J. Phys. Chem. Solids Pergamon Press 1964. Vol. 25, pp. 1407-1415. Printed in Great Britain.

THE GROWTH OF SEMICONDUCTOR CRYSTALS

FROM SOLUTION USING THE TWIN-PLANE
REENTRANT-EDGE MECHANISM
J. W. FAUST, Jr. and H. F. JOHN

Westinghouse Research Laboratories, Pittsburgh 35, Pa.

(Received 16 March 1964; in revised form 21 May 1964)

Abstract-Experimental conditions are described for growing crystals of diamond lattice and zinc
blende semiconductors from metal solutions using the twin plane reentrant edge mechanism. In
addition to the expected (. 2111 type
-_ twinned platelets, some unusual < 110 > extended forms with
intersecting twin configurations were obtained.-Etch techniques were used to study microresistivity
striations and to determine the growth history of the platelets. The relative number of nucleation
events at different sites and the possible effect of polarity on the growth of III-V compound platelets
are discussed. Electrical measurements are reported on some of the platelets.

1. INTRODUCTION rate at this twin plane reentrant edge (TPRE) will

THE growing interface of a crystal can under cer-
tain conditions be faceted with the result that the
crystal has a definite geometric shape, being
bounded by its slowest growing faces. When a
perfect crystal is completely bounded by its slowest
growing faces, a two-dimensional nucleation event
is necessary to start each new growth layer. Since
two dimensional nucleation is a relatively difficult
process, an appreciable undercooling or super-
saturation can build up in front of a faceted
interface.
Certain imperfections in the crystal surface aid
in layer initiation by creating sites for easy nuclea-
tion. If the imperfection has a specific direction,
as is the case with a screw dislocation, there will be
extended growth of the crystal in the direction of
the imperfection. Other sites for easy nucleation
were first formally discussed by STRANSKI;(~) these
embody various types of reentrant edges. An
effective means of producing a reentrant edge in
certain crystal systems is by the twinning operation.
In any orientation where the twin boundary does
not make an angle of 90” with the bounding crystal
planes, a reentrant edge will be formed which may
be a site for easy nucleation. For a given interfacial
undercooling or supersaturation the nucleation
5 1407
be much higher than on the faceted surfaces or
sharp corners.
The basic requirements for extended TPRE
growth have been given by JOHN and FAUST.(~)
These are, in somewhat amplified form:
(1) The embryo nucleus must contain one or
more twin planes.
(4 The growth front of the material must be
faceted.
(3) The twin plane must intersect one or more
stable facets at an angle different from 90”.
(4) The reentrancies must be indestructible,
i.e. any initial reentrancy must not fill in to
form a closed figure bounded by planes and
sharp corners.
(5) The growth direction must lie in the twin
planes.
Four crystal systems are presently known to meet
these requirements. They are the orthorhombic
requiring one twin plane,@) the hexagonal re-
quiring one twin plane for twinning in the (0001)
plane,@) the f.c.c. (including the diamond cubic
and zinc blende) requiring two twin planes for
(111) facetingcb-7) and one twin plane for (111)
and { 113) faceting, @) and the rhombohedral
requiring one twin plane.tg)
 1408 J. W. FAUST,
Growth from dilute solution is a very effective
means of utilizing the TPRE mech~ism because
of the strong tendency for faceted surfaces to form
and because the degree of supersaturation can be
carefully controlled over a wide range by adjusting
the cooling rate. In this paper we shall describe a
technique for growing twinned crystals of the
diamond cubic and zinc blende semiconductors
from liquid metal solutions and shall discuss some
of the information on nucleation and segregation
phenomena which can be obtained from the study
of these twinned crystals. In addition to the ex-
pected twinned platelets growing in the <211>
directions, a number of (110) crystal forms con-
taining intersecting twins were observed, some of
which apparently propagate because of preferred
nucleation at mismatch boundaries.
2. GROWTH OF THE TWDINED CRYSTALS
Figure 1 illustrates the generalized conditions
for obtaining TPRE growth from solution. When
the temperature of a solution containing the dis-
solved material is lowered past the liquidus tem-
perature I’B, no crystallization will occur im-
mediately unless nuclei are present. If the tem-
perature is lowered further, eventually sufficient
supersaturation will build up so that nuclei will
form spontaneously throughout the solution. Once
this happens, say at TQ, the supersaturation can be
relieved by growth onto these nuclei, restoring the
solution to the composition required by the
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Composition
Frc. 1. Generalized conditions For obtaining twinned
platelet growth from solution.
Jr. and H. F. JOHN
liquidus curve. If subsequent incremental de-
creases in temperature are small, all material which
comes out of solution will crystallize onto the
original nuclei. Some, or perhaps many, of the
original nuclei will be twinned. As shown in Fig. 2,
the presence of two or more twin planes provides
an indestructible reentrancy in the diamond cubic
or zinc blende crystal systems. Nucleation will be
easier at the grooves (G) than at the ridges (R) or
on the (112) faces. A growth form will be obtained
whose greatest extension will be in the (211 j
FIG. 2. Idealized three twin platelet bounded by (111)
planes.
d’erection. If the supersaturation is kept low by slow
cooling after the formation of the original nuclei
at Tc, only those nuclei which contain twin
planes will grow further. If the cooling rate is fast
so that a high supersaturation is built up, the
presence of reentrancies will be relatively of much
less advantage. In such a case the edges will be
favored growth sites, and the familiar “hopper”
growth will be obtained, as illustrated in Fig. 3
for Ge grown from an In solution cooled initially
at rate of about lOO”C[min.
Representative solutions and experimental con-
ditions for obtaining twinned platelets are listed
in Table 1 for Ge, Si, most of the III-V com-
compound, and one ternary
semiconductor with zinc blende structure. Com-
position (wt per cent) of the solute is given in
terms of the element if the solution was prepared
from the elements and in terms of the compound if
the solution was prepared by adding the compound
directly. The solubility of AlAs and &Se in AI
and Zn is quite Iow, so undissolved material as
well as recrystallized material was present at the
FIG. 3. Ge crystal exhibiting hopper growth, obtained from a
rapidly cooled In solution. 50 x .

