Czochralski growth Technique

 Czochralski system of crystal growth

is actually a much more complicated
system, compared to a Bridgman
system.

 But we can grow single crystals with

much less defects.

 Large size single crystal

 Dopant can be introduced easily.

 Contains many small amount of

impurities like carbon, oxygen, Iron
etc.
Czochralski System

Four main parts of the Czochralski crystal growth system.

1. Furnace.

2. Crystal Pulling mechanism

3. Ambient Control

4. Control systems
 We have a big quartz chamber with gas inlets, gas outlets.

 An opening through which a pull rod is passed.

 A crucible in which the charge is placed and this is made of

quartz.

 Quartz crucible is placed inside a graphite susceptor.

 A susceptor is just like an outer jacket i.e. a bigger cup of

graphite in which we have placed the quartz cup.

 Graphite susceptor is placed on a heater.

Crystal pulling mechanism:

We have a pull rod which is passed through a opening at the top and at
the end of the pull rod, a small seed crystal is fixed in a chuck.

Ambient control:

 We have a graphite susceptor and graphite heaters.

 Therefore, there must not be any oxygen inside the system.
 Evacuate the quartz chamber.
 Fill it up with an inert ambient - argon or nitrogen,
 Maintain atmospheric pressure or sometimes even reduced pressure.

Control Systems:

Temperature control and microcontroller based rod pulling system.

• Si used for crystal growth is purified from SiO2 (sand) through refining,
fractional distillation and CVD.

• The raw material contains < 1 ppb impurities. Pulled crystals contain O
(≈ 1018 cm-3) and C (≈ 1016 cm-3), plus any added dopants placed in the melt.

• Essentially all Si wafers used for ICs

today come from Czochralski grown
crystals.

• Polysilicon material is melted, held

at close to 1417 ˚C, and a single crystal
seed is used to start the growth.

• Pull rate, melt temperature are all

important control parameters.
Modeling Crystal Growth

We wish to find a relationship between pull rate and crystal diameter

Heat balance:

latent heat of fusion heat heat

(i.e. crystallization) conducted radiated
+ = =
through the away
heat conducted from crystal (C).
melt to crystal (B)

(A)
 L  latent heat of fusion
Freezing occurs between isotherms X1
dm
and X2.  amount of freezing per unit time
dt
dm dT dT
(1) L  kL A1  k S A2 k L  thermal conductivity of liquid
dt dx 1 dx 2 dT
 thermal gradient at isotherm x1
dx 1
(A) (B)
k S  thermal conductivity of solid
 A1,2 = Cross-sectional area
dT
 thermal gradient at x 2
dx 2

The rate of heat change is given above dm

 vP AN
• The rate of growth of the crystal is  dt (2)

where vP is the pull rate ( cm/hr) and N is the density ( gm/cm3) .

As, density = mass/volume.

The rate of heat transfer = Q/t = KA ((T2-T1)/d))

We can neglect the term in equation (1), as the latent heat of fusion is very-
very high as compared to other term ( conduction term of heat). The latent
heat is define as the heat which will release or require for phase transition.
.
 k S dT (3)
• Neglecting the middle term in Eqn. (1) we have: v PMAX 
LN dx 2

• In order to replace dT/dx2, we need to consider the heat transfer processes again in
solid phase.

• Heat radiation from the crystal (C)
is given by the Stefan-Boltzmann law

dQ  2rdx T4  (4)

Surface area of cylinder

• Heat conduction up the crystal is given

by:

 dT
Q  k S r 2
dx
(5)
 2 2
• Differentiating (5), we have dQ
dx
 k S r  
2 d T

dx 2
 r
dx
 
2 dT dk S
dx
 k S r  
2 d T

dx 2
(6)

d2 T 2 4
• Substituting (6) into (4), we have
2
 T 0 (7)
 dx k S r

• kS varies roughly as 1/T, so if kM is the TM

kS  kM (8)
thermal conductivity at the melting point,
 T

d2 T 2
 2
 T5  0 (9)
dx k M rTM



 5
1 2k M TM
v PMAX  (10)
LN 3r


Dopant incorporation during crystal growth
• Dopants are added to the melt to provide a controlled N or P doping level in the
wafers.
• However, the dopant incorporation process is complicated by dopant segregation.
• Generally, impurities “prefer to stay in the liquid” as opposed to being incorporated
into the solid.
• This process is known as segregation. The degree of segregation is characterized
by the segregation coefficient, ko, for the impurity.
• Segregation occurs due to the different solubilities of impurity atoms in two
phases.
C
kO  S
CL
CS and CL are the impurity
concentration just on the either
side of the solid/liquid interface.

Dopant behavior during crystal growth

CS
kO 
CL



Most k0 values are <1 which means the impurity prefers to stay in the liquid.
Thus as the crystal is pulled, dopant concentration will increase.
In other words, the distribution of dopant along the ingot will be graded.
Dopant incorporation during crystal growth
VO = initial volume of the melt

IO = number of impurities atoms

C0 = initial impurity concentration in the

melt

C0 = I0/V0

CL = impurity concentration in the melt

during growth
CS = impurity concentration in the solid
IL = number of impurities in the melt during
Vs = volume of impurities in the solid
growth.
CL and CO are the concentration in the
melt, where melt means silicon and VL = volume of the melt during growth.
impurity atoms both Or we can say in
*Liquid terms is for the melt near the interface
solution of silicon and impurity atoms. *Melt is for the liquid inside the container
CL = impurity concentration in the melt
during growth
Function of time

VL = volume of the melt during growth.

CS = impurity concentration in the solid Function of position

along the crystal if k ≠ 1
Vs = volume of impurities in the solid
If during growth, an additional volume dV freezes, the impurities
incorporated into dV are given by:

IL Due to small change in I from Io

dI=-k 0 c L dv=-k 0 dv to IL small amount of freezing is
V0 -VS
done from 0 to Vs
IL Vs dI = Cs dv and Cs = ko CL
dI dv
 =-k 0 
I0
IL 0
V0 -VS Minus is there as it extracted
from the melt. CL = IL / VL

VS k 0
 I L =I 0 (1- )
V0
 k0
I0  
V
 1- S
V0  I 1-f 
k0

CL =
IL
=   = 0 =C 0 1-f 
k 0 -1

VL V0 -VS V0 1-f

The impurity level in the crystal (Cs)

 CS =CO ko 1-f 
k 0 -1
Doping concentration versus position along the
grown CZ crystal for common dopants in silicon

Note the relatively flat profile produced by boron with a ko close to 1.

Dopants with ko << 1 produce much more doping variation along the crystal.
Dopant incorporation during crystal growth under partial stirring condition

Impurities concentration will be higher at the interface than at the melt in case of
partial stirring.

 As a result of it, crystal doping concentration of impurities will also exceed than that
obtained in case of full stirring.
Figure : Partial Stirring Condition
 Thickness of stagnant layer:

D1/3 v1/6
δ= -1/2
cm
(2Πn)

Where v is the viscosity of the melt, n is the rotational rate and D is the diffusivity of
the impurity in the melt. As a result of this boundary layer the concentration of the
melt at the interface exceeds the equilibrium concentration.
Now, Effective segregation coefficient is define as :

Ke = