for growth is shown in Figure 6 (after Panish,
Sumski & Hayashi) . The growth technique is continuous to obviate the diffi
culties of oxide formation associated with serial tippings. The seed is ar
ranged in a graphite slider, and appropriate solutions to grow layers 1 , 2, 3,
and 4 are placed in four wells on a graphite barrel clamped onto the slider so
FURNACE WALL
A A A A
GRAP H I TE
SL I D I N G
SOLUTION
HOLDER
PUSH ROD
FURNACE WALl.
FIGURE 6. Growth apparatus for the liquid-phase epitaxy of GazAh_zA. (after Panish,
Sumski & Hayashi 1970).
CRYSTAL GROWTH 273
TABLE 3. MAGNETIC ORTHOFERRITES'
Magnetic moment Wall energy Bubble

Material
411"Ms-gauss u..-ergs/cm2 diameter/mils
YFeO. 105 1 .8 3.0

NdFeOa 62 1.1 7.5
SmFeOa 84 1 .3 6.0
EuFeOa 83 1 .6 5.S
GdFeO a 94 1 .7 3.7
TbFeOa 137 1.7 1.7
DyFeOa 1 28 1 .8 2.0
HoFeOa 91 1 .7 4.5
ErFeOa 81 1 .6 6.0
TmFeOa 140 2 .4 2.3
YbFeOa 143 3 .9 3.8
LuFeOa 1 19 3 .9 7.5
Sm .6Er.•Oa 83 0 . 35 1 .0
Sm.55Tb.(oOa 108 0 . 30 0 . 75
• Data from Bobeck, Fischer, Perneski, Remeika & Van Uitert 1969.
that the seed may be moved into position under each of the solutions. The
furnace is designed to make the seed slightly hotter than the solutions. The
solutions are cooled at rates of (typically) a few degrees per minute, and the
seed is moved under each of the solutions in turn, to produce the desired
structure. Dimensions, cooling rate, translation speed, and melt compositions
are very critical.
Bubble domain materials.-Recently an exploratory materials-crystal

growth activity has focused on materials for use in the "bubble domain
memory." Crystals were prepared initially by flux-growth methods. The
requirement was for a uniaxial magnetic material capable of producing a
memory whose bubble diameter would be "" . 1-1 mil and whose domain wall
mobility would be ""'200- 1000 cm/sec/Oe (Bobeck 1967) . It can be shown
that bubble diameter B is related to magnetic properties so that (Theile
1969)
where K is the magnetocrystalline anisotropy (a function of domain wall

energy <Tw) and Ms is the magnetic moment (a function of the number of u n
paired electrons) .
Rare-earth orthoferrites were first investigated (Bobeck, Fischer, Per
neski, R e me i k a, & Van Uitert 1969) . As can be seen from Table 3, in general
the bubble size of orthoferrites is too large (although YFeOa may have some
applications because of the very high mobility- > 2000 cm/sec/Oe) . To
reduce K and thus reduce B, solid solutions of Sm with other rare earths
were investigated (Sherwood, Van Uitert, Wolfe, & LeCraw 1967). All rare
earth orthoferrites are canted-spin ferromagnetic materials. The easy mag
netic axis changes from a-+c by a spin reorientation process in all the com
pounds at the spin reorientation temperature C Tr) . Close to Tr the magneto
crystalline anisotropy is small. Tr for all rare earths except Sm is below room
temperature; Tr for Sm is 1 75°C. Thus, Tr can be made close to room tem
perature by substitution of an appropriate quantity of S m ; for instance,
Sm . 55Tb . 45FeOa (see Table 3) has small ow and B . Unfortunately, it was found
that <Tw and B are strong functions of temperature close to Tr so that device
requirements could not be met. Other substituents in the orthoferrites, such