[facing page 1408

FIG. S(a) InAs twinned platelet grown from In. 100 x .

FIG. S(b). Si twinned platelet grown from Sn. 100 x.

FIG. 7. Etched cross section of a five twin < llO> form near the tip. 50x.

FIG. 10. Cross section of < 110) Ge platelet with a Class IId twin structure.

FIG. 11. Segregation traces in an InAs two twin platelet. 200 x .

FIG. 12. Segregation traces in a GaSb twinned platelet grown
from Ga + Te + Zn. 200 x .

FIG. 13. (100) faceting at the apex of a GaAs platelet.

50x.
SEMICONDUCTOR CRYSTALS USING THE TWIN-PLANE
end of the experiments. The temperature used for
the AlP experiment (1OOO’C) was not sufficiently
high to take enough material into solution to
obtain conclusive results. Numerous other solu-
tions were prepared to study the segregation of im-
purities and to determine the influence of impuri-
ties on growth habit. The r/t values tabulated
are a measure of the length to thickness ratio of the
platelets and are useful for determining the rela-
tive number of layer creation events at the TPRE.
Figure 4 shows the geometry of a two-twin hex-
agonal and triangular platelet and defines r and t.
The dl/dz values are the ratios of the distance of
the two large (11 l} faces from the twin planes, the
significance of which will be discussed later.
-a-
Face View of Hexagonal and Triangular Forms
of Qll> Type Twinned Platelet
-et; 32
0 1
Side View of <211> Type Twinned Platelet
FIG. 4. Geometry of the twinned platelets.
Many of the (211) type platelets grown under
the conditions shown there are a few mm long and
a few tenths of a mm thick. The most perfect of
the (211) platelets have a hexagonal shape,
usually intermediate between a regular hexagon
and an equilateral triangle. Figure 5(a) shows an
InAs platelet of intermediate hexagonal form.
Figure 5(b) shows a side view of a thick Si platelet
on which the twin plane reentrancies can be seen.
There is one reentrant edge in each of the (211)
directions in a two twin platelet and two reentrant
edges in the three (2if) directions, but only one
REENTRANT-EDGE MECHANISM 1409
in the (211 ), in a three twin platelet. Thus, it
might be expected that the platelets with two
(or an even number) twin planes would tend to be
hexagonal and the platelets with three (or an odd
number) twin planes would approach a triangular
shape, with the growth being greater in the (2ii)
directions. This is apparently an oversimplification
because no consistent correlation of shape with
number of twin planes has been found. The better
formed platelets have very perfect facets. In
general, however, the majority of the platelets are
not perfectly formed, but exhibit distortion and
somewhat imperfect development due to mutual
interference during growth. The more perfectly
formed platelets, and particularly those from melts
cooled at slower rates, are generally free of in-
clusions of the solvent metal.
The data in Table 1 show that a fairly wide
range of cooling rates can be used for obtaining
the TPRE forms. Although no attempt was made
to optimize the cooling rate or to determine the
range which would yield TPRE forms, at least 90
per cent of the crystals obtained from most of
these melts were twinned. Neither was any attempt
made to assess the effect of the rate of cooling
between TA and TC on the formation of twinned
nuclei nor to determine what value of Tc was
actually necessary to produce the first nuclei.
Except for a few melts where the solubility of the
semiconductor was very low or imperfectly known,
