ELSEVIER

Separations Technology 6 (1996) 227-233

Optimal zone lengths in multi-pass zone-refining processes

Chii-Dong Ho*, Ho-Ming Yeh, Tzuoo-Lun Yeh
Department of Chemical Engineering, Tamkang University Tamsui, Taiwan, R O.C.

Received 16 April 1996; accepted 1 June 1996

Abstract
A method for determining the optimum zone length for maximum separation in multi-pass zone-refining processes is
described. Numerical values of the optimum zone lengths and their corresponding maximum separations for up to ten passes
are presented. The optimum zone length is found to increase with the distribution coefficient but decreases when the pass
number increases. Considerable improvement in separation may be obtained if zone refining is operated at the optimum zone
length, except for higher distribution coefficients.
Keywords:

Zone refining; Multi-pass; Optimum zone length

1. Introduction
The general

Heater
w--+

term zone refining denotes a family of

methods for controlling the impurities or solute concentrations in crystalline materials. Zone refining is
an extremely efficient puriiication technique for separating liquid or solid mixture [1,2]. The first important
application of zone refining was used to purify germanium in transistors [31. In multi-pass zone refining, a
series of closely spaced heaters is placed in relative
motion to a long solid ingot leading to a redistriiution
of solutes in the ingot, as shown in Fig. 1. The
advantage of multi-pass zone refining is the savings in
operating time, as succeeding crystallization begins
before the preceding one is completed. With proper
selections of the zone number and zone length, many
useful operations can be performed with solid ingots.
Birman has designed a matrix method to describe
the zone refining of a bar with non-uniform initial
solute concentrations
[4]. Zone refining with zone
length changing along the ingot has been studied
[5-81. Davies found in his studies that the optimum
ratios of zone length to ingot length are 1.0 and 0.3,
respectively, for the first and second pass [51. Jackson
and Harm discovered a method for producing a linear
gradient of solute concentration
by changing the
0956-9618/96/$15.00 0 1996 Elsevier Science Ireland Ltd. All rights reserved.
PII SO956-9618(96)00160-9

l-u
X

Moltenzone

(a) Single-pass wne refining

Ring heater ( Stationary )

Molten zone

@) Muti-pass zone refining

Fig. 1. Schematic diagram of zone refining apparatus.

C.-D. Ho et at! /Sepamtions

228

volume of a molten zone [a]. Wilcox developed a

theory for the determination of the non-constant distribution coefficient, and Yeh and Yeh developed the
separation theory and investigated the improvement
of separation in a two-pass zone refining process with
zone length varied along the ingot [7,81. A large body
ofsign&ant investigations devoted to some aspect of
applications in zone refining have appeared in the
literature during the last two decades. For instance,
the silicon-on-insulator (SOI) films [g-12] and semiconducting [13-B] and superconducting [16-181 substances were prepared by zone-refining processes.
The purpose of this work is to determine the optimum zone length for maximum solute removal in
multi-pass zone-relining processes and investigate the
improvement in separation which may be obtained
when the operation is performed at the optimum zone
length.
2. The basic equations

Technology 6 (1996) 227-233

zone length is no longer constant, and solute is no

longer taken in. The equation becomes:

= -c,wdx,

d[U -x)C,W/kl

(L-OSXSL
(2)

or
K,(x)

= ~C(X)dr,

(L-OSXSL

(3)

Note that above equations satisfy the boundary conditions:

at x=0,

C = (k/Z$C_

at x=L-1,

,(xMx

(4)

LC, - i-C,,(x,dx]

The basic differential equation applicable to multi-

(5)

pass II zone-relining process with same zone length 1

in each pass was derived independently by Lord [19]
and Reiss [20]:
Id[C,W/kl

= [C_,(X+ 0 - C(XMx,
OSXSL-1

(1)
k -0.5

with the meaning of the symbol given in the Notation

section. .
This equation is obtained by a mass balance of the
solute within the moving zone ABCD or A BCDas
shown in Fig. 2, and based on the following assumptions: (a) constant distribution coefficient; (b) uniform
composition in the liquid, (c) negligible diffusion in
solid; (d) constant zone cross-section; (e) no volume
change on freezing; (0 constant length of liquid zone.
After the front of the zone reaches the end of the
ingot, at x = L - 1, where L denotes ingot length, the

