Zone Melting

Techniques of Zone Melting and Crystal Growing
W. G. PFANN
Bell Telephone Laboratories, Murray Hill,New Jersey
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
11. The Distribution Coefficient and Normal Freezing.. . . . . . . . . . . . . . . . . . . . 426
1. Equilibrium Freezing.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
2. Segregation during Normal Freezing.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
3. Burton-Prim-Slichter Theory for the Effective Distribution Coefficient 431
4. Determining the Distribution Coefficient. . . . . . . . . . . . . . . . . . . . . . . . . . . 433
5. General Remarks on Conditions of Crystallization.. . . . . . . . . . . . . . . . . . 435
111. Principles of Zone R e h i n g . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
6. Definition of Terms; Fields of Application of Zone Melting.. . . . . . . . . . 437
7. Single-Pass Zone Melting.. . . . . . . . . . . . . . . . . . . . . . .
8. Multi-Pass Zone Melting.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
9. Calculation of Multi-Pass Distributions. . . . . . . . . . . .
10. The Ultimate Distribution. . . . . . . . . . . . . . . . . . . . . . .
11. Matter Transport.. . .............................. 451
12. Solid-Phase Zone Me .............................. 452
13. Continuous Zone Refining.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
IV. Practice of Zone R e h i n g . . . . . . . . . . . . . . . . .
14. General Considerations. . . . . . . . . . . . . . . .
15. Zone Refining with a Container.. . . . . . . . ..................... 457
16. Zone R e h i n g without a Container.. . . . .
17. Some Applications of Zone Refining.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
a. Germanium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
b. Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c. Other Semiconductors. . . . . . . . . . . . . . .
d. Aluminum. . . . . . . . . . . . . . . . . . . . . . . . .
e. Iron . . . . . . . . . . . . ................................ 465
f. Zirconium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
g. Gallium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
h. Bismuth . . . . . . . . . . . . . . . . . . . . . ...................... 467
...................... 467
k. Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
V. Zone Leveling ........................................... 468
.........
19. Simple Zone Melting with Starting Charge.. . . . . . . . . . . . . . . . . . . . . . . . 469
20. Starting Charge into Pure Solvent, .......................... 470
.......................... 470
423
424 W. G . PFANN
VI. Methods of Perturbing the Concentration ......................... 472

22. Perturbations by Changing the Composition of the Melt. . . . .
b. Remelt Method.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
b. Programmed Growth Rate in Normal Freezing.. . . . . . . . . . . . .
...............
VII. Temperature-Gradient Z ing . . . . . . . . . . . . . . . . . . . . . . . . . . . 493
a. Semiconductive Devices. . . . . . . . . . . . . . . . . . . . . . . . . . .
b. Single Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
c. Joining.. . . . . . . . . . . . . . . . . . . . . ............................. 499
VIII. Crystal Growth and Dislocations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
28. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
29. Fundamentals of Crystal Growth from the M e l t . . . . . . . . . . . . . . . . . . . . 501
a. Heat Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
b. Nucleation.. . . . . . . . . . . . . . . . ....................
G . Orientation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
d. Constitutional Supercooling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
30. Techniques of Growth from the Melt.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 506
a. Crystal Pulling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 506
b. ZoneLeveling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
31. Dislocations in Crystals Grown from the M e l t . . . . . . . . . . . . . . . . . . . . . . 513
32. Measurement of Crystal Perfection.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
I. Introduction
A perfect, pure crystal would be the ideal working medium for the
experimental solid state physicist. He is far from having it, although
much closer than he was a decade or so ago. One of his important activi-
ties is this very job of constantly improving the purity and perfection of
his experimental media. To an extent-being subsidiary to the main
problem a t hand-this activity has been neglected or glossed over, and
to this extent physics has often been the loser. Of what value is a detailed
investigation of some substance which contains unspecified impurities or
crystalline imperfections that later are shown to have a critical bearing
on its behavior?
Solid state physicists are paying more attention to such matters.
Not only has the single crystal more often become the sine qua non of the
experiment, but also the details of its composition and perfection are
increasingly taken into account. This new outlook is probably nowhere
more evident than in the field of semiconductors, where nowadays a grain
TECHNIQUES OF ZONE MELTING AND CRYSTAL GROWING 425
boundary is viewed with horror and a crystal containing one part per
million of an unwanted impurity is considered to be grossly contaminated.
The job of the experimenter seeking to improve crystalline quality
never ends. Should he have the fortune to achieve some margin of im-
provement in a particular material, a host of experimenters and theo-
retischers rush in and busily consolidate the advance he has made. Before
long they find that the new material is not nearly pure or perfect enough
for controlled studies, and our experimenter, barely having congratulated
himself on his recent success, again finds the pack a t his heels.
How far should the experimental physicist go in his search for crys-
talline perfection and means of placing solute atoms in crystals? We can
do no better than to quote Planckl-even though out of context, and with
distortion of his original meaning-who stated that “ . . Physics .
would occupy an exceptional position among all the other sciences if it
did not recognize the rule that the most far-reaching and valuable results
of investigation can only be obtained by following a road leading to a
goal which is theoretically unattainable . . . .1 ,
The scope of the present chapter can be described by reference to
Seitz’s classification of imperfections in crystals.2 He listed six primary
types of crystal imperfection; namely, (a) phonons, (b) electrons and
holes, (c) excitons, (d) vacant lattice sites and interstitial atoms, (e)
foreign atoms in either substitutional or interstitial position, and (f) dis-
locations. This list excludes transient imperfections; namely, light quanta,
charged and uncharged radiations, and special imperfections that may
exist, for example, in ferromagnetic materials. Of the six primary imper-
fections, (d), (e), and (f) can be regarded as being under the direct con-
trol of the person who prepares the crystal. These were referred to by Seitz
as the atomic t y p e , since they usually represent regions of relatively static
. ~ the three atomic types, (e) and (f),
atomic distortion in the l a t t i ~ e Of
namely foreign solute ato,ms and dislocations, are discussed here.
Techniques of preparing crystalline substances for purposes of re-
search are discussed in this article. Main emphasis will be given to the
removal of impurities and the controlled addition of desired solute atoms.
Zone melting methods, introduced in 1952, are a potent tool for jobs of
this sort; and the article is largely devoted to an account of pertinent
zone melting techniques. Related topics covered include conventional
Max Planck, “The Universe in the Light of Modern Physics.” Norton, New York,
1931.
F. Seitz, i n “Imperfections in Nearly Perfect Crystals” (W. Shockley, ed.), p. 3.
Wiley, New York, 1952.
Electrons and holes in a semiconductor are under control of the crystal grower of
course; b u t only indirectly, through control of atomic imperfections.
426 W. G. PFANN
solidification from the melt (normal freezing) , and the distribution coeffi-
cient, which is the most important parameter of the material itself in
matters of solidification.
Single crystal growing and control of solute distribution fall in over-
lapping categories. One can be done without the other, but often the two
are done together. We will not attempt a comprehensive review of crys-
tal growth techniques, as adequate reviews are available. We do, however,
discuss single crystal growing from the point of view of controlling the
content of dislocations. Techniques for combining single crystal growth
with zone melting are treated in some detail.
II. The Distribution Coefficient and Normal Freezing
A young physicist, wishing to determine the influence of a soluble
foreign element B on the behavior of a parent substance A , decided t o
prepare a single crystal of the desired solid solution. He melted a quantity
of substance A in a vessel, added the desired percentage of B , allowed
time for mixing, and froze the melt slowly from one end so as to produce
a single crystal. He found to his surprise that the property under study
varied from one end of the crystal to the other; arid he later learned th a t
this was because the content of B varied from a value less than th a t cal-
culated, a t one end of the crystal, to a value greater than th a t calculated,
a t the other. He spoke about this to a chemist friend, who told him th a t
he had encountered the phenomenon of impurity segregation, which
occurs whenever a solution is frozen slowly, and which arises from the
equilibrium difference in impurity content between a freezing crystal
and the solution from which it freezes. At this point the young physicist
decided that Mother Nature must have been in a perverse mood to create
a phenomenon so irritating . . . .
Of course the young physicist is not typical, despite the appearance
of occasional papers th at seem to mirror his experience. But his story
serves t o bring out a point; namely, th at what he regarded as irritating
is really a blessing in disguise. To begin with, the segregation he disliked
is the basis of the method of purification by repeated fractional crystalliza-
tion, which has been used for hundreds of years, and without which the
name Curie might not have become a byword. Furthermore, the exist-
ence of a concentration difference across a liquid-solid interface makes it
possible t o manipulate the impurity content of a growing crystal as as to
obtain many intricate and useful distributions. Lastly, the main “objec-
tion” t o the phenomenon-that it prevented one from obtaining a crys-
tal of uniform impurity concentration-has been obviated by a simple
procedure known as zone leveling.
We have mentioned th at the solute concentration in a freezing crys-
tal differs from t hat in the liquid. This difference arises from the equilib-
rium between liquid and solid phases of a binary solute-solvent system.
Although, during an actual freezing process, the liquid phase may not
have enough time to attain equilibrium with the entire solid phase, i t
does appear t ha t equilibrium is closely approached between liquid and
solid very close t o the interface, a t the freezing rates typical of controlled
freezing processes.
A parameter th at is very useful for discussing such matters is the dis-
tribution coefficient k . The equilibrium value of k , designated lco, can be
found from the phase diagram. Bu t the effective value of k , designated
k , will depend on conditions of freezing and on certain properties of the
material. I n this section we discuss the distribution coefficient and its
variation with freezing conditions. A related topic, normal freezing-by
which we mean melting an entire charge (instead of a short zone) and
freezing it progressively-is treated in parallel. We do this because the
study of normal freezing under different conditions of solidification is a
good way t o show the significance of k , and also because later we will
wish t o compare zone melting with normal freezing. The important prob-
lem of how t o evaluate Ic for a proposed zone melting process, as well as
some general facts about controlled freezing, are also treated.
1. EQUILIBRIUM
FREEZING
A portion of the constitutional diagram (or phase diagram) for a
binary system in which solute B lowers the melting point of solvent A
is shown in idealized form in Fig. l a . A solution containing concentration
C L of B is entirely liquid a t temperatures above the upper curve, or
liquidus. If the solution is cooled to temperature T , just below the
liquidus, i t begins to freeze. The first solid to freeze will be a crystal of
A containing concentration CS of B in solid solution, where Cs is given
by the intersection of the temperature horizontal with the lower curve,
or solidus. T h e equilibrium distribution coeficient ko is the ratio Cs/C,
taken from the constitutional diagram. I n Fig. l a , k o is less than unity,
since the liquidus and solidus slope downward. The corresponding dia-
gram for a solute th at raises the melting point of the solvent (for which
Lo is greater than unity) is shown in Fig. l b . I n general, k o depends on
concentration, except for very dilute solutions.
Consider the complete freezing of a solution such as th a t discussed
in connection with Fig. la. For definiteness, imagine the solution as a
long cylinder freezing from one end, as shown shmceatically in Fig. 2.
This operation will be referred t o as normal f r e e ~ i n g T. ~h e exact form of
the solid during freezing does not matter a t the moment, only the fraction
4 W. G. Pfann, Trans. Am. Znst. Mining Met. Engrs. 194, 747 (1952).
428 W. G . PFANN
that has frozen. The distribution of solute in solid and liquid during freez-
ing, and throughout the solid after freezing, will depend on ko and on the
conditions of freezing. The most important condition is the rate of freez-
ing, that is, the rate of advance of the solid-liquid interface. Almost as
important is the degree of mixing in the liquid. Depending on these con-
ditions, the solute distributing process may follow three or four distinctly
different courses.
(a1
SOLUTE CONCENTRATION - (b)
FIG. 1. Portions of constitutional diagrams in which the freezing point of the
solvent is, (a) lowered, (b) raised, by the solute.
FRACTION
SOLIDIFIED
r-----9-----7
LIQUID
0 I
FIG.2. Solidification by normal freezing (schematic).

One extreme of these is equilibrium freezing, which occurs only if the
gradients of concentration and temperature in the system are negligibly
small. This implies that the freezing rate is extremely slow, slow enough
to permit diffusion processes in the solid and liquid to erase any concen-
tration gradients. As the system of Fig. l a undergoes equilibrium freez-
ing, the concentration of solute in the solid is at all times ko times that in
the liquid. Since the freezing action rejects solute to the liquid, the con-
centrations in the liquid and freezing solid continually rise. The last
droplet freezes when it reaches concentration ratio C ~ / k owhere
, CL is the
initial concentration. The main distinction between equilibrium freezing
and processes described later is that, in the former, diffusion in the solid
maintains the concentration in the solid uniform a t all times, even

though that concentration is steadily increasing. Equilibrium freezing is
rarely approached in practice because diffusion rates in the solid are
usually low.
2. SEGREGATION FREEZING
DURING NORMAL
No segregation occurs in equilibrium freezing because time is allowed

for complete diffusion in the solid. If we assume that no diffusion occurs
in the solid-and this corresponds more closely to the fact-then segrega-
tion will occur during normal freezing. The degree of segregation will
depend on transport conditions in the liquid. Three cases can be distin-
guished: (1) complete mixing in the liquid, by diffusion and stirring (con-
centration uniform in liquid); (2) partial mixing in the liquid; and (3) no
stirring in the liquid, transport being only by diffusion. These will be
discussed in turn: case (1) in this section, cases (2) and (3) in the next.
Case (2) is by far the most important.
The conditions (a) no diffusion in the solid, (b) uniform concentration
in the liquid, lead to maximum segregation during normal freezing
(Case 1). These conditions can be approached by selecting a freezing rate
which is large compared to the diffusion rate of solute in the solid and yet
small compared to the diffusion rate in the liquid. Where there is insuffi-
cient difference between diffusivities in liquid and solid to make such a
selection possible, the liquid can be stirred, to increase the effective dif-
fusivity there. I n either event, conditions (a) and (b) can be approached
physically.
Segregation caused by normal freezing can be described analytically
by the following equation:
c = kCo(1 - g)k-’ (2.1)
in which C is the concentration in the solid in units of solute per unit
volume of solution, a t the point where a fraction g of the original liquid
volume has frozen, and Co is the mean concentration. The assumptions
used, in addition to (a) and (b) of this section, are that the distribution
coefficient k is constant and that the density does not change on freezing.
Under, and only under, conditions (a) and (b), the value of k that applies
to the equation is ko. (Later, use of an effective distribution coefficient
differing from ko will be discussed.) Equation (2.1) in one form or another
has been derived by several author^.^-^
6 G. H. Gulliver, “Metallic Alloys,” Appendix. Griffin, London, 1922.
BE. Scheuer, Z . Metullkunde 23,237 (1931).
‘A. Hayes and J. Chipman, Trans. Am. Inst. Mining Met. Engrs. 136, 85 (1939).
* R . H. McFee, J . Chem. Phys. 16, 856 (1947).
430 W. G . PFANN
The equation is an approximation, as it cannot hold for the entire

range of 9. I n any actual system, either an eutectic or peritectic composi-
tion will be reached by the liquid, whereupon the equation becomes
invalid, or the value of k must change with composition. (When k < 1,
co= 1 FOR A L L CURVES
0.02
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

FRACTION SOLIDIFIED, 9
FIG. 3. Curves for normal freezing, showing solute concentration G in the solid
versus fraction solidified 9, calculated from Eq. (2.1) for various values of the distribu-
tion coefficient k.
the equation calls for infinite concentration a t g = 1, which is impos-

sible.) Even so, it is a useful approximation until about 80% of the liquid
is frozen, especially for dilute solutions.
Curves of solute concentration versus fraction frozen, calculated from
Eq. (2.1) with k as a parameter appear in Fig. 3. These are for unit
mean concentration, and for g u p to 0.9. The severity of segregation,
which may be judged from the slopes of the curves, increases as k differs
from unity. Note th at the curves for k > 1 slope downward to the right.
Since ko is the extreme value of the effective distribution coefficient for
a given system, freezing conditions for which the effective k is k o are those
corresponding t o maximum segregation.
These curves show th at normal freezing can be a very effective method
of purification if the absolute value of (I - k) is about 0.5 or more.
Normal freezing is the elemental step in the method of purification by
repeated fractional crystallization.
3. BURTON-PRIM-SLICHTER
THEORY
FOR THE EFFECTIVE
DISTRIBUTION
COEFFICIENT
If freezing occurs slowly, as assumed in the last two sections, the
solute concentration in the liquid is uniform, and the concentration in
the freezing solid is ko times that in the liquid, where ko is the equilibrium
distribution coefficient. If freezing does not occur slowly, this is no longer
true. The advancing solid rejects solute more rapidly than it can diffuse
into the main body of liquid, and hence an enriched layer builds u p
ahead of the interface.9 The solute concentration in this layer, rather
than t ha t in the main body of liquid, determines the concentration freez-
ing out in the solid. Under this condition, the relation between concen-
tration in the solid Cs and th at in the main body of liquid C L can be
described by a n egective distribution coeflcient k equal to the ratio CS/CL.
(Throughout this article the symbol k will designate the effective distribu-
tion coefficient.)
It is important to know the steady-state value of k , for this value
will be used in zone melting calculations. It must lie, as we shall see,
between ko and 1. Bu t where? This problem has been analyzed by Burton
et ~ 1 . Their
l ~ approach is based on principles described b y Nernstll in
his theory of the kinetics of het,erogeneous reactions and results in the
following expression for the e$ective distribution coeficient:
Plots of this important equation for several values if ko as a function

of A = f s / D , are shown in Fig. 4. The dimensionless quantity f s / D may
9 We assume in this discussion that ko < 1. A similar argument applies to ko > 1,
except that a depleted, rather than an enriched layer builds up.
10 J. A. Burton and W. P. Slichter, in “Transistor Technology” (J. Shive, ed.), Vol. I,
Chapter 5, Van Nostrand, Princeton, N. J., 1957 (in press); J. A. Burton, R. C.
Prim, and W. P. Slichter, J. Chern. Phys. 21, 1987-1996 (1953).
11 W, Nernst, X. physik. Chem. 47, 52 (1904).
432 W. Q. PFANN
be regarded as a normalized growth velocity. It embodies the three

main parameters which can affect the value of k . Of these, the growth
rate f is usually known accurately in controlled freezing problems. Often
D the diffusivity in the liquid is unknown, but usually lies between
and 10-4 and cmz sec-I for liquid metallic solutions. The thickness 6 of
the liquid film, in which transport is only by diffusion, is not usually
obtainable directly, except where the details of the fluid flow in the melt
FIG. 4. Dependence of effective distribution coefficient k on normalized growth

velocity f 6 / D , for several values of equilibrium distribution coefficient ko.
are known. However, 6 / D depends only slightly on f.10 Hence, it can be
measured, using Eq. (3.1), by experimentally determining Cs/CL in crys-
tals grown at different growth rates, but with the same stirring conditions.
For example, such measurements show that 6 / D for a germanium crystal
rotated a t 60 rpm about a vertical axis, while being pulled from a melt,
is of the order of 100 sec-cm-'. This value has been used to fix the growth
rate scale a t the top of Fig. 4. If the fluid flow conditions are known, 6
can be calculated. A detailed calculation of 6 for a rotating crystal has
been given by Burton and Slichter.'" Figure 4 illustrates rather vividly
that all k's rapidly approach unity as the growth rate is increased beyond
a certain range. In zone refining, large [ I - kl is desired. Hence low
TECHNIQUES O F ZONE MELTING AND CRYSTAL GROWING 433
growth rate, combined, if possible, with some kind of forced convection

in the melt, should be used. I n zone leveling it is less important to operate
at large 11 - kl. In certain methods for making p-n junctions, the effective
k is deliberately varied.
The condition during freezing in which solute transport is entirely
by diffusion is worthy of mention, although it should be avoided in zone
refining. I n this case, k approaches unity if the melt is large enough.
This situation has been analyzed by Tiller et d . 1 2 While certain aspects
0
FRACTION SOLIDIFIED, CJ
FIG.5. Concentration of solute after normal freezing versus fraction solidified for:
(a) complete mixing in liquid, (b) transport in liquid by diffusion only.
of their treatment have been q~estioned,~~-16 they bring out the important
point that the over-all segregation in a diff usion-limited normal-freezing
process may be quite different from that where the liquid is stirred. A
qualitative comparison of normal freezing curves for complete mixing in
the liquid and for diffusion-limited transport in the liquid is shown in
Fig. 5 . I n comparing the curves, remember that the lengths of the initial
and terminal transient regions in curve (b) are arbitrary with respect to
total ingot length.
THE DISTRIBUTION
4. DETERMINING COEFFICIENT
It is important to know the distribution coefficient of the solute in
planning a zone melting experiment or process. The simplest approach,
if the data are available, is to consult a phase diagram and from it deter-
12 W. A. Tiller, J. W. Rutter, K. Jackson, and B. Chalmers, Acta Metallurgica 1, 428
(1953).
1 3 C. Wagner, Trans. Am. Inst. Mining Met. Engrs. 200, 1954 (1954).
1 4 W. G. Pfann, Acta Metallurgica 1, 763 (1953).
16 R. G. Pohl, J . Appl. Phys. 26, 1170 (1954).