TA was chosen several degrees above the liquidus
temperature TB. In most cases the melt was cooled
from TA at a uniform linear rate using a tempera-
ture programmer. Decreasing the control tempera-
ture manually in discrete intervals of lo-20°C to
give the same average cooling rate gave essentially
the same results. The size of these experimental
melts ranged from 2 to 20 g. Melts with volatile
constituents were always prepared in sealed quartz
capsules. Quartz or graphite containers were used
for the melts.
3. INTERSECTING TWIN CONFIGURATIONS
In addition to the (211) type twinned platelets
shown in Figs. 2 and 5, forms with extended
growth in the (110) directions were found in
many melts. Examination of these crystals showed
that they contained intersecting twin configura-
tions extending in the direction of growth. These
twin configurations fall into two general classes.
1410 J. W. FAUST, Jr. and H. F. JOHN

Table 1. Experimental conditions for solution growth of twinned platelets

Cooling
Composition TA rate
No. Solute Solvent (wt %) (“C) ‘/min rlt &/ds Comments

1 Ge Ga 30% Ge 600 0.7 1.7 1.3 Good segregation traces ; <211>

platelets and (110 ) intersecting
forms
2 Ge Sn 2.2% Ge 590 o-15 -1 <211) and <llO> forms
3 Ge Al 60% Ge 700 0.30 1.1 Good segregation traces; mostly
<211) platelets
4 Ge Cd 10% Ge 650 0.7 1.4 1.4 No segregation traces
5 Ge Sb 13% Ge 700 0.7 Good segregation traces
6 Si Al 25% Si 800 0.7 5.9 1.4 Excellent segregation traces ; (211>
platelets only
7 Si Ga 4.5% Si 980 1.5 0.8 Excellent segregation traces. Many
<llO> forms
8 Si Ag 5% Si 1000 0.7 0.8 1.3 Mostly (211> platelets, some
octahedra
9 Si Zn 1% Si 850 0.7 (1 -1 Octahedra, (211> and <llO) forms.
10 Si Sn 1.5% Si 980 1.5 0.8 Many <llO> forms
11 Si Sn 0.8% Si 1050 0.15 0.8 1.1 <211) and (110) forms; larger
crystals than those from melt cooled
at 1 .SO/min
12 Si Au 6.5% Si 800 0.7 0.75 A few <211) platelets and many
regular octahedra. (110) facets in
addition to { 111)
13 Si Au+Sb 6.5% Si, 0.5% Sb 800 0.7 1.0 Excellent segregation traces; <211>
platelets only
14 Si Au+Ga 6% Si, 7% Ga 1000 0.7 0.8 { 110) facets in addition to { 111)
15 GaSb Ga 17% Sb 650 0.7 2.08 1.84 Very good (211> platelets; (100)
faceting
16 GaSb Sn 15% GaSb 650 0.7 1.0 Good <211> platelets, segregation
traces; only slight (100) faceting
17 GaSb Pb 8% GaSb 650 0.7 0.9 Good <211> platelets; {lOO} faceting
18 GaSb Sb 7% Ga 710 0.7 -2 Very good <211) platelets
19 GaSb Ga 17% Sb+O.OSS% Te 650 0.7 0.8 Generally conform to standard
<211> platelet shape
20 GaSb Ga 17% Sb+O.ll% Te 650 0.7 -0.25
21 GaSb Ga 17% Sb+O*SS% Te 650 0.7 Twins present, but very little
platelet character
22 GaSb Ga 17% Sb+0.056% Zn 650 0.7 1.4 Well-shaped <211> platelets
23 GaSb Ga 17% Sb+0.056% Zn 650 0.2 1.9 -2
24 GaSb Ga 17% Sb+O.SS’% Zn 650 0.7 1.9 1.8 Good <211) platelets
25 GaSb Ga 0.28% Zn+0.055% Te 650 0.7 Platelets more typical of Te doping
than Zn doping
26 InSb In 23% Sb 480 0.7 0.90 2.54 Crystals rather irregular, mostly
<211> type; {loo} faceting
27 InSb In+Zn 23% Sb+0*3% Zn 480 0.7 Good segregation traces
28 InSb In+Te 23% Sb+l% Te 480 0.7 Good segregation traces
29 InSb Hg 5% InSb 325 0.7 2.0 240 Well developed <211> platelets,
more perfect than from In; segrega-
tion traces present
30 InAs In 23% InAs 800 0.7 2.54 1.70 Excellent (211) platelets; { 100)
faceting
31 InP In 20% InP 970 0.7 1.90 1.65 Excellent (211> platelets ; { 100)
faceting
SEMICONDUCTOR CRYSTALS USING THE TWIN-PLANE REENTRANT-EDGE MECHANISM 1411