as Co (Van Uitert, Sherwood, Gyorgy & Grodkiewicz 1970), increase coercive
force and therefore are of limited interest.
Hexagonal magnetoplumbite-type compounds such as PbFe12019 are
uniaxial with very high moments so that the resultant bubbles are too small
for practical devices. Substitution of nonmagnetic atoms such as Al reduces
the moment and increases bubble size to the useful range (Van Uitert,
Smith, Bonner, Grodkiewicz & Zydzik 1970); unfortunately the domain wall
mobility of such compounds was found to be much too small ("'1 cm/sec/
Oe) .
I t was decided to attempt the preparation of ordinarily cubic materials
with appropriate substitutions so as to make them uniaxial. Garnets were
selected (Bobeck et al 1970) because previous experiments provided a back
ground for modification of properties such as moment. I t was discovered
that when two or more appropriate rare earths were substituted at the rare
earth sites, R a Fe5012, which ordinarily has three equivalent ( 1 1 1 ) easy mag
netic axes, undergoes a slight distortion so that one of the ( 1 1 1 )s becomes
the unique easy magnetic axis.3 The moment could be reduced by substitu
tion of Al or Ga at the tetrahedral ion site, and device requirements could be
easily met. Flux growth of orthoferrites and garnets follows well-established
procedures (see Laudise 1970 for survey of flux growth of garnet and related
materials) in large fi ux f urnaces (Grodkiewicz, Dearborn & Van Uitert 1967) ,
but the most economical device configuration will almost certainly involve a
heteroepitaxial structure. Liquid-phase epitaxy (Schick & Nielsen, 1970),
chemical vapor deposition (Mee, Archer, M eade & Hamilton, 1967), and
hydrothermal growth (Kolb & Laudise 1970) have all been used to produce
epitaxial films of varying quality. Sufficient evidence is not presently in hand
to choose the ideal method.
V. CRYSTAL GROWTH TECHNIQUES
We will discuss growth techniques using Laudise's classification scheme

( 1967, 1970).
3 The substituted garnets are often called "uniaxial" and ordinarily YaFe.012 is
called "cubic." YaFe.012 is, of course, not strictly speaking cubic because of magneto
striction.
CRYSTAL GROWTH 275
SOLID-SOLID TECHNIQUES
Solid-solid techniques have received surprisingly little attention in view

of the inherent advantage of the phase equilibria control resulting from the
elimination of a phase change. I n particular, solid-solution systems can be
prepared as single crystals with uniform composition (but with structural
imperfections) and volatile component loss may be suppressed at the lower
temperatures.
The earliest techniques were called strain-anneal or solid-state recrystal

lization techniques and were used on highly pure metals with very high grain
boundary mobilities. Further recent improvements, such as those of Rosin

ger, Bratina & Craig (1970) on iron single crystals, emphasize the importance
of the starting condition of the sample and the necessity of moving the speci
men through high-temperature gradients (to minimize interference of high
mobility boundaries from other regions of the specimen) . These techniques
work well with critical prestraining at room temperature or with applied
strain at the annealing temperature. In addition to specimen purity, ambient
control is essential to reduce the surface pinning of grain boundaries.
Similar techniques have been used to grow single crystals in solids under
going a solid-state phase transformation. Single crystals of the low-temper
ature phase in zone-refined zirconium have been prepared by Mills & Craig
(1968) by passing a hot zone through a zone-refined Zr rod strained slightly
in tension.
Similar techniques have been recently used on polycrystalline semicon
ductors and ceramics to obtain large single crystals by discontinuous grain
growth. There are additional problems of solid-state reactions to achieve
uniformity (since melting is not usually permitted) and densification to
eliminate voids and porosity. Notable recent successes have been reported
by Sellers et al ( 1967) for the growth of 2-inch AbOa crystals by press-forging
(simple compression of ceramic pellets) and Brau et al (1971) for the growth
of similar size Hg",CdH,Te crystals by recrystallization in a closed system at
elevated pressures to reduce Hg losses. The starting material, in the case of
ceramic oxides, is usually hot-pressed to provide the required densification
or, in the case of semiconductors, melted and quenched under hydrostatic
pressure. Hot-pressing techniques have been developed to a very high degree
for lead zirconate titanate ceramics used in electro-optical applications (see
G. H. Haertling 1966, 1970) . Densities of > 99% can be achieved routinely
and the very low scatter of incident laser radiation has indicated high com
positional homogeneity. Ceramic growth techniques have been carried out
so far under isothermal conditions ; it seems likely that the use of temperature
gradients together with the proper application of strain at elevated tempera
tures will widen the applicability of this growth method.
Another class of solid-state methods is that of ion replacement by solid
state diffusion. Strictly speaking, the topotaxy of any solid-state precipitate
could be classified as crystal growth; the main attempts to controllably grow
a new third phase from the solid-state diffusion of two single-crystal starting
TABLE 4. THE PROPERTIES OF DIAMOND AND DIAMOND SUBSTITUTES
Refractive H ardness
Specific
index Dispersion (Moh's
gravity
N scale)
Diamond 2 . 417 0 . 044 10 3 . 53