434 W. G . PFANN
mine the equilibrium distribution coefficient k ~ From . ko and from a

knowledge of the growth conditions, the effective distribution coefficient
k can be estimated from Eq . (3.1).
Few published phase diagrams are accurate a t the very low solute
concentrations t hat are of interest where high purity is an object. How-
ever k o a t very low concentration can be obtained by extrapolation of the
k o solute concentration relation. Thurmond and Struthersl‘jshow th a t for
dilute solutions In ko should vary as the reciprocal of the absolute tem-
perature. Their conclusion is confirmed by data for dilute alloys of
Ge-Cu, Ge-Sb, and Si-Cu (the solute being second). The data are for
ko’s less than and show that the In ko versus 1/T relationship
holds over a t least 2 decades in ko.
If only the solidus concentration or the liquidus concentration a t a
given temperature is known, k o can be estimated by a thermodynamic
method based on the laws of dilute solutions. Hayes and Chipman? used
this approach t o estimate I;,, for several solutes in iron. The equation used
was
where AH is the heat of fusion of the solvent, Na(Z)is the mole fraction
of solute in the liquid, R is the gas constant, T is the absolute temperature,
and AT is the lowering of the freezing point,. I n general, however, solutions
are not dilute enough to permit one to obtain more than a rough estimat,e
of k o by the thermodynamic method.
A third approach is to determine lc by experiment. It has the merit
that the freezing conditions used to determine k can be made the same as
those t o be used in zone melting. Hence, the growth conditions do not
have t o be known mathematically; they merely have to be simulated.
A simple experimental method of determining k is to solidify a cylinder
of the material by normal freezing, determine solute concentration C as
a function of fraction solidified g b y some analytical means; plot concen-
tration against fraction solidified, and compare the result with calculated
normal freezing curves. A logarithmic plot of the normal freezing equation
is useful for this purpose because it is a straight line. Thus
c/co = k(1 - g)k-1 (4.2)
log (C/C,) = log k + ( k - 1) log (1 - 9). (4.2a)
By determining k experimentally from Eq. (4.2a) for two growth
rates but with the same stirring conditions (e.g., the same S/D), one can
from Eq. (3.1) estimate Ic,, which is the most favorable value obtainable.
C.D. Thurmond and J. D. Struthers, J. Phys. Chem. 67, 831 (1953).
As a last resort, for purposes of zone refining, one can determine by

trial and error the number of zones th at must be passed through a n ingot
to obtain a desired level of purification.
5. GENERALREMARKSON CONDITIONS OF CRYSTALLIZATION
Several aspects of normal freezing and of crystallization in general,

that bear on topics treated latjer, are brought out in this section. It was
mentioned earlier th at normal freezing is the elementary step in the well-
known separation method called fractional crystallization. Normal freez-
ing also occurs a t the end of each zone melting pass as the zone leaves the
ingot, and the solute distribution there may affect that in regions remote
from the end.
Where purification is desired, whether by normal freezing or by zone
melting, the freezing rate should be low enough so that a smooth solid-
liquid interface advances into the melt. At high freezing rates dendrites
will form. These are single or branched projections that extend into the
melt. Dendrite formation should be avoided because it increases the
effective film thickness 6. I n fact, dendrites can bodily entrap liquid, and
thereby negate the object of the freezing process.
At somewhat lower freezing rates a prismatic substructure, that has
been studied recently by Pond and Kessler," Rutter and Chalrners,l*
Walton et aZ.19 may appear. This substructure is columnar in the growth
direction, and it appears as a network of more or less hexagonal cells in
the liquid-solid interface. If the liquid is suddenly decanted from a solidi-
fying interface, the substructure may be seen as an array of slightly
rounded bumps projecting from a geometrical network of boundaries rich
in solute. Such boundaries confine solute and shield it from convection
currents in the liquid. Hence freezing conditions which lead to a cellular
substructure should be avoided where separation is an object. Walton
et al.,lg in experiments with tin containing up to 0.02% of lead, have
shown t ha t the cellular substructure will appear if the ratio G / R of tem-
perature gradient to growth rate is less than a critical value th a t increases
linearly with solute concentration. This was interpreted in terms of
the phenomenon termed constitutional supercooling b y Rutter and
Chalmers.lB For 0.01% lead in tin, the critical G / R was found to be
about 0.0075"C sec-cm-2 (with G = 3O0C-cm-' and R = 0.004 cm sec-l),
IT R. B. Pond and S. W. Kessler, Trans. Am. Inst. Mining Met. Engrs. 191, 1156
(1951).
l8 J. W. Rutter and B. Chalmers, Can. J . Phys. 31, 15 (1953).
D. Walton, W. A. Tiller, J. W. Rutter, and W. C. Winegard, J. Metals 7, 1023
(1955).
436 W. G . PFANN
under the conditions that the melt was unstirred, and freezing occurred
in a horizontal boat. A comprehensive discussion of this and related
phenomena has been given by Chalmers.20These findings have a critical
bearing on the travel rate a t which zone refining should be performed.
They indicate that the maximum travel rate for which k will differ ap-
preciably from unity decreases as solute concentration increases.
In discussing zone melting, we shall, in general, assume solidification
from the melt-that is, from a solution formed by heating the substance
in question. On the other hand, the practice of crystallization from sol-
vents to purify a substance has been widely used, especially by chemists.
The main object of this practice is to secure a separation more favorable
than might be obtained by freezing from the melt. The principles of zone
melting to be described later are as applicable to freezing from solvents
as to freezing from the melt. In the last analysis, the difference between
the two methods is largely one of degree rather than of kind. An important
physical difference between the techniques, however, is that freezing
from solvents often results in a mass of small crystals, and this entails
problems of liquid entrapment. Unusually low growth rates are required
to obtain a continuous, smooth, solid-liquid interface when freezing from
solvents.
The fields that have seen the most extensive use of zone refining to
date are semiconductors and metals. The method has been applied to a
number of organic chemicals and undoubtedly will be applied to many
others. However, zone refining (or fractional crystallization in general)
cannot be applied to all organics, because of certain difficulties which
accompany increase in molecular size; namely, high viscosity (low dif-
fusivity in the liquid phase), increased difficulty of nucleation, and lack
of a sharp melting point (as in the case of polymers that partly crystallize).
The technique of repeated fractional crystallization has been used for
hundreds of years. The procedure has been thoroughly analyzed, and
complicated schemes of recombining fractions for most effective separa-
tion have been devised. A detailed account of this technique has been
. given by Tipson.21Although many difficult separations have been made
by this method, such as isolation of radium by the Curies and separation
of the rare earths by James and co-workers, these are perhaps more a
tribute to the perserverance of the workers than to the efficiency of the
method. The main drawback of the method is the need for a troublesome
series of manipulations; namely, melting or dissolving the impure crystals,
slow freezing-out of a fraction of the melted crystals, removal of the pure
20 B. Chalmers, Trans. Am. Inst. Mining Met. Engrs. 200, 519 (1954).
81 R. S. Tipson, in “Technique of Organic Chemistry” (A. Weissberger, ed.), Vol. 3,
Chapter 6. Interscience, New York, 1950.
crystals from the remaining impure liquid, and recombination of the re-
moved fraction with other fractions.
111. Principles of Zone Refining
6. DEFINITIONOF TERMS:
FIELDS
OF APPLICATION
OF
ZONE MELTING
The field of application of zone melting might be described as the
field of controlled solidification or crystallization. This field encompasses
the careful preparation, from the melt or from solution, of crystalline
materials of all kinds including metals, semiconductors, and organic and
inorganic compounds. The general term zone melting denotes a family of
methods for controlling the distribution of soluble impurities, or simply
solutes, in such crystalline materials. In all these methods a short molten
zone travels slowly through a relatively long solid charge, and, as the
zone travels, it redistributes solutes in the charge. If the number, size,
and travel direction of the zones, as well as the initial makeup of the
charge, are suitably selected, many useful, and sometimes remarkable,
operations can be performed on the charge.
A molten zone traversing an ingot has two liquid-solid interfaces, a
melting interface and a freezing int,erface. The zone is able to redistribute
impurities mainly because of what happens at the freezing interface. At
the melting interface solid material is merely melted and mixed with the
contents of the zone-thrown into the hopper, so to speak. At the freez-
ing interface, however, the solute concentration in the just-freezing solid
generally differs from that in the liquid. If the solute (soluble impurity)
lowers the melting point of the solvent (charge substance), its concentra-
tion in the freezing solid will be lower than in the liquid. Hence solute
will be rejected by the freezing solid and will accumulate in the liquid.
If the solute raises the melting point of the solvent, its concentration in
the freezing solid will be greater than in the liquid, and the liquid will be
depleted of solute. Thus a freezing interface can reject certain solutes,
attract others.
These facts about the freezing of solutions are well known. They are
the basis of both fractional crystallization and zone melting. The main
difference between zone melting and fractional crystallization is that, in
the former, part of a charge, rather than all of it, is melted at one time.
This change in procedure has tremendously increased the efficiency of
crystallization as a separation technique, and has led to new ways of
using crystallization.
Of the operations which one might wish to perform on the solutes in a
438 W. G . PFANN
charge, probably the most important is removal, th a t is, purification or

separation. The general term zone rejining designates zone melting
methods having this object. I n zone refining, a series of molten zones
passes through the charge in one direction. Impurities travel with, or
opposite to, the zones, depending on whether they lower or raise the melt-
ing point of the charge-substance, respectively; and they become concen-
trated in one or the other end of the charge, thereby purifying the re-
mainder. The degree of separation increases with the number of passes
(the number of single zones which pass through the charge) approaching
a limit as the number of passes becomes infinite. Zone refining can be
used t o concentrate desired impurities as well as to remove undesired
ones. It can also be used in special circumstances as an analytical tool for
detecting impurities unobservable by conventional techniques. Principles
of zone refining are discussed in this section, which deals with single- and
multi-pass operations, and calculation of solute concentrations after such
operations. Of interest are the distribution after one pass, after any given
number of passes, and after an infinite number of passes. The first and
last are readily calculable; the second is not. The problem can be set u p
for analog computation by hand or machine; and some computed pass-
versus-concentration curves have already been published. A number of
iterative mathematical techniques have been proposed, which are com-
parable in labor t o the computational schemes. An account of these
methods appears in this part. Parts I1 and I11 comprise, in essence, a
design theory for zone refining. Given the distribution coefficient and the
parameters of the apparatus, one can, from information in these parts,
plan a process t o perform a desired separation.
Several miscellaneous topics th at fall in the realm of theory are also
treated in this part. These include zone “melting” by solid-solid trans-
formation, and transport of matter by a molten zone, which has a n im-
portant practical bearing on just how zone melting is carried out.
Although the physical operations of melting and freezing are essen-
tially simple, many practical questions arise. Such matters are treated in
Part IV, which is devoted t o techniques of zone refining. Particular atten-
tion is given t o the problem of zone refining reactive materials, for which
methods of zone melting without a container have been devised. To the
time of this writing, most zone refiners have been designed rather ineffi-
ciently from the viewpoints of time and power consumption. The writer’s
views on more ideal designs are given with a view to encouraging a trend
toward more effective apparatus. Part IV, in short, is a how-to-do-it
section.
Some results of the application of zone refining to various materials
olnrr ~ l ~ m m o , . ~ in
v o P~ o d TTi A l + h n r ~ m ho n m o nf thoon ..nnl.lto mnrr nnn.%
become outdated, they illustrate the state of the a r t and the scope of the
method.
Zone refining, as just described, is a batch technique, in that succes-
sive operations are performed on a single batch of material. As such, it
has certain inherent limitations, the most serious being the decrease in
efficiency of zone passes as their number increases. Although very favor-
able separations are ultimately possible, the time and expense required
to achieve the ultimate separation is usually prohibitive.
To circumvent this difficulty a continuous zone refining technique has
been devised in which feed enters, a t an intermediate point, a column
down which molten zones travel, while waste and product leave a t the
ends. Materials are caused to move through the column, in the necessary
directions and quantities, by means of voids that are created a t the ends
of the column and move toward the feed point. The voids are moved by
the heaters that move the zones. The zone void process, as it has been
called, provides, in the field of crystallization, a counterpart of the con-
tinuous fractionation column in the field of distillation. At this writing
a suitable mathematical design theory for the zone void method has been
worked out. Practice is in the laboratory stage. The method is described
in this part.
A second important zone melting operation is the controlled addition
of a desired impurity to a crystal. It is virtually impossible to obtain a
uniform concentration of a soluble impurity from one end to the other
of a crystal grown slowly from the melt by the conventional means. Be-
cause the freezing crystal differs in composition from its melt by a more
or less constant factor, the composition of the melt changes as freezing
progresses and the resulting ingot-segregation can be very great. By
using one of several zone melting techniques known as zone leveling, seg-
regation can be almost completely eliminated. While possibly less well
known and less generally applicable than zone refining, the zone leveling
techniques have solved an irritating problem of long standing in the field
of solidification and they have already been applied commercially. These
techniques are discussed in Part V.
Advent of new solid electronic devices such as the transistor, solar
battery, and silicon power rectifier has placed a high premium on methods
of precisely controlling solute concentrations in semiconductors. I n gen-
eral, two solutes are used to produce the p - n junctions that are the
building blocks of such devices. Not only must the concentration level
of each solute be carefully controlled, but these levels must be varied by
factors of 10 or more over regions of the order of mils or less in width.
Since techniques of melting and solidification have played a prominent
part in the development of these devices, Part VI has been devoted to an
440 W. G. PFANN
account of the solidification methods used to produce p-n and n-p-n

junctions. A number of zone melting techniques, as well as variations of
conventional solidification techniques, will be described and evaluated.
Still another zone melting method, called by the unwieldy name
temperature-gradient zone melting, has been devised for making n-p-n junc-
tions. It is treated separately in Part VII because it is quite different
from other zone processes in scale of size and manner of movement of the
zones. Extremely small zones are used. They may be sheet zones or wire
zones or dot zones whose smallest dimension may be of the order of mils.
The zones usually have a high solute content, so that they are liquid at
temperatures well below the melting point of the solid through which they
travel. They are caused to move, not by a traveling heater, but by a
stationary temperature gradient impressed across the charge. Potential
uses include joining, growing single crystals without a container, measur-
ing and studying diffusion in liquids, and making p-n and n-p-n junctions
in semiconductors. I n the last-named application, temperature-gradient
zone melting is unique in that it permits one to fabricate conductivity
regions of minute size or complex shape inside a semiconducting crystal.
ZONE MELTING
7. SINGLE-PASS
Consider a cylindrical ingot or charge consisting of two components
that form a binary solid solution. Let its composition by invariant with
distance x along the ingot. It might be a rapidly frozen casting or a mix-
ture of granular constituents. It might consist of two rods of the pure
components whose relative cross sections correspond to the mean com-
position Co. Cause a molten zone of length 2 to traverse the charge
slowly, as shown in Fig. 6. The zone might be produced by a ring-shaped
heater, as suggested in the figure. Assume k to be less than one.
Passing the zone through the ingot produces a solute distribution of
the form shown approximately in Fig. 7. The curve has three distinct
regions: an initial region, a level region, and a final region. These regions
arise as follows. When the zone, a t full length, is at the beginning of the
charge, its concentration is that of the melted material Co. As the zone
advances a short distance it freezes out, a t x = 0, a layer of solid of con-
centration kCo of solute, and it takes in, at x = I, by melting, a layer of
concentration Co. As a result, the zone is enriched and subsequently
freezes out higher concentrations. As the zone progresses, enrichment
continues, at a decreasing rate, until its concentration attains the value
C&. From this point on, the concentrations entering and leaving the
zone are equal and the concentration in the freezing solid remains CO
until the zone reaches the end of the ingot. Thereupon further movement
of the heater decreases the length of the zone, causing the solute concen-
tration t o rise.
The initial portion of the curve of Fig. 7 represents a region of the
charge which was purified, for the concentration there is less than average.
The level portion represents a region of the charge in which a solid solution
HEATER
UNMELTED SOLID
FIQ.6. Molten zone of length, 1 traversing a cylindrical ingot of length L (schematic).

of uniform composition was produced, which is the object of the zone
leveling methods described later. These two portions can be described by
a single equation Eq . (7.1), given below. The third portion can be de-
scribed by the normal freezing equation, Eq. (2.1).At 5 = L - I , where
0'
DISTANCE, X
L
FIQ.7. Approximate concentration of solute after passage of one molten zone

through a charge of uniform mean concentration CO.
L is the ingot length, both equations have the same value of solute con-
centration, but in general have different slopes. Since solute must be
conserved, the areas between the Co horizontal and the initial and final
transition regions must be equal.
The equation for the process of Fig. 7, which may be described as
zone melting of a uniform charge, is
C/Co = 1 - (1 - k)e-kz/' (7.1)
442 W. G . PFANN
where C is solute concentration in the solid and x is distance from the

starting end. The equation is valid in all but the last zone length. Its
derivation, which is credited to W. T . Read, appears in footnote 4.
Curves of C vewus x/E, the distance expressed in zone lengths, calcu-
lated from Eq. (5) for Co = 1, are plotted in Fig. 8 for k’s from 0.01 to
DISTANCE IN ZONE-LENGTHS, X/L
FIG.8. Curves for single-pass zone melting, showing solute concentration in the
solid versus distance in zone lengths from beginning of charge, for various values of
the distribution coefficient k .
5.0. The first nine zone lengths of a charge ten zone lengths long are
shown. The following features are noteworthy. (1) The curves for k < 1
are concave downward, in contrast with normal freezing curves. Hence,
less purification is achieved by one zone pass than by one normal freezing
step. (2) The transition region is a t least. ten zone lengths for k’s of about
0.4 or less, but only a few zone lengths for k > 0.9. Hence, for an ingot
ten zone lengths long, single-pass zone melting is largely zone refining for
k < 0.4, largely zone leveling for Ic > 0.9.
One can, in effect, operate nearer the left side of Fig. 8 by using a larger
zone length compared to the ingot length, and in this way accentuate the
refining action of a single zone pass. The ultimate would be to make the
zone length equal to the ingot length, which is, of course, normal freezing.
A more general differential form of Eq. (7.1) has been derived by
Reiss,22 and by which is useful where the initial concentration
can be expressed as a function of x. The equation is
where C,(z) denotes the concentration after the n th pass at distance x

from the beginning of the ingot, and C,-,(x +
I) is the concentration
+
after the (n - 1)st pass a t (x I). Equation (7.1) follows from Eq. (7.2)
upon substitution of Cofor C,-l(x +
I). Whether Eq. (7.2) can be solved
will depend, of course, on the complexity of the function for the initial
distribution.
8. MULTI-PASS ZONE MELTING
The merits of zone refining become evident when repeated crystalliza-
tions are desired. By using a series of closely spaced heaters, as in Fig. 9,
a number of molten zones traverse the charge in a single operation. The
,--RING HEATER (STATIONARY)
‘MOLTEN ZONE
FIG.9. Multi-pass zone refining (schcmatie).
elimination of the step of separating pure from impure fractions, as in

fractional crystallization, is probably the chief advantage of zone refining.
A second advantage is th at time can be saved, if the zones are close
together, because succeeding crystallizations begin before the first one
(first pass) is complete.
Other advantages arise from the small size of the molten region.
Where contamination of the molten liquid by the container or the atmos-
22 H. Reiss, Trans. Am. Inst. Mining Met. Engrs. 200, 1053 (1954).
23 N. W. Lord, Trans. Am Inst. Mining Met. Engrs. 197, 1531 (1953).
444 W. G. P F A N N
phere is a problem, zone refining has the merit, as compared with frac-
tional crystallization, in that a smaller proportion of the charge is liquid,
on the average. What might be called a physical advantage arises in the
refining of certain materials which are so reactive when molten that no
known container can hold them without contamination. Examples are
silicon, titanium, zirconium, and, to a lesser extent, iron. Several tech-
niques of zone refining without a container have been developed. These
have been possible because only a small part of the charge is molten at
a given time.
9. CALCULATION OF MULTI-PASSDISTRIBUTIONS
Without going into the mathematics of multi-pass, or intermediate

distributions, one can picture in a general way what form the curves will
assume. Consider the second pass through a first pass distribution like
that of Fig. 7. As the zone passes through the initial region, it accumulates
solute, and leaves behind it a lower and somewhat longer initial region.
When the front of the zone reaches the beginning of the normal freezing
region, the slope of the curve will rise sharply. Thus, the pileup at the
ingot end is reflected back one zone length during the second pass; and
back one additional zone length, with diminishing intensity, for each
succeeding pass. Additional passes, therefore, lower the concentration in
the initial region, raise it in the end region, and decrease the length of
the intermediate region. Ultimately the three regions can no longer be
distinguished.
It would be most helpful to have a general equation that expresses
solute concentration as a function of distance, for any number of passes
through an ingot of specified length. No such equation has been derived.
While the concepts of zone refining are simple, it is apparently difficult
to describe multi-pass operations mathematically. However, several
mathematical approaches have gone part way toward the goal of a gen-
eral equation. As might be expected, they are rather complicated and
involve considerable computational labor. Space permits but a brief re-
view of these.
Lordz3derived an exact expression for solute concentration as a func-
tion of distance x from the beginning of an ingot and the number n of
passes. It is limited to a semi-infinite ingot; that is, it does not account for
backward reflection of the pileup at the ingot end. Hence, for a finite
ingot of length L, it is applicable only to the region 0 < x < L - nl,
where I denotes zone length. Lord’s method is, in effect, a formula for
repeated integration of the differential equation given above [Eq. (7.2)].
Figures 10 and 11, copied from his paper, show distribution curves for
8 passes for k = 0.25 and k = 0.1.
The following equation, obtained by MillikenlZ4results from simpli-

fying Lord's expression by reducing its triple sum to a single sum.
s=i
+ (1 +a)]
7
- ka)(s (9.1)
where a denotes distance in zone lengths and 'Co denotes initial solute
concentration, assumed uniform.
FIG. 10. Curves showing solute concentration against distance in zone lengths,
with number of passes as a parameter, for a semi-infinite ingot. k = 0.25 (after Lord).
ReissZ2notred that the expression for C,(O), the concentration a t the

start of the ingot, is relatively simple, being
A method that permits one to go directly to the concentration in the

nth pass, and further, that can be extended to the finite ingot, has been
24 K. S. Milliken, Trans. Am. Inst. Mining Met. Engrs. 208, 838 (1955).
446 W. 0. PFANN
described by Reiss.22 This method is approximate, being accurate only

for 0.9 < k < 1.1. But it is for this very range of lc that a direct method
is valuable, since many passes are required and to compute these itera-
tively would involve prohibitive labor. Reiss’ curves for a finite ingot,
with k = 0.95, appear in Fig. 12. The concentrations a t x = 0 for large
n are not readable in the figure, and so are given in Table I.
DISTANCE IN ZONE-LENGTHS
FIG.11. Same as Fig. 10, except that k = 0.10.
Several computational methods have been proposed. These have the

one very attractive feature that they can be used for an arbitraryinitial
solute distribution (i.e., the assumption of uniform initial concentration
is necessary in the mathematical but not in the computational solutions).
Also, they can take account of normal freezing. However, they must be
used with caution if accuracy is important. An error of a few per cent may
TABLEI. VALUESO F C,(O)/Co IN FIG. 12
0 1
50 0.52
200 0.28
400 0.15
1000 0.037
2000 0.0058
m 0.00045
FIG. 12. Relative solute concentration C/Co versus distance 5, wit,h number of
passes n as a parameter, for k = 0.9524, I = 1, L = 100 (after Reiss).
448 W. 0. PFANN
be trivial for a single pass, but if multiplied in repeated passes it can

become surprisingly large.
Hamming’s method4 consists of considering the ingot divided into
cells of equal volume. A zone length is taken as an integral number of
cells, say 2 , 3 , 4 , or more and the zone is supposed to move in 1-cell jumps.
At each jump it freezes out, in the vacated cell, an amount of solute corre-
sponding to k times the concentration in the zone. After each jump, the
solute taken in from the next cell is added to that carried forward to ob-
tain the new concentration in the zone. I n the normal freezing region the
computation must take account of the decreasing zone length. All of the
solute in the zone must be deposited in the last cell, which introduces a
discontinuity. It may be desirable to deposit all of the solute uniformly in
the last zone length as this procedure would correspond to the practice
sometimes followed of freezing the last zone length rapidly, to save time.
(Rapid freezing results in an effective k of unity.) Figure 13 shows zone
refining curves for k = 0.5, L/l = 10 computed by R. W. Hamming.
Burris et a1.26 have published rather extensive calculations of typical
zone refining runs, made by Hamming’s method, with variations of their
own. Accuracy was assured by using a small jump distance (1% of bar
length).
An essentially computational method utilizing matrix algebra was
described by Birman.26 The ingot is divided into N segments comprising
an N X N square matrix. By operations of matrix algebra, the initial
matrix is converted into a matrix representing the distribution after a
desired number of passes. The final matrix is then reconverted to the
desired concentration distribution. The main advantage of the matrix
method is that for a given ingot length and zone length the basic matrix
need be evaluated only once for each value of the distribution coefficient
k , since it does not depend on the initial distribution. The method is
iterative,. although in this respect it appears to have an advantage over
one-pass-at-a-time methods, in that it enables one to go from pass n to
pass n2 in one operation. An idea of the work involved in an operation
can be gotten by assuming an ingot to be represented by 40 cells (perhaps
10 zone lengths). In this case the basic matrix would have 40 X 40 = 1600
terms. (It should be mentioned that the curves in Birman’s paper are
inaccurate at the lowest concentrations shown.)
A “poor man’s’’ zone melting analog computer, constructable from
parts available in the laboratory, has been devi~ed.~’ It utilizes liquid
z6L. Burris, Jr., C. H. Stockman, and I. G. Dillon, Trans. Am. Inst. Mining Met.
Engrs. 203, 1017 (1955).
2 6 J. L. Birman, J. A p p l . Phys. 26, 1195 (1955).
27 W. G. Pfann, “Zone Melting,” Chapter 3. Wiley, New York, to be published.

