Journal of Crystal Growth 62 (1983) 545—556
North-Holland Publishing Company
GROWTH OF KH2PO4 CRYSTALS AT CONSTANT TEMPERATURE AND SUPERSATURATION
G.M. LOIACONO, J.J. ZOLA and G. KOSTECKY
Philips Laboratories, Briarcliff Manor. New York 10510, USA
Received 29 October 1982; manuscript received in final form 15 March 1983
A large (144 liter) three-zone crystallizer system was constructed for growing KH2PO4 crystals under conditions of constant
temperature and supersaturation. Crystal growth rates exceeding 5 mm day were demonstrated for KH2 P04 using seeds measuring
5 X 5 cm in cross section.
1. Introduction
The crystal requirements for KH2PO4 in large
aperture laser systems for fusion research are pre-
sently beyond the state-of-the-art in solution
crystal growth. If one considers the size of the
crystals required (40 to 76 cm dia.) and evaluates
the growth technology available, the goal appears
unattainable. The basic limitation in technology is
associated with the acceptance of those in the
crystal business to use Holden type crystallizers
for growing crystals from solution. This limitation,
however, is not based on scientific data, but can be
attributed to general acceptance of historical pro-
cedures.
The Holden crystallizer, initially reported in
1949, was the first unit considered suitable for
production growth of large single crystals from
aqueous solutions [1,2]. During the past 33 years,
numerous improvements and modifications of the
original apparatus and procedure have been re-
ported and used for crystal growth [3—5].The
basic process for crystal growth with a Holden
crystallizer is simple. A saturated solution of the
material to be grown is introduced into the crystal-
lizer which contains the seed crystals. The temper-
ature of the crystallizer is maintained slightly above
the saturation temperature of the growth solution.
After the solution is transferred to the crystallizer,
the temperature is programmed down at a suitable
rate.
0022-0248/83/0000—0000/$03.00 © 1983 North-Holland
545
There are two major problems with this type
crystallizer; poor control over supersaturation and
a limit to the amount of solute available for crystal
growth. In growing large crystals of many materi-
als, KH2PO4 being typical, the growth rate, using
a Holden crystallizer, is limited to about I to 2
mm day ~.This limitation is determined by the
occurrence of crystalline defects (i.e. veils). These
defects are caused by fluctuations in growth rate,
which is directly related to the lack of suitable
control of supersaturation. Therefore, the key fac-
tor in obtaining a maximum growth rate is to
control supersaturation. One solution to this prob-
lem is based on the use of a crystallizer which
operates under constant temperature conditions
and maintains a constant supersaturation. Based
on published reports using small crystallizers of
this type, KH2PO4 crystals can be grown at rates
exceeding 5 mm day [5]. One goal of the
present study was to demonstrate that the maxi-
mum growth rate for large (5 x 5 cm seeds) of
KH2PO4 could exceed 5 mm day without caus-
ing the normal types of defects usually observed.
The problem of limited solute available for
growth can be appreciated if one considers that
the amount of solution required to produce a
KH2PO4 crystal of 76 cm cross section exceeds 40
kl. This represents the volume of the growth cham-
ber only, and the complete crystallizer system
would exceed 80 kI. It should be noted that the
bulk of solution growth technology has been de-
546 G.M. Loiocono et a!.
veloped using growth volumes in the 10 to 100 1
range.
This paper discusses the technical aspects of an
approach for growing large, optical quality crystals
of KH2PO4 at high growth rates. The technique is
not limited to KH2PO4 but is a universal method
which can be applied to other materials grown
from solutions. In fact, Buckley in 1951 com-
mented that “it would appear that the constant
temperature crystallizer is the most useful type of
crystallizer devised up to the present time for the
growth of large, nearly perfect crystals from solu-
tion” [3].
2. Theoretical aspects of crystallization from solu-
tion
The basis of all methods of solution growth is
illustrated by the Ostwald—Miers diagram shown
in fig. 1 [5,6]. The solid line represents a section of
the normal solubility curve for a solute/solvent
system. The upper dashed line is referred to as the
supersolubility line and denotes the temperature
and concentration where spontaneous crystalliza-
tion occurs. This boundary is not well defined as
its position depends on a number of experimental
growth parameters. However, for a fixed crystalli-
zation system, this boundary is defined and the
V “~
I
-
SUPERSATURATED (LABILE),,.v
V ~V
,,.,-‘~
V A second solution parameter which is useful is
D defined as the maximum or limiting supersatura-
~ ~ A tion in a system. This is represented by the dashed
UNSATURATED (STABL:)
(MIERS 1907)
TEMPERATURE c~c —p
Fig. I. Ostwald—Miers diagram for a solute/solvent system.
/ Growth of KH, PG
4 crystals
region between the two lines is the metastable
zone. It is within this zone that all single crystal
growth occurs.
The diagram can be evaluated on the basis of
three zones:
— the stable zone which is unsaturated and where
crystal growth is not possible;
— the metastable zone where spontaneous crys-
tallization is improbable but crystal growth on a
seed occurs:
— the labile zone where spontaneous nucleation
occurs.
When a solution represented by point A is
cooled without the loss of solvent, line ABC,
spontaneous crystallization will occur only when
conditions corresponding to point C are attained.
In some cases, additional cooling to point D may
he required to cause nucleation. This results from
an increased solution viscosity usually obtained
with highly soluble materials. Supersaturation can
be established by isothermal evaporation (AB”C”)
and spontaneous crystallization occurs at point
C”. The line AB’C’ illustrates the process where
both cooling and evaporation occur simulta-
neously. It is evident that controlled crystal growth
on a seed is only possible within the metastable
zone; thus this region is of prime importance. The
width of the metastable zone is indicated as the
range of supersaturation that be achieved without
spontaneous nucleation and is specified in units of
concentration. The most common expression for
supersaturation is the concentration driving force
~C.which is defined as
~C= C— C0, (I)
where, C = solute concentration in solution and
C1~=:quilibriumsolute concentration at a given
line CC’C” in fig. I. Synowiec, Nyvit and Sohnel
~:~:;~,t~5 parameter in the form of (2)
. . - .
where, ~1C01~ is the limiting supersaturation, k an
experimental constant, M the molecular weight of
solute (g mole~)and C’) the equilibrium satura-
 G.M. Loiacono et a!. / Growth of KH,P0
4 crystals 547