Strontium titanate 2 . 409 0 . 109 5-6 5 . 13
Yttrium aluminum garnet 1 . 833 0 . 028 8-1/2 4 . 55

phases have been reported by Katz & Roy ( 1970) . They grew M gGa204
spinel single crystals at the interfaces of MgO and {3-Ga20s crystals. Another
method for solid-solution ion replacement is the isothermal substitutional
growth technique of Albers & Verberkt ( 1970) . In this method, crystals of
SnS are packed in powder mixtures of SnSe, S, and Se to produce single
crystals of SnSxSeH' of very high uniformity. The method can be applied
to any solid-solution system where high static pressures may be required,
e.g. GaP",As1_z, GaN",As1-x, etc.
LIQUID,SOLID TECHNIQUES
The materials of greatest research and technological significance grown

from the melt continue to be semiconductors and optical materials. Czoch
ralski growth continues to be the most widely practiced method. Semicon
ductor crystals of Si with dimensions up to 3 inches in diameter and 4 feet
in length are regularly grown. Dislocation-free crystals of semiconductors
are regularly grown commercially, although there is evidence that in GaAs
high perfection is deleterious because of trapping of majority carriers (R. M .
Ryder, private communication) . The Czochralski growth of refractory oxides
is now nearly routine. Yttrium aluminum garnet, YaAls012 (YAG) , is pulled
in very large quantities and has found a considerable market under trade
names such as "Diamonair" as a gem diamond substitute (Crowingshield
1969) . A comparison of its properties and those of the most popular previous
diamond substitute, strontium titanate (Verneui! grown and often marketed
as "fabulite") , is instructive (see Table 4) . Casual inspection of the optical
properties would give little hope that YAG could substitute for diamond
better than strontium titanate. However, very careful cutting gives the
stone "fire" in spite of the low dispersion (strontium titanate has "fire" to
spare) . The lower index results in the stone only appearing brillant from cer
tain angles, but in spite of this, careful cutting combined with the improve
ment in hardness has made YAG a big seller at up to $60jcarat.
Progress in improving the perfection of Czochralski.grown nonlinear
materials has been in the increased understanding of the role of stoichiometry
in perfection (see Section VI).
CRYSTAL GROWTH 277
Liquid-phase encapsulation growth o f GaP has proceeded t o a point
where crystals as large as several inches in length are easily grown.
The growth of controlled shapes, including ribbons, rods, and tubes, has
been achieved for sapphire by pulling crystals through a shaped orifice
(LaBelle & M lavsky 1967, Jenkins & LaBelle 1970) . The basic process in
volves Czochralski growth through a die. Growth rates from fractions of an
inch to about an inch per minute are used. Lengths of many inches can be
grown. Low-angle grains, facets, and striated surfaces tend to be problems
which can at least partially be reduced by slowing the growth rate and reduc
ing the normally large thermal gradient near the interface by the adroit
placement of radiation shield afterheaters. Non-noble metal crucibles, dies,

