NASA Contractor Report 3370 

A Study of Crystal Growth 

by Solution Technique 

R. B. La1 

GRANT NSG-80 3 3 

JANUARY 1981 

nJAsA 

I 
TECH LIBRARY KAFB, NM 

NASA Contractor Report 3370 

A Study of Crystal Growth 

by Solution Technique 

R. B. La1 

Alabama Agriculture and Mechanical University 

Huntsville, Alabama 

Prepared for 

Marshall Space Flight Center 

under Grant NSG-803 3 

National Aeronautics 

and Space Administration 

Scientific and Technical 

Information Branch 

1981 
FOREWORD 

This report deals with work done under NASA Grant NSG-8033 

to the Alabama AeM University (AAMU) in Huntsville, Alabama. 

The work reported here was done under the technical supervision of Mr. Charles Schafer of NASA/MSFC, Fluid Dynamics 

Branch, Atmospheric Sciences Division, Space Sciences 

Laboratory,and his cooperation and comments are gratefully 

acknowledged. 

The author thanks the NASA Office of University Affairs for 

the award of this grant which evolved into a flight experiment for the SL 3 Mission. 'The author also thanks Dr. Leon 

Frazier, Dr. Bessie W. Jones, and Dr. M. G. George (all of 

AAMU) for their continued interest and support during the 

'progress of this work. 

ii 
I. INTRODUCTION 

TABLE OF CONTENTS 

II. OBJECTIVES 

III. BACKGROUND 

IV. CRYSTAL GROWTH FROM SOLUTION 

IV. 1. Advantage of Growth from Solution 

IV. 2. Effect of Impurity Adsorption on Kinetics of 

Crystal Growth from Solution 

IV. 3. Uncertainties Regarding Crystal Growth in Low 

Gravity Environment 

V. EXPERIMENTAL PROCEDURE 

v. 1. Test of Thermal Stability of the System 

v. 2. Growth of TGS Crystals 

v. 3. Evaluation Plan 

VI. ADDITIONAL TASKS UNDER THE GRANT 

REFERENCES 

BIBLIOGRAPHY 

Page 

1 

3 

4 

5 

5 

9 

10 

11 

16 

17 

19 

20 

21 

22 

iii 
I. INTRODUCTION --------_-____ 

The promise shown by the results of Skylab I and II and the ASTP experiments, 132 on materials science are in confirmation of the possibility of 

processing of materials in space on a routine basis. These results have 

logically placed an emphasis on simple crystal systems. The results of different 

flight experiments on various missions have shown excellent promise and have 

prompted a closer look at the opportunities for more complex and more valuable 

compound materials. 

The NASA materials processing in space (MPS) program is intended to 

develop applications of space flights in materials science and technology, 

including both research and manufacturing activities. Its initial goal is to 

demonstrate the value of space for materials work by achieving significant scientific results and/or developing specific useful materials and products. 

Many technologies are dependent on single crystal materials to varying 

degree. The materials can be processed for making efficient semi-conductors 

for use in the field of communications, materials which will make better superconductors for control and distribution of energy, materials for energy conversion devices, materials for various kinds of detectors, and materials for 

non-linear optical devices. The eventual processing of materials in space is 

likely to become a major reality with the operational space shuttle in the 

80’s. 

-l- 
The advantages of weightless environment for materials processing include: 

a) absence of buoyant convection, b) absence of density segregation, c) absence of sagging, and d) opportunities of containerless processing. With 

regard to the growth of crystals, the primary advantage is the absence of buoyant 

convection. A growing crystal extracts materials from and/or releases heat 

into the surrounding fluid, thereby lowering the fluid's density. So on earth 

under l-g conditions, a growing crystal is surrounded by a rising convection 

current. In most cases, this convection is unstable and gives rise to growth 

rate instabilities which cause impurity distribution fluctuations and defects 

such as fluid inclusions. 3-7 

It would, therefore, be expected that crystals grown in low-gravity environment would be more uniform in composition and have fewer defects than 

their one-g counterparts. 

-2- 
II. OBJECTIVES __--- 

The objective of this investigation is to study the mechanism of 

crystal growth by the solution technique with special reference to 

materials for electro-optical devices. 

During this investigation, a flight experiment entitled, "Solution 

Growth of Crystals in O-Gravity," was proposed to NASA. The proposal 

was accepted by NASA in September 1977, and the experiment is now approved 

for flight on the SL-3 mission under a separate NASA contract. 

-3- 
.: III. ,BACKGROUND 

In recent years, new applications for non-linear optical devices have 

been found for ferroelectric single crystals such as Triglycine Sulfate (TGS) 

(NH2CH2COOH)3 H2S04 , crystals of iodate family and others. Single crystals of TGS may be used for infra-red image parametric up-conversion due to 

their phase match ability and for image tubes for television displays of 

thermal scenes using their large pyroelectric effect. There is, also, an 

increasing interest in detectors requiring less cooling or no cooling at all, 

even if they have low performance, which may lead to systems with greater costeffectiveness. However, the undisturbed operation of these devices and techniques requires single crystals of high optical quality, i.e., of high purity, 

high homogeneity concerning the physical properties, low density of structural 

ions and strains. The long-durat ion orbital 

era will definitely allow growth of these crystals 

defects and free from inclus 

flights in the space shuttle 

using solution technique. 