FIQ.13. Curves showing solute concentration versus distance in zone lengths, with
number of passes n as a parameter, for L/Z = 10, k = 0.5.
450 W. G . PFANN
levels in vertical tubes to simulate concentration. While it is no match

for an electronic computer, it is nevertheless useful and instructive.
As time goes on, and more calculated data become available in tabular
or graphical form, the need for these mathematical methods should
decline. Meanwhile, together with a knowledge of the effective distribu-
tion coefficient, they enable accurate planning of zone refining processes.
10. THE ULTIMATEDISTRIBUTION
After many passes, the solute distribution approaches a steady state,
or ultimate distribution, which cannot be altered by further passes. This
ultimate distribution is seldom reached in batch zone refining, because
the efficiency of zone passes declines as the number of passes increases.
Nevertheless, it is of interest because it represents the maximum separa-
tion possible for a given ratio LIZ of ingot length t o zone length. More-
over, a steady state is reached in continuous zone refining, which for
operation a t “total reflux” is the same as the ultimate distribution in
batch zone refining. The ultimate distribution is closely represented b y
the equation
C = AeBz (10.1)
where A and B are constants obtainable from
lc = BE/(eBz- 1) (10.2)
A = CoBL/(eBL- 1) (10.3)
which are derived in footnote 4.Extremely sharp separations are possible,
as shown by Fig. 14. A simpler, approximate description of the ultimate
distribution is obtainable from the stage concept. The number S of stages
is the number of factors of k in the ratio of the final concentration, meas-
ured a t x = 0, to the mean concentration. The ratio A / C o , obtainable
from Eq. (10.3) is just that. By solving this equation for a wide range of
k and LIT, i t was found empirically th at S is given approximately by
s = fL/l (10.4)
wheref is a fairly constant factor having a mean value around 1.4. (More
accurate values appear in footnote 28.) Equation (10.4) states the elegant
fact that the number of stages in the ultimate distribution is proportional
to the number of zone lengths in the ingot. The equation does not hold
for k > 1.
Can an ingot of length L th at has been purified to the ultimate dis-
tribution be further purified by cropping a t some length L’, removing the
impure end, and zone refining to a new ultimate distribution? The answer
28 W. G. Pfann, Trans. Am. Inst. Mining Met. Engrs. 203, 297 (1955).
is a qualified no. If rerefining is done at the new length L', nothing is

gained. If rerefining is done by letting the cropped length L' fill the orig-
inal length L, then further purification is possible. But-about the same
results can be obtained by starting with a longer ingot originally (of
length 2L - L'), without the need for cropping.
A =CoBL/(eBL-i)
L = 10,L-I
0 I 2 3 4 5 6 7 8 9 10
,
DISTANCE X
FIG.14. Ultimate distribution attainable by zone refining, for several values of k,

for an ingot 10 zones long.
11. MATTERTRANSPORT
When a molten zone traverses an ingot in an open horizontal boat,
the ingot usually becomes t a ~ e r e d .Although
~ ~ , ~ ~ the taper may be slight
after one pass, it can become prominent after repeated passes, even caus-
ing an overflow of matter at the end of the boat. Such matter transport by
a molten zone arises from the change of density on melting. The magni-
tude and direction of matter transport correspond to the magnitude and
sign of the density change. The mechanism of matter transport is basically
similar t o the mechanism of solute transport. In fact, the phenomena are
so similar that they can be described by similar equations. Contraction on
melting causes forward transport, that is, transport in the direction of
zone-travel. Expansion on melting causes reverse transport. Matter
transport can be avoided in horizontal zone refining in an open boat or
partly filled tube by tilting the ingot a t a small angle with the horizontal. 29
Matter transport can be a serious problem if vertical zone melting is
done in a closed tube. Assuming the tube to be closed at the bottom and
completely filled with solid, the recommended direction of zone travel
29 W. G. Pfann, Trans. Am, Inst. Mining Met. Engrs. 197, 1441 (1953).
30 S.E . Bradshaw, J . Electrochem. SOC.101, 293 (1954).
452 W. G . PFANN
will depend on whether the ratio a of solid density to liquid density is

less or greater than one. T o avoid cracking of the tube by volume changes
on melting or freezing, the zone should start a t the bottom for a < 1, a t
the top for a > 1. Even this precaution is no guarantee of success, for
differences in lengthwise thermal expansion between the solid charge and
the container can lead to cracking of the tube, especially if the solid is
adherent, or keyed into roughnesses in the surface of the tube.
Matter transport can be useful as well as annoying. Thus, i t can be
used t o eject pure or impure material from the ingot end during multi-
pass batch refining, or even as a means of causing a general movement of
material through the refiner in continuous zone refining.
12. SOLID-PHASE
ZONE MELTING
The principles outlined above are not limited to processes utilizing
the liquid-solid transformation. The solid-solid transformation may be
used as well. Such processes will be called solid zoning to distinguish them
from zone melting, which may, analogously, be called liquid zoning.
Two requirements are essential t o the success of any zone process
having solute distribution as an object. These are (1) the two phases in
question must differ in solute concentration a t equilibrium, i.e., k must
differ from unity. (2) The diffusivity or rapidity of mixing of solute must
be substantially greater in the phase th at comprises the zone. Both of
these requirements are generally met in liquid zoning; especially the sec-
ond, as transport is generally much more rapid in the liquid than in the
solid. A feature of all liquid zoning processes is th a t the zone phase is
always the high-temperature phase.
I n solid zoning, requirement (1) is met by transformations such as the
eutectoid or peritectoid type, of which there are many. Requirement (2)
is much more restrictive. There are very few systems in which diffusivi-
ties of a solute differ in adjacent transforming phases by a factor of 10 or
more; one notable example of this kind is the iron-carbon system.31
ZONE REFINING
13. CONTINUOUS
A continuous zone refining process has several advantages. It elimi-
nates much of the difficulty of handling small batches of material. And-
more important-it enables practical operation close to the ultimate dis-
tribution. I n batch refining it is usually impractical to approach the ulti-
mate distribution, because the pass effciency decreases as the number of
passes increases. I n a continuous process it is feasible to have a long
starting period in which the steady state is approached, because, once that
J. K. Stanley, Trans. Am. Inst. Mining Met. Engrs. 166,752 (1949).
state is reached, all material subsequently going through the refiner re-
ceives the maximum separation, but in relatively few zone passes.
The essential features of a continuous zone refining process are rep-
resented in highly generalized form in Fig. 15. A series of molten zones
produced by moving heaters travels slowly d o w n the column or charge
(to the left in the figure). (The process will be discussed in terms of a
distribution coefficient k less than unity. It is equally effective for k > 1.)
If there were no flows of feed, waste, or product, the process would be
batch zone refining, the action of the molten zones being to sweep solute
d o w n the column, solvent u p the column. For the process to be continuous,
WASTE
e
- -
PRODUCT
DIRECTION OF ZONE TRAVEL
FIG.15. Continuous zone refining apparatus (generalized).
with stripping and enriching sections in the column (we borrow from dis-
tillation for terminology), feed must enter, and waste and product must
leave, as indicated. (The solute is regarded as an impurity to be removed,
and the solvent as the desired product.) A method known as the zone-
void method has been devised2*to accomplish these objectives, namely
the indicated zone movements and material flows, with a minimum of
apparatus. Zones are moved by moving heaters, just as in batch zone
refining. Materials are made to flow by creating voids a t the waste and
product exits and causing these voids to move to the feed inlet. Since
there must be a net flow of material from the feed inlet to each of the
outlets, the indicated movements of voids are in the desired directions,
because movement of a void in a given direction corresponds to flow of
material in an opposite direction.
I n order t o produce the desired movements of voids, the column is
folded into two vertical sections having the feed inlet in common a t their
upper ends. Voids are displaced upward by the liquids in the molten zones
and their travel is actuated by the motions of the zones. I n the enriching
section the voids travel with the zones and move continuously, while in
the stripping section they travel opposite to the zones and move inter-
mittently. Creation and travel of voids will now be examined in detail.
The enriching section of a column in operation, with its void generator,
is shown in Fig. 16. The column section is a vertical tube around which a
series of closely fitting, regularly spaced heaters travel slowly upward.
Each heater produces a molten region, the temperatures of the heaters
and the cooling between heaters being controlled so as to maintain the
454 W. G. PFANN
molten zones approximately constant in size. A void is normally present

atop the molten zone in each heater. As the heater rises, it continuously
melts solid above it, which drips through the void into the molten zone
and continuously freezes out solid below it,
of concentration k times that of the liquid
in the zone. When a molten zone and void
reach the feed inlet, which is kept molten,
the void is displaced by an equal volume
of feed liquid.
tt Figure 17 shows how a void of controlled

size is produced in the enriching section.
The void generator is a tube of small cross
Q
w s
I
0vl
+
section, provided with lateral heat-conduct-
ing fins which sense the position of the
heater. Liquid can escape only when the
entire outlet tube is within the heater. If
any part of the outlet tube is outside the
heater, liquid cannot escape, since the walls
of the tube, being cool, freeze the liquid and
thereby block the tube. I n (b), the maximum
1
volume of liquid that can escape is shown,
and its escape has created a void of volume
1
V . I n (c) and (d) the void is seen moving
FIG. 16. Enriching section of
zone void refiner. “down” the column atop the molten zone.
Thus, a molten zone of length 1 and a void
of length h - 1 is produced by a heater of length h, where 1 is the length
of the outlet tube, each time a heater travels past the end of the column.
(The volume of the outlet tube is assumed negligible.) Many other
designs of void generator are feasible, including simply a constricted tube
a t the column end.
I n the stripping section, voids are created much as in the enriching
.-o
‘HEATER
(ONE-HALF SHOWN)
(0) (b) (C1 (d 1

FIG.17. Creation and travel of void in enriching section of zone void refiner.
section, even though the heaters move downward, and move upward
intermittently. Better control of zone length is required in the stripping
section, because a t times there are two solid zones and a void between a
pair of heaters.
Thus, in both sections, material flows through the column contin-
uously in controlled amounts, despite the blocking of the column at all
times by plugs of solid material. A complete zone-void refiner is shown
WASTE 1 PRODUCT
FIG. 18. Complete zone void refiner (schematic).
schematically in Fig. 18. The heaters move with reciprocating motion,

traveling forward slowly and backward rapidly a distance equal to the
heater interval. A mechanically simpler zone-void refiner can be con-
structed with but one heater in each section, or even with one heater in
all. It could produce separation equivalent to th a t of a multi-heater
refiner, but the yield per unit ttime would be less.
The differential equations for the steady state of a zone-void refiner
have been solved by H. Reiss; the solutions are given in footnote 28 in
terms of the length of column required to effect a desired separation,
given k , I, and h. Constructional details for other designs, including spiral
456 W. G. PFANN
columns, are given in footnote 32. I n essence, the ratio l / ( h - I) of molten

zone volume to void volume is analogous to a reflux ratio. The ratio is
infinity a t total reflux, which condition is really batch zone refining, since
no material is removed. The minimum permissible reflux ratio is limited
by the value of k , which here is analogous to a separation factor in
distillation.
At this writing, development of the zone-void method is in the experi-
mental stage. Although refiners have been successfully operated, no re-
sults have been published. Choice of a column material is a problem, in
that cracking of the tube walls must be avoided. I n the author’s opinion
some version of the method will find use for low-melting metals or chem-
icd s in the near future.
IV. Practice of Zone Refining
14. GENERALCONSIDERATIONS
The primary object of zone refining apparatus is t o pass molten zones
through a charge. An important secondary object is to do so in the least
time consistent with a desired yield of material of specified purity. The
design problem amounts to optimizing the following parameters: zone
length I; interzone spacing i; travel rate f ; and film thickness 6, which is
determined by stirring conditions in the zone. I n general, small 1 is de-
sired because i t makes for better separation (at least for large numbers
of passes). Small 1 and i make for small time per pass. (Small i involves
multi-heater operation.) Large f also makes for small time per pass, but,
as was shown in Part 11, the distribution coefficient k approaches unity
rapidly as f increases beyond a certain range. Forced convection, as by
stirrers, permits increase in f without increase in k , by reducing 6. Both
f and 6 have equivalent effect on Ic; 6 varies approximately inversely as
the square root of the velocity of fluid flow parallel to the freezing
interface.
If k is fixed, by fixing f and 6, then the number of passes for a given
separation is fixed. Choice of the remaining parameters I and i will be
determined by an economic compromise between the short running time
afforded by low 1 and i, and the added expense of maintaining short, close
zones. This expense will result from the provision of more precise tem-
perature control, or from the higher power required for steeper tempera-
ture gradients between hot and cold regions, or both.
Something can be gained by changing the zone length during the
process. Long zones transport more solute per pass than short ones, in
a2 W. G. Pfann, U. S. Patent 2,739,045, March 20, 1956.
the early stages of refining, when concentration gradients are small, but
short zones are more effective when the gradients are large. A combina-
tion of m long zones followed by n short zones generally can provide a
better yield than (m + n) zones of equal length. Burris et aLZ6give com-
putations for this method, and Harman33has used it to refine InSb.
Practical travel rates used for metals and semiconductors generally
range from about 1 t o 25 cm/hr. This range includes cases of induced-
current stirring, but none of mechanical forced convection. These rates
generally might be regarded as low, and lead one to consider means of
increasing the cross section of the zone. Although so far most zone refining
has been done with cross-sectional areas of the order of square inches, it
appears quite feasible to use areas of the order of square feet. An impor-
tant proviso is that one dimension of the cross section be kept small, so
tha t short, close zones are possible. Thus a flat charge, about the size and
shape of a heavy table top, say 3 ft by 2 in. in cross section, is preferable
to one of circular cross section and equal area.
15. ZONEREFININGWITH A CONTAINER
The problem of zone refining becomes much simpler if a suitable con-
tainer can be found. Particular materials for particular metals will not be
discussed here, as these, and the problems of finding them, will be known
from other melting experience. Instead, we make a few general remarks on
the chemical and physical properties of the container that pertain to
zone refining. The main problem is to find a material that will not con-
taminate the melt. Contaminants may be agents on the surface of the
container, gases in interstices of porous containers, impurities occluded
or in solid solution in the substance of the container, or the very material
of the container. Where high purity is an object, these sources of con-
tamination must be minimized. Physically as well as chemically, it is
desirable that the liquid not wet or adhere to the container, as this may
result in cracking due to differential thermal contraction. For best con-
trol of zone length and spacing, the longitudinal thermal conductance of
the container should be lower than or comparable to that of the charge. At
the same time, and for the same reason, lateral heat transfer should not
be limited unduly. A conducting container, such as graphite, is useful
in heating by induction, for it can serve as a heat source for the charge
within. It is better yet to heat the charge directly so as to minimize con-
tamination from the container.
Many methods of heating the zones have been used or proposed.
These include resistance heaters, induction or dielectric heating, gas
flames, electron beams or arcs, focused radiation, such as infrared radia-
3 3 T. C. Harman, J. Electrochem. SOC.103, 128 (1956).
458 W. G. PFANN
tion34~35or sunlight. Immersion heaters are particularly effective, although

they add to the mechanical complexity of the apparatus. Joule heating
of the substance itself, concentrated near an electrode has been proposed. 36
Ingots of straight, circular, and helicoid form have been used. A cir-
cular or spiral charge, contained in a groove in the upper surface of a
turntable rotating about a vertical axis, has much to recommend it.
Stationary heaters may be placed at intervals around the periphery,
(C)
FIG.19. Methods of passing n molten zones through a n ingot of length L : (a) one
+
heater, n passes; (b) n heaters, one pass; (c) L / d heaters, n (L/d) - 1 reciprocating
strokes of length d. Ingot is shown full a t beginning of stroke, dashed a t end.
above or below the charge. For a spiral of several turns, each heater may
melt several adjacent zones. A helicoid charge, contained perhaps in
plastic tubing, rotating about a horizontal axis, can provide many zones
in a short space using a single heat source and heat sink. Such an arrange-
ment can be used for zone melting a substance that is liquid a t room
temperature, by having the lower half of the coil rotate in a freezing mix-
ture while the upper half is exposed to a heat source, such as an infrared
lamp.
A reciprocating heater arrangement is economical where straight
34 R. Handley and E. F. G. Herington, Chemistry & Industry p. 304 (1956).

36L. R. Weisberg and G. R. Gunther-Mohr, Rev. Sci. Instr. 26, 896 (1955).
36 F. C. Hull, P. H. Brace, G. Comenetz, and A. W. Cochardt, U. S. Patent 2,743,199,
April 24, 1956.
TECHNIQUES O F ZONE MELTING .AND CRYSTAL GROWING 459
charges must be used. A number n of zones can be passed through a

straight ingot of length L in the following three ways, illustrated in Fig.
19, which are equivalent in purifying effect. (1) By n passes through one
heater. This method wastes time. (2) By one pass through n heaters.
This method does the job in the least possible time, but requires marly
+
heaters if n is large. (3) By a series of (n H - 1) short, reciprocating
strokes, using H heaters, as in Fig. 19C, where H = L / d and where the
stroke length is the heater interval d . A stroke begins with the leading
edge of the ingot about to emerge from the first heater. The ingot ad-
vances slowly a distance d , whereupon it
rapidly returns to its starting position, trans-
ferring each molten zone to the next heater.
Any number of zones can be passed by repeat-
ing the cycle. Further details including an
analysis of the economics of the technique,
appear in footnote 37.
16. ZONE REFININGWITHOUT A CONTAINER

Certain metals and semiconductors are so
reactive that they cannot be zone refined to
high purity in any known container. Several
methods of zone melting without a container
have been proposed to handle these. While the
methods impose certain limitations on the
operation, they have resulted in some of the
purest materials ever produced. The most
widely used t o date is the $outing zone tech-
nique, in which a molten zone is held in place
by its own surface tension between two pIG. 20. Floating
vertical colinear solid rods, as shown in Fig. technique (schematic).
20. The method has been described by Keck
and G ~ l a y ,E~ m
* e i ~and ,~T ~ h e ~ e r e r ,the
~ " first application being to silicon.
The first p u b l i c a t i ~ ngave
, ~ ~ the method its name and stimulated much
work on i t (although the technique appears to have been developed inde-
pendently by several others).
The stability of floating zones has been analyzed mathematically.
37M. Tanenbaum, A. J. GOSS,and W. G. Pfann, Trans. Am. Inst. Mining Met.

Engrs. 200, 762 (1954).
38 P. H. Keck and M. J. E. Golay, Phys. Rev. 89, 1297 (1953).
39 R. Emeis, 2.Naturforsch. 9a, 67 (1954).

4oH. C. Theuerer, Trans. Am. Inst. Mining Met. Engrs. 206, 1316 (1956).
460 W. G . PFANN
Thus Heywang and Ziegler,41 and later H e y ~ a n g 4in~ greater detail,

showed that the maximum length of zone that can be supported by its
own surface tension increases linearly with rod radius for small radii and
approaches a limit a t large radii; alsi, th at the limiting maximum length
is a function of the material, the critical parameter being d&,where u
denotes surface tension and p denotes density. It has been demonstrated
that zones up t o 1.2 cm in diameter can be supported, and even larger
values have been reported. There appears to be no theoretical maximum
diameter, a t least for diameters of the order of several centimeters. An
earlier analysis,43which stated th at only certain discrete zone lengths
were stable and that a maximum diameter exists, appears to be in error.
H e y ~ a n has
g~~ also considered in some detail the stability conditions for
a process in which the upper rod is smaller than the lower (and moves a t a
correspondingly faster rate). A single crystal of silicon being grown by
the floating zone process is shown in Fig. 21. The method has been used
successfully for iron, zirconium, titanium, molybdenum, and other metals
(see below).
Most floating zone experimentation has been done with induction
heating, although graphite or tungsten heating elements also have been
used. Davis et al.44have described a floating zone technique in which
focused electrons from a ring-form tungsten filament melt a zone in
tungsten.
The levitating action arising from the repulsion between induced and
inducing can be utilized. For example, some additional support
can be given to an inductively heated floating zone by cooling the lower
rod so that the zone lies above the induction coil. A technique called
cage zone refining has been described,46 in which an inductively melted
zone is supported in a vertical square ingot having longitudinal ribs,
which do not melt. The zone is supported by surface tension abetted by
the ribs. The authors state th at the levitation effect described above gives
added support. They gave some data for titanium; to date, no detailed
results have appeared.
A magnetic suspension method, based on a principle set forth by
Faraday, was described and analyzed by Pfann and Hagelbarger.47 The
41 W. Heywang and G. Ziegler, 2. Naturforsch. 9a, 561 (1954).