Table l-continued

Cooling
Composition TA rate
No. Solute Solvent (wt %) (“C) “/min rlt dllds Comments

32 GaAs Ga 20% GaAs 1050 1.3 2.2 2.0 Excellent (211> platelets; promi-
nent { lOO} faceting
33 GaP Ga 1.3% GaP 1050 0.7 1.6 1.6 Relatively small <211) platelets with
{ 100) faceting
34 GaP Sn 0.7% GaP 1050 0.5 Poorly formed, black platelets ;
segregation traces
35 AlSb Al 8% Sb 960 0.7 2.2 2.4 Excellent (211> platelets ; { lOO}
faceting
36 AlAs Al 3.2% As, 950 1.3 Very small twinned platelets
37 SnZnAsa Sn 1.4% Zn 800 1.3 Small well formed twinned platelets
38 ZnSe Zn 3 ‘A ZnSe 950 1.3 Very small twinned platelets

What we shall call Class I consist of those con-
figurations which contain single twins radiating
from a common point. The cross-sections of these
forms are irregular. In most cases they contain a
mismatch boundary in addition to twin planes.
Since there are no true twin plane reentrancies in
the direction of growth, these crystals must pro-
pagate by means of a different kind of directed
imperfection. According to the standard treatment
of interphase interfaces, the angle 0 formed in a
two-phase system at a grain boundary is
cos (O/2) = y11py12
Fig. 6. This form is apparently a favorable one for
extended propagation, since it is often much
longer than other twinned forms obtained from
the same melt. Cross-section analyses, such as
shown in Fig. 7, of these forms confirm this
structure. The five twins and the mismatch
boundary, radiating from a common point, can be
seen in this cross-section. Micro-resistivity stria-
tions can also be seen and will be discussed later.
Three types of reentrancies are present on the
side of this type of crystal. The monocrystalline
reentrancy (II) usually fills out. Reentrancies I