tion concentration [7—9].For non-hydrated salts, -

the factor k in the temperature range 20 to 80°Cis

63’, 6 —

0.855)< iO~ e°°’

where i is the temperature (°C).Thus for a specific ~ 5 -

growth system, there is a limiting supersaturation,

the width of the metastable zone can be de- -

termined, and these data can be used to develop

the crystal growth process. 3 -

According to current solution growth theory, ~

the growth rate of a crystal can be described by 2 -

~“hk1 = K AC”, (3)

where V~,is the growth rate in a particular crys- 1 -

tallographic direction [hk/],K a constant and the

exponent n varies from 1.4 to 1.6 [5]. It is also 0100 20° 300 40° 50° 600 70° 80°

clear from present theory that the growth rate can TEMPERATURE, °C

be linear at low supersaturations and at high val-

- Fig. 2. Maximum supersaturation versus temperature for
ues of supersaturation have a cubic dependence KH,P0
4.
[10—13]. -

The mathematics describing the growth rate of

a crystal under conditions of constant supersatura-
tion and temperature, in a multiple zone appara-
tus, has been detailed by Kozlowskii and Novotny
[14,15]. Constant supersaturation is maintained by
circulation of the growth solution at a fixed flow
rate. A minor problem in the technique is the
occurrence of spontaneous nucleation in the growth
chamber and in the tube connecting this chamber
with the saturator. However, if the width of the
metastable region is known, as described above,
the maximum supersaturation (~C~,4~) level can
be avoided because the temperature difference
(AT) which defines ~C51~,0is known. Therefore,
large values of supersaturation can be achieved
without the occurrence of spontaneous nucleation.
The maximum value of iiC as a function of tern-
perature, for KH2 P04 was estimated by the method
described above (see eq. (2)). These results are
given in fig. 2. From these data, the maximum ~T
which can be obtained in the KH2PO4 system is
approximated by
= (dc*/dT) ~T (4)
where dc*/dT is the slope of the solubility curve
in the temperature region of growth. For a temper-
ature of 35°C in the crystallizer chamber, the
maximum value of ~T is about 7.6°C.
Crystal growth rates normally reported in the
literature are on the order of 1 mm day~ for a
wide range of materials. Based on the discussion
given above, it is reasonable to assume that the
supersaturation level used was at a low level. A
high supersaturation, which is required for large
growth rates, can be neither obtained nor main-
tamed in standard Holden type crystallizers. This
is due to the lack of control of supersaturation and
the frequent occurrence of spontaneous nucleation
in these crystallizers.
3. Crystallizer system
The concept of solution growth under condi-
tions of constant temperature and supersaturation
was first reported by Kruger and Finke in 1910
[16]. Subsequent experiments were then described
by Valeton et al., Nacken, Hostetter and Gerlach
[17—20]. The design of the three-zone crystallizer
system used in the present study was derived from
the earlier version of Christensen, Walker and
Kohman [2 1,22]. The system consists of three
chambers, viz., crystallizer, superheater. and
saturator, all of which are interconnected via
heated tubes, thus forming a closed loop system
548 G.M. Loiacono et a!.
271 SATURATOR
C-)
~ i_
40! CRYSTALLIZER / -
LSOLID KDP
Fig. 3. Schematic of three-zone crystallizer.
(fig. 3). The total internal volume of the system is
