CENTRE FOR NANOSCIENCE AND ENGINEERING, INDIAN

INSTITUTE OF SCIENCE

Assignment 1, NE 203

Sumit Kumar, M.Tech, CeNSE, S.R. No.: 12099

August 31, 2015

Using CZ method

a) Initial Concentration of impurities = Cm cm 3

Distribution Coefficient = k
Ignoring density differences,
Volume of the melt,
V0 = A.l
Where,
A = Area of impure cylindrical rod of Si
l = Length of the rod
Hence total amount of impurities,
S0 = Cm .V0 = Cm .A.l
As we grow the crystal, amount of impurities in the melt generally depends on k
i.e. distribution coefficient. If k>1, the amount in the melt would decrease and
if k<1, the amount of impurities in the melt would increase. For Si, generally
all impurities have k<1. So the impurities in the melt would increase.
b) Let Cl (x) = Concentration of impurities in the melt after x length of crystal
is grown.
So,
Cl (x) = S(x)/V (x)
where,
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S(x) = No. of impurities after crystal growth of length x

V(x) = Volume of melt after crystal growth of length x
Also, k =
Cs (x)/Cl (x)
[Cs (x) is the concentration of impurity in the crystal at the interface]
So,
Cs (x) = K.S(x)/V (x)
If the pure Si ingot is of same diameter as impure Si ingot, the volume of the
ingot after crystal growth of length x = A.x
So , Volume of the melt,
V (x) = V0 A.x
V (x) = V0 (1 x/L)
where, A= Area of the ingot
c) Number of impurities in the dx length of the crystal,
ds = Cs (x).A.dx

d) As earlier stated,
Cs (x) =

K.S(x)
V0 (1 x/L)

Therefore,
ds =

k.S(x).A.dx
V0 (1 x/L)

(Here Negative sign is used in the above equation because whatever is the increase in the impurities of the melt is the decrease in solid crystal)

k.S(x).A
ds
=
dx
V0 (1 x/L)

ds
k.A.dx
=
S(x)
V0 (1 x/L)
Z S(x)
Z x
ds
k.A.dx

S(x)
V0 (1 x/L)
Sm
0

ln

S(x)
= k. ln(1 x/L)
S0

S(x) = S0 .(1 x/L)k

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where,
S0 is the total impurities in the melt when no crystal has been formed.
e) Now Putting the value of Cs (x) in the equation above we get,
Cs (x) =

k.S0 .(1 x/L)k1

V0

Cs (x)
= k.(1 x/L)k1
Cm

f) The Semilog Plots are as follows

The above figures are log

Cs (x)
vs x/L plots for k=0.3 and k=0.03 respectively
Cm

The above figures are log

Cs (x)
vs x/L plots for k=0.003 respectively
Cm

g) The area under the curve is given as,

Z x
Z x
Cs (x)
x

.dx =
k.(1 )k1 .dx = k
C
L
m
0
0
So, the area under the curve gives the value of distribution constant i.e. k.

Using FZ method

a)Volume of the melt= A.w (A is the area of the ingot and w is the width of
the melt)
Cl (x) = S(x)/V (x)
where, Cl (x) is the concentration of impurities in the melt
Cs (x) = k.Cl (x)
Cs (x) = k.S(x)/V (x)
The Volume of the melt remains constant till 0 < x < L w. Hence, V(x)=A.w
Cs (x) =
4

k.S(x)
A.w

b) As dx length of Si crystallizes, change in the impurities of the solid at x

is given by,
ds = Cs (x).A.dx Cm .A.dx
Cm is the initial concentration of the impure Si and Cs (x) is the final concentration of Si crystal at x. Following are the set of equations.
i)Cl (x) = S(x)/A.w)
ii)Cm (x) = Sm /A.w
iii)Cs (x) = k.S(x)/A.w
where, Sm is the total number of impurities in the melt initially
c) In the molten Si part change in impurity is given by ds
ds = (Cs (x).A.dx Cm .A.dx)
k.S(x).A
ds
= Cm .A
dx
A.w
ds
Sm
k.S(x)

dx
w
w
Z S(x)
Z x
ds

=
dx
Sm
k.S(x)
Sm
0

w
w
k.S(x)
Sm

w
w
= K.x/w
ln
Sm
k.Sm

w
w
Sm
S(x) =
[1 (1 k) exp(k.x/w)]
k

d) As we have Cs (x) = k.S(x)/A.w we get,

Cs (x) = Cm [1 (1 k) exp(k.x/w)]
e) Its apt that the above equation is not valid when the melt reaches the boundary. The differential equation for the last molten part is given by,
ds = Cs (x).A.dx