where yu is the interfacial free energy of the grain

boundary interface and yls is the interfacial free
energy between the two phases. Since the energy
of this type of mismatch boundary would be
expected to be relatively high, particularly when 4
compared to the low energy of a twin boundary, it
is thus possible that a stable reentrancy is created
at the mismatch boundary. However, an analysis
which incorporates the effect of torque terms, of the
type developed by HERRING,@@ along with a
knowledge of the values of ~1 and yla and their
variation with orientation, would be necessary to
describe quantitatively such a reentrancy.
Class II configurations contain at least one
multi-twin grouping and no mismatch boundary. --------Mismatch Boundary
The cross-section is more regular and is bounded A = 70’ 32’
by parallel (111) planes. These structures can be B = 77o 52’
propagated by the same TPRE mechanism which
operates for the ( 211 > type twinned platelets.
One of the most prevalent of the Class I con-
figurations is that containing five twins as shown in FIG. 6. Class I configuration with five twins.
1412 J. W. FAUST,
and III are apparently not as effective sites for
nucleation as that which exists on the tip of the
crystal, since the growth is much greater axially
than radially. This five twin intersecting configura-
tion has apparently been found in diamond
crystals grown by high pressure techniques.(ll)
For diamond, however, it has been reported that
the area between the first and last twin is filled with
polycrystalline material, while in this work the area
is a single crystal with a mismatch boundary. A
five-fold symmetry has also been reported in
copper crystals produced by electrodeposition.
Class I configurations can be visualized as
twinning joined at a central point with each suc-
cessive twin plane spaced 70” 32’ apart. In addition
to the five twin structure, a number of other
structures can be obtained, as shown in Fig. 8.
. = Mismatch Boundary
d
--- = att#N;fwth
for Monocrystalline
FIG. 8. Class I configurations.
An easy way of studying these drawings and of
“building” other possible configurations is to con-
sider them as made up of basic rhombohedral
blocks (untwinned) bounded by (11 l} planes. Two
blocks may be put together in a twinned or un-
twinned relationship; however, the twinning laws
must be obeyed when they are placed together in a
twinned relationship. The drawings are (110)
cross-sections and growth extends perpendicular
Jr. and H. F. JOHN
to the section. The dashed lines indicate mono-
crystalline reentrancies which will normally grow
out. It will be noticed that there will be a mis-
match boundary in one segment of the cross section
in all cases except structures a and g in Fig. 8.
This mismatch boundary is necessary because the
twinning operations do not return to the same
orientation.
Most of the structures shown in Fig. 8 have been
encountered in more or less perfect form. Con-
figurations a and g, which have no mismatch
boundary to aid in directed growth, are relatively
rare and may simply be freak forms with no special
ability for extended growth.
Several possible Class II configurations are
sketched in Fig. 9. It is a necessary, but not suffi-
cient, condition that the sum of the twin planes in
a path around the periphery be even in Class II
configurations. An odd number of twin planes
requires that one of the rhombohedral blocks
contain an internal boundary (other than a twin
boundary) as was shown for Class I structures.
Structures a and d have occasionally been ob-
served during solution growth for Ge, Si and
C f
FIG. 9. Class II configurations.
SEMICONDUCTOR CRYSTALS USING THE TWIN-PLANE REENTRANT-EDGE MECHANISM 1413

several III-V materials. Figure 10 shows an etched
cross section of a d structure. These are apparently
very favorable configurations. When they occur,
they give an extended form very much longer than
any other crystal from the same melt, even longer
than the Class I configurations. Structures b and e
have been observed, but less frequently than
structures a and d.
“pure” Group III element may actually come from
residual impurities in the starting materials or
from impurities picked up from the containers
during growth. Impurities are readily incorporated
into Ge and Si crystals grown from Group III,
Group V, or neutral metal solutions to the extent
of the solid solubility, which is mostly in the range
of 1018 to 1081 for the elements listed in Table 1.

4. PROPERTIES OF THE CRYSTALS Microsegregation and crystal perfection

Electrical properties
Resistivities have been measured directly on
some of the III-V crystals. Hall mobilities have
been measured in a few cases and chemical analyses
have been used to determine impurity concentra-
tion in other cases. These data are summarized in
Table 2. The impurity concentrations given are
probably not more accurate than a factor of 2
because of uncertainty in the analyses or in the
mobility values. The number of carriers in the
Te-doped specimens is likely to be at least a factor
of l/3 of the Te concentration a8 determined by
chemical techniques, since it is believed that Te
goes into the crystal as GasTe8 with one charge
carrier for each three Te atoms.
The resistivity measurements (as well as etching
studies) indicate that the amount of Group III
element incorporated into III-V crystals is very
small. There is some reason to believe that the
impurities in the III-V crystals grown from the
Resistivity striations of the type described by
FAUST, JOHN and O’HARA(~~) are found in the Ge
and Si platelets grown from almost all metal
solutions. Similar striations are found in III-V
compound crystals grown from solutions contain-
ing certain added impurities, but not from solu-
tions of pure Group III element. Both type A and
B striations@) are present, the former outlining
the solid-liquid interface at a particular time and
the latter outlining the loci of the intersection of
interfaces. Examples of these resistivity striations
a8 revealed by chemical etching are shown in
Figs. 11 and 12, which illustrate the range of
complexity encountered. These traces are valuable
for determining the growth history of the crystals.
The InAs crystal (impurity unknown) shows a
relatively uncomplicated development, where the
outline of the (111) faces are quite apparent. The
twin planes are too closely spaced to resolve traces
between them. The GaSb twinned platelet was