144 1. The main differences between the previously
described system and the new version are:
— all chambers are water jacketed for thermal
stability;
— growth solution contacts only Teflon and glass
surfaces;
— valve system to isolate each chamber;
— temperature controllers capable of maintaining
±0.005°C over the range 0 to 100°C;
— saturator contains 100 ~tm glass pre-filter;
— superheat chamber contains:
(i) a 0.6 ~.tm millipore filter;
(ii) submersible Teflon gear pump;
(iii) sufficient capacity to contain entire volume of
crystallizer chamber.
The jackets for the main chambers were fabri-
cated from commercially available stainless-steel
tanks. These tanks were modified by welding-in
dual observation ports and tube connections. The
inner chambers which contain the growth solution
were constructed from large Pyrex bell jars. These
jars were modified to permit the solution tubes to
penetrate the jar walls. All connections are con-
structed of Pyrex or Teflon. The water bath con-
tamed in the jacketed tanks is stirred by three
1500 RPM motors. The crystallizer chamber has a
/ Growth of KH,P0
4 crystals
STORAGE LEVEL
\\OPERA~NG LEVEL
SUPERHEATER
variable speed motor for rotating the seed tree.
The main saturator and superheat chambers are
each stirred by a high efficiency Teflon propeller
driven by a 1500 RPM motor. The solution pump
is powered by a variable speed motor. The solu-
tion flow was monitored by an in-line flowmeter
constructed of glass and Teflon. A minor problem
was observed with the pump rate in the initial
stages of the crystal growth cycle. During the
saturation period, a considerable amount of dirt
accumulated on the millipore filter, thereby re-
stricting the flow rate. To maintain a constant
solution-flow rate, it was found necessary to re-
place the filter just prior to loading the growth
solution and, subsequently, once again within 72 h
after initiation of the growth cycle. This technique
resulted in the maintenance of a flow rate (typi-
cally 4 1 h ~‘) stable to within ±0.5 1 h
The temperature of each chamber is controlled
by a YSI model 72 proportional temperature con-
troller using YSI series 400 thermistor probes for
temperature sensing *, The temperature stability
of the outer crystallizer chamber was measured
and continuously monitored for both long and
* Yellow Springs Instrumeni Company. Yellow Springs, OH,
(iSA.
 G.M. Loiacono et al. / Growth of KH, P0
4 crystals 549

short term stability. The short term stability was
better than ±0.001°C. while the long term drift
did not exceed ±0.005°C over a seven day period.
The temperature control and stability in this sys-
tern exceeds what is normally observed in a Holden
type crystallizer [23]. Note that the recorded tern-
perature is that of the jacketed bath; the tempera-
ture of the crystallizer chamber is at least a factor
of two more stable.
4. Experimental
ditions; therefore, the MCB No. PX1566 was the
best and was selected for further study.
Four solubility points were determined using
saturated solutions at pH 4.9. The data are in
excellent agreement with published values [51.
These data were then used to establish the correla-
tion between the temperature difference of the
crystallizer and saturation chambers (AT) and the
supersaturation for the three-zone crystallizer ex-
periments. The bulk supersaturation in the crystal-
lizer chamber is given by:
~C= C01 — C02, (5)