&

1.0

molten zone AEKD or AWCI)

y
.,I*-..*..-**...
0.0

0.2

. *. . . . *. . .
0.4

0.6

0.8

1.0

Fig. 2. Schematic diagram of zone refining operation.

Fig. 3. The effect of zone length on the concentration distribution

of zone refming after two-pass operation (k = 0.5).

C.-D. Ho et al. /Sepamtions

The solutions of Eqs. (6) and (7) associated with the

boundaxy conditions, Eqs. (8) and (91, are:

Setting
4,(X)

229

Technology 6 (1996) 227-233

= C,(X)/C,
X=x/L
Y=I/L

Eqs. (1) and (3) can be rewritten

&J(X)

&%(X)=

= [A_ ,(X+

=C#J
1-X

as:

O~X~l-Y

(6)

l-YSXI;l

(7)

n(XMX,

= k(1

4(X)

Y) - 4JX)lG

/oy4n_Io~,
-xjk- F,(Y),

4 = ($)[l-

l-Y<XSl

(11)

I;,(Y)
=Y-k 1- $-y+JtMC

atX=l-Y,

(10)

where

and the boundary conditions are

at X= 0,

OI;XI;l-Y

(12)

(8)

2.1. One-pass opemtions

(9)

For one-pass operation, it = 1, and 9&X + Y> =

4,(X) = 1. Thus, the concentration
distribution in
the ingot after one pass is obtained from Eqs. (lo-121

Jy-y4(X)dx]

O
9 O

1
k =OS

01 /
0.0

0.2

0.4

06

0.8

IO

X
Fig, 4. The effect of zone length on the concentration
of zone refining after two-pas operation (k = 1.5).

distribution

Fig. 5. The effect of zone length on the concentration

of zone refining after five-pass operation (k = 0.5).

distribution

C.-D. Ho et al. /Sepamtions Technology6 (1996) 227-233

230

as

C&(X) = k(1 -XIk= 1 - (1 - k)e-kYx

&(X>

Os;X<l-Y

F,(Y),

1 -Y<Xls

1 (17)

where
(13)

&(X)

=k(l

1 - YzzX<

-Xjk-F,(Y>,

F,(Y) = (1 + [l - e-k(-Y)/Y](l

(14)

(18)

(15)

The results for k = 0.5 and 1.5 are presented graphically in Figs. 3 and 4, respectively.
For further-pass operations, the concentratibn distributions are readily obtained if we perform the
calculations of Eqs. (lo-121 repetitively. Figs. 5 and 6
show the concentration distributions of five-pass operation for k = 0.5 and 1.5, respectively.

- k)/k)/Yk-

2.2. Multi-passoperations
For two-pass operation, n = 2 and the concentration distribution may be calculated numerically from
the following equations with the use of Eqs. (13-15)

3. Optimum zone length

OI;X<

1 -Y

(16)

Since the initial dimensionless concentration d,,(X)

is equal to unity, the solute removal can be calculated

0.5

/OO

0.1
0.0

0.2

0.4

0.6

0.8

1.0

Fig. 6. The effect of zone length on the concentration

of zone refining after five-pass operation (k = 1.5).

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

distribution

Fig. 7. The effect of zone length on solute removal after two-pass

operation UC< 1).

