Materials"Science and EngineeringA, 102 (1988) L1 -L4
Letter
An ImprovedBridgman-Stockbarger
Crystal-Growth System
D. NICOAR~ and l. NICOARJk
Department of Physics, Universityof Timi~oara, 1900
Timi~oara (Romania)
(Received February 2, 1987; in revised form April 7, 1988)
Abstract
A n improved type of heater for crystal growth,
using the vertical Bridgman technique, is presented.
With its help, C a ~ single crystals of good optical
quality were obtained.
The use of the vertical Bridgman technique [1]
for the production of single crystals is based in part
on its simplicity, the relative ease with which com-
plete automation can be achieved, and also on its
applicability to a wide range of materials. The main
problems involved in crystal growth are polycrystal-
linty, cracking and variable optical quality. The
analysis of heat flow in directional solidification and
crystal growth by Bridgman-type processes has
recently received considerable attention [2-5]. The
shape of the solid-liquid interface is an important
factor in this type of growth since it influences the
stress, the incidence of polycrystallinity, the chemi-
cal perfection of doped crystals and the optical
quality of transparent crystals.
In the design of vertical Bridgman-type direc-
tional solidification experiments it is important to
predict the thermal profiles in the specimen. The
position and shape of the solidification interface
and the axial thermal gradients on each side of the
interface are of particular interest in controlling the
process.
Fu and Wilcox [3] investigated the possibility of a
three-zone furnace, i.e. one in which the hot and
cold zones were separated by a short "isolated"
zone, their computer modelling using a finite differ-
ence scheme. It was shown that the use of an iso-
lated zone significantly reduced the curvature of the
0921-5093/88/$3.50
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isotherms between the hot and cold zones and
allowed for much better control over the shape of
the melt interface. The gradient between zones is
directly dependent on this isolation [6, 7].
The relatively high axial temperature gradient
necessary in order to obtain crystals with large
diameters (~b> 20 mm) cannot be obtained by means
of a single heating element; two independently con-
trolled heaters, between which a high temperature
gradient is obtained, are necessary. Difficulties arise
when ordinary resistance heating (kanthal, for in-
stance) can no longer be used in the process of
growing crystals with melting points above 1300 C,
when graphite, molybdenum, silicon carbide etc.
heaters must be used. The use of graphite heaters in
the vertical Bridgman technique is not new [8-11]
but the high temperature gradient necessary at the
crystallization interface is obtained either by sup-
plementary heaters [8, 11], by thermic screen trans-
lation [9] or by using two heaters with a moving
temperature gradient and a stationary crucible [ 10].
Taking into consideration the analysis of Jasinski
et al. [5], which recommends a certain proportion
between the lengths of the three zones -- hot, cold
and gradient zone -- relative to the diameter and
the length of the crystal, several types of graphite
heaters have been designed [12-14] whose char-
acteristics would satisfy the above-mentioned
demands.
In the present paper we propose a new type of
graphite heater which eliminates the need to use
two heating elements independently controlled and
with an intermediate diaphragm as recommended in
the Bridgman technique; this heater can produce
temperatures of up to 2200C in a vacuum of
10-4_10 5 Torr. The model contains an "isolated"
zone and a booster-heater zone that can be used to
increase the thermal gradient near the solidification
interface. A scheme of the Bridgman-type furnace
used in the present study is shown in Fig. 1. For a
working temperature of 1400C the electrical
power is 4.2 kW with a voltage supply of 16 V and
50 Hz, and is about 8 kW for a temperature of
2200 C; an electronic control and automation sys-
tem ensures the thermal stability of the furnace. In
order to eliminate the vibration produced by the
lowering system a magnetofluidic fitting is used.
Elsevier Sequoia/Printed in The Netherlands
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Fig. 1. Scheme of the crystal growth apparatus: (1) water-
cooled wall; (2) crucible; (3) screens; (4) graphite heater; (5)
to vacuum pump; (6) water-cooled power line; (7) lowering
mechanismwith a magnetofluidicfitting.
Figure 2 illustrates the longitudinal section of the
three types of heaters and the corresponding axial
temperature distribution. The type HI furnace pro-
duces a relatively fiat temperature profile in the hot
N I
g l ix.\ I
I
I
I
, I
m 1200 1250130013501400
Temperature (C)
Fig. 2. Longitudinal section of the three types of heaters and
the temperature distributions along them.
zone B-C, necessary for the melting of the sub-
stance. The booster heater (C zone for type I) is
designed as a meander-type resistance heater by
means of which the maximum temperature is
obtained in the upper zone of the heater. The D
zone is inserted for heat-transfer improvement to-
wards the upper part of the heater, while the E
zone, which consists of a wall thickening, acts as an
"isolated" zone, necessary to produce the high tem-
perature gradient. In order to avoid thermal losses,
the graphite heater is surrounded by a set of con-
centric screens made of molybdenbum, graphite
and stainless steel. The necessary temperature
gradient during crystal growth is obtained in the
D - E zone; when the type I furnace is used the tem-
perature distribution inside it is such that the
desired temperature gradient is obtained starting
from the mid-part of the C zone.