Three sources of KH2PO4 were investigated as
starting materials for the growth experiments. Each
material was evaluated by small scale growth in a
Holden type crystallizer using the temperature re-
duction method. Table 1 summarizes the results of
these experiments. The pH values listed are for the
saturated solutions at 22°C. Table 2 lists the im-
purity content as determined by mass and flame
emission spectrometry of the three materials tested.
While the Ultrex material appears to contain very
low levels of impurities normally associated with
color and tapering in KH2PO4, single crystals
grown from this material were green and had an
11 ° taper. The IMCB No. PX 1566 is a special low
absorbance grade of KH2PO4 and the tests showed
this material had less color than the Ultrex and 0°
taper. All of these materials were tested in the
same growth chamber under identical growth con-
where C01 is the saturation concentration at tem-
perature T1 of the saturator and C02 the saturation
concentration at temperature T2 of the crystallizer.
Using the solubility date and eq. (5), the rela-
tionship between the temperature differential of
the saturator and crystallizer chambers and the
actual bulk supersaturation was calculated. With
these data and the value of z~Cmax calculated from
eq. (4) for 35°C operation, it appears that the
upper limit of ~T is about 7.6°C.
4.1. Seed crystals
The seed crystals used in these experiments
measured 50 x 50)< 10 mm with the [001] per-
pendicular to the plate. Prior to loading, the plates
were water polished and beveled on one edge to
facilitate mounting. Initially the seeds were glued

Table I
Influence of KH2PO4 raw material on crystal growth by Holden technique

Ultrex °> MCB h) MCB

L#74—9l02 PX1565 PX1566
run No. 3—303 run No. 1—297 run No. 3—301

pH at 22°C 4.8 4.6 4.9

Saturation temperature (°C) 45.39 39.85 45.79
Volume (I) 2 1.7 2
dT/dt (°Cday ‘) 0.06 —‘0.15 0.05 —.0.3 0.05 —° 0.3
Seedstmm(OOl)l 25x25 25x25 25x25
Taper angle (deg) II 9 0
~T, total (°C) 11.1 8.8 10.5
Flowvelocity(cms’) 15 15 15
Yield (g I ‘ °C ‘) 6.34 — 6.86

Ultrex — J.T. Baker Chemical Co., NJ, USA.

h) MCB — MCB Manufacturing Chemists Inc., OH, USA.
550 G.M. Loiacono et a!. / Growth of KH,P0
4 crystals

Table 2 superheater to be no greater than 0.5°C.The time

Impurity analysis of KH2PO4 raw materials (ppm by weight) required for loading was fixed by the pump 1. After
rate
Element Ultrex MCB MCB and was typically
- 4 h at a rate of 10 1 h
L~74—9I02 PX1565 PX1566 the crystallizer chamber has been loaded with
solution, the temperature differential (/.~T) be-
Ba <2 5 tween the crystallizer and saturation chambers was
Bi <5 — adjusted to the desired level by increasing the
Ca 0.7 <100 <10 temperature of the saturator. Concurrent with this
Cd <0.4 - <10 operation, the temperature of the superheat cham-
Co <~ — <~ ber was raised to establish a differential of 10 to
Cr <5 <5 <5 -

Cu 07 <5 1 15 C with the crystallizer chamber. Thermal equi-

Fe 1 <20 <5 librium was established within 12 h. The temper-
Mg 0.3 <10 10 ature of the transfer tubing was usually adjusted to
Mn <1 <10 <5 coincide with the temperature of the superheat
Na 18 <100 <100 chamber.
Initial saturation of the bulk growth solution
Si 0.5 <10 10 required nearly seven days. The equilibrium at
saturation was determined by sampling the solu-
tion over a seven day period and measuring the
pH and gravimetrically determining the total
in place using Lucite holders previously described amount of dissolved solids.
[23]. However due to the large amount of X—Y The total growth along the [001] was measured
growth observed in the initial experiments, seeds by photographing the entire crystal, at fixed mag-
were subsequently mounted using pins in the nification, on a daily basis. These pictures were
classical Holden method [2]. Two growth runs (PL then analyzed and by use of a known dimension
17 and 18) were made using seeds in the form of (seed holder thickness), the growth in mm was
completed caps. calculated. The estimated accuracy of these mea-
surements is ±0.1mm.
4.2. Crystal growth parameters