42 W. Heywang, 2. Naturforsch. lla, 238 (1956).
43 P. H. Keck, M. Green, and M. L. Polk, J . A p p l . Phys. 24, 1479 (1953).
4 4 M. Davis, A. Calverly, and R. F. Lever, J . A p p l . Phys. 27, 195 (1956).
46D. M. Wroughton, E. C. Okress, P. H. Brace, G. Comenetz, and J. C. R. Kelley,

J . Electrochem. Sac. 99, 205 (1952).
4 6 P . H. Brace, A. W. Cochardt, and G. Comenetz, Rev. Sci. Znstr. 26, 303 (1955).
4 7 W. G. Pfann and D. K. Hagelbarger, J. A p p l . Phys..27, 12 (1956).

method is as follows. Through a horizontal round rod of the material to

be zone melted, pass a direct current I . Provide, where the zone is to be
melted, a uniform, constant magnetic field of strength H , normal to the
FIG.21. Single crystal rod of silicon being grown by floating zone technique using
induction heating (courtesy of H. C. Theuerer).
rod and horizontal, as shown in Fig. 22. There will result a vertical force
F , which will exactly counterbalance the force of gravity if
HI = lOpg7rd (16.1)
where p and a are density and radius, and g is the acceleration due to
gravity. If now, with H I determined from Eq. (16.1), a molten zone is
formed in the rod, it will remain stably suspended if certain conditions
are met. These are that the length of the zone be less than its circum-
462 W. G . PFANN
ference and less than an absolute value that depends on the material.
For aluminum and silicon the maximum length I, is about 3 cm, which
is significantly larger than lmsxfor the floating zone method. The authors4'
give a general expression for Lax.
Certain difficulties arise in practice, which stem from differences in
current density that may arise in the zone. The zone may become un-
stable if it develops a marked bulge or neck. It is difficult to establish a
zone if the electrical conductivities of liquid and solid differ greatly, as
they do for germanium. The magnetic method as well as the floating zone
method, therefore, are useful for materials having a high ratio of surface
F
1
FIG.22. Magnetic suspension of a molten zone (schematic).
tension t o density. These include light metals such as aluminum, and

denser metals of high melting point (surface tension generally increases
with melting point) such as iron and titanium. It seems less favorable
for chemicals of low melting point. The methods still leave something t o
be desired where volume production is an object. Both methods would,
of course, work ideally in a space station.
Less elegant, but probably in the long run, the answer to the need for
volume production, are techniques in which the charge serves as its own
container. A horizontal slab can be melted from the top so that the zone
does not penetrate completely through the cross section. This approach
poses control problems, and untraversed material must either be removed
or traversed by succeeding zones. I n addition to making large volumes
feasible, this technique enables the establishment of a series of zones in
the ingot, in contrast to the single-zone floating-zone technique. This
technique can be combined with the magnetic suspension technique to

keep zones from running over the side of the ingot.
17. SOMEAPPLICATIONS OF ZONE REFINING
Examples of the application of zone refining to semiconductors.

metals, and chemicals will be reviewed. It is not intended to cover the
field exhaustively, but merely to give enough examples to indicate the
scope and possibilities of zone refining. Since the semiconductor germa-
nium was the first material to be extensively purified by zone refining,
and since more germanium than any other substance has been zone re-
fined, we choose it as our first example.
a. Germanium
This material has been widely used in semiconductor diodes and
transistors. The invention of the transistor brought pressure for germa-
nium of extremely high purity with respect to certain elements. These
FIG.23. Induction-heated zone refining apparatus used for germanium.

are the conductivity-producing elements, of Groups 3 and 5 of the
Periodic Table, and certain others; and elements that impair carrier
lifetime, such as copper, nickel, iron, and others. (Impurities in germa-
nium were reviewed by Burton.48)Six zone passes through an ingot of
the then purest commercially available germanium sufficed to reduce
these elements to concentrations less than 1 in 1 0 ' 0 atoms of germanium,
a truly spectacular result.49This process was quickly adopted by manu-
facturers. Typical apparatus using 1 or 2 lb ingots is shown in Fig. 23.
The success of the process with germanium can be attributed to favorable
distribution coefficients, the low reactivity of molten germanium, and the
availability of a suitable crucible material, high purity graphite. With
respect to elements not detectable by measurements of electrical conduc-
tivity or carrier lifetime, zone-refined germanium has been shown to
contain less than 1 part in lo7 of any element detectable on the solid
mass spectrograph.60 There are a host of elements in this class, but
48 J. A. Burton, Physica 20, 846 (1954).
49 W. G. Pfann and K. M. Olsen, Phys. Rev. 89, 322 (1953).
6 0 N. B. Hannay and A. J. Ahearn, Anal. Chem. 26, 1056 (1954).
464 W . G. PFANN
hydrogen and oxygen, whose lines are present in the background in all
mass spectrograph measurements, are not included. Recent work by
Kaiser et ~ 1 . and
5 ~ by Thurmond et aL5' has indicated t h a t as much as
-100 ppm of 0 2 aiid Hz may possibly be soluble in germanium (although
not necessarily present after zone refining). The effectiveness of zone
refining in removing small concentrations of these elements is being
studied.
b. s'ilicon
Silicon has come into favor as a material for diodes, transistors, and
solar hat,teries. Here too, extreme purity is essent,ial, especially for tran-
sistor applications. However, silicon is much more difficult t o purify than
germanium. One of its common impurities, horon, has a distribution coeffi-
cient of about 0.8, which is much higher than the /i's for germanium.
Moreover, silicon is extremely reactive. The most widely used container,
fused silica, is slowly attacked by molten silicon, contaminating the melt
with horon, oxygen, arid probably other elements. Neverthcl -r ess conven-
tional, horizontal-boat zone refining has been used with good effect.53
Boats of extremely thin quartz are used, as the solid silicon adheres to
the quartz, and thick boats would crack. For higher purity, the floating
zone technique has been quite succlessful. For example, Kaiser et aL5'
have shown that a floating zone treatment in vacuum reduces the oxygen
content of silicon below the limit of detection, < 1 ppm. The purest
silicon of which the author is aware has heen prepared by a combination
gas-liquid reaction and floating zone refining. The method, which is due
to Theuerer,4f1removes horori hy M atcr vapor oxidation, performed on a
floating zonc, and removes other impurities by conventional floating zone
passes.
c. Other Scmiconrlitctors
The 3-5 csompourrtls, such as InSh, AlSh, GaAs, aiid InP are sernicon-
ductors with the same type of lattice as silicon, which is in Group 4 of the
Periodic Zone r c h i n g has bcen uscd extensively to prepare these.
I t is common practice to zotic refine one or 110th of the components, and
also thc compound itwlf. IZcsults have h e n published for A1Sb,55I I ~ S ~ , ~ ~ ,
51 LV. Kaiser, 1'. H . Iicck, ; ~ r i t l C:. F. Lange, PhU.s. Ir'ev. 101, 1264 (1956).
52 C. D. Tlriirmontl, IV. G . Grildner, and A. 1,. Bcach, J . E'(ectrochem. S O C . 103, 603
(1956).
53 F. H. Horn, private, conrmiinic*ation.
5 4 H. \Vclker, X. :Vnlii&rsch. 7a, '744 (1952).
5 5 11. A. S c h d l , Z. Alela((kunrle 46, 58 (1955).
5 6 M. Tnnenbauiri and H. R. Briggs, I'hys. Rev. 91, 1561 (1953).

InP J 57GaAs15' and others. The paper by H a ~ - m a nis~an

~ excellent exam-
ple of the use of zone refining as an analytical tool. Results for other
semiconductors have been reported; for example, Bi2Te3,68and Te.69
Preparation of certain semiconducting compounds, such as GaAs, is
complicated by the high vapor pressure of one component: Furthermore,
even where this problem does not exist, the composition of maximum
melting point is not necessarily the stoichiometric composition. Such
matters are discussed in a series of papers by H. van den Boomgaard and
co-workers. 60-63
d. Aluminum
Perhaps the first published example of unusual physical properties
accompanying zone refining of a metal is that of aluminum as reported
by Montariol et aL64 Three zones, formed by induction heating, were
passed through an ingot of electrolytically refined aluminum in a boat
of A1203 a t a very slow rate (5 mm/hr). The lead end of the ingot was
decidely purer than the starting material, as judged by activation analysis
and by low-temperature electrical resistivity. The unusual physical char-
acteristic of the zone-refined material was its recrystallization t o a large
grain size even when rolled and stored a t temperatures well below room
temperature. These results are described in further detail by Albert and
Le H e r i ~ y . ~ ~
e. Iron
Smith and Rutherford66reported on the purification of iron and other
metals by the floating zone method. Iron rods u p to 6 inch in diameter
were heated by induction in an atmosphere of purified helium. After 8
passes a t 2 in./hr, a clean microstructure was obtained in a vacuum-
melted Fe-0.3%C alloy. The content of radioactive phosphorus P32in
Swedish iron was reduced to 2% of its original value at the starting end
of the rod by 6 zone passes. Zone refining of a specially prepared ingot of
b7 0. G. Folberth and H. Weiss, 2.Naturforsch. 10a, 615 (1955).

68 T. C. Harman, S. E. Miller, and H. L. Goering, Bull. Am. Phys. Soc. 30,35 (1955).
63 R. E. Stajdohar and H. H. Hall, to be published.
G o J. van den Boomgaard, K. A. Kroger, and H. J. Vink, J. Electronics 1, 212 (1955).
81 J. van den Boomgaard, Philips Research Repts. 10, 319 (1955).
82 J. van den Boomgaard, Philips Research Repts. 11, 27 (1956).
8 3 J. van den Boomgaard, Philips Research Repts. 11, 91 (1956).
64 F. Montariol, R. Reich, P. Albert, and G. Chaudron, Compt. Rend. 238 (7), 815
(1954).
66 P. Albert and J. Le Hericy, Compt. Rend. 242, 1612 (1956).
88 R. L. Smith and J. L. Rutherford, J. Metals 9, 478 (1957).
466 W. G. PFANN
iron produced, at the pure end, material that exhibited a ductile failure
in tension a t 4.2"K-a highly significant result.
Studies such as this, and that of Kneip and Betterton on zirconium
(see below), illustrate an important application of zone melting tech-
niques in the metals field-namely, research on the effects of small con-
centrations of certain impurities on the behavior of some of the more
reactive, high-melting metals such as Fe, Zr, and Ti. Such studies include
mode of allotropic transformation, mechanisms of deformation, and the
various strength properties.
f. Zirconium
Kneip and BettertonG7have described the purification of zirconium
by the floating zone method. Available zirconium, made by the iodide
decomposition process, contained sufficient impurity to cause the a-/3
transformation to occur over a temperature range from 16" to 70"C,
depending on the lot. Such zirconium is unsuitable as a base material for
studying effects of solutes on the a-p transformation. Trace amounts of
Fe and Ni are particularly injurious. Three to six zone passes at 6 in./hr
reduced the Fe and Ni contents to less than 2 ppm and reduced the
temperature range of transformation of a particular lot from 18" to 8".
It is interesting to note that in all these examples of metal purification
(Al, Fe, Zr) the workers concerned used radio-active tracers or activation
analyses to measure the small concentrations involved. Albert68has de-
scribed such techniques in some detail.
g. Gallium
Two approaches have been made in zone-refining gallium. Detwiler
and Fox69 refined gallium directly in a reciprocating refiner utilizing
refrigerated coils to maintain solid regions between zones. Their analyti-
cal results as described were a bit indefinite, as lead was the only impurity
shown to be moved (although no others were detected in the zone-
refined material). A roundabout approach was used a t the Services
Electronics Research Laboratory in England.'O Gallium was converted
to its salt GaC13, which was given 20 zone passes and reconverted to
metallic gallium. Impurities such as Cu, Fe, Ca, Mg, Si, All and Ag,
present originally in amounts ranging from 10 to 70 ppm were reduced to
less than 1 ppm by the technique. I n both instances extremely pure
gallium was desired for semiconductor applications.
6' G. D . Kneip, Jr. and J. 0. Betterton, Jr., to be published in J. Electrochem. SOC.
6* P. Albert, Chimie & industrie 76, 275 (1956).
6 9 D. P. Detwiler and W. M. Fox, J . Metals 7, 205 (1955).
~ I Chem.
I Eng. News, p . 2887, June 11, 1956.
h. Bismuth
Purification of bismuth by zone refining has been investigated by
Sajin and Dulkina.7’ They used a circular tubular container rotating in a
horizontal plane through a series of heaters a t a rate of 1.1 cm/hr. Re-
moval of Zn, Sb, Cu, and Ag was studied with the help of radioactive
tracers of these elements added in concentrations All four im-
purities were moved, Sb to the front, the others to the rear, of the charge.
They give data on crystallization by the Czochralski crystal pulling
technique also, as a function of pull rate. The results suggest that im-
purities were also removed by oxidation.
Zone refining of bismuth has also been explored by Wernick et a1.72
They used induction-heated zones and sealed the ingot in an evacuated
Pyrex tube. Ag, Cu, Pb, Sn, Nil Mg, Ca, and Fe were moved by the zones.
The first four were not detectable spectroscopically at the front of the
ingot. Because lc > 1, Fe was concentrated a t the front; Nil not detect-
able in the original material, was found concentrated a t the end of the
ingot; Mg and Ca were still detected, being moved slowly. Twelve passes
a t 1.8 in./hr we% sufficient to make Ag, Cu, Pb, Sn undetectable by
spectroscopy at the front of the ingot. The total impurity content near
the front of the ingot, but beyond the iron-rich region, was less than
10 ppm.
i. Antimony
Limited data on the zone refining of antimony have been given by
, ~ ~ by Tanenbaum et a1.37Pure antimony was desired for pre-
S ~ h e 1 1and
paring semiconducting compounds. Sche1148 reported that all impurities
having an estimated distribution coefficient k < 0.2 were removed.
Tanenbaum et aL37 showed that the concentrations of Nil As, Pb, Ag,
and Cu were reduced by a factor of 10 or more by 7 zone passes in a ni-
trogen atmosphere. Arsenic, having lc l, was not removed, but is re-
movable by chemical means. After 10 zone passes through material thus
treated, the only impurities detectable by mass spectroscopy were Zn
and As, in concentrations of about 1 part in 10 million.
j . Tin
Very preliminary data on the zone refining of tin37show that 99.99%
Sn can be converted to 99.999% Sn by 40 or fewer zone passes in Pyrex
N. P. Sajin and P. Y. Dulkina, in “International Conference on the Peaceful Uses

of Atomic Energy,” Vol. 9, p. 265. United Nations, New York, 1956.
72 J. H. Wernick, K. E. Benson, and D. Dorsi, to be published in J . Metals.
468 ’ W. G. PFANN
glass, Pb, Cu, and F e being moved. High-purity tin and antimony, made
using zone refining, are available commercially.
k . Chemicals
A few publications on the purification of organic and inorganic chem-
icals by zone refining have appeared, These include napthalene,73*74ben-
zoic acid,34~ y r e n ea1ithracene,~4
,~~ c h r y ~ e n eand
, ~ ~benz01,~~
the last being
a material that melts below room temperature. New applications in this
field are rapidly increasing.
Several general articles have appeared in which details of apparatus
and techniques of zone melting, experimental results, possible uses, etc.,
are d i s c u ~ s e d . ~ ~A- *comprehensive
~ treatment of the entire subject of
zone melting appears in Zone Melting by W. G. Pfann.81
V. Zone Leveling
The young physicist mentioned in Part I1 would not have soured on
Mother Nature had he known about zone leveling methods,4 for these
methods were specially designed to avoid the impurity segregation that
irritated him. When we use the term segregation, we refer not to large
castings whose freezing is accompanied by growth of dendrites, evolution
of gas, formation of shrinkage cavities, and the various and complicated
phenomena of normal and inverse segregation. We refer, instead, to slow,
directional solidification, a t rates and with precautions akin t o those used
in growing single crystals, where the many complications of large scale
ingot freezing are absent. A high commercial premium is placed on such
careful preparation of materials in fields such as semiconductors and scin-
tillation crystals. Single crystals of precisely controlled impurity content
and perfection are increasingly regarded as essential in research on solids.
I n this part we discuss various methods of zone leveling in idealized
terms. Practical applications of these techniques will be discussed underJ
single crystal growing (although i t will be understood that zone leveling
does not necessarily imply single crystal growth).
73 H. C. Wolf and H. P. Deutsch, Naturwissenschaften 41, 425 (1954).

74 E. F. G. Herington, R. Handley, and A. J. Cook, Chemistry & Industry p. 292
(1956).
75 H. Rock, Naturwissenschaften 4, 81 (1956).
7 6 W. G. Pfann and K. M. Olsen, Bell Lab. Record 33, 201 (1955).
77 W. G. Pfann, Chem. Eng. News 34, 1440 (1956).
7 8 F. Montariol, C h i d e & zndustrie 76, 57 (1956).

79 C. H. L. Goodman, Research (London) p. 168, May, 1954.
8 0 W. G. Pfann, U. S. Patent 2,739,088, March 20, 1956.
$1 W. G. Pfann, “Zone Melting.” Wiley, New York, in preparation.

ZONE MELTING
18. SIMPLX
It was shown in Part I11 that passing one zone through an initially
uniform charge can produce a region of uniform concentration between
two end regions of nonuniform concentration. The extent of the uniform
region depends on k and the ingot length. For an ingot 10 zones long, a t
least 70% will be within 20% of the mean concentration Co for k > 0.5,
including all k > 1. This method of zone leveling is especially useful if
lc is substantially greater than unity. An example of its use is the addition
of boron t o germanium (D. Dorsi, private communication), k for boron
being about 5 a t a growth rate of about 0.0025 cm-sec-l. For k < 0.5,
one of the following methods will generally be better.
CHARGE
19. SIMPLEZONE MELTINGWITH STARTING
The initial transition region in simple zone melting results from the
fact that the zone must travel some distance before it accumulates enough
solute, for k < 1 (or loses enough, for k > 1) to attain concentration
tC
U
z
0
K
F
z
Y
s
W
-
F
A
0
u)
01 I
0 LENGTH SOLIDIFIED, X
FIG.24. Zone melting with charge adjusted at first zone to eliminate initial transi-
tion region.
C o / k . Once this concentration is attained, the concentrations entering and

leaving the zone remain constant until the zone reaches the ingot end and
normal freezing commences, as was shown in Fig. 7. The initial transition
region can be eliminated by arranging the starting charge so as to have a
concentration Co/k in the first zone length and Co in the remainder, as
shown in Fig. 24. Practical ways of so arranging the starting charge are
simple. For example, the two-rod technique mentioned in Part I11 can
be modified by appropriately adjusting the cross sections in the first
zone. This and the preceding method have been used to produce homoge-
470 W. G . PFANN
neous single crystals of Ge-rich Ge-Si alloys,s2which are extremely prone

to segregation, k for Si in Ge being about 3.
Zone leveling using a volatile solute has been investigated mathemati-
cally and experimentally b y J. van den B o ~ m g a a r d . ~ ~
20. STARTINGCHARGEINTO PURESOLVENT
This method is extremely effective if k is very small, less than about
0.1. Solute is placed only in the first zone length of the starting charge.
The remainder is pure solid solvent. The concentration C in the solid
after one pass is given, except in the last zone length, by
C = kCie-hz/l (20.1)
where Ci is the concentration of the charge in the first zone length. Cal-
culated concentration curves for a range of k’s appear in Fig. 25. While
most of these fall sharply with distance in zone lengths x/Z, that for
k = 0.01 falls only 10%in ten zone lengths. (This may be contrasted with
a rise of 1000% in the first 90% of a normally frozen ingot for the same k.)
Even this decrease can be prevented by reducing the volume of the
zone as i t travels, so as to maintain the concentration in the zone con-
stant. For a charge of constant area a, the zone length 1 must be decreased
as follows:
1 = I, - kx (20.2)
where l o is the initial zone length. If I is to be held constant, then a must
be varied in accord with
a = aoeZ/D (20.3)
where
D = Z/log, (1 - k) (20.4)
and a0 is the area a t z = 0. Equation (20.2) is applicable only to a charge
of finite length Zo/k, for a t that value the Z must become zero. Equations
(20.2) and (20.3) are valid only for k < 1. They are derived in footnote 4.
The method in which the zone length is constant has been extremely
effective for preparing ingots of ge~rnanium,~g and also silicon.40 The
solute concentrations involved are usually very small, atom frac-
tion. It is used commercially for germanium.
21. REPEATEDPASS
If enough back-and-forth passes are made in a straight charge, all
deviations from a uniform composition can be eliminated, except in the
last zone to freeze. I n this respect, the zone may be likened t o a weighted
s2 A. J. Goss, private communication; C. C. Wang and B. H. Alexander, Semicon-
ductor Symposium of American Institute of Mining and Metallurgical Engineers,
New York City, February 15, 1954 (Oral).
drag, moved across soil in order to level it. The drag picks up soil at high
spots, drops it at low spots. Similarly the molten zone eliminates points
of high and low concentration in the charge, the action being particularly
effective if 11 - kl is large. For a starting charge of mean composition
ZONE -LENGTHS SOLIDIFIED,X/L
FIG.25. Calculated curves for zone melting with starting charge having all of the
solute in first zone, pure solvent in the remainder. Curves show solute concentration
in solid versus zone lengths solidified x / l , for various k’s.
Co, not assumed uniform, and length L, the final concentration C f of the
uniform charge is given by
Cf/C, = kL/[kL + Z(1 - k)]. (21.1)
An alternate technique is to pass one or more zones in one direction

around a continuous ring-shaped charge. Repeated-pass methods are
useful especially where the concentrations and distribution coefficients
472 W. G. P F A N N
of the solutes in the charge are unknown. However, they are more time-
consuming than the methods described in Sections 18-20.
VI. Methods of Perturbing the Concentration
Up t o this point we have discussed solidification either by normal
freezing or zone melting, under the assumptions that the freezing rate
and stirring conditions were constant, th at materials were neither added
to nor taken from the melt, and (in zone melting) th a t the volume of the
zone was constant. I n this part we discuss methods of perturbing the con-
centration so as to obtain solute distributions differing from those of
“standard ” normal freezing or zone melting operations. By the term
perturbations we generally mean abrupt changes in concentration, as
a t n-p-n junction^,^^ but we also mean gradual changes in concentration
designed, for example, to modify the normal course of the over-all ingot
segregation.
One could, without great difficulty, list many ways of perturbing the
concentration of a solidifying melt. We do not attempt this, but instead
discuss a few general categories into which most or all of these methods
fall, giving examples of the more well-known ones. The assumptions a t
the beginning of the preceding paragraph form the basis of classification.
Accordingly, we discuss methods of perturbing the concentration by
changing (a) the composition of the melt, (b) the volume of the melt, and
(c) the conditions of growth. A fourth category discussed involves a solid
state diffusion treatment following one of methods (a) to (c).
22. PERTURBATIONS
BY CHANCING
THE COMPOSITION
OF MELT
THE
Consider how one might avoid the segregation resulting from the
normal freezing technique described in Part 11. As freezing progresses,
the solute concentration in the melt rises, for a solute having k < 1, or
falls, for k > 1. It would appear therefore, that t o obtain a uniform con-
centration in the ingot, one must continuously remove solute for k < 1,
or add i t for k > 1. Removal is feasible for a solute of high vapor pressure.
I n this case the freezing rate must be programmed so th a t volatilization
of solute from the melt! just compensates for enrichment of the melt by
segregation. For k > 1, the solute may be added in gaseous, liquid, or
solid form. When solute is added, the melt generally must be stirred so
as to maintain a uniform concentration. Where a single crystal is desired,
the addition and mixing of a solute compound the problems of obtaining
it.
An effect equivalent to removing solute may, of course, be achieved
83 W. Shockley, “Electrons and Holes in Semiconductors.” Van Nostrand, New York,
1950.
by adding solvent. Thus a germanium crystal doped uniformly with anti-

mony (for which k < I), could be grown by a crystal pulling method in
which a germanium rod is dissolved into the melt a t a rate such as to
maintain a constant concentration of antimony therein. Such a procedure
has been described,84and various other versions have been tried. They
amount, from one point of view, t o variations of zone leveling-more
troublesome variations, it might be added.
The solute concentration in a growing crystal can be increased ab-
ruptly by adding a pellet of solute to the melt during crystal growth.
The solute may be the same as that already in the melt, or it may be
different. If the melt is a semiconducting material, such as germanium,
a p - n junction can be produced by adding a donor element (or Group 5
of the Periodic Table) to a melt containing an acceptor element (of
Group 3).a5 This method, and in fact all p-n junction techniques, take
advantage of the phenomenon of compensation, described by Scaff
et aLlE6in which the observed conductivity corresponds to the atomic
excess of donor solutes over acceptor solutes in the solid.
The abruptness of such a junction, th at is, its concentration gradient,
increases with increased turbulence in tjhe melt and with decreased growth
rate. Certain properties of p - n junctions, e.g., capacitance, depend on the
concentration gradient a t the junction; and the turbulence of the melt or
the growth rate can be used to control this gradient. To produce a step
junction, having an extremely high concentration gradient, ‘(pilldoping”
followed by the “melt-back ” technique, introduced in another connec-
tion by HalllE7can be used. I n this technique, after doping, and with con-
tinued agitation of the melt, the growing crystal is melted back a short
distance and then growth is resumed.
An n-p-n junction can be made by double-pill doping, that is, by drop-
ping an acceptor-doped pill into a melt doped lightly with a donor, and
then dropping a donor-doped pill into the melt to reconvert it to n-type
producing. 88 The first high-quality n-p-n germanium transistors were
produced by this technique. Limitations of the method are that, in gen-
eral, i t can produce only one n-p-n junction per crystal, and that the thin-
ness and uniformity of the p layer are limited by the impossibility of
84 H. Nelson, “Transistors I,” p. 66. R.C.A. Laboratories, Princeton, New Jersey,

1956.
85 G. K. Teal, M. Sparks, and E. Buehler, Proc. Z.R.E.40, 906 (1952).
8 6 J. H. Scaff, H. C. Theuerer, and E. E. Schumacher, Trans. Am. Znst. Mining Met.
Engrs. 186, 383 (1949).

s 7 R .N. Hall, J. Phys. Chem. 67, 836 (1953).
88 W. W. Bradley, in “Transistor Technology” (J. Shive, ed.), Vol. I, Chapter 7. Van
Nostrand, Princeton, New Jersey, 1957 (in press).
474 W. G . PFANN
achieving instantaneous mixing of the a,dded solute with the melt. The
advantages and limitations of the technique have been analyzed in detail
by Bradley.ss Intermediate layers well below 0.0025 cm thick are
feasible.
Mooresg proposed a variation of the doping scheme for producing
p-n and n-p-n junctions. It comprises rotating the growing crystal into
a series of melts of compositions such that desired n- or p-type conduc-
tivities are produced.
I n general, in this section, we have been discussing small concentra-
tions of solute, so small as to have no appreciable effect on the melting
point of the solvent. At the other extreme lies the “alloy process” for
making p-n or n-p-n junctions, which is used commercially to make
diodes and transistors, and which can be useful as an experimental tech-
nique in work with semiconductors and other crystalline materials. I n
this technique a small pellet of indium, for example, is placed on a crystal
of n-type germanium. Both are heated sufficiently to form a molten
germanium-indium alloy, containing a percentage of germanium which
is determined by the alloying temperature and which is usually of the
order of a few per cent. On subsequent cooling, a layer of germanium,
saturated with indium, regrows on the parent crystal, producing a p-n
junction. The bulk of the indium finally refreezes, providing a metallic
contact t o the p layer. The alloy process has been widely used for germa-
nium and silicon devices and much experimenting has been done with
alloy compositions, alloying temperatures, cooling rates, etc. The process
is usually carried out well below the melting point of the parent crystal.
The In-Ge process, as used to fabricate p-n-p transistors, has been de-
scribed in some detail by S a b ~Further. ~ ~ details on alloying appear in
footnotes 91-93.
A noteworthy feature of the alloy process is the inffuence of crystal
orientation on the shape of the dissolved region formed during the heating
cycle. If a (111) plane is parallel to the surface of the crystal, the bottom
of the crater tends to be very flat and parallel to (111). Advantage is taken
of this anisotropy of solution to produce uniformly thick intermediate
layers.94
89 A. R. Moore, “Transistors I,” p. 77. R.C.A. Laboratories, Princeton, New Jersey,
1956.
9 0 J. S. Saby, Proc. I.R.E. 40, 1358 (1952).
9 1 R. R. Law, C . W. Mueller, J. I. Pankove, and C. D. Armstrong, Proc. I.R.E. 40,
1352 (1952).
92 G. L. Pearson and B. Sawyer, Proc. Z.R.E. 40, 1348 (1952).
93R. N. Hall, Proc. I.R.E. 40, 1512 (1952).