-4- 
IV. CRYSTAL GROWTH FROM SOLUTION 

Crystal growth from solutions is simple in principle and has many 

applications. The technique is particularly useful for growth of materials 

which have high vapor pressure or decompose irreversibly at the melting point. 

Crystals will be grown from solution if the solution is supersaturated, i.e. 

it contains more solute than it can hold in equilibrium with the solid. 

The growth methods! are based on solvent used, because the equipment, range 

application, problems and approach are to a large extent determined by the 

choice of the solvent. However, the more fundamental delineation of the 

methods could be made on the basis of the methods of producing supersaturation. 

The growth methods can be divided on this basis. 

1. Isothermal methods (constant temperature methods) 

A. Solvent evaporation or solvent concentration change (mainly used 

in aqueous and molten salt growth) 

B. Temperature differential (mainly used in hydrothermal, aqueous and 

molten salt growth; also includes temperature-gradient zone melting 

when the gradient is moved through the sample). 

C. Chemical or electrochemical reaction (mainly used in aqueous growth) 

2. Non-isothermal methods (temperature variation.methods) 

A. Slow cooling (mainly used in aqueous, liquid metal solvent, and moltensalt growth) 

B. Temperature-gradient zone melting (when the gradient is imposed over 

the whole sample)? 

IV. 1. Advantages of Growth from Solution -- ___- 

In general solution growth can be accomplished at temperatures considerably below the melting point of the material, and the use of lower temperature 

alleviates many of the problems associated with the melt growth process. 

-5- 
The main advantages are listed below. 

1) The most important advantage of crystal growth from solution is the control that it provides over the temperature of growth. This makes it possible 

to grow crystals that are-unstable at their melting points or that exist .in 

several crystal forms depending upon temperature. 

2) A second advantage is the control of viscosity, thus permitting crystals 

that tend to form glasses when cooled from melts to be grown. 

3) Crystals grown from solution usually have well-defined faces as compared 

with those from melts. 

4) It avoids strains, reduces vacancy concentration, and sometime reduces 

dislocations and low angle grain boundaries associated with high temperature 

growth. 

5) Solution growth or low temperature growth is experimentally more convenient. 

Higher temperature processes are often more demanding on equipment and difficult to control, and harder to keep clean so that products are pure. 

Solution growth has had its main success in the preparation of bulk 

crystals. 

There are some disadvantages of a polycomponent growth and they are 

enumerated below. 

1) The additional component will be contaminant and will have solid stability 

in the grown crystal. 

2) Elimination of the additional component at the growing interface will 

setan upper limit on rate of growth. Diffusion will be important in this 

process. This may be an advantage in low-gravity and will be a dominant factor. 

3) Because of the concentration gradient at the growing interface, constitutional supercooling will often occur; facets effects, cellular growth and 

dendritfc growth can thus be problems. 

-6- 
The process of crystallization involves simultaneous mass and heat transport between the crystal surface and the surrounding fluid. In almost all 

cases, this causes a reduction in the density of the fluid. So a growing 

crystal is usually surrounded by a rising convection current. Chen et al.' 

have demonstrated this in a recent paper. Janssen-van Rosmalen et al. 10 have 

demonstrated the influence of hydrodynamic environment on the growth and formation of liquid inclusions in large KDP crystals grown by solution technique. 

It was proposed that veils of liquid inclusions are not a result of starvation in the laminar boundary layer, as suggested earlier, but of depletion in 

the closed wake at the rear. Growing crystals from a fluid phase under 

normal gravity conditions involves coupling of the gravitational field with 

density variations in the fluid, resulting in the generation of convection 

currents. The spatial and temporal density variations in the fluid media are 

due to thermal and solutal variations. 

Nearly all crystal growth processes involve both a solid and a fluid 

component. Since internal binding forces in solids are much larger than 

l-g forces, only the properties of the fluid are expected to be significantly 

influenced by gravity. In the liquid state, intrinsic forces such as cohesion 

or surface tension are of the same order as l-g forces, and the familiar 

properties of liquids are the result of the interaction of intermolecular 

forces and the gravitational forces. If the gravitational forces are reduced 

considerably, the behavior of fluids will be determined by molecular forces 

alone. Thus, the environment of the orbital space-lab will have significant 

influence on the fluid behavior which is expected to affect the crystal growth 

process. In the absence of convection, diffusion will be much more significant 

for the mass transport process. 

-7- 
The process of crystallization from solutions represents a typical phase 

transition in a condensed system. This process is influenced by the creation 

and structure of the supersaturated solution. The proper crystal growth on 

the seed inserted into a supersaturated solution is influenced by various 

factors. 

(a) the degree of supersaturatior-bwhich determines the rate and also the 

mechanism of growth. 

(b) the hydrodynamic conditions in the solution, specially at higher 

degrees of supersaturation,which influences the transfer of the 

material from the solution to the crystal through the diffusion 

layer. 

(c) the temperature of crystallization. 

(d) the quality of the seed used and the chemical purity of the solution. 

(e) Another problem in the growth of large, high-quality single crystals 

is the strain induced during growth by the method used in holding 

the original seed. This is specially evident in solution crystal 

growth where strain induces optical inhomogeneities, cracks and regions 

of non-uniform growth rates. Recently, Loiacono et al!' have used 

a cylindrical seed method to the solution growth of large single 

crystals of TGS. The method permits the strain-free mounting of 

oriented seed crystals. 