and afterheaters, especially Mo, seem to be feasible if the ambient environ
ment is not oxidizing. The ultimate hope is to competitively produce elec
tronic substrate material in ribbon form.
I ndeed the Czochralski growth of spinels received great impetus from
electronic substrate needs, and we may expect that the growth of nonmag
netic garnets will be an expanding activity due to the need for substrates for
the heteroepitaxial growth of magnetic uniaxial bubble domain memory
garnets (see Section IV) .
Aside from Czochralski growth, the principal other area of activity in
melt growth seems recently to be directed at eliminating the perennial bete
noire, crucible contamination. The classic crucibleless configuration is the
floating zone which is subject to two difficulties-it's hard to heat and it has
a disturbing tendency to fall out, due to the well-known zone height oc; sur
face-tension/density constraint (Heywang 1956) . The hollow cathode has
been extended (Storey & Laudise 1970) as a heat source to materials with
melting points about 3500°C. TaC (MP 3800°) the highest-melting solid was
easily melted. The principal limitation of the hollow cathode is that the
vapor pressure in the system may not exceed ",1 mm for the plasma to be
sustained. Even when the vapor pressure over the melt of interest is < 1 mm,
differential (incongruent) volatility of melt constituents can be a severe
problem. One solution is float-zone growth with focused image heating;
here ambient gas constraints are relaxed (at least several atmospheres of
permanent gases are easily contained in glass systems) . Carbon arcs are
unwieldy short-lived heat sources, theater projection lamps (Osram, etc.)
are a great improvement (see Laudise 1970 for a review of focused image
growth) , and recent work (Gasson & Cockayne 1970) indicates that the CO 2
laser may offer the advantages of sman beam divergence (long focal lengths
permit separation of the optical system from hot regions) and high absorp
tion in oxides (,...,, 1 00% compared to 1-2% for an arc lamp) . However the
real limitations of focused image growth probably are that the grown crystals
are strained due to the large gradients needed to localize the zone and that
the upper pressure limitation is a few atmospheres. Cold-hearth techniques
have been adopted for crystal growth (Reed 1968) . They may be more easily
modified with afterheaters and used in a Czochralski growth configuration
278 LAUD ISE, CARRUTHERS & JACKSON
so as to reduce gradients causing strain and eliminate the surface-tension/

density constraint on zone height. Cold-hearth techniques conceivably could
be combined with liquid encapsulation methods to increase the volatile range
of amenable materials.
The availability of environments in space stations would, of course, even
tually allow growth in large-diameter float zones without gravitational con
straints, albeit with considerable other complications, not the least of which
is expense.
VAPOR-SOLID TECHNIQUES
New vapor growth techniques have arisen from the different ways of
bringing the various components to the substrate surface for deposition. In
chemical vapor deposition techniques, the use of organic compounds of gal
lium (trimethy- and triethylgallium) with group V hydrides has allowed the
use of lower deposition temperatures, simpler temperature distributions, and
insulating substrates (Manesevit 1969) for I I I-V epitaxial growth. Oxide
crystal growth has been accomplished by the high-temperature hydrolysis
oxidation of the mixed vapors of the pertinent metal halides at the substrate
surface (Mee 1967, Mee et al 1969) . A very important feature of the oxide
work is the concept of a shifting reaction zone where the substrate is held at
the deposition temperature but in a nondeposition zone until the gas deposi
tion conditions have reached steady state; then the substrate is moved into
the reaction zone. Thick epitaxial films of transition metal oxide garnets have
been deposited in this fashion on nonmagnetic garnet substrates.
Very recent advances in molecular beam crystal growth have been made
in the epitaxial deposition of GaAs and Ga",Ah-xAs (doped and undoped) on
GaAs-using Knudsen effusion cells as molecular beam sources (Cho, Panish
& Hayashi 1970) . Such epitaxial films offer the advantages of low-tempera
ture deposition, small thickness, and compositional control not found in
liquid-phase epitaxial methods. In addition the film surface structure can
be monitored in situ by electron diffraction techniques. The most important
application of such films will be to produce the confinement regions required
for high-efficiency laser diode operation (see Section IV) .
Apart from advances i n transport mechanisms, vapor growth has also
been used to prepare epitaxial single-crystal deposits of the new compound,
GaN ( Maruska & Tietjen 1969) , by the reaction of gallium subchloride and
ammonia over a sapphire substrate. This material has potentially interesting
electroluminescent properties because it has a direct-energy bandgap of 3.39
eV. The film thicknesses were 50 to 150 p. and nitrogen nonstoichiometry
appeared to be a problem.
SOLUTION TECHNIQUES
Conventional solution growth from aqueous solutions by temperature dif