9 4 C. (W. Mueller and jN. H. Ditrick, “Transistors I,” p. 121. R.C.A. Laboratories,
Princeton, New Jersey, 1956.
23. PERTURBATIONS
BY CHANGING
THE VOLUMEOF THE MELT
I n this section we discuss methods of perturbing the concentration
along a growing crystal by methods that involve only changing the vol-
ume of the melt or zone. Assume, for the present, freezing to be done a t
low enough rates and vigorous enough stirring conditions that rate effects
at the interface are negligible.
The normal freezing process itself offers some latitude if more than
one freezing interface is used. Assume a cylinder of liquid solution, as in
Fig. 2, containing a solute for which k < 1, for example. Freeze a small
portion a t the left end; then, holding the left interface constant (or per-
haps melting back a trifle), freeze a portion of the remaining liquid
beginning a t the right end. Then, holding the right interface constant,
resume freezing a t the left interface. A step in which solute concentra-
tion rises with distance (“rising step”) will have formed. By variations
of this sequence a series of rising steps can be produced from each end of
the ingot inward. Concentration gradients of magnitude between that in
a step and that obtained by freezing the melt from one end only can be
obtained in principle by slowly advancing the interface of interest while
the second interface advances more rapidly.
Zone melting offers wider latitude for operations of this kind. Consider
a molten zone of length I traveling to the right in a cylindrical ingot of
mean concentration Co, Fig. 26a. Assume the zone to be a t the steady
state, that is, that the concentrations entering and leaving the zone are
equal to Ca and the concentration in the zone is Co/k. For simplicity,
assume k to be small, so that the concentration in the zone is determined
principally by its volume. If, now, the freezing interface a is held fixed,
while interface b is retracted to c, and then travel to the right is resumed,
a rising step in concentration will be produced, as in (1) of Fig. 26b. As
the zone advances, the excess concentration (over Co) will decay exponen-
tially, according to Eq. (20.1), to the value Co. Curve (2) of Fig. 26b
shows the result of increasing the zone length to ad by this procedure.
Curve (2) has a form corresponding to Eq. (7.1). If, instead, the zone
lengths are changed while the left interface continues its travel, perturba-
tions having the general form shown in Fig. 26c will result, (1) being for
decrease, ( 2 ) for increase, in zone length. The perturbation reaches its
extreme value when the zone resumes travel a t constant length.
Results like those of Fig. 26c also can be obtained by moving a zone
of constant length through a point in the ingot where the cross section
changes. Perturbations of pulse form can be produced by first decreasing
the zone length, then increasing it, according to the procedure shown in
Fig. 26b. The sign of the pulse, that is whether the concentration increases
476 W. G . PFANN
or decreases, will be opposite for k > 1 from that indicated in the

figure.
The zone perturbation methods can be used to make p-n or n-p-n
junctions in semiconductors by using two solutes, one a donor, the other
an acceptor, and preferably one having k > 1, the other k < 1. (An
example is the pair, boron ( k > 1) and antimony ( k < I), in germanium.)
k--l
a c b d
---
I I
--I--
(a)
I
DISTANCE, X -
Fro. 26. Perturbing the concentration by changing the volume of a molten zone:
(a) zone in ingot; (b) concentration profiles with left interface stationary during
volume change; (c) with left interface moving during volume change.
The concentration profiles can be made to cross twice during the forma-
tion and decay of a step, so as t o produce an n-p-n junction. Limitations
of this technique are: (1) that the maximum proportionate change in
concentration at, a step is the ratio of zone volumes before and after;
(2) extremely precise control of concentration or extremely small zone
length is required to obtain very thin p layers.
a. Segregation Junctions
The ordinary normal freezing operation can be used to produce a
p-n junction, without perturbing the process in any way, by choosing
the proper ratio of concentrations of two solutes having different k’s.
The slop'es of the normal freezing curves of Fig. 3, a t any g, increase as

(1 - lc) increases. (Since the curves are plotted on a logarithmic scale of
concentration, a given curve can be compared with another, by shifting
it vertically in Fig. 3.) A p-n junction, that is, a cross-over, will occur if:
k l < kz and l c l C o 1 < l c L ' 0 2 , where 1 and 2 designate two solutes, one a
donor, the other an acceptor. Expressions for the location and concen-
tration gradient of such a p-n junction have been derived by Pfann96 and
are used in Section 23(b), which follows.
b. Remelt Method
In the preceding, techniques for producing steps in concentration by
changing the volume of the melt or zone were described. A limitation of
techniques of this sort in making p-n or n-p-n junctions is that they do
not always lead to a sharp distinction between two solutes, and hence it
is difficult to control the crossing over of the concentration profiles. To
illustrate, when the zone of Fig. 26a expanded to twice its length, the con-
centration within it went from Co/k to (C,/k +
C 0 ) / 2 ,which, for any k
less than about 0.1, is very nearly Co/2k. Thus, the magnitude of concen-
tration step is determined almost entirely by the volume change of the
zone and is quite insensitive to values of k in this range.
I n this subsection we describe a perturbation technique that is ex-
tremely sensitive to the value of k , and completely independent of the
volume of the liquid region. It is the remelt methodg6which, though de-
scribed here in the context of n-p-n junction fabrication, should be re-
garded as a general technique of perturbing concentrations. There are
two classes of remelt method, simple remelt and remelt with additions.
We discuss first simple remelt with one solute.
I n a block of material containing a uniform concentration Coof solute,
melt a zone of length l o and freeze it back slowly, as shown in Fig. 27.
Under the assumed conditions of freezing, the solute concentration in the
first solid t o form, a t the remelt boundary, will be kCo and the solute
concentration C in the remainder of the remelt zone after freezing will be
given by the normal freezing equation4 (2.1):
c = kCo(1 - gy-1
where g is the fraction of the remelt layer that has solidified. Thus, as
shown in Fig. 27, remelting produces a discontinuity in concentration, of
magnitude Co(l - k ) a t the remelt boundary and a gradient of concen-
tration in the remelt layer. If k differs appreciably from unity, large
W. G. Pfann, Trans. Am. Inst. Mining Met, Fngrs, 200, 294 (1954).
478 W. G . PFANN
percentage changes in concentration can be produced a t the remelt

boundary.
It is important in practice to consider the effect of diffusion in the
solid during remelting, particularly in the period just before freezing
begins. For k < 1 solute will tend to diffuse to the molten zone. If the
diffusion coefficient D is small, but appreciable, then rounding of the
step may occur as indicated by the dotted curve in Fig. 27. If D is large
REMELT
BOUNDARY
-uNMELTED&-REMELT ZONE-
I
I DIRECTION OF
REFREEZING
I I
0 DISTANCE FROM
REMELT BOUNDARY
FIG. 27. Concentration of a single solute as a function of distance from remelt

boundary. Remelting produces a step in concentration a t the remelt boundary and a
gradient of concentration in the remelt zone.
and sufficient time elapses, the solid and liquid will attain concentrations
C , and Cfflk,respectively. C, can be determined readily from a solute bal-
ance if the volumes of liquid, VL, and solid, V,, are known, as follows
CO(VL + Vd = C,V, + Cf VL'

(Even though a temperature gradient must exist, it is assumed to be
small.) If IC is very small, most of the solute will eventually diffuse into the
molten zone.
By using two solutes with different k's, one a donor the other an accep-
tor, a step p-n barrier can be produced a t the remelt boundary. Consider
a block of semiconductor containing uniform concentrations Co, and COZ
of solutes, one of which is a donor, the other an acceptor. Let CM be
greater than Cozand let k z be greater than k ~ Upon . remelting, a p-n
barrier may, or may not, form a t the remelt boundary, depending on the
lc’s and the CO’S.The condition th at a barrier will form is k2CO2> klCol or
COl > coz > -

k l COl.
k2
(23.1)
Since Col > COZ, the original material must be of conductivity type 1
and the material just inside the remelt boundary must be of type 2.
Since there was an excess of solute 1 throughout the original material,
I
I
I
I
I I
0 LPn 3
DISTANCE FROM
REMELT BOUNDARY
FIG.28. Concentrations of two solutes, one a donor, the other an acceptor, after
simple remelting. Remelting produces a step p-n barrier at the remelt boundary and a
graded p-n barrier in the remelt zone.
and since a deficit of solute 1 exists in the first-to-freeze portion of the

remelt zone, the conductivity must revert to type 1 during the freezing
of the remainder of the remelt zone. Hence, if the conditions of Eq.
(23.1) are met, remelting produces two p-n barriers, a “step” barrier a t
the remelt boundary and a “graded” barrier in the remelt layer. Figure
28 illustrates this formation schematically. A unique and most significant
feature of remelting is that the concentrations which freeze out a t the
remelt boundary are independent of the volume of the remelt zone. Thus
step barriers of various shapes and sizes but of similar properties can be
made from a given starting material by the simple steps of melting and
slow refreezing.
It is assumed that the remelt zone solidifies by normal freezing and
480 W . G . PFANN
that another p-n barrier is formed in it by differential segregation. Equa-

tions for the location and concentration gradient of such a barrier have
already been derived.95The location, in terms of g p n the fraction solidified,
is given by
g P n = ~ p , , / ~ o= 1 - T l / ( k l - k O (23.2)
where
r = ~~COZ/~ICOI. (23.3)
The concentration gradient, d ( A C ) / d l is given by
Hence, with the concentrations and k’s of the solutes in the starting
material and the length of the remelt zone known, the conductivities on
either side of the step barrier and the location and concentration gradient
of the segregation barrier can be computed.
As shown in Fig. 28, the greater the difference in the individual con-
centration gradients in the remelt zone, the easier it will be to control
the location of the cross-over point and obtain very thin p layers. Exami-
nation of Eqs. (23.2) to (23.4) will show that this desideratum is favored
by having k~ very large. Such is the case for boron in germanium; its k
is greater than unity; Bridgersg7quotes the value 17 a t zero growth rate.
Hence the combination of boron as acceptor with antimony (ko = 0.003)
as donor in germanium is extremely effective for making n-p-n junctions
by simple remelting.
Many of the advantages of simple remelting will be retained, and
others can be gained, if the addition to the remelt zone of solutes not pres-
ent in the original material is permitted. Thus, whereas in simple remelt-
ing the concentrations in the remelt zone are entirely determined by those
in the original block, in remelting with additions, they are largely inde-
pendent of those in the original block. One method of addition is to place
solute on the surface of the block and subsequently to permit it to dissolve
in the remelt zone when the latter is formed. Upon refreezing, the concen-
trations a t the remelt boundary will be the sum of those arising from
simple remelting, which are independent of the volume of the remelt
zone, and the concentrations of added solutes, which vary inversely with
the volume of the remelt zone. Advantages of remelting with additions
as compared with simple remelting are th at greater control over the con-
centrations a t the step barrier and the location of the graded barrier
can be had.
The remelt process has a number of unique advantages for producing
g 7 H. E. Bridgers, J. Appl. Phys. 27, 746 (1956).
n-p-n junctions. It can be used on various scales of size and shape. The
step-junction usually serves as the emitter junction of the transistor, and
it can be tailored to have a relatively large conductivity on the n-type
side, which makes for a high current multiplication factor a in the transis-
The graded junction serves as collector, for which it is well suited
by virtue of its inherent low capacitance and large breakdown voltage.
Even the gradation of conductivity in the p-type layer is useful, for it
provides a built-in electrostatic field that accelerates carriers from emitter
to collector, thereby improving the frequency response of the transis-
t ~ r .As~ described
~ , ~ ~here the freezing of the remelt layer is done moder-
ately slowly. The advantages of this process can be increased by freezing
the remelt layer more rapidly, as will be discussed in the following
section.
24. PERTURBATIONS
BY CHANGING CONDITIONS
THE GROWTH
Methods of perturbing the concentration by changing the growth

conditions utilize the liquid film adjacent the liquid-solid interface. The
effectivethickness of this film-that is, the thickness over which transport
may be regarded as taking place only by diffusion-and the solute concen-
tration in this film a t the interface, can be changed by changing the
growth conditions, e.g., rate of advance of the interface and degree of
turbulence in the liquid.
This film (or “diffusion layer”) has received the attention of many
workers. Kernstll postulated that the rate of a heterogeneous chemical
reaction-of which crystal growth is an e x a m p l e i s determined entirely
by the diffusion-dominated transport of atoms to the interface and on this
basis he formulated a mathematical treatment of the problem. Riddi-
fordlOOand others have argued that the chemical reaction itself may play
a part. The treatments discussed in this chapter assume that the process
of incorporation of solute in a crystal growing from its melt is determined
largely or entirely by transport conditions in the liquid. l o l
The Burton-Prim-Slichter theory, discussed in P a rt I1 indicates that,
under a given set of growth conditions, there will be a steady-state dis-
tribution coefficient k lying between unity and the equilibrium distribu-
98 These transistor terms are explained in footnote 83.

gs H. Kromer, Arch. Elektrischen Ubertragen 8, 223 (1954); 8, 363 (1954).
l o o A. C. Riddiford, J . Phys. Chem. 66, 745 (1952).
l o ’ A distinction from some of the earlier applications of Nernst’s theory to crystal
growth should be noted. The theory has been applied largely to the rate of growth
(or dissolution) of the crystal itself from a liquid solution in which the material of
the crystal was dissolved. Here we discuss the rate of incorporation of (usually)
very small concentrations of solute in a crystal growing from its own melt.
482 W. G . PFANN
tion coefficient ko. Their treatment assumes some measurable degree of

turbulence in the main body of the melt, by forced or natural convection;
and i t can be considered valid only where the length of the melt is large
compared t o the film thickness 6 . They consider also the transient re-
sponse t o an abrupt change in concentration in the bulk of the melt
(but not in the diffusion-dominated film) a t a given growth velocity f.
A transient case of greater importance for what follows is the approach
to the steady-state k from zero growth rate. Whether the growth changes
from zero rate t o the steady-state rate f, by rising almost instantaneously
or gradually, there will be a transient change of solute concentration in
the freezing crystal from a value corresponding to ko, a t the onset of
growth, to a value corresponding to the steady-state k . Such a transient
rise is indicated by the dashed curve in Fig. 3, which is the rise of concen-
tration from a value corresponding to a k o of 0.1 a t the start of freezing
to a value corresponding to a steady-state k of 0.2. The more rapid the
growth rate, the more rapid this rise will be. The time constant for such
changes is probably of the order P / D , where D is the diffusivity in the
liquid. This estimate is discussed by Brid g er ~ .~ ’
I n the following we discuss solute distributions using diffusion layer;
first, where the growth conditions are held constant over large regions of
the crystal, and, second, where the growth conditions are changed rapidly.
I n the latter category, we discuss p-n junctions in particular.
a. Difusion- Dominated Normal Freezing
The extreme case of a normal freezing process in which transport of
solute in the liquid occurs only by diffusion has been treated in some
detail by Tiller et We have seen, in Fig. 5, the general form of the
resulting solute distribution for the case k < 1. It has three regions of
interest : a n initial transition region, a central region of uniform concen-
tration, and a terminal region. The initial region may be regarded as a
transient in which the enriched layer builds up in concentration and
thickness until the concentration a t the interface attains the steady-state
value Co/k, where Co is the mean concentration. From this point on, the
concentrations entering and leaving the enriched layer are both equal to
Co, and the uniform region is produced. The terminal region is produced
when tlhe leading edge of the enriched layer reaches the end of the
container.
The distribution shown in Fig. 5 will occur only where transport is
limited completely by diffusion and only if the vessel is large enough SO
that the concentration in the bulk liquid changes negligibly. Unless steps
are taken t o avoid it, natural convection will probably come into play, a t
growth rates usually used for single crystal work, and the distribution to
be expected will be the normal freezing distribution for a n effective k

between ko and unity, with an initial transition region as indicated in
Fig. 3.
Wagner13 has considered the influence of the enriched film under fairly
constant freezing conditions, and has derived expressions for the effective
distribution coefficient which, although of somewhat different form, agree
in general with those described here. He treated the following cases:
solidification without convection, with natural convection, with convec-
tion due t o ascending gas bubbles, and with forced convection. He also
considered the effect of the concentration difference in the enriched film
on the geometrical stability of the interface, along the lines followed by
Rutter and Chalmers, l o 2 and the limitation on freezing imposed by heat
transfer into the mold wall.
The reader is warned that each of the treatments of the effective dis-
tribution coefficient cited (Burton et al., Tiller et al., and Wagner) differ-
ently define the thickness of the enriched film. I n the treatment of Burton,
the film thickness is fairly constant over a range of growth conditions,
while Tiller and Wagner use a parameter sensitive to the growth rate.lo3
Hayes and Chipman' have discussed the role of the enriched film in
the freezing of steel ingots. They bring out an important point-that a
second phase can appear where a single phase is expected, because of the
concentration rise in the film. They discuss the evolution of gas bubbles
of this origin, and their influence on the ingot structure.
b. Programmed Growth Rate in Normal Freezing
One may ask why diffusion-dominated normal freezing cannot be
used as a practical means of avoiding segregation. The answer is that
sometimes it can and sometimes it cannot. In germanium crystal growth,
for example, the growth rate required to obtain an effective k of unity is
usually so large as to preclude attainment of high crystal perfection.
Furthermore, as we shall see, forced convection is helpful, and even neces-
sary, in certain crystal growing operations, so that a diff usion-dominated
process is precluded.
The extent t o which the enriched film can be used to prevent segrega-
tion during the normal freezing of germanium has been illustrated by
Burton et aZ.lo4They used a germanium crystal containing arsenic as
solute (for which ko = 0.04). The crystal was grown by the pulling proc-
lo2 J. W. Rutter and B. Chalmers, Can. J . Phys. 31, 15 (1953);B. Chalmers, ibid. 31,
132 (1953).
1°3 The writer is indebted to J. A. Burton for pointing this out.
l o 4 J. A. Burton, E. D. Kolb, W. P. Slichter, and J. D. Struthers, J.rChem. Phys. 21,
1991 (1953).
484 W. G . PFANN
ess.86 The first portion was grown a t a fast rate, so as to build u p the
enriched film; a portion, of uniform solute concentration, was then grown
by progressively reducing the growth rate in a programmed manner.
Thus the tendency for the concentration to rise by the usual normal
freezing action was countered by decreasing the concentration of solute
in the film. It is evident that such a procedure cannot be continued for
the whole growth period. Eventually, as the growth rate decreases, the
minimum value of k , that is, ko, is approached and the concentration
FIG.29. Variat,ion of resistivity with distance in a germanium single crystal, con-

taining arsenic, that was grown with a programmed growth rate (after Burton et ~ 1 . ' ~ ~ ) .
begins t o rise. Regions of uniform concentration extending over about a