(f) finally even the manipulation with the crystal as grown (taking the 

crystal out of equipment, etc.) can strongly influence its properties. 

To investigate the crystallization conditions of TGS in view of growing 

environment, a crystallizer is required which can be used for growing crystals 

in absence or with a minimum mechanical disturbance in the growing solution. 

-8- 
Growth of crystals on earth is always accompanied by gravity-driven convection 

currents as well as diffusion fronts. 

IV. 2. Effect of, Impurity Adsorption on Kinetics of Crystal Growth 

FromSolution. 

12 

Recently it has been reported by Davey, that a presence of a third corn; 

ponent can often have dramatic effects on the crystal growth kinetics (third 

component may be an impurity). Adsorption of impurities onto the crystal 

faces changes the relative surface free energies of the faces and may block 

sites essential to the incorporation of new solute into the crystal lattice. 

These effects may result in changes in growth kinetics and,hence, habit modification of the crystalline phase. 

From the studies of Davey (lot. tit) it seems worth noting the following 

points in relation to the 'mechanism of growth rate reduction by impurity 

adsorption. 

a) Impurity adsorption results in the blocking of key sites on the 

crystal surface. 

b) Impurities which bear a structural resemblence to the crystallizing 

component may be most effective in kink and step sites, while impurities which are structurally dissimilar to the crystallizing 

component may be limited to ledge sites. 

The following requirements of an experimental study may be elucidated. 

1. Substantiation of growth mechanism for pure solution. 

2. Measurement of growth rate as a function of impurity concentration 

at a fixed supersaturation. 

3. Observation of step systems on faces growing in pure and impure solutions. 

4. Measurement of adsorption isotherm of the impurity onto the crystal 

faces under consideration. 

5. The selection of experimental system in which the structural nature 

of the impurity in solution is known. 

The experimental data should then be correlated with different available 

models of crystal growth in solution. 

-9- 
IV. 3. Uncertainties Regarding Crystal Growth in Low-Gravity Environment 

For a detailed study of the crystal growth processes in low-gravity environment, uncertainties about residual, transient and non-buoyant convection 

present and their effect on impurity distribution and the formation of defects 

in the crystal must be considered. Another area of uncertainty is caused 

by our poor understanding of the basic mechanisms of crystallization. 13-14 

Choices between competing theories depend on accurate measurements of growth 

rate as a function of the adjacent thermal and concentration gradients and 

on interface kinetics terms. All these measurements, when perfomed on earth 

in one-g, are distorted by the effects of convection. Measurement of such 

data in a fluid in a solution growth experiment will be extremely beneficial 

to the crystal growth theorists. 

Also, the effect of low-frequency g-levels on the crystal quality is a very 

important parameter. Displacements produced by low-frequency (~10 Hz) g-levels 

are most harmful to solution crystal growth and must be accounted very carefully. 

-lO- 
V. EXPERIMENTAL PROCEDURE* 

A low temperature solution growth system for growing TGS was designed 

and fabricated (fig. 1.). The system includesan outside bath 27.5 cm x 27.5 cm x 

17.5 cm made out of 0.9 cm plexiglass. The bath is heated with two vertical 

quartz heaters each of 350 watts. The fluid in the outside bath,which is 

distilled water, is stirred with two stirrers running at 20 rpm using a.c. 

synchronous motors. The input to the heaters is controlled using a Fisher 

proportional temperature controller with an accuracy of +O.Ol'C. The actual 

accuracy of the bath is measured at present only to +Q.l'C using NBS calibrated thermometers. The growth solution is kept in a 10 x 10 x 10 cm3 

cell made out of 0.6 cm thick plexiglass. The growth cell is surrounded on 

all sides (except top) by the outside constant temperature bath. The seed 

crystal is mounted on a specially designed sting which is inserted in the 

inner cell at a proper time. Details of the sting are given in fig. 2. A 

stainless steel tube is encapsulated by a plexiglass tube machined to fit the 

stainless tube. A narrow outer jacket is left between the plexiglass and the 

stainless tube. A desired flow of high-purity argon gas can be maintained 

between this narrow jacket. The desired flow of argon gas is monitored through 

a flow meter. 

*This work was done in conjunction with other NASA Contract NAS 8-32945. 

-ll- 
-r 7 CM lHEATER 

lHERMOMETER 

TEMPERATURE .PROBE 

\ 

20 RPM 

o-9 q+---e;:{ 

SOLUTION CRVSTA; GROWTH SYSTEM 
I 

4 

w 

I 

ICM - 

I 

.6 CM 

t 

lCM TUBE 

1.1 CM HOLE 

1.75 CM D 

7CM 

1 

.35 CM HOLE 

I-) -i 

FIG. 2 

DESIGN OF STING 
,‘:,‘J.:,‘):,. . . 

,c7, I 1 ‘: ; .‘. -:>., :_ e,“‘,, 

.. . . 

I..._ 

. p ~.-7 - .., . ..- .._,l,_,.,_., 

,. . __ . . 

I. 