Taking into account the analysis made by Jasinski
et al. [5], the length of the zones is chosen according
to the characteristics of the crystal which is to be
grown (diameter, length, heat capacity, thermal con-
ductivity), ensuring the necessary dimension of the
temperature-gradient zone for obtaining an approx-
imately flat solid-melt interface during crystal
growth. By decanting experiments the melt-solid
interface shape was studied and shown to be
approximately flat which demonstrates that the fur-
nace characteristics and growth parameters were

well chosen. Curve I in Fig. 2 represents the tem-
perature distribution in the type I furnace when no
crystal is grown. The temperature distribution
within the furnace is measured by means of a
P t - R h - P t thermocouple which is moved along the
furnace axis. During crystal growth, the tempera-
ture is also measured by placing the thermocouple
within the lower part of the crucible, about 1 mm
from the starting part of the growing crystal; curve
I a is the temperature recorded during the growth of
a crystal 30 mm in diameter at a growth rate of 4
nun h- 1 using the type I furnace. By comparing the
two curves I and I a one can see that the furnace
parameters were well chosen, the axial temperature
distribution remaining approximately stable, which
ensures proper conditions for crystal growth.
By using all three types of heater mentioned
above, fluoride single crystals with a diameter of up
to 50 mm and 150 nun in length were obtained (Fig.
3). For crystals with diameters less than 20 mm,
type 1I or type HI heaters could be employed, the
temperature distribution along the furnace being
appropriate. In order to grow crystals up to 10 mm
in diameter the meander zone C is not necessary,
the temperature profile being realized by wall-
thickness modification of the heating element.
The quality of the crystals was studied by exam-
ining the dislocation-density distribution using a
method described elsewhere [15]. Dislocation dis-
tribution analysis taken at different levels of the
etched cross-section of crystals grown under differ-
ent conditions indicates that crystals of different
diameter, but with about the same dislocation den-
sity of 1 0 4 cm -2, can be obtained by taking into
consideration the following conditions.
(i) For crystals with small diameters ( 4 = 6 - 1 2
nun) the necessary temperature gradient is 7-10 K
cm 1 for pulling rates of about 5-6 mm h - 1 (condi-
Fig. 3. P h o t o g r a p h of various C a F 2 crystals.
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tions offered by the simplest construction of the
type III heater (Fig. 2)), the temperature profile
being obtained by choosing the correct wall thick-
ness for the heating element and the appropriate
screens. Since the necessary temperature gradient is
reached under the E zone the crucible is positioned
in such a way as to obtain the optimum conditions
for crystal growth.
(ii) The type Ii furnace is used in order to pro-
duce crystals 12-26 mm in diameter with the same
dislocation density of 104 cm-2; since a higher tem-
perature gradient (10-15 K cm -I) is necessary, the
crucible position is determined accordingly by the
fact that the above-mentioned temperature gradient
is reached within and under the E zone (Fig. 2,
curve II).
(iii) The type III heaters are useful when crystals
of large diameter (~b>26 mm) are grown with a
pulling rate of about 3-5 mm h-1 and a tempera-
ture gradient of 20 K cm-1. According to the
screens used this temperature gradient is obtained
starting from the mid-part of the C zone and up to
the E zone.
25 5 I0 2 . 5 ~.m
I 00 ~ ~ -v------'--"- ~--'~ '
8O
~ 4 0
2O
0 ,
40 ~o 2'o 5
x I 0 0 cm - I
Fig. 4. IR transmission of a C a F 2 crystal 1 m m thick.
_ _ "
Fig. 5. Typical dislocation distribution on a (111) cleavage
surface of C a F 2 crystals. T h e etch conditions were 2 N HC1
at 30 C for 1 h.
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The crystals were grown from "ultrarein" C a F 2
from Merck Co., Darmstadt, ER.G. Using the con-
ditions mentioned above the crystals have no twins
or voids but are clear, colourless and have good
cleavage surfaces. The transmission coefficient was
measured by Specord UV-VIS and Specord type-
C, Zeiss-Jena spectrophotometers. Regardless of
the crystal diameter, for a cleaved slide 1 m m thick,
the transmission coefficient is about 98% in both
visible and IR regions up to 9 p m for CaFz and
1 2 / t m for B a F 2 (Fig. 4).
The dislocation density of the crystals, on aver-
age 104 cm -2, was determined by employing the
above-mentioned method [15]; sometimes in crys-
tals of large diameter ( 4 > 35 nun) the dislocation
density reaches 105-106 cm -2. The typical disloca-
tion distribution on a (111) cleavage surface is
shown in Fig. 5 with the etch conditions being 2N
HC1 at 30C for 1 h. By examination b e t w e e n
crossed polars, the birefringence of crystals up to
30 m m in diameter is about 20 nm cm -1 and
reaches 30 nm cm-~, owing to thermal stresses, in
the case of crystals of larger diameters.
The major advantage of these types of heaters is
in the complete automation of the growth process,
because the axial temperature distribution is
reproducible if the power supply is constant. At the
same time, it is possible to reduce the thermal
stresses by subsequent heating of the crystal within
the same set-up and allowing it a more gradual
cooling rate to room temperature. After the crystal
pulling is finished, the crucible is raised in the B - C
zone and by using an automatic system the power
supply is gradually lowered. From our experiments
it can be concluded that the use of these types of
heaters (built as a single body) in the vertical Bridg-
man technique to obtain high quality fluoride crys-
tals is advantageous because the same heater can be
used for about one hundred growth cycles, the
process being reproducible and easy to control.
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