C.-D. Ho et al. /Separations

231

Technology 6 (1996) 227-233

Mathematically, the optimum zone length Y* for

maximum W, is obtained by solving the equation,
dW, /dY= 0, with the use of Eqs. (13-15). Since (dW,
/dY) < 0 for k < 1 and (dW,/dY) > 0 for k > 1. In
order to meet both situations, therefore, Y must be as
large as possible, i.e. normal freezing for all values of
the distribution coefficient. This is the same result
obtained by Davis [5]. Accordingly, the optimum zone
length for the first pass is

II

I*=LorY*=l

k=1.7

(21)

and the concentration distribution is readily obtained

from Eqs. (14) and (15) by setting Y = Y* = 1
4;(X)

05x5

= k(1 -Xjk-,

(22)

while the maximum solute removal W, max is calculated by substituting Eq. (22) into Eq. (2b). The result
is shown in Fig. 10 for n = 1.
3.2. Multi-pass operations
The optimum zone length Y* for ma$mum H(,
after multi-pass operations can be obtained from Eq.

k =1.1

045

o17.

01

02

03

04

0.5

06

07

08

0.9

1
n=2

Y
04

Fig. 8. The effect of zone length on solute removal after two-pass

operation (k > 1).

bY
0 35

/,.j, 1 - &,(X)ldx

= 0.5 - iO%#JJX)dX,

w, =

for k < 1
/O.5[ +JX)

- I]&=

~~5~n(xMx-

03

0.5,

fork>

1
(19)

The optimum zone length Y* for maximum separation may be obtained by partially differentiating W,
with respect to Y and solving Y* from the equation
dW,/dY=

n=4

>

0 25

n=5

0;

n=v

=I

0.

n=9

n=IO

3.1. One-pass operations

0 I!

For one-pass operation, Eq. (19) becomes

fork<

0.5 - ~.s$,(x)dx,

01

00

02

04

06

08

(20)

w, =
/

&(x1&-

0.5,

for k > 1

10

12

14

16

18

2.0

Fig. 9. The optimal

processes.

zone

length

of multi-pass

zone

refining

232

C.-D. Ho et al. /Sepamtions

Technology 6 (1996) 227-233

4. The improvement in separation

The improvement in separation by operating at the

optimum zone length Y* is best illustrated by calculating the percentage increase in separation based on
that operating at Y

Ill=

Wn ,max
w

wnx 100%

(23)

For illustration, the results for n = 2 and 5 were

calculated by Eqs. (19) and (23) with the use of Figs.
3-6 and are given in Tables 1 and 2.

5. Results and discussions

0 I5

0.1

005

lit.........

0
00

0.2

0.4

0.6

08

1.0

1.2

1.4

1.6

1.8

2.0

k
Fig. 10. The maximum solute removal of multi-pass zone refining
processes.

(19) numerically with c$ (X1 calculated previously

from Eqs. (10-12). For illustration, Figs. 7 and 8 are
the graphical representations for the effect of Y on
W,, as well as for determination of Y* with two-pass
operation for k < 1 and k > 1, respectively. An alternate representation for Y* with two- and five-pass
operations are also shown in Figs. 3-6. The results up
to ten-pass operations are given in Figs. 9 and 10 for
Y* and W,. max,respectively.

The effect of zone length on the separation efficiency in multi-pass zone-refining processes has been
investigated with the distribution
coefficient
as
parameter. The concentration distributions &, after
nth-pass operation were calculated from Eqs. (10-12)
numerically. Figs. 3-6 illustrate the concentration distributions along the ingot for two- and five-pass operations. The solute removals W, were calculated from
Eq. (19) and the optimum zone length Y* for maximum solute removal W,, max were determined by the
condition: dW,/dY= 0 at Y = Y*. Figs. 7 and 8 show
the existence of optimum zone length with two-pass
operation as example. The existence of Y* with twoand five-pass operations are also shown in Figs. 3-6.
The results up to ten-pass operations are given in
Figs. 9 and 10 for Y* and W,,,,,, respectively.
It is shown in Figs. 9 and 10 that the optimum zone
length increases with the distribution coefficient but
decreases when the pass number increases while the
maximum solute removal increases as the distribution
coefficient goes away from unity at which no solute is