, 

-._ 
This serves the purpose.of cooling the sting and the seed crystal. The 

seed crystal is mounted using RTV silicone adhesive at the end of the stainless tube which barely projects out of the plexiglass rod. Two copper-constantan thermocouples have been installed in the sting. One is behind the seed 

crystal inside the rod and the other on the outside wall of the sting mounted 

flush to the surface of the sting. The emf of the two thermocouples is 

measured using a Keithley 610C electrometer. Omega company copper-constantan 

O°C temperature compensator is used for O°C reference junction. 

The inner growth cell is tightly covered with a plexiglass cover to avoid 

any appreciable loss of liquid due to evaporation. 

An overall picture of the experimental setup is given in fig.3. 

-15- 
v. 1. Test of Thermal Stability of the System 

The thermal stability of the growth system was tested for a desired set 

temperature (between 30°C - 50°C) over a period of 8-12 hours. The stability 

of the cell temperature greatly depends upon the stirring provided to the 

outside bath. In the initial run,commercially available Fisher Scientific 

stirrers were used. It was found that there was a large variation of temperature ( t4'C) between the lowest and the top level of the water in the outside 

bath. The design of the stirrers was modified so that they can stir about 

4" of vertical depth of water below the top surface. The bath temperature 

was then maintained within less than tO.l'C between different layers of water 

all around the growth cell. The growth cell was also tested for cool-down and 

heat-up rates. The outside bath can be brought to a desired temperature within +O.l'C in a period of 20 minutes. Due to the poor conduction of plexiglass, 

the inner cell takes about 2 hours to reach a steady-state temperature,which 

was found to be l°C below the outside bath for a particular cell. 

-16- 
v. 2. Growth-of TGS Crystals 

Initially seed crystals of TGS were grown by spontaneous'nucleation and 

grown in about 2 or 3% supersaturated solution. Saturated solutions of TGS 

were prepared from BDH high-purity crystalline Trigylcine sulfate using doubledistilled water. Solution is filtered at a temperature of a few degrees centigrade above the saturation temperature. At the present time crystal growth 

experiments have been performed in the ferroelectric range,which is below 

the transition temperature of TGS (.Tc = 49'C). 

before the start of the experiment,the outer bath was set at 37'C. The 

inner cell was filled with 800 ml of 36'C saturatedsolution of TGS. The pH of 

the solution was measured as 2.4 kO.1. The cell was left for two hours in 

the constant temperature bath till its temperature reached a steady value of 36'C. 

The experiment was initiated by inserting the sting, mounted with a polyhedral seed of TGS using RTV silicone adhesive, in the solution. A slow 

purge of prepurified Argon at 2 p.s.i. was maintained through the sting. In 

this initial run no thermocouple was mounted at the tip of the sting so no 

temperature reading of the tip and the growth solution were recorded during 

the growth of the crystal. The Argon gas provided a constant cooling of the 

sting and a constant supersaturation near the seed crystal. The growth process 

continued for 26 hours. The crystal grew about four times the size of the 

seed. The total mass deposited in 26 hours was 2.79679 g. This gives an 

average growth rate of 0.15 mm/hour, but no precise calculation of average 

mass transfer coefficient (k) has been made at this time. This growth rate 

is appreciably faster than required for a laminar growth. In this growth, 

an under-cooling of l°C was maintained on the tip of the sting. At the end 

-17- 
of the experiment the crystal was removed from the growth solution, dried 

and stored. Due to some inaccuracy in the saturation curve there were 

some crystallites seen at the bottom of the growth cell. 

No evaluation of the grown sample has been done at this time. It is 

planned that measurement of dielectric constant, specific heat and domain 

structure studies will be performed. Crystalswill be grown at different 

supersaturation, growth temperatures and by varying the pH of the solution. 

-18- 
v. 3. Evaluation Plan 

a) Transitiion Temperature 

The transition temperature Tc can be determined for each sample by plotting the temperature variation of the dielectric constant using a General 

Radio model 1620-AP capacitance measuring assembly. 

b) Domain Structure 

The dielectric properties of TGS as defined by the electric permittivity 

E" and E" and the spontaneous polarization, Ps, depend strongly on the conditions in which the crystals are grown. Crystals grown above the Curie point 

at a constant temperature and the onesgrown below the curie point have been 

-- 

found to show different domain structure.'5 Domain structure will be studied 

in crystals grown in ferroelectric and paraelectric range. 

c) Specific Heat Measurements 

The relative perfection of ferroelectric crystals can be assessed by 

the evaluation of the specific heat (c,) curve in the vicinity of a phase 

transition. In particular, the width and displacement of Cp curve at the 

transition is significant. Crystalline defects and/or gross impurities produce internal electrical fields and stresses which can cause broadening of the C 

11 

P 

curve and a reduction of C at the transition. 

P 

The specific heat (C,) for a crystal grown earlier was measured with a 

Perkin Elmer (DSCI) differential scanning calorimeter.* The measured value of 

Cp = 0.3155 cal/g'C corresponds to values reported earlier. The precisiion 

of the instrument was not adequate to detect any changes in C 

We are trying to improve the sensitivity of 

P 

for O.l'C change 

in temperature. measurements.* 

*These measurements were made at the Physics Department of the University Of 

Alabama in Huntsville. 

-19- 
REFERENCES 

1. 

2. 

3. 

4. 

5. 

6. 

7. 

8. 

9. 

10. 

11. 

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13. 

14. 