ferential or slow cooling has not seen any recent startling developments.
However, a recent monograph does an excellent j ob of summarizing tech-
CRYSTAL GROWTH 279
niques (Petrov et al 1969) . Activity in gel growth has been also reviewed
recently (Henisch 1970) . The role of "cusps" in containing a local aqueous
region about the growing crystal in gel growth has been discussed by Hanoka
( 1969) . However, whether unusually high supersaturations can be sustained
is still unsettled, convectionless conditions have not been explored, and the
quality of a reasonable sized gel grown crystal has yet to be assessed. How
ever, gel growth has recently been used to prepare metal azides which explode
spontaneously during ordinary solution growth (Ranadive et al 1969) .
Considerable progress in the use of complexers (mineralizers) to increase

the solubility or ordinarily insoluble materials to a point where they can be
readily crystallized has been recently made. Mineralizers, e.g. (OH)- , have
of course long been used in hydrothermal growth. However, recently Se has
been crystallized at near ambient and hydrothermal conditions from a sulfide
solution in which the solubility was increased by the reaction (Kolb &
Laudise, in press)
Anlogous earlier use of S= to crystallize HgS (Scott & Barnes 1969, Arming
ton & O'Connor 1970, Toudic & Aumont 1969) and of CI- to crystallize C uCl
in a gel media (Henisch et al 1965, Armington & O'Connor 1967) make it
apparent that this technique bears further i nvestigation.
Flux growth continues to be practiced in time-honored fashion. Laurent
( 1969) has written a recent review of the technique. The flux growth of
uniaxial bubble domain materials from a very large crucible was discussed
in Section IV. Although top-seeding experiments continue to be reported,
convincing evidence of good quality growth of large-seeded crystals in the
flux has been reported in only a few cases. Perhaps the best quality top-seed
flux-grown crystal is Ba Ti03 (Von H ippeI 1963). The solute (BaTi03) is pres
ent in such a high concentration that diffusion and constitutional supercool
ing problems are much fewer than in most solution growth. BaTiOa is grown
from a melt containing excess Ti02 where the "solvent" (Ti02) concen
tration is from 50-70 mole % Ti02• Thus the " solute" BaTiOa constitutes from
80-100% of the melt. I n most other flux-seeded materials so far studied
(see Laudise 1970 for a compilation) , constitutional supercooling causes
dendritic growth, and severe flux inclusions. Large gradients to repress
constitutional supercooling near the seed are important in obtaining reason
able quality crystals. Hetereoepitaxial growth of thin layers, especially of
uniaxial garnets, has recently been reported (Shick 1970) . Solution growth
of GaP and other I I I -Vs from liquid Ga by tipping continues to be the best
way to get high-efficiency electroluminescence (see also the discussion of
laser diodes in Section IV) .
Scholz & Kluckow's (1967) technique for suppressing spontaneous nuclea
tion during growth, which was first applied to vapor growth (see vapor-solid
techniques) , has been shown to be applicable to flux (Hintzmann & MUeller
Vogt 1969) and hydrothermal (Kolb & Laudise, in press) growth. In this
technique the temperature of the growth zone is cycled. During high-tem
perature periods (corresponding to low-supercooling or supersaturation
periods) of the cycle, small nuclei are destroyed. Thus, only a few large
nuclei survive to grow during the low-temperature periods of the cycle, with
the result that the yield of large crystals is increased. It is likely, however,
that the technique's drastically changing conditions of growth will make it
difficult to prepare highly homogeneous crystals.
By careful choice of seed and conditions it has recently been shown pos
sible to grow large-volume dislocation-free specimens of quartz hydrother

mally (Gordienko et al 1969) . Of special interest is the recent successful use
of the technique in heteroepitaxy to crystallize magnetic garnets hydro

thermally onto nonmagnetic substrates (Kolb & Laudise, in press) . The use
of electrocrystallization, except in £lux media (Wold et al 1964, Kunnman,
1971) continues to be overlooked.
VI. CHARACfERIZATION OF CRYSTALS