The following growth parameters were held 5. Results and discussion

constant:
— solution pump rate: 4 ±0.51 h - 5.1. General
— solution velocity (at seeds): 15 cm s’;

— filters: saturator, 100 ~sm; superheater. 0.6 p.m;
— seed tree rotation sequence:
23 s CW: 6 s delay;
25 s CCW: 7 s delay,
The three parameters varied in the experiments
were the pH, supersaturation and growth temper-
ature.
The initial loading sequence was determined
empirically. Several attempts to load the crystal-
lizer with a high initial supersaturation resulted in
spurious nucleation. The procedure developed re-
quires the temperature differential between the
crystallizer and saturator to be less than 0.1°C.
and the differential between the crystallizer and
A total of ten growth experiments was made
with the new crystallizer system. The main objec-
tives of the experiments were to determine the
feasibility of a 5 mm day growth rate for large
optical quality KH-,P0
4.
The initial growth of KH2PO4 from a (001)
seed plate can be described as a capping process.
This involves the development of the {lOl) type
facets and is characterized by a period of rapid
growth accompanied by solvent inclusions. The
process is illustrated in fig. 4. The first indication
that growth has started is the appearance of a
frosting over the seed plates (t = 0). The (101)
facets then proceed to develop as shown, finally
 (., t/. / ala, an,, c’t a! (ir,,wil, a/. A/-/, !‘04 en ool.s 55 I

t=Oh

t= 12h t=48h t=72h

t=104h t=124h t=150h

1-ig. 4. Capping process in KH~PO

4.
552 G.M. Loiacono eta!. / Growth of KH,P0
4 crystal.s

Table 3

Summary of KH2PO4 crystal growth

Run pH at 22°C Pump flow Solution Growth Super- Average

No. rate velocity temperature saturation, growth rate
(I h~’) (cms~) (°C) itT [0011
(°C) (mm day ‘)
PL-I0 4.8 — — — — —

PL-11 4.8 2.1—4.7 31 29.0 1.0—4.0 0.8—1.6

PL-12 3.6 0.5—6.2 31 30.5 0.5—5.1 0.8—3.2
PL-13 3.8 1.0—2.3 31 35.7 1.9—5.2 1.7—6.3
PL-I4 2.9 4.1—6.1 31 35.1 0.04—1.9 1.6—4.2
PL-15 3.1 3.8—6.2 24 36.1 0.9—1.8 2.3
PL-16 2.6 3.0—7.4 31 34.1 2.0—4.8 4.1—5.5
PL-17 2.6 6.5 24 35.1 1.0
PL-18 2.2 4.8 24 35.1 3.1—4.0 0.9—3.4
PL-19 2.0 3.5—4.2 4—24—93 35.1 1.4 1.2—5.2

resulting in a completed cap. At this point, clear,
unflawed growth is observed and growth rate mea-
surements for the [001] are obtained by the photo-
graphic process. The total time required to estab-
lish the cap varied from 2 to 12 days, depending
on the supersaturation. This should be compared
with a typical capping time of from 4 to 8 weeks
for 5 X 5 cm seed plates grown by temperature
lowering in a Holden system [23].
The results of the growth experiments are sum-
marized in table 3. The first run (PL 10) was
aborted when the seed crystals fell out of their
holder due to excessive dissolution. This was a
direct result of attempting to load the crystallizer
before the saturator had reached equilibrium. Run
PL 17 was terminated in two days due to complete
blockage of the flow tubes.
5.2. Growth rate measurements
The measurement of growth rate in this study
was direct and relatively accurate. However, inter-
pretation and analysis were conplicated by several
factors. First, it became evident that the linear
growth measurements were taken before the super-
saturation had reached equilibrium. An analysis of
the total system volume and solution pump rate
predicted a minimum of 50 h to completely equi-
librate the growth solution after a temperature
change. This analysis assumed perfect mixing in
the various system chambers. It was experimen-
tally determined that equilibrium actually was
acieved in 140 to 160 h by analyzing the growth
rate data from PL 14 and 19.
Another problem in defining the growth rate
was the fact that opposite ends of the same boule
grew at significantly different rates. In addition.
measurements of (101) growth (4 per boule) also
demonstrated significant rate fluctuations. Table 4
summarizes the raw data on run PL 11. The growth
rates in the three orientations were calculated from
these data and are illustrated for the [001] in fig. 5.
It is apparent that the growth rate for a particular
crystallographic direction is not constant. One
possible cause of these fluctuations in rate could
be a nonuniform level of supersaturation near the
liquid/solid surface. This could arise from insuffi-
cient mixing of the growth solution due to made-
quate solution velocity across the growing crystal
surface. Partial confirmation of this assumption
was obtained in PL 19. Under a set of constant
growth conditions, the solution velocity was varied
from 4 to 93 cm/s. and the results indicated a
constant growth rate was achieved at higher solu-
tion velocity. Further work is needed to corn-
pletely understand and develop a procedure for
controlling this behavior. In view of the difficulties
described above, the growth rates for these experi-
ments were calculated by averaging four [0011 and
eight (101) measurements.
 G.M. Loiacono et al. / Growth of K/-I ,P0
4 crystals 553