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-2o- 
BIBLIOGRAPHY 

-2l- 

- 
FAPiRS ON SOLUTION CRYSTAL GROWTH 

A Simple Method for growing crystals from Solutions A. V. Belyustin; 

Sov. Phys. Crystallogr. 10, 651 (1966). 

A Method of Growing Crystals from solution under static conditions. 

A. V. Belyustin. N. S,. Stepanova. 

(1966). 

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- 

Occlusion of Mother liquor in solution grown crystals-Richard Brooks, 

Avery T. Horton and John L. Torgesen, 

(1968). 

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Crystallization from solution; factors influencing size distribution. 

M. A. Larson, Editor. 

g, (1971). 

Chemical engineering progress symposium series. 

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crystals from solutions. J. Novotry. Kristall and Technik 6, 343 (1971). 

Methode de Croissance en Solution des Monocristaus par L'addition 

Graduelle D'un Reactif. I. F. Nicolau, M. Ittu and R. Dabu. 

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Equipment from single crystal growth from aqueons solution. John L. Torgesen, 

Avery T. Horton and Charles P. Saylor, Journal of Research of The 

National Bureau of Standards- Chemical Engineering and Instrumentation. 

67c, (1973). 

Crystallization apparatus for the growth of crystals at constant supersaturation 

of the solution. A. I. Munchaev. Sov. Phys. Crystallogr. 18 566 (-1974). -' 

Einflub von magnetischen and elektromagnetischen Feldern auf die 

Kristallisation aus Wa brigen Losungen. C. Barta, L. M. Beljajew, 

G. F. Dobrzanskiji, S. L. Kreinin, M. P. Schaskolskaje, J. Zemlicka, 

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A Crystallizer for growing large single crystals from solution under 

Steady-State Concentration Convention Conditions. I. F. Nicolau 

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P. Bennema, Crystal Growth from solution theory and experiment, J. Cryst, 

Growth, 24/25, 76 (1974). 

A. R. Konak, Single versus suspension growth, J. Cryst. Growth, 22, 67 (1974).. 

-22- 
pApERS ON SOLUTION CRYSTAL GRo!fTH (CONT.) -v--L 

Mitsuhiko Hayashi and Takaki Shichiri, Theoretical and experimental study 

of the growth of perfect crystals, J. Cryst. Growth, 2J, 254 (1974). 

A. I. Munchaev, Crystallization apparatus for the growth of crystals at 

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H. Nelson, Liquid Phase Epitaxy - its role in crystal growth technology, 

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B. K. Tanner, The Perfection of flux grown crystals, J. Cryst. Growth, 24/25, 

637 (1974). 

J. C. Brice, The stability of facets on growing crystals, J. Cryst. Growth, 

26, 59 (1974). 

R. 1. Moon, The Influence of growth solution thickness on the LPE Layer 

Thickness and constitutional supercooling requirements for diffusion -- 

limited growth, J. Cryst. Growth, 27, 62 (1974). 

I. F. Nicolau, A crystallizer for growing large single crystals from solutions 

under steady-state concentration convention conditions, Kristall and 

Technik, 2, 1331 (1974). 

G. I. Distler, A. N. Lobacher, Growth of Single Crystals through Interfacial 

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H. M. Manasevit, A Survey of Heteroepitaxial growth of Semi-conductor films 

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Space Processing of Crystals for Opto-electronic devices-The case for solution 

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Crystal Growth Contract NAS8-31152 10 Sept. 1975. 

Influence of Gravity-Free Solidification on Solute Microsegregation. 

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George E. Moore, Sr., et. al., Worldwide wafers standardization facts or fancy, 

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-23- 
Papers on Solution Crystal Growth (cont.) 

P. Bennena and C. Van Leeuwen, Crystal Growth from vapour phase, Confrontation 

of Theory with experiment, J. Cryst. Growth, Xl-, 3 (1975). 

G. K. Steel and M. J. Hill, Analysis of the transfer function governing crystal 

growth in the czochralski process, J. Cryst. Growth, 30-, 45 (1975). 

R. Janseen van Rosmalen P. Bennena and J. Garside, The Influence of volume 

diffusion on crystal growth, J. Cryst. Growth, 2!& 342 (1975). 

J. Garside, R. Janseen van Rosmalen and P. Bennena, Verification of Crystal 

Growth rate equations, J. Cryst. Growth, 29, 353 (1975). 

V. R. Phillips and J. W. Mullin, A technique for observing growth layers and 

adjacent faces of crystal growing in solution, J. Cryst. Growth, 2!& 352 

(1975). 

J. C. Brice, J. M. Robertson and J. Vander Heide, A new method of stirring 

for LPE growth, J. Cryst. Growth, 30 375 (1975). - 

R. C. DeMattei, R. A. Huggins and R. S. Feigelson, Crystal Growth by the 

Electrochemical Czochralski Technique (ECT), J. Cryst. Growth, 34. 1 

(1976). 

J. R. Davey, The effect of impurity absorption on the Kinetics of crystal 

growth from solutions, J. Cryst. Growth, 34, 109 (1976). 

George D. Stareev, A new method for liquid-phase epitaxy, J. Crystal Growth, 

32, 189 (1976). 

Influence of the Supersaturation on the mode of thin film growth. I. 

Markov, R. Kaischew. Kristall and Technik 11, 685 (1976). 