O ur understanding of crystal-growth processes is limited by our ability
to evaluate the physical properties, structure, and composition of the grown
crystals, and thus to relate these measurements to the growth variables.
For this purpose, an adequate knowledge of measurement techniques is
essential to the success of any crystal growth program. Since crystals are
grown with a specific application in mind, One or more property measure
ments are usually made first, and generally they are made quite thoroughly.
The problem is that growth processes are not simply related to the properties
of fundamental or applied solid-state interest which are usually measured.
Thus, no matter how important conductivity and mobility, for instance, may
be to a semiconductor device designer or solid-state band theorist or how
important magnetic susceptibility and moment may be to a magnetician,
they are not related in any simple way to the growth process. I ndeed if our
object is to either understand the growth process or control the properties,
we must examine more basic chemical and structural properties which are
on the one hand related directly to the growth process and on the other hand
coupled closely to the properties of fundamental and applied solid-state
electronic interest. If we know the nature and location of all the atoms in a
solid, it is fully characterized. The location and nature of the atoms are di
rectly controlled by the growth process and directly affect the properties of
fundamental and applied solid-state interest. The development of an armory
of techniques and a cadre of scientists and technicians interested in charac
terization is thus very important for the future development of both crystal
growth and solid-state science and technology. The problem was considered
in detail in a study and report by the M aterials Advisory Board of the
National Academy of Science (MAB Report-229-M 1967) . Characterization
includes traditional analytical chemistry, especially the use and develop
ment of subtle new techniques of quantitative and qualitative analysis.
However it also includes the use and refinement of physical methods for
CRYSTAL GROWTH 281
TABLE 5. CsEMICAL ANALYTICAL TECHNIQUES
Trace analysis
Activation analysis
Emission spectroscopy
Mass spectrometry
Atomic absorption
Chromatography
M icroanalysis
Electron probe microanalysis
Laser emission spectrography
High-precision techniques
Wet analysis
Vacuum fusion
Trace microanalysis
Positive ion microprobe
-
studying the location of atoms from the atomic scale up through the scale
where grain boundaries and texture are determined. Because of space, we
will only list presently used crystal evaluation techniques in Tables 5 and 6.
The techniques of Table 6 tell us where the atoms are. The techniques of
Table 5 tell us their identity. I n addition, many "conventional" measure
ment techniques (Table 7 lists the more important of these) which solid-state
researchers employ may be used under appropriate circumstances to char
acterize crystalline materials. The reader is referred to the MAB report for
further details on individual techniques.
I t is important to realize that although the list of methods is very exten
sive, there is no general procedure to be followed in using the information to
study crystal growth. The most obvious approach is to measure carefully a
property or concentration which changes reproducibly with a change in only
one growth variable. Some of the more obvious successes have been the cor
relation of defect structures with crystal temperature gradients and of solute
segregation with liquid convection effects. More recently nonstoichiometric
compositional variations have been studied in nonlinear optical materials
by comparing measurements such as Curie temperature and N M R line
width between crystals (growth from known melt compositions) and ceram
ics (of known solid composition) (Carruthers et al 197 1 , Barns & Carruthers
1970, Carruthers & Grasso 1970, Peterson & Carruthers 1969) . These studies
have measured the compositional shifts due to freezing and thus located the
congruently melting composition at which compositional variations may be
minimized. Similar information can be gained by comparisons of X-ray
lattice parameters between crystals and ceramics. I n addition nonstoichio-
metric deviations can be studied in detail by comparisons of X-ray and

pycnometric densities on crystals (see, for example, Barns & Carruthers
1970) .
As well as enhancing our understanding of the dynamics of crystal
growth, characterization procedures may also allow growth kinetics to b e
studied. The pulsed interface and etching studies o f Witt & Gatos ( 1967)
have provided some insight into some of the differences between faceted and
nonfaceted growth. Further experiments of this type will play a large role
in our understanding of crystal growth kinetics.