third of the crystal have been produced in this manner. Burton et al.lo4
give the following expression for the growth rate program in the level
region :
e-f6/D = (1 - X O ) / O - X ) (24.1)
where X denotes fraction of the total volume frozen, and Xo denotes the
fraction frozen when the growth rate has been progressively reduced to
zero. Figure 29, taken from their paper, shows resistivity (which is in-
versely proportional to solute Concentration) versus distance along a
programmed germanium crystal containing arsenic.
c. Analogy between Enriched Film and Molten Zone
It is instructive to examine an analogy between the enriched film and
a traveling molten zone. In Part I11 an expression, Eq. (7.1) for the con-
centration after passage of a molten zone through a charge of uniform
solute concentration Co, was given as follows:
C/Co = 1 - ( 1 - k)e-kz/l.
I n deriving it, the assumptions were that the zone length I and k were
constant, the value of k not necessarily being ko. The equation derived by
Tiller et a1.12for the solute concentration after a diffusion limited normal
freezing process is
C/Co = (1 - k ) [ l - e--(kzR/D)] lc + (24.2)
which may be transposed to
C/Co = 1 - (1 - k)e-(kzR/D) (24.2a)
and is the same as (7.1), except that k designates k o and the zone length
I is replaced by characteristic distance D / R of Tiller and co-workers.
They state that the solute distribution in the enriched film is exponential
with distance and can be described in terms of a characteristic distance
D / R (where R is the growth rate and D the diffusivity), in which the
excess concentration above that in the bulk liquid falls by a factor e.
Thus, the length of a molten zone is analogous to the characteristic
distance D / R of the film. Hence one can expect th a t perturbations like
those caused by changes in zone length (or volume) (as described in
Section 23) should be obtainable by changing D / R in a diffusion-
dominated process. Since D may be assumed constant, D / R varies in-
versely with R. Hence, increasing the growth rate should (just as when
the zone length is decreased) result in a temporary increase in solute con-
centration (for k < 1) during the period of increase. This effect, in the
diffusion-dominated case, has been discussed by Tiller et ~ 1 . who~ ' ~point
out t ha t larger R requires a larger concentration gradient in the enriched
film a t the interface, and therefore a smaller total content of solute. On
increasing the growth rate the excess solute is lost by enhanced diffusion
down the gradient, and also by the temporary freezing out of a higher
concentration in the solid.
d . p-n Junctions by Variation in Growth Conditions
p-n Junctions were made accidentally by growth variations before they
were made deliberately. It is instructive to examine how these accidental
junctions were produced. Pfann and Scaff described microstructures of
directionally frozen ingots of silicon. These contained as impurities boron,
an acceptor, and phosphorus, a donor. The concentrations and k's were
such ( k >~ k p , k C o B > kCop) th at a p-n junction normally formed by
segregation96 a t some point in the columnar region of these ingots. I n
' " 6 W. G. Pfann and J. H. Scaff, Trans. Am. Inst. Mining Met.Engrs. 186,389 (1949).
486 W. G . PFANN
general, however, not one, but often a series of interlocking p-n junctions
were observed, as shown in Fig. 30; and this was ascribed to disturbances
in the liquid a t the interface which caused the sign of the difference in
concentration between boron and phosphorus to change repeatedly. The
FIG.30. Interlocking strips of n- and p-t,ype silicon in progressively frozen silicon

ingot. Magnification-1000 X.
situation is illustrated by the curve of Fig. 31, which shows the effect
of the fluctuations superimposed on the general trend of the over-all
segregation.
I n principle, one could make p-n junctions in a reproducibie manner,
based on the above scheme, by first ensuring a steady-growth condition
substantially free of accidental fluctuations, and then imposing controlled
fluctuations in growth rate or stirring. T o make n-p-n junctions with a
thin p layer by this method would involve extremely precise control of
the growth conditions. Hal187~106 described an important improvement in

this process by introducing the step known as melt-back and using it to
produce n-p-n junctions by the method known as rate growing.
( 1 ) Rate growing. Preparing p - n junctions by rate growing requires
the presence in the melt of two opposite-type impurities whose distribu-
tion coefficients vary differently with growth rate. Hall showed that gal-
lium (an acceptor) and antimony (a donor) in germanium were such a
FIG.31. Relation between difference concentration and distance in ingot like that
of Fig. 30.
combination, antimony showing the larger variation.lo6By suitably ad-

justing the relative concentrations of these impurities in the melt, it was
possible to produce an excess of antimony a t high growth rate, and of
gallium a t low growth rate.
When periodic variations in growth rate are made by cycling the input
power t o the crystal-growing furnace, the thermal inertia of the melt
usually results in a more or less sinusoidal variation of growth rate. An
example of the type of p-n junction produced in this manner, when the
variation is small enough so th at growth is always in the positive direc-
tion, is shown in Fig. 32a. Up to point (a), growth is rapid, and antimony
is in excess in the solid. At (a) a heating pulse was applied, so as to slow
the growth t o a minimum value a t (b), after which it rose to its original
steady, rapid value a t (c). The cross-overs of the concentration curves are
gradual, and two “graded” p - n junctions were produced. One of the
advantages of this way of using the technique is th a t such graded junc-
106 R. N. Hall, Phys. Rev. 88, 139 (1952).
488 W. G. PFANN
tions are produced; however, it is difficult to produce very thin p-type

layers controllably.
If now the amplitude of the sinusoidal growth-rate change is made
greater than the steady growth rate, then melt-back occurs during the
heating cycle, and growth resumes a t zero growth rate. The result is a
“step” p-n junction, followed by a graded junction, as shown in Fig. 32b.
Very thin p-type layers can be produced controllably in this way by
having the growth rate rise rapidly after the melt-back. Moreover, the
over-all configuration has particular advantages for transistor use, as was
pointed out in Section 23 under Remelt.
z
0
5a
c
z
W (b)
y0 Sb
V
--------------
Gd
FIG.32. Schematic concentration curves showing n-p-n junction produced by rate

growing: (a) without melt-back, (b) with melt-back.
Many p-n junctions can be produced from one normally frozen melt
by rate growing. A t first this might appear puzzling, because one would
expect the ratio of antimony-to-gallium concentrations in the melt to
change, due t o the over-all segregation that accompanies normal freezing
and t o the difference in the mean values of the respective distribution
coefficients (Ico(Ga) = 0.1; Ico(Sb) = 0.003). However, as shown by Fig. 3
the segregation curves for two such solutes are almost parallel, and hence
their proportions in the melt change slowly. Nevertheless, this change in
proportions is a limitation of rate growing when used in a normal freezing
process. It disappears when rate growing is done in a zone leveled crystal.
A second limitation is that the actual changes in Ic are not large
enough t o provide as much control of the excess solute concentrations in
the individual p and n regions as is generally desired in transistor design.
The maximum growth rate consistent with a high degree of crystalline
perfection in germanium appears to be around 0.008 em-sec-1. The dis-
tribution coefficient of antimony changes by a factor of about 3 between
zero rate and this value; that for gallium changes by about 40%, a t a
crystal rotation rate around 200 rpm.87r97This may be contrasted with
the simple remelt process, described in Section 23b, in which the ratio of
antimony concentrations a t the remelt boundary is several hundred, and
that for gallium is about 10.
The advantages of boron over gallium as an acceptor in germanium,
which were pointed out in connection with the remelt process, hold also
for rate growing. Bridgesg7 has shown th at the proportionate rate of
change of k with growth rate is far greater for boron than for any other
solute used for germanium. This arises directly from the large value of
k~ for boron, about 17, as Eq. (3.1) shows. Tetrode n-p-n transistors
having extremely thin and highly graded p layers have been made from
junctions using boron and antimony in germanium prepared by Bridgers
and Kolb.lo7
The relative proportions of boron and antimony change rapidly in
the normally freezing melt used in crystal pulling. Hence relatively few
n-p-n junctions can be prepared by rate growing. These exhibit a decreas-
ing p-layer thickness, so the last few can be selected for highest frequency
transistor^.^^ Here also, a zone-leveling process eliminates the over-all
segregation and makes uniform junctions possible.
Bridgersg7has discussed comprehensively the merits of rate growing
and has defined a figure of merit for choosing a favorable donor-acceptor
pair. Tanenbaum et al. have produced n-p-n junctions in silicon by rate
growing. lo8
( 2 ) Stirring modulation. Bridgersg7has shown that multiple p-n junc-
tions can be produced by varying the stirring rate rather than the growth
rate. The stirring rate was controlled by varying the rate of rotation of
the growing crystal. The method is illustrated by Fig. 34, which is like
Fig. 33, except that two curves are shown for both gallium and antimony
in germanium a t two different rotation rates. The concentration ratio of
Ga and Sb in the melt was adjusted so that the two pairs of curves inter-
sect a t two growth rates, one for each rotation rate. Thus, rate fc8 corre-
sponds t o slow rotation, and fcf to fast rotation. If the growth rate is
held constant a t a value f l between fce and fcf, n-type crystal is grown a t
slow rotation (30 rpm) and p-type a t fast rotation (230 rpm). By this
1°7 H. E. Bridgers and E. D. Kolb, J. A p p l . Phys. 27, 746 (1956).
108 M. Tanenbaum, L. B. Valdes, E. Buehler, and N. B. Hannay, J. A p p l . Phys. 26,
686 (1955).
490 W. G. PFANN
procedure p-n-p-n structures were grown in which the inner layers were
a few mils thick. It would appear that the time required for the enriched
film t o reflect changes in turbulence in the melt would limit the thinness of
layers obtainable by this method to the indicated order of magnitude.
The fact that p-n junctions can be produced by stirring modulation
sheds light on a difference in interpretations of the rate growing process.
FIG. 33. Effective distribution coefficients of antimony, boron, and gallium in

germanium as a function of growth rate a t the indicated rate of rotation of the pulled
crystal (after Bridgers97).
Hal187,106ascribed the rate-sensitivity of lc, in large part a t least, to

entrapment of solute by the growing crystal. His argument was that the
diffusion rate of antimony in the solid is comparable to the growth rate
of the solid, and hence that changes in growth rate should change the
amount of entrapped antimony. (He attributed the entrapment of anti-
mony t o the existence of a higher-than-equilibrium concentration in the
layer of atoms in the solid a t the interface.) He claimed further th a t varia-
tions in rotation rate had little effect on k. Since that time many careful
experiments have been conducted along these lines, and their outcome
appears to be that, for the solutes mentioned, growth rate phenomena in
germanium are mainly controlled by processes occurring within the liquid.
( 3 ) Remelt with rapid freezing. The leap-frog nature of work in this
field was illustrated, soon after the remelt and rate-growing methods
4
10‘
5
w
g lo-’
U
W
U.
8
z
Em
a
t
5
O
r5 lo-;
U.
U
Y
c fCf I
IO-~ I ! I I I j I
0.002 0.004 0.006 0.008
GROWTH RATE IN CENTIMETERS PER SECOND
FIG.34. Junction-formation by “stirring modulation.” By growing a t a fixed rate

f ~ n-type
, or p-type crystal can be grown at slow or fast rotation, respectively (after
Bridgers).
were introduced, by the emergence of a process combining the best fea-

tures of each. This is the process of remelt with rapid freezing, versions of
which were described by Pankove,’Og and R. N. Hall (unpublished). The
method utilizes the large swing in concentrations a t the remelt junction
characteristic of the remelt process, and the rapid variation of concen-
tration with distance obtained by rate growing with melt-back. The
lo9 J. I. Pankove, Proc. I.R.E. 44, 185 (1956).
492 W. G . PFANN
version described by Pankove, called the melt-quench process, involves a

period of fairly slow refreezing, in which the p region is produced, fol-
lowed by extremely rapid growth in the remainder of the remelt zone; the
second p-n junction is produced a t the beginning of rapid growth.
Pankove does not make clear why a period of slow growth is used-or
if i t is simply assumed.
25. DIFFUSIONTECHNIQUES
A comprehensive review of p-n junction techniques or of diffusion
techniques in general will not be given in this article. These techniques
have been reviewed by Dunlap, 110 and Thurmond and Dacey. 111 However,
the use of solid state diffusion in making p-n junctions will be mentioned,
partly because of its importance and partly because of its relation t o
crystal growth phenomena. At the present time diffusion of donors and
acceptors into germanium or silicon, usually from the vapor, appears
t o be the method offering most precise control of junction layer thick-
nesses. Single, double, and triple diffusions have been used t o make p-n,
n-p-n, and n-p-n-p junctions. High-frequency germanium transistors
made by a single diffusion (of arsenic into p-type germanium) followed
by precision alloying of emitter and base connections were described by
Lee.l12 High-frequency silicon transistors made by double diffusion (of
aluminum and antimony into n-type silicon) were described by Tanen-
baum and Thomas.l13 The layer thicknesses in these devices were gen-
erally less than 2 microns. Layers produced by solid-state diffusion can
be controlled by controlling the time and temperature of diffusion, the
choice of diffusant, the concentration in the vapor, and the sequence of
diffusion operations, which last>may be simultaneous, sequential, or both.
Diffusion from one solid region into another has been used to make
n-p-n junctions. A discontinuity in the concentrations of two solutes is
made by doping a growing crystal, or by the alloy process. The junction
is formed during a subsequent heating operation, usually by taking ad-
vantage of the difference in diffusivities and concentrations of the donor
and the acceptor.
Step junctions produced by crystal growing can be rounded by diffu-
sion; that is, the concentration gradient can be decreased. Tanenbaum
l1O W. C. Dunlap, Jr., in “Handbook of Semiconductor Electronics” (L. P. Hunter,

ed.). McGraw-Hill, New York, 1956.
G. C. Dacey and C. D. Thurmond, in “Germanium and Silicon, Part 2. Applica-
tions,” to be published in Metallurgical Revs. London, 1957.
117 C. A. Lee, Bell System Tech. J. 36, 23 (1956).
I L 3 M. Tanenbaum and D. E. Thomas, Bell System Tech. J . 36, 1 (1956).
et ~ 1 . have
' ~ ~ utilized a heat-treatment effect found in silicon crystals to
reduce the p-layer width in n - p - n junctions made by rate growing.
The liquid zone a t certain times may act as a getter for solutes in the
solid. In simple remelting for example, a solute for which k < 1 in the
solid will diffuse to the liquid if enough time is allowed, because the equi-
librium concerftration in the liquid is l / k times that in the solid. Un-
doubtedly some rounding of the step junction often occurs in simple
remelting. Gettering by a molten, low melting point, alloy layer has been
germanium (D -
utilized to remove copper from germanium. Copper diffuses rapidly in
cm2-sec-1) and has a very low k . Presumably k is
also low for a molten indium-germanium alloy in contact with solid
germanium. Removal of copper and other impurities from solid germa-
nium by molten liquids has been discussed by Logan and S c h w a r t ~ , " ~
Kromer, 115 Trousil, 1 1 6 and Wang.
VII. Temperature-Gradient Zone Melting
26. PRINCIPLES
The problem of creating minute p- or n-type regions may be attacked
by using extremely small zones. This method is known as temperature-
gradient zone melting.118 It will be examined here briefly, because it is a
new technique that can be used in a variety of ways not limited to
semiconductors.
Consider the system A B in Fig. 35, where B is a solute that lowers the
melting point of A , the solvent. Sandwich a thin sheet of B between two
blocks of solid A . Place the sandwich in a temperature gradient normal to
the plane of layer B , such that the temperature of the layer exceeds the
lowest melting temperature of the system. Surrounded by an excess of
A , the layer will dissolve A , become molten, and grow thicker. As solution
of A continues, a t both interfaces, the mean concentration of the zone
will move toward the A-rich end of the phase diagram of Fig. 35a, until
a t temperature T 1the liquid a t the cooler interface reaches the liquidus
concentration C1. Solution of A thereupon ceases because the liquid a t
T 1 is saturated with A a t concentration C1. The liquid a t the hotter
interface, being a t temperature Tf, is not saturated with A a t concentra-
tion C1. Hence solution ol A continues there and concentration Cs is
approached. A concentration gradient is thus set up in the layer, causing
'14 R. A. Logan and M. Schwartz, Phys. Rev. 96, 46 (1954).

H. Kromer, "Transistors I," p. 132. R.C.A. Laboratories, Princeton, New Jersey,
1956.
Il6 Z. Trousil, Czechoslov. J . Phys. 4, 251 (1954).
117P. Wang, J . Phys. Ch,em. 60, 45 (1956).
494 W. G. PFANN
A to diffuse toward the cool interface, B toward the hot. As a result, the
liquid a t the cool interface becomes supersaturated and a layer of crys-
talline A containing concentration kC1 of B in solid solution freezes.
Continued solution, diffusion, and recrystallization moves the layer
through the hotter block.
Sheet zones or wire zones or dot zones, of the order of mils or less in
their smallest dimension can be moved distances of the order of 1 cm
without major change in shape by this technique. As a zone travels up
(A+ 81
FIG. 35. Temperature-gradient zone melting scheme, showing: (a) portion of

phase diagram; (b) temperature gradient in system; (c) physical system comprising
molten zone containing A and B traveling through solid A .
the temperature gradient, its composition climbs through a corresponding

temperature range on the liquidus curve for the system. Isothermal travel
is possible if the temperature is lowered a t the proper rate. The length of
the zone (thickness of the layer) will vary as the zone moves up a tem-
perature gradient. It may increase, or may decrease, even going to zero
length, that is, the zone may “d ry up.”
The travel rate is proportional to the temperature gradient, which, in
turn, determines the concentration gradient. The method can be applied
to the measurement of diffusivities in liquids since the zones can be made
so thin that convectiou is negligible. The diffusivity D will be given
approximately by
(26.1)
where F is the flux of diffusing component. Wernick used the temperature

gradient zone melting technique to measure diff usivities of molten
aluminum-rich and gold-rich wire zones in germanium and silicon. 119

He estimated t hat the influence of thermal diffusivity, which is unavoid-
ably present, is, for the conditions used, negligible. On the other hand,
he found a larger activation energy for diffusion than seems reasonable
for liquid metals. He ascribed this to the presence of a rate limiting step
other than diffusion, namely solution a t the hotter interface. He also
showed, by means of wire zones traveling across a surface, th a t crystal
orientation affects the shape of a wire zone. This anisotropy was utilized
to produce extremely straight zone fronts, by aligning the wire with a
favorable crystal direction, namely (110), and moving it in an (001) or
(190) direction.lZ0
27. APPLICATIONS
a. Xemiconductive Devices
A sheet zone can be moved through a block of semiconductor to pro-
duce a large-area p-n junction, as shown schematically in Fig. 36. For
example, the blocks may be of n-type silicon; the sheet may be 0.0075 cm
thick aluminum. The orientation of the lower block prevails, provided the
3 i’i 1
I
FIG.36. Movement of acceptor-doped sheet zone through upper block to produce

a large area p-n junction by temperature-gradient zone melting; (a) before, (b) after
(schematic).
interfaces are clean and in good contact a t the start. Figure 37 shows a
p-n junction made in this way. The process was stopped for demonstra-
tion purposes, before the sheet zone left the upper block.
An n-p-n or p-n-p configuration with a rather thin intermediate layer
can be made by passing a wire zone through a single crystal slab. The
technique is shown schematically in Fig. 38. For a wire zone about 0.01
in. or less in diameter, the orientation of the parent crystal appears in
119 J. H. Wernick, J . Chem. Phys. 26, 47 (1956).
lz0 J. H. Wernick, to be published.
496 W. G . PFANN
the traversed layer. Figure 39 shows a p-type layer, 0.001 cm thick,

which was produced by sweeping an aluminum-rich wire zone through
an n-type germanium cxystal (courtesy of J. H. Wernick). The boundaries
of the layer are delineated by etching. Such a layer is too heavily doped
FIG.37. Large-area p-n junction made by sweeping Al-rich sheet zone through
upper block of Si. Blocks are about 0.25 c'm thick.
with aluminum t o serve as the base region of a n n-p-n transistor. How-

ever, lightly doped layers can be made using an inert carrier metal, such
as tin or lead, containing a small concentration of an acceptor.
A unique feature of temperature gradient zone melting is that it can
be used to fabricate semiconductive devices whose active regions do not
HEAT
FIG.38. Movement of wire zone through single crystal to produce an n-p-n con-
figuration by temperature-gradient zone melting (schematic).
intersect an external surface of the semiconductive body. This is done by

using crossed zones. An example is shown in Fig. 40, in which upper case
denotes high conductivity, lower case low conductivity. The regions
marked N were made by sweeping a dot zone vertically, in the plane of
the page, through a P-type crystal. The p layer was made by sweeping
a lightly doped wire zone horizontally through the crystal, bisecting the
FIG.39. Etched cross section showing 0.001 cm thick player produced by sweeping
a n Al-rich wire zone through a crystal of n-type Ge. Section is normal to travel direc-
tion (courtesy of J. H. Wernick).
N region, El 6 , and B denote emitter, collector, and base connections,

respectively, of the transistor. The device is an n-p-n transistor whose
active region is confined to the portion of the p layer between the N
regions. Injection of electrons from the emitter N region to the P region
surrounding it laterally is negligibly small because the conductivity of the
P region is high. The device is free of effects such as “floating emitter
potential,” which arise from surface conduction across the base layer of a
498 W. G . PFA4NN
IE
-P
FIG.40. Cross section through n-p-n transistor whose active region is entirely
within the semiconductive body.
FIG. 41. Etched section showing intersection of crossed wire zones in N-type
germanium. A vertically moving acceptor-doped wire zone produced the P region;
a horizontally moving donor-doped wire zone then produced the n region. P-N and
P-n junctions stand in sharp relief; n-N junctions (indicated by arrows) are faint.
conventional n-p-n sandwich. Moreover, the relatively large P regions

provide an excellent ring connection to the base layer, and they obviate
the need for precision contacting of the thin base layer. Further details on
this and related devices appear in footnote 121. An example of conductiv-
ity regions a t crossed wire zones in germanium appears in Fig. 41.
b. Single Crystals
Another aspect of the technique shown in Fig. 36 is its possibilities
for growing single crystals. Temperature-gradient single crystal growing
techniques using much larger liquid volumes have been described some
time ago.lZ2Use of a very short (thin) sheet zone has a number of ad-
vantages: (1) the apparatus is simple and has no moving parts, even the
temperature need not be altered; (2) the volume of liquid is so small that
a container is unnecessary and contamination and nucleation therefrom
are avoided; (3) the chance for spontaneous nucleation is minimized by
the smallness of the liquid volume arid the absence of stirring or convec-
tion. On the other hand, a foreign substance will be left in solid solution-
although innocuous ones can be used-and excessive temperature gra-
dients can produce plastic strain.
Single crystals of germanium saturated with lead have been produced
by the temperature gradient technique of Fig. 36 by the writer and
D. Dorsi. It was found that the carrier lifetime was still over 30 micro-
seconds, despite the presence of lead in solid solution (J. W. Peterson,
private communication).
c. Joining
The technique shown in Fig. 36 has yet another aspect. It is a joining
technique, in which the sheet zone may be regarded as a solder layer
joining the two blocks; unlike conventional solder layers, the sheet zone
migrates away from the original join to the surface of one of the blocks,
where i t can be removed. I n this way, mechanical, thermal, or chemical
weaknesses of soldered joints can be eliminated. It should be noted again
that some of the solute substance will remain in the traversed block in
solid solution.
VIII. Crystal Growth and Dislocations
28. INTRODUCTION
The field of single crystal growing is broad and variegated. Methods
used encompass all of the three possible transformations : liquid-solid,
vapor-solid, and solid-solid. Materials grown may have metallic, covalent,
lZ1 W. G. Pfann, U. S. Patent 2,770,761, November 13, 1956.
122 E. Buehler and A. C. Walker, Sci. Monthly 69, 148 (1949).
500 W. G. PFANN
or ionic bonding; they may be elements, compounds, or alloys; they may

be ductile or brittle a t room temperature; they may be chemically in-
nocuous, or so reactive that no known container will hold them; they may
or may not have a high vapor pressure; they may be grown from the melt
or from solution. These differences have led to a large variety of tech-
niques of crystal growth.
We do not attempt here to cover this field comprehensively, as other
reviews are available. Instead we concentrate on an important aspect of
crystal growth techniques that has up to now received inadequate treat-
ment, namely, careful specification of the perfection and purity of the
crystal, and the correlation of perfection with details of the growth
method. The subject will be confined to growth from the melt, both by
zone melting and normal freezing, and largely to the materials germanium
and silicon. The growth of crystals of these materials and the study of
their imperfections has received much attention in recent years; they are
the only substances, a t present, in which the occurrence and habit of
dislocations has been extensively correlated with growth techniques.
Moreover, they are among the most perfect of crystalline materials
produced. The discussion is intended to be sufficiently general to pertaic
to growth of other crystalline substances from the melt as well. I n the
following, we discuss fundamental growth phenomena, techniques, occur-
rence of dislocations, and measurement of crystal perfection.
Comprehensive reviews are available for readers whose interests go
beyond the scope of this article. Growth of metal crystals has been re-
viewed by H 01d en .l~The ~ theory of crystal growth and techniques for a
variety of substances were discussed a t a symposium of the Faraday
Society.124A short, general review of techniques was made by L a w s ~ n ; ’ ~ ~
and a recent excellent review by Tanenbaum126 is both comprehensive
and fundamental in its approach. Crystal habit and morphology are dis-
cussed by B ~ c k l e y ; and
’ ~ ~ nucleation, habit, and growth, particularly in
metals, were treated a t a recent AIME SymposiurnL28by Hollomon and
Turnbull and by Mehl.
123 A. Holden, Trans. Am. Soc. Metals 42, 319 (1950).
124 “Crystal Growth,” Dicussions of the Faraday Society, No. 5, Gurney and Jackson,
London, 1949.
1-25 W. D. Lawson, Telecomm. Research J . pp. 60-89 (1952).
126 M. Tanenbaum, in “Solid State Physics” (K. Lark-Horovitz and V. A. Johnson,
eds.), Vol. VI of Methods of Experimental Physics (L. Marton, ed.-in-chief).