The Effect of Impurity Absorption on the Kinetics of Crystal Growth from 

Solution. R. J. Davey. J. Crystal Growth 34, 109 (1976). 

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R. C. Demattei, R. A. Huggins and R. S. Feigleson, J. Crystal Growth 

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Crystal Growth by Electrolytic Concentration L. M. Rouse and E. A. D. White. 

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Determination of Linear Growth Rates of Crystal (I) Calculation of Linear 

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and Technik ll-, 149 (1976). 

Determination of Linear Growth Rates of Crystals (11) The Shape Factors 

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-2u- 
Papers on Solution Crystal Growth (cont.) 

J. R. Carruthers, Origin of Convective temperature oscillations in crystal 

growth from melt, J. Cryst. Growth, 32, 13 (1976). 

K. Kawamma and Tatsuo Yamamoto, New Apparatus for multilayer liquid-phase 

epitaxy, J. Cryst. Growth, 32, 157 (1976). 

T. Surrek, Theory of Shaped Stability in crystal growth from the melt, J. 

Appl. Phys., 47, #lo, 4384 (1976). 

New Empirical Kinetic Equation of Size Dependent Crystal Growth and its use. 

Z. Rojkowski. Kristall and Technik 12 1121 (1977). - 

Growth from the vapour by Surface Nucleation. L. M. Rouse. Kristall Technik. 

12, 531 (1977). 

An Unusual Type of Epitaxial Growth. A. Hadni, R. Thomas and C. Erhard. 

Phys. Stat. Sol. (a) 39 419 (1977). - 

Growth of Epitaxial layers from a limited volume of melt-solution. A. 

A. Litvin and I. E. Marochuk. Sov. Phys. Crystallogr. 22, 242 (1977). 

Physiochemical aspects of the hydrothermal growth of crystals. I. C. Ganeev 

and V. N. Rumyantsev. Sov. Phys. Crystallogr. 22, 91 (1977). 

A phenomenological Analysis of Crystal Growth from Solutions as an Irreversible 

Process. Tomoya Ogawa. Jap. J. Appl. Phys. 16, 689 (1977). 

The Weighing Method of Automatic Czochralski Crystal Growth. II Control 

Equipment. W. Bandsley, D. T. J. Hurle, G. C. Joyce and G. C. Wilson. 

J. Crystal Growth 40, 21 (1977). 

Simple Pressure Chamber for Liquid Encapsulate Czocharalski Crystal Growth. 

E. Buehler, J. Crystal Growth 43, 584 (1978). 

Computational Simulation of the Melt flow During Czochralski Growth. 

N. Kobnyashi. J. Crystal. Growth 43, 357 (1978). 

A New Technique for Determining The Kinetics of Crystal Growth from the Melt. 

S. Pech and M. Vignes-Adler. J. Crystal Growth 43, 123 (1978). 

Condition for Constant Growth Rate by LPE from a cooling, static solution. 

M. B. Small and R. Ghez. J. Crystal Growth 43, 512 (1978). 

A Crystallizer for growing single crystals from a solution, with precise 

temperature control. 

230 (1978). 

J. Mastner and J. Janta. Czech. J. Phys. B2J, 

Evaluation of supersaturation in Crystal Growth from Solution, P. T. Cardew, 

and R. J. Davey, J. Crystal Growth, 46, 534 (1979). 
Papers on Solution Crystal Growth (cont.) 

Thermodynamic Driving Force for Crystallization from Solution, 0. Sohnel, 

J. Crystal Growth, 4&, 238 (,1979). 

Crystallization of Salts from Supersaturated Solutions: Diffusion Kinetics, 

I. V. Meliklov, and L. B. Berliner, J. Crystal Growth, 46, 79 (1979). 

On the driving force for crystallization, the growth activity, C. Van Leeuwen, 

J. Crystal Growth, 46, 91 (1979). 

On the presentation of growth curves for growth from solution, C. Van Leeuwen, 

J. Crystal Growth, 4fj, 96 (1979). 

-26- 
PAPERS ON TGS 

The Thermodynamic Theory of Ferroelectric Semi-Conducting Solid Solutions. 

V. E. Yurkevich and B. N. Rolov; Ferroelectric 5, 67 (1973). 

X-Ray Damage on TGS: A Thermodynamic Theory. C. Alemany, J. Mendiola, 

B. Jimenz and E. Maurer, Ferroelectrics 5, 11 (.1973). 

Incident Electron Energy effect on the Ferroelectric Properties of TGS. 

Cz. Pawlaczyk and B. Hilczer; Ferroelectrics 6, 33 (1973). 

Evaluation of Domain wall thickness in TGS crystals from Thermal Diffusivity 

Measurements. 

845 (1973). 

T. Krajewski and F. Jaroszyk; Acta Phys. Polon. E, 

Effect of Growth Conditions on The Thermal Diffusinity and Thermal Conductivity 

of TGS Crystals. 

831 (1973). 

T. Krajewski and F. Jaroszik Acta Phys. Polon. E, 

Effect of Growth Conditions on the Domain Structure of Triglycine Sulphate 

Crystals. 

(1973). 

J. Stankowska and E. Czosnowska, Acta Phys. Polon. &, 641 

Characterization of Fully Deuterated Triglycine Sulphate (N0,C0,C000),D2S0,. 