Materials science in general and crystal growth in particular are, we be
lieve, entering an era of great opportunities. First, this is because the tools,
concepts, and techniques of macroscopic theory are now well developed and
TABLE 6. SmucTURAL OBSERVATION TECHNIQUES
1. Light microscopy
Reflection
Dark field
Phase contrast
Interference contrast (together with well-developed etching and staining
techniques)
Transmission
Phase contrast
Interference contrast
Polarized light
Schlieren
Infrared
Ultramicroscopy (scattering)
2 . Electron microscopy
Reflection
Low-energy diffraction (LEED)
High-energy diffraction
Scanning beam
Transmission
Medium-energy
High-energy ( > 200 kV) (direct image and diffraction)
Radiography
Replication
3 . X-Ray microscopy
Diffraction
Topographic methods (Berg-Barrett, Lang, Schulz, etc.)
Indirect methods (double crystal, divergent beam, precession, powder,
diffuse scattering, precision lattice parameter)
Radiographic
Point and contact projection microradiography
CRYSTAL GROWTH 283
TABLE 7. PROPERTY MEASUREMENT TECHNIQUES
1 . Electric field
Resistivity
Dielectric constant
2 . Magnetic field
Magnetic susceptibility
Coercive force
Uniaxial anisotropy
3 . Gravitational field
Density
4 . Optical field
Refractive index
B irefringence
Spectroscopic absorption (bandgap)
5 . Thermal field
Thermal conductivity
Heat capacity and heat of transition
Thermal expansion
6 . Stress field
Elastic moduli
Mode of permanent deformation
7 . Multiple fields
Coefficients
Thermoelectric, photoelectric, photoelastic, elasto-optic, piezoelectric, pyro
electric, electro-optic, acousto-optic, magneto-optic, lifetime of carriers,
mobility of carriers, residual resistance ratio, electroluminescence, photo
luminescence
Transitions
Superconducting temperature, Curie temperature, phase-matching tempera
ture, spin reorientation temperature
Resonance
Nuclear magnetic, paramagnetic, Mossbauer, cyclotron, nuclear double
resonance
have been applied in enough instances to demonstrate their power in explain

ing growth behavior. Indeed, this understanding has proven essential in the
preparation of technologically useful crystals in a number of recent instances.
Second, microscopic theory, especially statistical mechanical modeling, is
progressing at a rate where it can be expected to make quantitative con
nections with experimental realities. Finally, we believe that the next
decade of crystal growth will be especially demanding because high-quality
single crystals are needed now more than ever. I ndeed we hope that the
field succeeds in combining the "new" scientific requirement, relevance, with
the old cultural badge of science, elegance.
ACKNOWLEDGMENTS
We would like to thank K. Nassau and L. G. Van Uitert for discussions.

CRYSTAL GROWTH 285
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ANNUAL
REVIEWS Further
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CONTENTS
STRUCTURAL CHARACTERIZATION OF MATERIALS BY USE OF ELECTRON

MICROSCOPY AND SPECTROSCOPY, Victor A. Phillips and Eric
Lifshin 1
DEVELOPMENT AND ApPLICATION OF THEORETICAL TECHNIQUES TO

PROBLEMS IN MATERIALS SCIENCE, J. C. Phillips 93
ANOMALOUS PROPERTIES OF THE VANADIUM OXIDES, John B. Good-

enough 101
THE STRUCTURE OF DEFECTS IN SOLIDS, J. H. Crawford, Jr., and L.

M. Slifkin 139
MODELS OF THE GEOMETRICAL, ELECTRONIC, AND VIBRONIC STRUC-

TURES OF IDEAL CLEAN SOLID SURFACES, C. B. Duke 165
SOLID-STATE PHASE TRANSFORMATIONS, C. M. Wayman 185
SOLUTION THERMODYNAMICS IN METALLIC AND CERAMIC SOLID SyS-

TEMS, C. B. Alcock . 219
CRYSTAL GROWTH, R. A. Laudise, J. R. Carruthers, andK. A. Jackson. 253
SOLID THIN FILMS, E. Kay 289
PHYSICS OF STRENGTHENING MECHANISMS IN CRYSTALLINE SOLIDS,

William D. Nix and Ricardo A. Menezes. 313
ELECTRONIC AND OPTICAL PHENOMENA IN SEMICONDUCTORS, M. E.