Academic Press, New York, to be published.
12’1 H. E. Buckley, “Crystal Growth.” Wiley, New York, 1951.
1 2 8 “The Solidificaton of Metals and Alloys.” American Institute of Mining and Met-
allurgical Engineers, New York, 1951.

29. FUNDAMENTALS
OF CRYSTAL
GROWTHFROM THE MELT
a. Heat Flow
The main factor influencing the growth rate of a rather pure single
crystal from its melt is generally believed to be the rate a t which the
latent heat of solidification is extracted from the liquid-solid interface.
This, in turn, depends on the rate of removal of heat through the solid
by conduction, convection, and radiation and on the rate of arrival of heat
from the liquid a t the interface. By a pure substance we mean a material
containing < -0.1 atomic per cent of solute. At higher solute concen-
trations, the growth rate and character of the interface may become
strongly influenced by factors other than heat extraction-factors stem-
ming from the solute-rich film a t the interface. If “solute” concentration
becomes very large, more than say SO%, we have growth from solution,
in which the rate of growth is now limited by the rate a t which atoms of
the major substance of the crystal arrive a t the interface. We shall be
concerned largely with the first, and to some extent with the second, of
these conditions.
To grow a n oriented crystal from the melt, a seed crystal is placed in
contact with an dequilibrated with the cool end of the melt. Then its tem-
perature is slowly reduced so as to cause the interface to advance through
the melt. Various particular means are used: the seed may be dipped into
a melt of fairly constant (with time) temperature and then withdrawn; or
the seed may be integral with the main body of the melt or charge (being
prevented from melting by virtue of a temperature gradient between the
cool end of the seed and the hot part of the melt) and then the whole may
be withdrawn from a furnace; or the whole may be cooled, without
motion, by lowering of the furnace temperature.
It is generally believed, for metals a t least, th a t atoms can leave the
liquid state and enter a well-aligned crystalline array a t rates much larger
than those commonly used in crystal growth.lZ9This is the basis for the
earlier statement that single crystal growth rates are determined mainly
by the rate a t which heat of solidification can be extracted. Assuming the
first assertion t o be correct, why are crystals not grown a t rates corn-
mensurate with their “natural crystallization velocities”? A partial
answer can be had by examining the heat flows a t the interface of a
growing pure crystal. Assume a cylindrical melt, 1 cm2 in area, having a
heat source a t one end, a sink at the other, axial heat flow only, and heat
transport by diffusion only. Equating the heat flows entering and leaving
129 G. Tammann, “State of Aggregations.” Van Nostrand, New York, 1925.
502 W. G. PFANN
the interface, we have

~ s G s= R Z 4-YLGL (29.1)
where y denotes thermal conductivity, G temperature gradient R growth
rate, H heat of fusion in volume units, and subscripts S and L denote
solid and liquid.
The maximum conveivable growth rate R , is th a t for which GI, is
zero, which from Eq. (29.1) is seen to be rsGs/H. For a representative
metal, such as tin, for which y A 0.14 in calorie units, and H is (14 X 7.3)
cal/cm3, R, is about 0.0027 cm/sec a t a temperature gradient in the solid
GS of 20"C/cm. Actually, if the melt contains even a small amount of
impurity, the growth rate cannot be this large, as a finite gradient in the
liquid is necessary if spurious nucleation is to be avoided. (This is dis-
cussed in Section 29d.) A gradient in the liquid will produce a heat flux
which reduces the heat flux in the solid available for removing heat of
fusion. One might attempt an order-of-magnitude increase in growth rate
by increasing Gs. But this would first of all impose practical difficulties in
a melt > -1 cm in length; and more important, the large temperature
gradient in the solid would tend to produce thermal stresses sufficient to
introduce dislocations by plastic flow.
There is another way, which is almost an ideal method, of removing
heat of fusion from the interface, even in the case of one-dimensional heat
flow. This is t o utilize the Peltier effect. By passing a direct current
through the interface, heat can be absorbed a t a rate proportional to the
product of current and Peltier coefficient P S L . Pfann et aZ.l3O have utilized
this technique for germanium in several ways, and the idea has also been
discussed by 1 0 f f e . l ~Pfann
~ et al.130 have found PsL for germanium against
its own melt t o be around 0.1. Thus a current of 10 amp/cm2 can extract
heat of fusion a t the rate of about 1 watt. The technique is useful for
substances having large PsL and large enough electrical conductivity so
that Joule heating does not override the effects of Peltier cooling.
b. Nucleation
Turnbull et ~ 1 . have
1 ~ ~ shown that many pure metals can be super-
cooled far below their melting points. Hence the problem of avoiding
nucleation in growing a crystal from the melt is largely one of eliminating
foreign sources of nucleation such as unmelted impurity particles, or
dust, or oxidation products a t the surface of the melt. The container itself
l3O W. G. Pfann, K. E. Benson, and J. H. Wernick, J . Electronics (1957), to be pub-
lished.
l a 1 A. F. Ioffe, Zhur. Tekh. Fiz. 26 (2), 478-489 (1956).
184 D. Turnbull et al., see reference 128, Chapter 1, for bibliography and summary.
must always be regarded as a potential source of nuclei. However, a
technique described by C h a l m e r ~for
l ~ ~boat-grown crystals appears to be
very effective in nullifying nucleation a t the container. It is to arrange
conditions such that the advancing interface is convex toward the liquid.
Then the growth direction a t the container wall has a component directed
laterally outward. Hence any nucleus th at forms will tend to grow out
of the melt. Unless precautions are taken to avoid it, the usual interface
is concave toward the liquid, owing to lateral heat losses in the solid. A
concave interface is very likely to occur if the thermal conductance of the
boat exceeds that of the crystal.
Spurious nucleation can occur only if the liquid is supercooled. In-
creasing the temperature gradient in the liquid reduces the extent and
degree of supercooling. A remarkable nucleation effect found by Ellis134
in germanium is that all of the grains in polycrystalline ingots of germa-
nium prepared by directional freezing in a graphite cylinder were twin-
related; orders of twin-relation up to 4 were found. It was established
that twinning occurred by twin-oriented nucleation during freezing. This
phenomenon is discussed in greater detail by Ellis and Fageant135for
germanium, by Salkovitz and von B a t ~ h e l d e r 'for ~ ~ silicon, and by
H a a ~ e n for
' ~ ~InSb.
Further light was cast on the phenomenon of twin-oriented nucleation
by Billig'38 and by Bolling et ~ 1 . They
l ~ ~ concluded that germanium and
silicon have a strong tendency to grow in the ( h , h - I , 1) directions; if
the liquid-solid interface deviated from the normal to this direction,
twinning became likely. The latter workers demonstrated the relationship
of the phenomenon to supercooling, by showing that additions of solute
to the melt provoked twinning, presumably by increasing the amount of
constitutional supercooling.
c. Orientation
Does its orientation to the growth direction influence the perfection
of a seeded single crystal carefully grown from the melt? There appears
little doubt that velocity is strongly influenced by orientation in crystals
not carefully grown. Tammann, l Z 9 who conducted the first systematic
133 B. Chalmers, Can. J. Phys. 31, 132 (1954).

13* W.C.Ellis, Trans. Am. Inst. Mining Met. Engrs. 188, 886 (1950).
1 3 6 W.C.Ellis and J. Fageant, Trans. Am. Znst. Mining Met. Engrs. 200, 291 (1954).
E. I. Salkovita and F. W. von Batchelder, Trans. Am. Inst. Mining Met. Engrs.
194, 165 (1950).
1 3 7 P. Haasen, Trans. Am. Inst. Mining Met. Engrs. 209, 30 (1957).
E. Billig, see ref. 143.
139 G.F. Bolling, W. A. Tiller, and J. W. Rutter, Can. J . Phys. 34, 234 (1956).
504 W. G . PFANN
investigations (on organic, transparent liquids) of growth from the melt,

formulated the idea of a constant velocity of growth. This he defined as the
rate a t which a crystallographic plane is propagated parallel to itself.
It was found t o be especially large for certain crystallographic orienta-
tions, and t o depend on the amount of supercooling in the liquid. The
existence of preferred orientations in the columnar grains of metal and
alloy castings is well documented (Ba~-rett,’~O Mehl141).Preferred growth
directions are (100) for face-centered cubic and body-centered cubic im-
pure metals, (110) for P-tin (tetragonal), (111) for bismuth (rhombohe-
dral), for example. The existence of preferred orientation in a group of
columnar grains growing from the wall of a mold to the center of the melt
may be less a matter of growth velocity than of ability of the preferred
grains to crowd out less favored neighbors by spreading laterally. Chal-
mers, 1 4 2 in experiments with seeded bicrystals showed that the boundary
(originally parallel to the axis of the boat) tended to grow parallel to the
axis a t low growth rates, but deviated from the axis increasingly with
higher growth rate; the deviation was such that the crystal of “pre-
ferred” growth direction widened. He concluded that the preferred direc-
tion of growth was (001) for fcc metals, (10x0) for hcp metals, and (110)
for tin, which is body-centered tetragonal. At that time no clear explana-
tion for the widening process was apparent. Recently W. A. Tiller has
provided an explanation backed by rather convincing experimental data,
which is discussed in Section 29d. A remarkable feature of this theory is
that i t indicates that the preferred growth direction for extremely pure
fcc metals is not (loo), but (111).
I n columnar regions of silicon ingots, grown slowly but not carefully
enough for single crystal production, (112) is the favored direction (W. C.
Ellis, private communication). Recently Billig143has shown that rather
flat dendritic plates of germanium and materials having the diamond
cubic or zincblende structure can be produced by rapid growth from a
seed crystal into a supercooled melt. The growth direction was (211) and
the faces of the dendrite plates were parallel to (111) planes.
Thus, i t seems clear that crystals (‘like” to grow in certain directions;
but, t o return to the original question, will they be more perfect if they
do? The weight of available evidence suggests that they will. However,
a t this writing no carefully gathered evidence th a t clearly answers this
I4O C. S. Barrett, “Structure of Metals,” 2nd ed., p. 510. McGraw-Hill Co., New York,
1952.
141R. F. Mehl in “The Solidification of Metals and Alloys,” p. 40. American In-
stitute of Mining and Metallurgical Engineers, 1951.

B. Chalmers, Can. J. Phys. 31, 15 (1953).
1 4 3 E. Billig, Proc. Roy. Soc. 229A, 346 (1955).
question in terms of dislocation densities or precise x-ray orientation
measurements has appeared to date, although it soon may.
d. Constitutional Supercooling
The concept of constitutional supercooling, and the ideas stemming
from it, are, in the opinion of the writer, one of the two significant ad-
vances of the last decade in the field of crystal growth from the melt-
the other being the development of experimental methods for detecting
dislocations. This concept, pointed out by Rutter and Chalmers, 144 stems
from the existence of a solute-rich film a t the advancing liquid-solid
interface of a melt containing even a small content of solute for which
lc < 1. (The concept is equally valid for the case lc > 1.) For each com-
position in the film, there is a definite temperature a t which freezing can
I
DISTANCE FROM INTERFACE
FIG.42. Constitutional supercooling (after C h a l m e r ~ ' ~ ~ ) .

begin, this temperature being lowest at the interface where the solute
concentration is greatest. This freezing point-temperature relationship
is the upper, or liquidus, line T L in Fig. 42, in which the straight line T
is a plot of actual melt temperature versus distance into the liquid from
the interface. Thus, even though the temperature in the liquid rises with
distance, there still may be a region in which the actual temperature is
below the liquidus temperature. Such a region is said to be constitutionally
supercooled. As Cha1mersl46has pointed out in an excellent comprehensive
review on the subject of solidification, a region which is constitutionally
supercooled has three possible consequences. First, it is a region of tem-
perature inversion, a t which a smooth interface is unstable. (This in-
stability is discussed also by Wagner.13) Thus a series of projections form.
These lead t o the formation, by lateral diffusion of solute from the tips of
the projections, to a longitudinal cellular structure which, seen in cross
144 J. W. Rutter and B. Chalmers, Can. J . Phys. 31, 15 (1953).
145 B. Chalmers, Trans. Am. Inst. Mining Met. Engrs. 200, 519 (1954).
506 W. G . PFANN
section, often resembles a hexagonal chicken-wire network, in which the

cell boundaries are regions relatively very rich in solute. Later papers by
Walton et aZ.I9 for tin base alloys and by Tiller and R ~ t t e r for
' ~ ~lead-
base alloys, discuss the cellular substructure in greater detail. I n partic-
ular they show that it appears below a critical ratio G / R of temperature
gradient t o growth rate and that the critical G / R increases linearly with
solute concentration.
A second consequence of constitutional supercooling, pointed out by
Winegard and Chalmers,I4' is th at dendritic growth can occur in a direc-
tion of rising temperature. A third consequence is that it permits the
nucleation of new crystals in the region ahead of the interface. As a n
example, the oriented nucleation of twins in germanium was shown to be
related to solute content, and hence to the prevalence of constitutional
supercooling, by Bolling et ~ 1 . as
' ~discussed
~ in Section 29b.
The importance of avoiding a cellular substructure in zone refining,
and thus entrapment of solute in cell boundaries, was pointed out in
Pa r t 11. Such substructure can be avoided by lowering the growth rate,
increasing the temperature gradient, or by agitating the melt. It should
be avoided for reasons of crystal perfection as well as purity. The rather
sharp difference in solute content between the cell and its boundary
may result in a difference in lattice constants which can nucleate edge
dislocations.
Recently Rosenberg and TillerI4*have established that the preferred
growth direction in verypure lead prepared by zone refining is not < 100>
but < 111> . Tiller149proposed a theory that accounts for this change in
preferred growth direction with increasing purity. The explanation will
not be given in detail here, but it involves the manner in which new
growth platelets nucleate and spread on the cellular projections arising
from constitutional supercooling. The phenomena involved not only shed
light on preferred orientations, but also on the fundamental mechanism
of crystal growth from the meet.
30. TECHNIQUES
OF GROWTHFROM THE MELT
a. Crystal Pulling
The technique of growing a single crystal by lowering a seed crystal to
a melt and then allowing the melt to solidify progressively either by with-
j46 W. A. Tiller and J. W. Rutter, Can. J. Phys. 34, 96 (1956).

147 W. C. Winegard and B. Chalmers, Trans. Am. SOC.Metals p. 46 (1953).
1 4 8 A. Rosenberg and W. A. Tiller, to be published.
149 W. A. Tiller, to be published in J . Metals.

drawing the seed (CzochralskilS0)or by freezing in situ (Kyropoulos161)
has the advantage that the solid-liquid interface does not touch the con-
tainer. An improved version of these techniques was introduced to germa-
nium technology by Teal and Little,152developed further by Teal et aZ.,85
by Bradleyls8and by many others. The technique resulted in the first
crystals of germanium available in any real quantity whose perfection
approached that of the best present day crystals, and their availability
undoubtedly contributed to the speed of advance of the science and
technology of the transistor. The method, as generally used, involves
solidifying an entire melt by withdrawing the seed. Hence i t is basically
a normal freezing operation. Perturbations of the normal freezing concen-
tration distribution, namely, producing level regions and n-p-n junctions,
were discussed in Part VI. Here we consider only matters relating to
crystalline perfection.
The most comprehensive description available of the technique of
crystal pulling of germanium is that of Bradley,s8who also discusses the
temperature control technique, solute distributions, fundamental con-
siderations of heat flow, etc. The method will be described briefly here.
A seed crystal is cut with a diamond wheel usually with its long axis
parallel to a low index crystallographic direction. After deep etching to
remove strained material, the seed is mounted in a chuck and lowered to
the surface of a melt, Figure 43 shows a typical setup, using radio-
frequency heating. The preferred seed orientation has been dictated as
much by process requirements as by considerations of perfection. However,
< 111 > , < 100 > , < 110 > , < 112 > and nonrational growth directions have
been used apparently with equal success (E. Buehler, private communica-
tion). The crystal is usually rotated a t a rate of the order of 100 rpm to
produce convection in the melt and to even out asymmetries in the heat
flow. Rotated crystals tend to develop more or less flat faces, parallel to
the growth direction, of a number indicating the symmetry for the par-
ticular growth direction, e.g., four for < l o o > , three for < 111 >. Billig143
has commented on these in some detail. Pains are taken to keep the melt sur-
face free of particles, such as graphite, or germanium oxide, as these tend
to nucleate twins; they may also upset the radial symmetry of heat flow
if present in the form of a floating skin. Crystals of germanium weighing
up t o several pounds have been grown by the method. Shapes can be
controlled by specifying temperature and pull rate. For a given tempera-
ture condition, the diameter decreases as pull rate increases. A tempera-
ture control mechanism, used with a 450 kc radio-frequency generator,
160 J. Caochralski, 2.physik. Chem. 92, 219 (1918).
S. Kyropoulos, 2. anorg. u. allgem. Chem. 164, 308 (1926).
162 G. K. Teal and J. B. Little, Phys. Rev. 78, 647 (1950).
508 W. G. PFANN
was developed by L0zie1-l~~ for germanium crystal growing. It has ex-

tremely rapid response and can maintain the crucible temperature
within +_O.l”C.Growth rates are usually in the range from 2.5 to 75
microns per second. The uniformity of shape attainable in such apparatus,
using programmed growth rate and temperature, is illustrated by the
t
,.
PULL
DONOR OR ACCEPTOR
ADDITION
-QUARTZ ENVELOPE
SINGLE CRYSTAL - -
----COIL FOR R F
HEATING
H2 OUTLET
FIG.43. Apparatus for growth of germanium single crystals by the crystal pulling
method (Burton et ~ 1 . 1 0 ) .
crystals shown in Fig. 44. The variation in width reflects the resistivity
programming shown in Fig. 29. A constant diameter could have been
programmed just as easily-in fact, more easily.
Silicon crystals have been prepared successfully by crystal pulling in
a modified form of the apparatus shown in Fig. 43. Because the melting
point is much higher (1412OC, as compared with 937°C for germanium),
the radio-frequency generator usually has a capacity greater than 10 kw,
and the quartz furnace tube tnay be water-cooled on the outside. Because
of silicon’s reactivity, a fused quartz liner is used inside the graphite
153 J. C. Lozier, in “Transistor Technology” (J. Shive, ed.), Vol. 1. Van Nostrand,
Princeton, New Jersey, 1957.
crucible t ha t also serves as a susceptor. Even so, the entire melt must be
pulled from the quartz, as otherwise the remainder would adhere to the
quartz and crack it on freezing. Molten silicon reacts with quartz, al-
though not vigorously, as a result of which silicon monoxide is liberated
in gaseous form, and the melt (and crystal) become contaminated with
oxygenb1and boron.
Crystals of silicon and germanium grown by the pulling technique can
be expremely perfect. Dislocation densities, as determined by etching,
commonly are -lo3 to 105 in manufactured crystals. Much lower densities
FIG.44. Germanium crystals grown with automatically programmed growth rate

and temperature (Bradleyss) .
have been produced in the laboratory, and crystals said to show no dis-
locations over areas -1 cm2 in cross section have been made in both
silicon and germanium. X-ray half-widths of < 15 seconds for germanium,
and <10 seconds for silicon have been measured by Bond (private
communication).
The chief obstacles to crystalline perfection appear to be nucleation
by foreign particles on the melt surface, fluctuations in growth rate
caused by poor temperature control or variations in the ambient, plastic
deformation produced by thermal strains during the growth and cooling
process, and presence of solute atoms in the crystalline lattice. Some of
these items are considered in Section 31.
b. Zone Leveling
Single crystal growth is not a necessary concomitant of zone leveling
(or zone refining). However, the two are often performed together in
preparing materials such as semiconductors, in which control of crystal
510 W. G . PFANN
perfection as well as composition is essential. K a p i t ~ a , 'and