The differential equation is same used in CZ method.

f) As we did in CZ method,
ds
K.S(x).A
=
dx
A.(L x)
where A.(L-x) is the volume of the melt left.
Z

S(x)

SLw

ln

ds
=
S(x)

Lw

k.dx
Lx

S(x)
Lx
= k. ln
SLw
w

S(x) = SLw .(
Since,Cs (x) =

1 x/L k
)
w

k.S(x)
A.(L x)

So,
Cs (x) = Cs (L w).(

L x k1
)
w

g) For, 0 < x < L w,we have Cs (x) = Cm [1 (1 k) exp(k.x/w)

L x k1
and for L w < x < L, we have Cs (x) = Cs (L w).(
)
w
where Cs (L w) = Cm .(1 (1 k)exp(k.(l w)/w)
The semilog plots are as follows

The conclusions from the above graphs are as follows:

1) If the length of the ingot is infinite as compared to molten part then the
concentration of the crystalline solid would quickly saturate to Cm i.e. initial
concentration of the impure ingot as it is apparent from the graph where k=0.3
and w=L/100. The part which is pure in w=L/100 is compensated from the
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part which is impure.

2) Therefore there is more uniformity in FZ method as seem from the graph for
the part 0 < x/L < L w
h) The semilogy plot is below

i) a) For the purity perspective, CZ method should be chosen as apparent from

the graph.
b) Well considering uniformity, FZ method is better as the variation of concentration is less but the its very less pure as compared to the CZ method.
c)Also the Float zone method gives poly crystalline Si.
Therefore FZ method is far more better than CZ method.

j) It is very true that even though the basic idea of zone refining is same in
both FZ and CZ, the math is pretty different. In CZ method new pure crystal
was formed directly from the melt but in FZ method, the melt passes through
the solid and there change in the concentration of the impurities in the solid.

2nd pass Float Zone Refining

As in the first pass FZ method the concentration of the impure ingot was constant i.e. Cm but for the second pass of float zone concentration varies as:
For 0 < x < L w,
Cs (x) = Cm .(1 (1 k)exp(k.x/w)
For L w < x < L,
Cs (x) = Cm .(1 (1 k)exp(k.(l w)/w).(

l x k1
)
w

The concentration is a function of x here. If dx length of crystal solidifies, then

change in impurities is given by,
ds = C2 (x).A.dx Cs (x + w).A.dx

So, Change in the melt is given by,

ds = (C2 (x).A.dx Cs (x + w).A.dx)
where, S(x) = (C2 (x).A.w)/k
Putting the value of SX in the above equation we get the differential equation
as i.e.
dC2
= Cs (x + w) C2 (x)
k.dx
The above differential equation can be solved for 0 < x < L 2w numerically.
For this problem we will use Mfile approach in MATLAB,
function dcdt = second(x,c)
A=fzmethod(0.3,x+0.1,10);
B=c;
dcdt= 0.3*(A-B);
end
Using ode45 to solve the problem,
>> xspan=[0 0.8];
>> c0=Cs (0.1); This is the concentation after 1st float zone
>> fname=second;
>> [x c]=ode45(fname,xspan,c0);
The solution can be given as plot command
>> plot(x,c);
where fzmethod gives the values Cs (x) in the first pass of the Float zone

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For, melt being present at L 2w < x < L w the crystal would be formed
from the ingot present between L w < x < L. Here the Cs (x) would change
as,
l x k1
Cs (x) = Cm .(1 (1 k)exp(k.(l w)/w).(
)
w
Similarly using ode 45 to solve for L 2w < x < L w we
dC2
= Cs (x + w) C2 (x)
k.dx
where,
Cs (x) = Cf loatzone (L w).(L x/w)k1
So between L 2w < x < L the semilogy plot i.e. log10(C(x)/Cm) would go to
infinity.
It is apparent from the graph that FZ second pass has high uniformity i.e.
there is very less variation. Although the concentration of impurities is high as
compared to one in CZ method in the beginning.

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