Jones and R. T. Bate 347
CORROSION SCIENCE, 1970, David A. Vermilyea 373
AUTHOR INDEX 399
SUBJECT INDEX 411
vii

Crystal Growth

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ANNUAL

Copyright 1971. All rights reserved

CRYSTAL GROWTH 8507

Bell Telephone Laboratories, Inc., Murray Hill, New Jersey

II. MICROSCOPIC THEORY

.8 • 0' .. o.� o 0' .. 2.0

portant development (Jackson 1 958) was a categorization of growth be­

INTRINSIC GROWTH KINETICS

The intrinsic growth rate of a crystal depends on the mobility of the

where L is the latent heat associated with the transformation, k is Boltz­

TWO DIMENSIONAL CRYSTAL

(10) FACE (Ill FACE

1 Metals from melt

6 Most organic compounds from melt

compounds have normalized entropies of fusion in the range 4-8. Trouton's

materials having various entropies of fusion Uackson & Miller 1969).

in a compound composed of more than one element. Some improvement in

have presented calculations of interface roughness using a quasichemical (or

FIGURE 3. Roughness of a crystal surface for various models of the interface.

FIGURE 4. Calculated growth rates as a function of undercooling for zeroth- and

layer. The first-order model introduces an ordering parameter which makes

INTERFACE STABILITY AND CELLULAR GROWTH

the constitutional supercooling condition. I n addition, their treatment was

When the undercooling is large, dendritic growth can occur. I n fact,

illustrated by Jackson (1967). More impurity, or lower bath temperature,

Tarshis (1969) developed a different (but also approximate) method of

Dendritic growth is understood in principle from these studies. The ap­

III. MACROSCOPIC ASPECTS OF CRYSTAL GROWTH

but it may be expected to become of increasing concern in the growth of

Any discussion of compositional control must recognize that, for any

interface is no longer at equilibrium and the degree of disruption of the

Iowa factors (Section II) will reach compositional equilibrium at rates

MAss AND HEAT TRANSPORT

Horizontal growth.-At one time, the solute distribution during horizontal

growth was thought to be diffusion controlled in the sense that, if natural

fusion boundary-layer thickness (Benson 1965, Carruthers 1967). The per­

fluid motion due to both crystal and crucible rotation.

Vapor transport methods.-The two common arrangements for vapor

larger crystals to be grown.

IV. CRYSTAL GROWTH AS AN EXPLORATORY

Lasers.-Progress in low-threshold optically pumped solid-state lasers

YaAI5012:Nd+a can be pumped with an ordinary incandescent lamp and

I t was recognized quite early that an attractive means of generating addi­

TABLE Z . MATERIALS FOUND USING LARGE POLARIZABILITY CRITERIA

Lithium niobate" x Boyd et al 1964.

Lithium tantalate" x x Ballman 1965. Lenzo

et aI 1966. Warner 1965

Barium sodium niobate" x x Geusic et al 1967.

Van Uitert et al 1968,

Lead molybdate" x Pinnow H al 1969

qualitative estimates of volatility, congruent melting, and ease of growth.

Semiconductor lasers.-Semiconductor lasers offer important advantages

FIGURE 5. Schematic structure of a semiconductor confinement laser.

fined to region 2 because it is sandwiched between regions 1 and 3, both of

TABLE 3. MAGNETIC ORTHOFERRITES'

Magnetic moment Wall energy Bubble

YFeO. 105 1 .8 3.0

Bubble domain materials.-Recently an exploratory materials-crystal

where K is the magnetocrystalline anisotropy (a function of domain wall

requirements could not be met. Other substituents in the orthoferrites, such

V. CRYSTAL GROWTH TECHNIQUES

We will discuss growth techniques using Laudise's classification scheme

Solid-solid techniques have received surprisingly little attention in view

portant development (Jackson 1 958) was a categorization of growth be

where L is the latent heat associated with the transformation, k is Boltz

Dendritic growth is understood in principle from these studies. The ap

fusion boundary-layer thickness (Benson 1965, Carruthers 1967). The per

I t was recognized quite early that an attractive means of generating addi

The earliest techniques were called strain-anneal or solid-state recrystal

boundary mobilities. Further recent improvements, such as those of Rosin

Conventional solution growth from aqueous solutions by temperature dif

sible to grow large-volume dislocation-free specimens of quartz hydrother

of the technique in heteroepitaxy to crystallize magnetic garnets hydro

have been applied in enough instances to demonstrate their power in explain

ed. H. S. Peiser, 441. New York : Per Chem. 4 :53