Table 2. EIectrical properties of some GaAs and GaSb twinned platelets

Crystal Solution p, n-cm pi, cm2/V-set N, cm-s

-
GsAs Ga 3 .o x 10% 4400 4.4 x 101s
GaSb Ga 1.5 x lo-1p 100 (a) 4.0 x 10’7
GaSb Ga+0.50/‘, Sn 1.5 x lo-sp 4.0 x 10=‘(b)
GaSb Ga+O*OS% Si 1.1 x lo-3p 5.7 x 10=‘(b)
GaSb Ga+0*028% Zn 1.5 x 10-9 4.0 x 101*(b)
GaSb Ga+0.056% Zn 3.5 x lo-sp 100 (a) 1.8 x 101s
GaSb Ga+0.28% Zn 2.0 x lo-sp 3.1 x lOls(b)
2.6 x 10’*(c)
GaSb Ga+0+35% Zn 1.2 x lo-sp 5.2 x10’s(b)
3.2 x lO’g(c)
GaSb Ga+O.OSS’$& Te 11 3x 10”(C)
GaSb Ga+0.55% Te 11 2x 1019(c)
GaSb Ga+l*7% Te n 5x 1020(c)

(a) Probably a minimum value

(b) Using a mobility of 100 cm2/V-see
(c) From chemical analyses
1414 J. W. FAUST, Jr.
grown from a Ga solution containing 0.28 per cent
Zn and 0.055 per cent Te. The Te promotes
nucleation on the (11 l} faces and therefore changes
the relative advantage of the TPRE as a nucleation
site. This pattern indicates a relatively complex
development, with the foci of layer development
changing during the growth of the crystal. Never-
theless the reentrancies formed by the twin planes
are apparent. The development of a (100) facet
within the wider lamella (left side) is also revealed.
The type of pattern shown in Fig. 11 is very
similar to that revealed in the core of highly-doped
dendritic ribbons grown from supercooled melts
by the TPRE mechanism.(s) The dendritic rib-
bons are, however, constrained by the necessity to
dissipate the heat of crystallization rapidly and the
growth sequence as shown by the segregation
pattern reflects this. The twinned platelets, because
of their relatively slow growth, see only crystallo-
graphic constraints. Growth and the segregation
traces are more regular, extending symmetrically
in directions determined by the TPRE.
A number of the crystals have been examined
for dislocations by chemical etch techniques. The
dislocation density ranges from essentially zero to
a moderate level, with no particular consistency
or any obvious dependence on experimental
conditions.
(100) Faceting
Zinc blende materials may exhibit stable {loo>
facets as well as the more usual {ill) facets.(l@
Platelets of all the III-V compounds grown by the
techniques described here which were large enough
for conclusive examination showed {loo> faceting,
as shown in Fig. 13 for a GaAs platelet. (100)
faceting is also present on the InAs platelet shown
in Fig. 4(a), otherwise all of the side facets would
not be visible from the top. The (100) faceting
changes the morphology of the platelets from the
(111) bounded form shown in Fig. 2. Although
this does not alter the basic nucleation and growth
mechanism, it has been shownfr4) that the presence
of (100) facets can modify and stabilize reentrancies
in various ways and that the intersection between
a (100) and a (111) plane may be a favorable site
for nucleation of molecular chains. The {loo)
facets are small relative to the large (111) facets
parallel to the twin planes. The prominence of the
(100) facets apparently depends on the solvent.
and H. F. JOHN’
For example, GaSb crystals grown from Ga
exhibit more prominent (100) facets than GaSb
grown from Pb, which in turn are more prominent
than { 100) facets present on GaSb grown from Sn.
5. IXSCUSSION
The morphology of a crystal is determined in
general by heat flow, solute flow, and atomic kinet-
ics of interface attachment. I-Ieat flow will play a
very minor role during the growth of the twinned
platelets because of their relatively slow growth
rate and the high thermal diffusivity of the solution.
Solute flow will be important in determining the
morphology at high supe~aturation and fast
growth rates, as it is, for example, in the hopper
forms. For relatively low supersaturation and slow
growth rates, however, the kinetics of layer crea-
tion will be the dominant factor in shaping the
platelet. Although solute flow effects could not be
neglected in any quantitative treatment of the
kinetics of platelet growth, information on the
relative order of layer creation events at the TPRE
and on (111) facets can be obtained from simple
kinetic and geometric considerations. Neglecting
solute flow effects and any difference in the