Table 4 5.3. X— Y growth

Growth rate of KH2PO4 (PL II)(mm day~)(pH 4.8, itT=
2.0°C, T= 29°C, V= 15 cm s~’) There are numerous references in the literature
Time Growth Growth rate Growth rate regarding the effect of pH and impurities on X— Y
(h) direction seed No. I seed No.2 growth in KH2PO4 [3,5,24—29]. The taper effect is
Left Right Left Right also described and discussed in these references.
24 [0011 0.9 1.5 0.8 0.8
While there is no clear consensus, the general
[1011 00 0.6 0.4 0.3 conclusions can be summarized in two statements:
11101 0.0 0.4 0.3 0.0 — The more acidic the growth solution, the less
48 10011 1 0 (.5 1.0 0.7 growth in the X— Y directions.
[101] 1.0 0.9 II 1.4 — Taper is caused by the presence of impurities
3~and Fe3~.The in
72 11101
[0011 1.0
1.2 1.4
0.2 0.8
1.6 2.7
1.3 the growth solution, typically Cr
green color observed is due to incorporation of
[1011 1.4 0.9 1.4 1.1 Cr3t
[1101 2.4 0.8 1.2 0.2 The results of the present experiments demon-
144 [00l[ 1.6 1.6 1.6 1.6
strate that these statements are not applicable to
[101] 1.2 1.2 07 0.7 the growth conditions used in this study. X—Y
[1101 0.7 0.2 0.9 0.9 growth has been observed over the entire pH range
of 2.0 to 4.9. Based on the work of Mullin et a]., it
168 [001] 1.4 1.2 0.8 1.5
[101] 0.1 0.6 0.7 05 would appear that the dominant factor affecting
[110[ 0.1 0.3 1.1 1.2 both X—Y growth and taper is the supersaturation
and not the pH or impurities [24,30]. This behav-
ior is discussed in more detail in a separate paper
[311.

3.0 —

• . [001] L SEED #1
o——--o [0O1]R
£ [001] L SEED #2
~~—----e~
[0o1]R

2.0

U
I-
~

I
I—

1.0
0

0 I I I
0 20 40 60 80 100 120 140 160 180 200

TIME, h

Fig. 5. Variation of crystal growth rate in KH

2PO4.
554 G.M. Loiacono eta!. / Growth of KH,P0
4 crystals

5.4. Maximum growth rate of KH,P04
The results shown in table 3 clearly demon-
strate that growth rates up to 6.3 mm day can
be obtained for KH2PO4 when growth occurs
under the conditions of constant temperature and
supersaturation. The maximum growth rate is de-
fined as the rate at which visible defects are first
generated. The literature has numerous references
to a “critical growth rate”, with the assumption
that the larger the crystal, the lower the critical
rate [32—35]. However, in none of these references
is an actual critical growth 2rate cited. section.
in cross Run PLThe15
for KH2PO4 has not been determined but is cer-
tainly above the 5 mm day level.
The average growth rates observed from runs
PL 11 through PL 14 are shown in fig. 6. The
growth rate dependence on supersaturation, or
temperature differential (AT), was compared with
the data of Mullin et al. and Nicolau [30,411.
These results are summarized in fig. 7 and show
good agreement. Only three of Mullin’s data points
would fit this graph because at a z~Tof 6.5°C and
growth temperature of 35°C, his growth rate was
above 15 mm day . Also, no data points at
i~T=2°Cinwere
observed theirobtained because
system below i~tCgrowth was not
= 2g/lOOgH