~ ~ later
Andrade and Roscoe155used a traveling zone to produce single crystals.
The zone was a means of producing a temperature gradient a t the freez-
ing interface; they do not mention its potentialities as a distributor of
solutes.
The requirements on the control of a molten zone for single crystal
growth and for zone leveling are different in part, but, forunately, are
not mutually exclusive to any great extent. For zone leveling, constancy
of zone volume and of travel rate of the freezing interface are extremely
important. Variation in either of these quantities results in variation in
solute concentration. Constancy of the rate of heater motion and tem-
perature, and a high-temperature gradient a t both interfaces, tend t o
CRYSTAL
FIG. 45. Schematic diagram of apparatus for growing zone-leveled germanium

crystals.
minimize such variations. Agitation of the liquid, as by inductive stirring,

is desirable, in that it tends to eliminate differences in concentration over
the area of the interface, and in th at it minimizes fluctuations in concen-
tration arising from fluctuations in growth rate. For single crystal growth,
fluctuations in growth rate or convection are undesirable; a planar, or
possibly convex-toward-the-liquid, interface and a low-temperature gra-
dient a t the interface are generally desired. The only requirements th a t
are a t all incompatible are those on temperature gradient a t the freezing
interface.
A simple apparatus useful for producing zone-leveled single crystals
of germanium and other materials was developed by W. G. Pfann and
K. M. O l ~ e n . ~The
g , ~apparatus
~ is shown schematically in Fig. 45. The
furnace tube is clear fused silica, about 2 in. in bore and about 3 ft. long.
A four- to seven-turn induction coil, powered by a 450 kc generator, is
wound outside the tube. Inside the coil is a graphite susceptor consisting
of a cylinder with a +-in. wall, 3 to 3 in. long, having a wide slot cut along
+
the top so as to expose about to 8 of the periphery. The purpose of the
slot is to permit some direct inductive heating of the molten zone, which
agitates the liquid, while yet retaining the advantages of the susceptor.
164 P. Kapitza, PTOC.Roy. SOC.119A, 358 (1928).
165 E. N. da C. Andrade and R. Roscoe, Proe. Phys. Soc. (London) 49, 152 (1937).
These are good control of zone length and of interface shape. A thermo-
couple inside the susceptor enables precise temperature control by means
of an electronic controller developed for crystal pulling applications uti-
lizing induction heating.153The charge is contained in a fused silica boat
of semicircular cross section and radius about 0.5 in., coated on the inside
with soot from a paraffin candle. The coating method, developed by
D. Dorsi and C. F. Larkin, has been largely responsible for the success
of the method. The inside of the quartz boat is sand-blasted with car-
borundum and etched lightly for cleaning, leaving pores. A coating of
soot is deposited by moving the inverted boat over a paraffin candle
flame. This is rubbed into the pores, and will suffice for growing many
crystals. Usually another flame coating is applied before making a crys-
tal; it provides a soft, porous surface which not only prevents adhesion
but also minimizes keying of the frozen crystal to small irregularities in
the boat. A hard coating made by pyrolytic decomposition of a hydro-
carbon was not nearly as successful.
FIG.46. Photograph of zone-leveled germanium single crystal about 14 inches long.
The boat is centered axially in the susceptor and slides on a track

comprised of quartz rods lying in the furnace tube. The charge is an ingot
of zone refined germanium, usually about 12 inches long, shaped to fit
the boat closely. A 2-inch length of seed crystal is usually used to control
the orientation. A small pellet of Ge-Sb or Ge-In addition alloy is placed
at the starting position of the zone. Then a small portion of the seed is
melted into the zone and the crystal is grown at a rate usually in the range
from 0.1 to 2 mils/sec. Such crystals usually exhibit less than 10% varia-
tion in solute concentration throughout the entire ingot, except for the
last zone length. One is shown in Fig. 46. Dislocation densities are -lo4
per cm2, as measured by etch-pit counts.
A method leading to a significant improvement in crystalline perfection
of germanium was developed by Bennett and Sawyer.lS6This is a zone-
leveling method using a long after-heater to control the temperature gradi-
ent a t the interface and to minimize the radial loss of heat from the cooling
crystal. The development was a direct outgrowth of their observations of
dislocation distributions in crystals grown by the pulling method. They
156 D. C. Bennett and B. Sawyer, Bell System T e c h J . 36, 637 (1956).
512 W. G . PFANN
observed, in < 111> grown crystals, a “star” pattern of etch pit lines, in
which etch pits due to dislocations were found aligned in the intersections
of the three (111) slip planes with the (111) plane normal t o the growth
axis. This result indicated that the dislocations were produced by plastic
deformation of the hot crystal. They attributed the deformation to differ-
ences in thermal contraction arising from a temperature difference be-
tween center and surface of the crystal a t a given distance from the inter-
face. (Such a temperature difference arises if d T / d x is not constant along
a cylindrical crystal.)
T o minimize such thermal stresses, they added a rather long after-
heater to the molten zone heater. It consists of a loosely wound induction
coil, inside of which rests a long graphite cylindical susceptor. They im-
posed a relatively low temperature gradient a t the interface, about 10°C
per em. Because the lower temperature gradient leads to greater fluctua-
tions in interface position and zone length, they found it advisable to
grow a t a lower than usual rate, about 2.5 p per see in order to maintain
uniform electrical conductivity. Data for several hundred crystals show
an average variation of electrical conductivity (which is proportional to
solute content) over the ingot length of 9%) and over the cross section
of 3 %, a highly satisfactory result. Average dislocation etch-pit densities
were about 1500 per cm2, an order of magnitude lower than were obtained
with no after-heater. Recent data show an average of 900, and a few
crystals have shown, over several cubic inches of volume, -100. Disloca-
tion counts are discussed in more detail in Section 31, but it is clear th a t
these crystals are much freer of dislocations than the most perfect metallic
crystals.
Pulled silicon and germanium crystals have been prepared with dis-
location etch-pit counts less than 100 per em2; an after-heater being used
in the preparation of some of these.
Thus, i t seems clear that plastic strain due to cooling can be a major
source of the dislocations in a nearly perfect crystal. A belief current
among certain workers in this field might be criticized here. It seems
generally accepted that a nonlinear temperature gradient gives rise to
such strain (see for example, Billig167).However, the belief, expressed by
some, that a flat liquid-solid interface will guarantee avoidance of such
strains appears to be incorrect, for certainly the isotherms can change
from flat to curved, with distance along the crystal, if there is radial
heat loss (or gain). Perhaps the empirical observation that a flat inter-
face corresponds to a low dislocation density is attributable to orientation
effects such as discussed by Bollirig et ~ 1 . ~ ~ 9
Single crystals of silicon also have been grown b y the floating zone
15’ E. Billig, Proc. Roy. SOC.236A, 37 (1956).
method. These crystals are not as perfect as germanium crystals made

by pulling and zone-leveling techniques. However, there is no reason to
believe that application of the ideas just described will not result in
crystals as perfect as those grown by the other technques.
31. DISLOCATIONS
IN CRYSTALS
GROWNFROM THE MELT
The end of a long review on zone melting and crystal growing is not
the place t o begin a comprehensive discussion of dislocations in real crys-
tals. Nor is the present time propitious, in view of the fast-changing
character of this particular field. Nevetherless, the facts that dislocations
exist in real crystals and that they can be observed directly have had a
large impact on crystal growing. Therefore, this field is reviewed briefly.
The mechanism of crystal growth by dislocations of screw orientation
was reviewed by Frank.*58This mechanism is limited to crystal growth
from dilute solution or the vapor, and Frank stated that it is not direckly
applicable t o growth from the melt. A host of experimental findings
followed, which left no doubt of the existence of dislocations of screw
orientation. The subject of direct observations of dislocations in crystals
(edge and screw), to the end of 1953 was reviewed comprehensively by
Forty. 159
Progress in identifying edge dislocations and aggregates and networks
of dislocations was slower. It was suspected that alignments of etch pits
in subgrain boundaries in aluminum,160and networks of photolytic silver
in deformed crystals of silver bromide161indicated dislocations. But these
findings were generally not accepted as conclusive, a t the time. More
positive identification of individual edge dislocations resulted from a find-
ing growing out of the development of the germanium zone-leveling single-
crystal method. During the development of this process, it was repeatedly
noted t ha t faint lineage boundaries were observable in etched cross sec-
tions, t ha t they persisted in successive cross sections for many inches,
and t ha t they were invisible in longitudinal sections. H. E. Corey ob-
served concentrations of random etch pits, which reappeared on regrind-
ing and re-etching, and concluded th at these were line defects. Hearing
this, the writer recognized that the aforementioned linear boundaries
undoubtedly consisted of parallel edge dislocations according to the model
proposed by Burgers,162and examination of such a boundary in an etched
F. C. Frank, Advances in Phys. 1, 91 (1952).

169 A. J. Forty, Advances i n Phys. 3, 1 (1954).
l 6 o P . Lacombe and L. Beaujard, Compt. Rend. 218, 878 (1944); J. Znst. Metals 74,
1 (1948).
J. M. Hedges and J. W. Mitchell, Phil. Mag. 44, 223 (1953); ibid. 44, 357.
l 8 2 J. M. Burgers, Proc. Phys. SOC.62, 29 (1940).
514 W. G. PFANN
cross section a t high magnification indeed showed a very regular align-

ment of etch pits (Fig. 47). It remained to demonstrate that the pits
corresponded t o edge dislocations. This was done by measuring by x-rays,
the small orientation difference between the relatively perfect blocks on
FIG.47. Low-angle lineage boundary in germanium.
either side of several boundaries. These measurements were performed

by F. L. Vogel, using a double-crystal apparatus made available by
W. L. B ~ n d . ' ~Later
~ , ' ~work
~ on plastic deformation further confirmed
that dislocations of edge, and probably screw, orientations could be re-
vealed, one-for-one, as etch pits in germanium166 and in iron-silicon
alloys. 166
Is3F. L. Voge1,W. G. Pfann, H. E. Corey, and E. E. Thomas, Phys. Rev. 90, 489
(1953).
l64 F. L. Vogel, Acta Metallurgica 3, 245 (1955).
166 F. L. Vogel, Trans. Am. Inst. Mining Met. Engrs. 206, 946 (1956).
W. R. Hibbard and C. G. Dunn, Acta Metallurgica 4, 306 (1956).
The development of etch pits requires very careful techniques, since

it depends on the usually small difference in rates of attack between mate-
rial a t or near the dislocation and the matrix. Etching methods have been
developed for germanium,16’ silicon, 168,169 iron-silicon, aluminum contain-
ing critical impurities,ITazinc containing cadmiurn,l7’ sodium chloride,
lithium fluoride,173and others. For the examples given, the evidence is
quite conclusive that the observed etch pits correspond to dislocations.
I n certain instances edge and screw orientations apparently can be dis-
tinguished by the shape of the etch pit,172j173 although more conclusive
evidence is desirable.
I n a particular material, such as germanium, etch-pit densities can
be a function of the etchant and even of how it is used. Hence the etch-
pit technique t o determine dislocation densities must be used with care.
Only when the etch pits aggregate in a manner clearly attributable to
dislocations, or produce distinct orientation effects (as a t a low-angle
boundary), or exhibit (indirectly) motions explainable only by disloca-
tions, can they be safely regarded as representing dislocations. Ellis174
has observed etch pits in germanium, which he attributes to “com-
posite dislocations,” but as yet there is little supporting evidence that
these very numerous pits actually represent dislocations.
The technique of decorating dislocations inside a crystal and then
examining them by light of suitable wavelength provides perhaps the
best visual information on dislocations, but, on the other hand, it is
usually a destructive measurement, in th at the nature of dislocations
may be altered by decoration. Early observations of dislocations dec-
orated by photolytically deposited silver were made by Hedges and
Mitchell. 161 Amelinckx‘’6 has decorated dislocations in NaC1, revealing
complex networks. Dash168decorated dislocations in silicon with precip-
itated copper and examined them with infrared radiation by means of a
snooperscope. He found that each decorated dislocation demonstrated
conclusively that etch pits correspond to dislocations. He showed beauti-
ful photographs of Frank-Read sources marked in motion by the decora-
tion. by observation of stress birefringence a t infrared wave-
167 W. G. Pfann and F. L. Vogel, A c t a Metallurgica (1957), to be published.
W. C. Dash, J . A p p l . Phys. 27, 1193 (1956).
leg F. L. Vogel and L. C. Lovell, J . A p p l . Phys. 27, 1413 (1956).
G. Wyon and J. M. Marchin, Phil. Mag. 46, 1119 (1955).
l f l J. J. Gilman, Trans. Am. Inst. Mining Met. Engrs. 206, 998 (1956).
S. Ameiinckx, Acta iMetaZZurgica 2, 848 (1954).

I 7 3 J. J. Gilman and W. G. Johnston, J . A p p l . Phys. 27, 1018 (1956).
1 7 4 s . G. Ellis, J. A p p l . Phys. 26, 1140 (1955).
I76 S. Amelinckx, Phil. Mag. 1, 269 (1956).
W. Bond, Phgs. Rev. 101, 1211 (1956).
516 W. G . PFANN
lengths, showed the stress pattern around individual undecorated

dislocations in silicon.
The development of dislocation etch pits in the metals listed, requires
a process akin to decoration, in that small amounts of impurity are
necessary for the operation of any particular etchant. Not only must the
impwitty be present, but it must have had time to diffuse to the disloca-
tions in order for an etch pit to form. In germanium, impurities donot
appear to be necessary, although the proof is not as yet conclusive. I n
FIG.48.Random dislocation etch pits in germanium. 150 X.
LiF, judging by the ease with which a moving dislocation can be re-
vealed by etching, as shown by Gilman and Johnston,173an impurity is
unnecessary.
Silicon and germanium are a t present the only crystals for which
dislocation habit has been extensively correlated with growth procedure.
An example has already been discussed (Bennet and Sawyer). Billig16’
has discussed the effects of growth conditions on dislocations in germa-
nium and silicon crystals grown by pulling. His paper contains much
interesting experimental information, although certain of the conclusions
must be regarded as tetative. He emphasizes, as did Bennett and Sawyer,
the effects of thermal stresses, and makes a rough estimate of the ex-
pected dislocation density, which agrees with observation.
Pfann and V ~ g e l ’ ~summarized
’ the etching behavior and habit of
dislocations in several hundred germanium crystals grown by zone level-
ing. It was shown that dislocations form etch pits in CP-4 only if the sur-
face of the sample is within 8 or 10" of a (111) or (100) plane, but that a
more or less circular pit appeared for angles between the dislocation line
and view plane ranging from 90" to 24". Dislocations appeared as random
pits (Fig. 48), in straight orderly boundaries (Fig. 47), and in irregular
boundaries grading into randomness (Fig. 49). The straight boundaries
were pure tilt boundaries, in which the boundary plane was usually (1lo),
that is, normal to the Burgers vector. Thus the boundary planes were
FIG. 49. Boundary changing to random distribution of dislocation etch pits in

germanium. 150 X .
characteristic of a polygonized state. Straight boundaries lying in (100)

planes were found; these appear to consist of two sets of dislocations
whose Burgers vectors were normal to each other and a t 45" to the bound-
ary, in accord with the model of Read and S h ~ c k l e y . ~The
~ ' boundary
dislocations themselves lay in the three < 112> directions closest to the
growth direction in < 111> grown crystals, and in the <001> direction in
<001> grown crystals. The boundaries lay in (110) planes parallel to the
growth direction in each case. Thus, in the <111> grown crystals, even
though the dislocation lines were oblique to the growth axis, the disloca-
tions did not grow themselves out of the crystal. I n these same crystals
L and T intersections of tilt boundaries (Fig. 50) were studied by Pfann
W. T. Read and W. Shockley, Phys. Rev. 78, 275 (1950).
518 W. G. PFANN
and L0ve11.'~*The linear densities of dislocations in the branches of the

intersections agreed well with those calculated. A m e l i n c k ~ lmade
~ ~ sim-
ilar observations on NaC1. The above-mentioned observations on germa-
nium were made on crystals containing -lo4 dislocations per cm2, and
the observed distributions are more or less what is expected for the
annealed or polygonized state. In no case were dislocations found lined
up on slip planes, (i.e. (111)). This is in contrast with the findings of
Bennett and Sawyer, l b 6and Billiglb7on pulled crystals.
FIG.50. T intersection of dislocation tilt boundaries in germanium. 450 X.

Differcnccs in solute concentration within a specimen can lead to the
formation of large numbers of dislocations. Frank158has speculated on the
possibility that a continuous change in solute content will nucleate a
lineage structure. A different mechanism is rather strikingly illustrated by
photomicrographs of germanium -6% silicon alloys obtained by Goss
et Silicon is soluble in germanium and changes its lattice constant.
During crystal growth, the silicon content a t the interface fluctuated.
Sharp changes in lattice constant thus occurred along surfaces parallel to
successive positions of the interface and the atomic misfit was taken up
by grids of edge dislocations, as shown in Fig. 51. Dislocations formed by
this mechanism can be expected for mean solute concentrations as low as
-O.l%, depending of course on the solute and degree of fluctuation.
W. G. Pfann and L. C. Lovell, Acta Metallurgica 3, 512 (1955).
A. J. Goss, K. E. Benson and W. G. Pfann, Acta Metallurgicu 4, 332 (1956).
Impurities and imperfections in general were discussed a t an ASM

Seminar179nin 1954; several papers deal with lattice vacancies and inter-
stitials, a topic not covered in this review.
FIG.51. Dislocation etch pits along concentration contours in germanium -6%

silicon crystal. 200 X. (Goss et a Z . 9
32. MEASUREMENT PERFECTION

OF CRYSTAL
As we have seen, rapid progress has been made toward the physicist’s
goal of crystal perfection. In fact, the actual progress appears t o be out-
stripping the means for its measurement. A very powerful tool has been
provided-techniques for the direct observation of dislocations. It is
both macroscopic and microscopic. Provided it can be relied on, it prob-
ably will be the most precise measure of crystalline perfection we h a v e
insofar as crystalline perfection is measured by dislocations alone. How-
ever, dislocation counting techniques are not available for many sub-
1790 “Impurities and Imperfections,” American Society for Metals, Cleveland, Ohio,
1955.
520 W. G. PFANN
stances (although they will be, in time), and even for those materials
studied most, more rigorous proof is required th a t one etch pit-or one
decorated marking inside a crystal-corresponds to each and every dis-
location. T o attain this proof, crystalline perfection must also be demon-
strated by other methods.
The methods most commonly used to judge the perfection of germa-
nium and silicon crystals are dislocation counts, x-ray rocking curve
widths, and carrier lifetimes. There are two difficulties with x-ray rocking
curve measurements. First, the best crystals are so perfect that the
measured half-width closely approaches the natural half-width for a per-
fect crystal, about 15 sec for CuKxl radiation in germanium, less in
silicon (W. L. Bond, private communication; Kurtz ef ~ 1 . ~ ~ Second,
0 ) . a
model must be assumed. It is clear th at the observed half-width will be
very sensitive to the particular model; and it has been shown that dis-
locations can arrange themselves in a variety of ways. Hence, to provide
a number corresponding to a dislocation density, x-ray rocking curve
data must be accompanied by information on the actual distribution of
dislocations in the sample. It would appear that a promising area of in-
vestigation would be the careful correlation of x-ray data with known
dislocation distributions (determined by direct observation), including
random distributions and special, anisotropic distributions. Gay et al. lR1
have discussed models for correlating half-width with dislocation density,
which while undoubtedly helpful as far as they go, have been used per-
haps too freely by later investigators. Kurtz et aZ.lX0discuss theoretical
and experimental relationships among dislocation densities, carrier life-
times, and x-ray half-widths in germanium crystals. Although they
show correlations among these three quantities, their interpretation of
which dislocations are revealed by etching differ from others16’ and their
lifetime versus dislocation density correlation disagrees by one or two
orders of magnitude with Okada, l X 2and with Wertheim and Pearson.lX3
A detailed review on “Mosaic Structure” by P. B. HirschlX4has
appeared very recently. After going into the historical background of the
field of crystal perfection, the author discusses experimental evidence for
dislocations in crystals; and he considers in detail the evaluation of dis-
location densities by x-ray techniques. He points out th a t intensities of
reflected x-rays, as well as half-widths of rocking curves, can provide a
A. D. Kurtz, S. A. Kulin, and B. L. Averbach, Phys. Rev. 101, 1285 (1956); J.

Appl. Phys. 27, 1287 (1956).
181 P. Gay, P. B. Hirsch, and A. Kelly, Acta Metallurgica 1, 315 (1953).
182 J. Okada, J . Phys. Soc. (Japan) 10, 1110 (1955).
183 K. Wertheim and G. L. Pearson, Bull. Am. Phys. Soc. 1 (7), 331 (1956).
184 P. B. Hirsch, Progr. in Metal Phys. 6, 236 (1956).
sensitive measure of imperfection. Dislocation densities of the order of

1000 per cm2 or less cannot be measured accurately by present x-ray
techniques. Hence it appears th at corroboration of etch pit counts of this
order will have t o be sought in some other measurement.
Carrier lifetimes in semiconductors can provide an extremely sensitive
measure of recombination centers. Dislocations are centers for hole-
electron recombination. The data of Vogel et al.1s5show the effectiveness
of disolcations, in low angle boundaries in germanium, as recombination
centers. However, many impurities are recombination centers also
(Burton4s), and therefore an uncertainty generally exists as to whether
lifetime data are a measure of dislocations or of impurities.
Strength properties of dislocation-free crystals have been widely
heralded. It appears certain that sizeable volumes of apparently (etch-
pit) dislocation-free crystal are becoming available. Should they have the
high yield strength of ideal crystals, the evidence will be convincing that
they are really dislocation-free. Should they not, it will appear that they
still contain dislocations not revealed by etching-or that, as often hap-
pens, something has been overlooked in the theoretical model.
F or a method of observing individual dislocations, based on the Moire
effect, the reader is referred to the work of Hashimoto1s6and Menter.ls7
l86F. L. Vogel, W. T. Read, and L. C. Lovell, Phys. Rev. 94, 1791 (1954).
H. Hashimoto, A d a C ~ y s t10,
. 143 (1957).
lS7 J. W.Menter. PTOC. Roy. Sac. A236, 119 (1956).

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Techniques of Zone Melting and Crystal Growing

VI. Methods of Perturbing the Concentration ......................... 472

b. Programmed Growth Rate in Normal Freezing.. . . . . . . . . . . . .

FIG.2. Solidification by normal freezing (schematic).

maintains the concentration in the solid uniform a t all times, even

No segregation occurs in equilibrium freezing because time is allowed

The equation is an approximation, as it cannot hold for the entire

co= 1 FOR A L L CURVES

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

the equation calls for infinite concentration a t g = 1, which is impos-

Plots of this important equation for several values if ko as a function

be regarded as a normalized growth velocity. It embodies the three

FIG. 4. Dependence of effective distribution coefficient k on normalized growth

growth rate, combined, if possible, with some kind of forced convection

16 R. G. Pohl, J . Appl. Phys. 26, 1170 (1954).

mine the equilibrium distribution coefficient k ~ From . ko and from a

As a last resort, for purposes of zone refining, one can determine by

5. GENERALREMARKSON CONDITIONS OF CRYSTALLIZATION

Several aspects of normal freezing and of crystallization in general,

111. Principles of Zone Refining

charge, probably the most important is removal, th a t is, purification or

account of the solidification methods used to produce p-n and n-p-n

FIQ.6. Molten zone of length, 1 traversing a cylindrical ingot of length L (schematic).

FIQ.7. Approximate concentration of solute after passage of one molten zone

where C is solute concentration in the solid and x is distance from the

DISTANCE IN ZONE-LENGTHS, X/L

where C,(z) denotes the concentration after the n th pass at distance x

,--RING HEATER (STATIONARY)

FIG.9. Multi-pass zone refining (schcmatie).

elimination of the step of separating pure from impure fractions, as in

Without going into the mathematics of multi-pass, or intermediate

The following equation, obtained by MillikenlZ4results from simpli-

ReissZ2notred that the expression for C,(O), the concentration a t the

A method that permits one to go directly to the concentration in the

described by Reiss.22 This method is approximate, being accurate only

FIG.11. Same as Fig. 10, except that k = 0.10.

Several computational methods have been proposed. These have the

be trivial for a single pass, but if multiplied in repeated passes it can

27 W. G. Pfann, “Zone Melting,” Chapter 3. Wiley, New York, to be published.

levels in vertical tubes to simulate concentration. While it is no match

is a qualified no. If rerefining is done at the new length L', nothing is

FIG.14. Ultimate distribution attainable by zone refining, for several values of k,

will depend on whether the ratio a of solid density to liquid density is

DIRECTION OF ZONE TRAVEL

FIG.15. Continuous zone refining apparatus (generalized).

molten zones approximately constant in size. A void is normally present

tt Figure 17 shows how a void of controlled

(0) (b) (C1 (d 1

schematically in Fig. 18. The heaters move with reciprocating motion,

columns, are given in footnote 32. I n essence, the ratio l / ( h - I) of molten

IV. Practice of Zone Refining

tion34~35or sunlight. Immersion heaters are particularly effective, although

34 R. Handley and E. F. G. Herington, Chemistry & Industry p. 304 (1956).

charges must be used. A number n of zones can be passed through a

16. ZONE REFININGWITHOUT A CONTAINER

37M. Tanenbaum, A. J. GOSS,and W. G. Pfann, Trans. Am. Inst. Mining Met.

39 R. Emeis, 2.Naturforsch. 9a, 67 (1954).

Thus Heywang and Ziegler,41 and later H e y ~ a n g 4in~ greater detail,