Lecture 2a

Crystal Growth (contd)

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Distribution of Dopants
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As a crystal is pulled from the melt, the doping concentration

incorporated into the crystal (solid) is usually different from
the doping concentration of the melt (liquid) at the interface.
The ratio of these two concentrations is defined as the
equilibrium segregation coefficient, ko.

Cs
ko =
Cl

(1)

Where Cs and Cl are, respectively, the equilibrium

concentrations of the dopants in the solid and liquid near the
interface.

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Equilibrium Segregation Coefficients

for Dopants in Silicon

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Dopant

ko

Type Dopant

ko

Type

8 x 10 -1

As

3 x 10 -1

Al

2 x 10 -3

Sb

2.3 x 10 -2

Ga

8 x 10 -3

Te

2 x 10 -4

In

4 x 10 -4

Li

1 x 10 -2

1.25

Cu

4 x 10 -4

--

7 x 10 -2

Au

2.5 x 10 -5

--

0.35

CZ Crystal Growth
|

Consider a crystal being grown from a melt having an

initial weight Mo with an initial doping concentration Co
in the melt (i.e., the weight of the dopant per 1 g of
melt).
At a given point of growth when the crystal weight M
has been grown, the amount of dopant remaining in
the melt (by weight) is S. For incremental amount of
the crystal with weight dM, the corresponding
reduction of the dopant (-dS) from the melt is CsdM,
where Cs is the doping concentration in the crystal (by
weight).

dS = Cs dM
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(2)

CZ Crystal Growth (2)

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Now, the remaining weight of the melt is Mo-M, and

the doping concentration in the liquid (by weight), Cl ,
is given by

S
Cl =
Mo M

Combining Eqs. 2 and 3 and substitute to Eq. 1

dM
dS
= ko
S
Mo M
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(3)

(4)

CZ Crystal Growth (3)

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Given the initial weight of the dopant, CoMo, we can

integrate Eq. 4:
S

Co M o
|

M
dM
dS
= ko
S
Mo M
0

(5)

Solving Eq. 5 and combining with Eq. 3 gives

Cs = ko Co 1
Mo
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k o 1
(6)

Curves for growth from the melt

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As crystal growth
progresses, the
composition initially at
koCo will increase
continually for ko<1 and
decrease continually for
ko>1. When ko =1, a
uniform impurity
distribution can be
obtained.

Curves for growth from the melt showing the

doping concentration in a solid as a function of
the fraction solidified (M/Mo).

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Effective Segregation
Coefficients
|

While the crystal is growing,

dopants are constantly
being rejected into the melt
(ko>1). If the rejection rate
is higher than the rate at
which the dopant can be
transported away by
diffusion or stirring, then a
concentration gradient will
develop at the interface.
The segregation coefficient
given by eq 1 is ko=Cs/Cl(0).

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Doping distribution near the

solid-melt interface.
8

Effective Segregation
Coefficients
|

The effective segregation coefficient ke, which is the

ratio of Cs and the impurity concentration far away from
the interface:

Cs
ko
ke
=
Cl ko + (1 ko )e v / D

(7)

where
v = crystal growth velocity
= melt width, and
D = dopant diffusion
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FZ Crystal Growth
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To evaluate the doping

distribution of a float-zone
process, consider a simplified
model shown here.
The initial uniform doping
concentration in the rod is Co
(by weight). L is the length of
the molten zone at a distance
x along the rod, A is the
cross-sectional area of rod, d
is the specific density of
silicon, and S is the amount of
dopant present in the molten
zone.

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Float-zone process. (a) Schematic setup.

(b) Simple model for doping evaluation.
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FZ Crystal Growth (2)

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As the rod traverses to a

distance dx, the amount of
dopant added to its advancing
end is CodAdx, where the
amount of dopant removed
from it at the retreating end is
ke(S dx/L), where ke is the
effective segregation
coefficient. Thus,

ke S
dx
dS = Co d Adx
L
k S

dS = Co d A e dx
L

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(8)

11

FZ Crystal Growth (3)

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So that
x

dx =
0

S
S Co d A (ke S / L)
o

(8a)

where So = CodAL is the amount of dopant in the zone when it

was first formed at the front end of the rod.
From eq 8a, we obtain

e
or

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ke x / L

Co d A ( k e S o / L )
=
Co d A ( k e S / L )

Co d AL
k x / L
S=
1 (1 ke ) e
ke

(9)

(9a)
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FZ Crystal Growth (4)

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Since Cs, ( the doping concentration in the crystal at the

retreating end) is given by Cs = ke(S dx/L), then

Cs = Co 1 (1 ke )
|

(10)

If it is desirable to dope the rod rather than to purify it, consider the
case in which all the dopants are introduced in t first zone (So =
ClAdL), the initial concentration Co is neglibly small. Equation 9
gives:

So = S * e
|

ke x / L

ke x
L

(11)

Since Cs = ke(S/AdL), we obtain the following equation from 11.

C s = k e Cl e k e x / L
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(12)
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Problems
1.

2.
3.

4.

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A silicon ingot which contain 1017 boron atoms/cm3, is to be grown by

the Czochralski technique. What concentration of boron atoms should
be in the melt to give the required concentration in the ingot? If the
initial load of the silicon in the crucible is 60kg, how many grams of
boron (atmic weight 10.8) should be added? The density of the molten
silicon is 2.53g/cm3.
Plot the distribution of arsenic at distances of 10, 20, 30, 40, and 45
cm from the seed in a silicon ingot 50 cm long that has been pulled
from a melt with an initial doping concentration of 1017 cm-3.
In silicon, the lattice constant is 5.43 angstrom. Assume a hard sphere
model. (a) Calculate the radius of the silicon atom. (b) Determine the
density of silicon atoms in atoms/cm-3. (c) Use Avogadro constant to
find the density of silicon.
We use the float zone-process to purify a silicon ingot that contains a
uniform gallium concentration of 5x 1016 cm-3. One pass is made with
molten zone 2 cm long. Over what distance is the resulting gallium
concentration below 5x 1015 cm-3.
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