H. P. Beerman, Ferroelectrics 8, 653 (1974). 

The Influence of The Loss of TGS-Fragments in Ultra-high-Vacuum on The 

Spontaneous Polarization and The Coercive Field Strength. V. Ziebert; 

Ferroelectrics S, 645 (1974). 

Unipolar FEatures in Strong elec$iic fileds of TGS crystals and of The Rochelle 

Salt Crystals Doped with Cu . J. Eisner: Ferroelectric 8, 621 (1974). 

Internal Field2in Ferroelectric Triglycine Sulphate Crystals as Studied by 

EPR of VO Impurities. 

611 (1974). 

M. Fujimoto and L. A. Dressel; Ferroelectrics S, 

Evaluation of the free energy expansion coefficient in TGS. J. Z. Zerem and 

A. Halperin, Ferroelectrics 1, 205 (1974). 

Change in the permittivity, The Dielectric loss and the Resistance of TGS 

caused by the loss of TGS-Fragments in Ultra-High-Vacuum. H. Schmitt 

and V. Ziebert; Ferroelectrics 5, 151 (1974). 

Dielectric Properties of TGS and TGFB Monocrystals under high pressure. 

J. Stankowski, A. Galezewski, S. Waplak, U. Gruszczynska and H. Gierszal; 

Ferroelectrics 5, 209 (1974). 

-2z- 
Papers on TGS (cont.) 

Alanine Doped TGS/TGSE Crystals for pyroelectric applicantions. 

K. L. Bye, P. W. Whipps, E. T. Keve, and M. R. Josey; Ferroelectrics 7, 

179 (1974). 

- 

Vapour Pressure of Triglycine Sulphate (TGS) Below 13O'C. 

Ferroelectrics 5, 157 (1974). 

Forward Velocity of Domain Walls in the switching of TGS. 

and J. Gonzalez 1 Beas. Ferroelectrics 5, 203 (1973) 

V. Ziebert., 

V. Lopez Rodrignez 

Growing of TGS and TGSE Single Crystals at various pH of solution, 

M. S. Tsedrik, V. N. Ulasen, G. A. Zaborovski., Kristall and Technik 10, 

49 (1975). 

Domain Structure and Dielectric Properties of TGS and DTGS Sinqle Crystals Depending on Growth Conditions. M. S. Tsedrik, G. A. Zaborovski, N. P. Demidorich, 

L. N. Margolin., Kristall and Technik 10, 55 (1975). 

Effect of X-Ray Irradiation on The Dielectric Properties & Optical Absorption 

of Triglycine Sulphate Single Crystals. S. Govinda & K. V. Rao., Indian 

J. Pure & Appl. Phys. 13, 175 (1975). 

Growth of Triglycine Sulphate Crystals from Aqueons Solution on Cleaved (.OlO) 

Surfaces. 

125 (1975). 

R. J. Davey and E. A. D. White., Journal Crystal Growth 30-, 

Influence of Growth Temperature on The Dielectric Properties of Triglycine 

Sulphate (TGS) Crystals. 

Polon. A47, 85 (1975). 

J. Stankowska and L. Pawlowicz Acta Phys. 

Critical Behavior and Internal Bias of TGS and Isomorphous Crystals Depending 

on growth conditions. 

Technik 11, 373 (1976). 

M. S. Tsedrik, G. A. Zaborovski, Kristall and 

The Growth of Large Area, Uniformly Doped TGS Crystals. E. A. D. !dhite, 

J. D. C. Wood and V. M. Wood. Journal Crystal Growth 32, 149 (1976). 

- 

Physical Properties of Ferroelectrics in the Curie Point Region. B. A. Strukov. 

Ferroelectrics E, 97 (1976). 

Recent Structural Studies of the KH2P04KD2P0 System. N. S. J. Kennedy, 

R. J. Nelmes and F. R. Thornley and d 

591 (1976). 

. D. Rouse., Ferroelectrics 14, 

Structural Studies of TGS. Part II: After X-Irradiation/Field Treatment 

(Structure B) S. R. Fletcher, E. T. Keve and A. C. Skapski., Ferroelectrics, 

l4-, 789 (1976). 

-28- 
Papers on TGS (cont.) 

Depolarization effects in this ferroelectric films. P. Wurfel and 

I. P. Batra., Ferroelectrics, 12 55 (1976). - 

Structural Studies of Triglycine Sulphate Part I: Low Radiation Dose 

(Structure A) S. R. Fletcher, E. T. Keve and A. C. Skapski., Ferroelectrics 14, 775 (1976). 

Microwave Dielectric Dispersion in Triglycine Sulphate, Abhai Mansingh, 

S. S. Bawa & Gulshan Rai., Indian J. Pure & Appl. Phys. l4-, 298 (1976). 

Growth of Large Area, Uniformly Doped TGS Crystals. E. A. D. White, 

J. D. C. Wood and V. M. Wood., Journal Crystal Growth 32, 149 (1976). 

Growth Investigations of Single Crystal Sulphates Containing Molecular 

glycine groups. L. Szezepanska. Kristall and Technik 11, 265 (1976). 

Growth of Ferroelectric Triglycine Sulphate Single Crystals. K. N. Srivastava 

and Bachchan singh., Indian J. Pure Appl. Phys. 14, 146 (1976). 