used a seed plate 161.3 cm 2O

results of this experiment show that increasing
2 had the
no observa- which is equivalent to a ~T= 3.2°C. Growth
observed in the present study even below this was
sizeeffect
ble of theon
seed plate rate
growth fromin25comparison
cm with other value, as shown in the figure. The spread in growth
experiments under similar growth conditions. Ref- rate values between 0.7 to 3.5 mm’day at ~XT=
erences to “fast” growth rates also occur fre- 2°C is indicative of the absence of equilibrium
quently in the literature. The first, for NH
4H2PO4, during these experiments.
was given by Walker in 1947 [36]. In particular for A few comments regarding the data presented
KH2PO4 growth rates as high as 16 to 35 mm in fig. 7 should be considered. The maximum
day~ are reported [27,30], and typical rates of 5 values shown for i~T=1.4 and 1.9°C are true
to 10 mm day~ cited [11,27,37—401. From the equilibrium values. The three data points at LXT=
results of this present study and the literature 5.2°C show that the growth rate was increasing,
cited, it is clear that the maximum rate of growth and the point at 6.3 mm day ‘ is not a true

8.
o~—o PL—11
-‘ .—. PL-12
7
0—0 PL—13

a—~-a PL-14
E 6-
E
w
H

I a
4’ 2

0
o ~.

w a
0
~ 2-~ a
>

1- °

0 I I I I I I I I i I
0 20 40 60 80 100 120 140 160 180 200 220 240

TIME, h
Fig. 6. Average growth rates for KH,P04 [001].
 G.M. Lolacono et at. / Growth of KH,P0
4 crystals 555

12 - - 0 growth rates did not affect the optical quality of

• PRESENT WORK KH2PO4.
11 - 0 MULLIN [24] Two representative samples were tested at the
A NICOLAU [35] Lawrence Livermore Laboratories for laser damage
10 [42,43]. Single shot threshold values of 8.4 and 8.1
J cm~ were measured, which are equivalent to
- median values obtained from commercially availa-
V ble KH2PO4. In addition, laser peak fluxes of
8 - 15—16 J cm~ did not appear to increase the total
uI number of damage sites.
I-
< 7 - An X-ray topographic study of the crystals is
- presently in progress [44]. Preliminary results mdi-
F-’
~ 6 - cate that the defect density is not significantly
- different from crystals grown at lower rates.
0
w
0
w 4 6. Conclusions
>
S
3 • . . -• The results of this study clearly show that in a
three-zone crystallizer, under conditions of con-
S
2 - 8 * • stant supersaturation and growth temperature,
growth rates in excess of 5 mm day are possible
S
1 - 8 for large KH2PO4 crystals. The maximum rate of
growth lies somewhere above this value and could

0
8
1
I I
2 3
I
4 5
I I6 I
~ be in the 10 was
crystallizer to 15shown
mm day
to be region. The three-zone
a superior apparatus

~T, °c in comparison to the Holden crystallizer for grow-

Fig. 7. Maximum growth rates for KH2PO4 [001]. ing crystals from solution — in particular KH2PO4.

maximum because the experiment was terminated
due to flow problems in the system. Similar flow
problems were encountered with the data points at
~T= 2.1 and 4°C.With these facts considered, an
assumption can he made that the maximum growth
rate lies above the highest data points shown in
fig. 7. Further experimental studies are in progress.
5.5. Crystal quality
The crystals grown in these experiments were
examined by the laser scattering technique using a
He—Ne laser. In particular, scattering was sought
in the <l0l~ because the variation of growth rates
may have caused inclusions or veils which were
not visible to the eye. None of the crystals ex-
hibited scattering. This indicates that the fast
Acknowledgements
This study was partially supported by Contract
No. 1738801 from the Lawrence Livermore Na-
tional Laboratory. The authors would like to thank
S.E. Stokowski for many fruitful discussions and
J.E. Swain for the laser damage testing of our
crytals.
Special acknowledgement and thanks are due to
P. Bennema and his staff at Catholic University,
Nijmegen, The Netherlands, for stimulating theo-
retical discussions and a demonstration of his
three-zone system.
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