Table 1
Improvement in separation for two-passes operations
Y= 0.2

Y= 0.4

Y*

w2mx

w,

I2

w2

0.1
0.3
0.5
0.7
0.9
1.1
1.3
1.5
1.7
2.0

0.421
0.424
0.427
0.428
0.430
0.433
0.433
0.434
0.435
0.438

0.4860
0.4019
0.2852
0.1639
0.0513
0.0475
0.1314
0.2011
0.2583
0.3248

0.4792
0.3700
0.2420
0.1287
0.0376
0.0330
0.0871
0.1289
0.1614
0.1873

1.419
8.622
17.851
27.350
36.436
43.939
50.861
56.012
60.037
73.412

0.4860
0.4016
0.2847
0.1634
0.0511
0.0473
0.1306
0.1997
0.2564
0.3026

Y=O.6
-

Y=O.8

12

w,

12

w,

12

0.000
0.075
0.176
0.306
0.391
0.423
0.613
0.701
0.741
7.336

0.4709
0.3736
0.2589
0.1470
0.0457
0.0424
0.1175
0.1808
0.2338
0.2779

3.207
7.575
10.158
11.497
12.254
12.028
11.830
11.228
10.479
16.877

0.4487
0.3354
0.2250
0.1256
0.0388
0.0360
0.1002
0.1553
0.2026
0.2432

8.313
19.827
26.756
30.494
32.216
31.944
31.138
29.491
27.493
33.553

C.-D. Ho et al. /Separations

Technology 6 (1996) 227-233

233

Table 2
Improvement in separation for five-passes operation
Y = 0.2

Y=O.4

Y = 0.6

Y= 0.8

Y*

W5,max

15

W5

15

W5

1s

's

0.1
0.3
0.5
0.7
0.9
1.1
1.3
1.5
1.7
2.0

0.188
0.215
0.229
0.237
0.243
0.247
0.250
0.251
0.252
0.254

0.4998
0.4801
0.3952
0.2490
0.0809
0.0749
0.2019
0.2972
0.3651
0.4288

0.4998
0.4799
0.3929
0.2449
0.0786
0.0722
0.1936
0.2848
0.3507
0.3972

0.000
0.042
0.585
1.674
2.926
3.740
4.287
4.354
4.106
7.956

0.4953
0.4479
0.3458
0.2095
0.0669
0.0620
0.1689
0.2528
0.3165
0.3640

0.909
7.189
14.286
18.854
20.927
20.806
19.538
17.563
15.355
17.802

0.4733
0.3827
0.2687
0.1533
0.0477
0.0440
0.1214
0.1858
0.2391
0.2830

5.599
25.451
47.079
62.427
69.602
70.227
66.310
59.957
52.698
51.519

0.4491
0.3362
0.2257
0.1260
0.0389
0.0361
0.1004
0.1554
0.2027
0.2433

11.289
42.802
75.100
97.619
107.969
107.479
101.096
91.248
80.118
76.243

removable. The improvement in separation by operating at the optimum zone length is illustrated for twoand five-pass operations, as shown in Tables 1 and 2,
respectively. it was found in these tables that the
improvement Z,, increases with the distribution coefficient.
Notation

solute concentration in the freezing

solid at solid-liquid interface, (g/cm3)
C,(x) solute concentration freezing out
of the zone at distance x in the nth pass,
(g/cm3>
solute concentration in the main
body of the liquid zone, (g/cm3)
d%(X) dimensionless concentration C,,(x)/C,
uniform solute concentration, (g/cm3)
C
the
percentage of separation
1
improvement defined by Eq. (23)
k
distribution coefficient defined by C/C,
L
ingot length, cm
1
zone length, cm
separation defined by Eq. (19)
Wn,max
W, obtained in the process with
optimal zone length
x
distance from the starting end
of the ingot, cm
Y
dimensionless zone length, Z/L
Y*
optimal value of Y
X
X/L

w,

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