Homogeneity of Triglycine Sulphate Crystals. E. A. D. White, V. M. Wood., 

Journal of Materials Science ll-, 612 (1976). 

Observation of Domain Wall Motions in Alanine Doped Triglycine Sulphate 

Ferroelectric Crystal. Armand Hadni and Robert Thomas. Appl. Phys. 10 

91 (1976). 

--' 

Triglycine Sulphate Single Crystals Growing Doped with Copper and Colbalt 

lons and Study of their Dielectric properties. M. S. Tsedrik, E. M. 

Kravchenya. Kristall and Technik 11, 49 (1976). 

Effects of deuteration and external factors on grain-boundary relaxation in 

TGS Crystals E. V. Peshikov. Sov. Phys. Crystallogn. 20, 743 (1976). 

Spontaneous polarization in thin TGS Single Crystals. N. D. Gavrilova, 

V. S. Deriglazov, V. A. Koptsik, V. K. Norik, V. G. Poshin and 

B. V. Selyuk. Sov. Phys. Crystallogr 20, 700 (1976). 

Growth of TGS Crystals in the form of Oriented block and a study of their domain 

structure. V. P. Konstantinova and N. G. Maksimova. Sov. Phys. Crystallogr. 

22, 127 (1977). 

Crystallization Par Germination Epitaxique. Armand Hadni, Robert Thomas et 

Christian Erhard. Journal Crystal Growth 37, 194 (1977) . 

Tellurium Thin-Film Field-Effect Transistor Deposited on TGS Crystal. 

Yoshizumi Yasuoka, Housuke Hirayama and Toyo-o Miyata ., Jap. J. Appl. 

Phys. 16, 1195 (1977). 

-29- 
Papers on TGS (cont.) 

On the slope of Growing Pyramids. Christo N. Nanev., Kristall and Technik 

lZ-, 587 (1977). 

The Physical Properties of TGS Single Crystals, Grown from Aqueous TGS 

Solutions Containing Anili:ne. J. Eisner. Phys. Stat. Sol. (a) 43, 

KI‘ (1977). 

Reversal of Polarization in triglycine sulphate crystals and the dependence 

of this process on defects already existi‘ng in the crystals. 

N. S. Komlyakova, A. B. Lirhov, Z. Malek, V. M. Rudyak, and L. A. Shuvalov. 

Sov. Phys. Crystallogr 22, 323 (.1977). 

Production of Large Area, Doped and Undoped TGS Crystals by Rotating Disc 

Method. B. J. Lillicrap and J. D. C. Wood. Journal Crystal Growth 41, 

205 (1977). 

On The Thermodynamic Formalism for adsorbed Layers in Crystal Growth from 

solution. H. E. Lundager Madsen. 

(1977). 

Journal Crystal Growth 2, 250 

The Physical Properties of TGS Single Crystals, Grown from Awneous TGS 

Solution containing aniline. J. Eisner. Phys. Stat. Sol. (a) 43, 

Kl (.1977). 

An unusual type of Epitaxial Growth A. Hadni, R. Thomas, C. Erhard. Phys. 

Stat. Sol. (a) 2, 419 (-1977). 

Crystal Growth from Solution using cyclindrical seeds. G. M. Loiacono and 

W. N. Osborne. J. Crystal Growth 43, 401 (1978). 

The Influence of the hydrodynamic Environment on the Growth and the formation 

of Liquid Inclusions in large KDP Crystals. R. Janssen-Van Rosmalen, 

V. H. Van Der Linden E. Dobbinga, V. Visser. Kristall and Technik 13, 

17 (1978). 

-3o- 
NASA CR-3370 

1. TITLE AND SUBTITLE 5. REPORT DATE 

January 1981 

A Study of Crystal Growth by Solution Technique 

7. AUTHOR(S) 

R. B. La1 

6. PERFORMING ORGANIZATION CODE 

6. PERFORMING ORGANIZATION REPOR r 

3. PERFORMING ORGANIZATION NAME AND ADDRESS 

Department of Physics 

Alabama Agriculture and Mechanical University 

Huntsville, Alabama 35762 

2. SPONSORING AGENCY NAME AN0 ADORESS 

10. WORK UNIT, NO. 

M-318 

11. CONTRACT OR GRANT NO. 

NSG-8033 

,S. TYPE OF REPORT & PERIOD COVERE 

Contractor Report 

National Aeronautics and Space Administration 

Washington, D. C..20546 

5. SUPPLEMENTARY NOTES 

Marshall Technical Monitor: Charles Schafer 

Final Report 

6. ABSTRACT 

1.1. SPONSORING AGENCY CODE 

The purpose of this investigation is to study the mechanism of crystal growth 

by solution technique. A low-temperature solution crystal growth setup is developed. 

Crystals of Triglycine Sulfate (TGS) are grown using this arrangement. Some additional tasks were performed toward fabrication of some experiments for future space 

flights. 

7. KEY WORDS 

Crystal growth 

Solution crystal growth 

Spacelab 3 mission 

16. DISTRIBUTION STATEMENT 

Unclassified - Unlimited 

Subject Category 76 

). SECURITY CLASSIF. (of thim report) 20. SECURITY CLASSIF. (of this page) 21. NO. OF PAGES 22. PRICE 

Unclassified Unclassified 33 A02 

FIX Salle by Nationd Technical Springfield, 

NASA-Langley, 1981