dependence of the two types of layer creation
events on supersaturation should not change this
order.
Qualitatively speaking, the shape of a platelet
will depend on the relative number of layer crea-
tion events on the large {ill} facets as compared
to the side facets. Two types of layer creation
events occur on the side facet, those of a two-
dimensional nature taking place on the (111) sur-
face of the facet and those originating at the TPRE.
If the number of layer creation events at the TPRE
on one side facet (NT) is of the same order or
larger than the number of events (NA) occurring
on a (Ill] facet, the growth form will be of the
platelet type, As Nr]i?r~ becomes smaller the
growth form will tend to become more nearly
equidimensional. Thus
Depending on the assumptions which are made
concerning the constancy of shape during growth,
the proportionality factor in this expression will be
in the range of 1 to 3 for platelets having an
r/t > 15, but would not necessarily have the same
value for all platelet sizes and shapes.
SEMICONDUCTOR CRYSTALS USING THE TWIN-PLANE
Average values of r/t for several types of plate-
lets are given in Table 1. With the exception of a
few melts, in particular Si-Au, Si-Ag, Si-Sn,
GaSb-Ga+Te, and InSb, which have smaller
than average r/t values and Si-Al, AlSb-Al, and
In&-In, which have larger than average r/t values,
the values of r/t for most platelets are about the
same within the limits of error of determination
and selection. Neither do the r/t values appear to
be very sensitive to experimental conditions, such
as cooling rate, within the limits used for the experi-
ments reported here. Thus for all the platelets
described here the number of layer creation events
at the TPRE on each side facet is only a few times
larger than the number of layer creation events on
a large (11 l} facet.
An asymmetric position of the twin planes
relative to the two large (111) faces would be
expected to reflect physical constraints in the
system, thermal asymmetries, differences in the
amount of solute available for recrystallization, or
any differences in the ease of layer creation caused
by differences in polarity of the two faces. Since
one of the large (1 ll} faces of the III-V com-
pound platelets is always a Type A (iii), ter-
minating in Group III atoms, and the other a Type
B (ill), terminating in Group V atoms,(15) the
measurement of twin displacement might give
some qualitative insight into the effect of polarity
on layer creation and completion processes.
The position of the twin planes has been
measured for a number of different hinds of plate-
lets. The data are given in Table 1 as the average
of a large number of individual measurements of
the ratio of the thicknesses, dJd2, on either side of
the twin planes. The relative displacement in the
Ge and Si platelets, whose opposite (1 ll} faces
are identical, should reflect the influence of
physical asymmetries in the type of solution growth
experiment reported here. Any displacements in
the III-V compound platelets appreciably greater
than those found in Ge and Si might be related to
polarity effects. The tabulated data suggest that
there is indeed an additional factor influencing the
displacement in the III-V compounds. The rela-
tive twin displacement sequence
InSb > AlSb > GaAs > InAS N InP N GaP
REENTRANT-EDGE MECHANISM 1415
does not, however, seem to correspond to any
sequence based on polarity, such as that presented
by GOODMAN, who has calculated the ionic and
covalent character of the energy gap. It can only be
concluded that more careful experimentation, in-
cluding identification of the A and B faces on each
platelet, would be required to determine conclu-
sively any effect of polarity on solution growth
processes.
Acknowledgement-We wish to express our thanks to
Dr. W. A. TILLER for helpful discussions, to Dr. R. H.
Moss for providing some electrical measurements on
GaAs platelets, to Dr. M. RUBENSTEINfor solubility data
for several III-V compounds, and to Mrs. S. HILLBECK
and Mrs. H. LARSONfor valuable assistance in carrying
out this work.
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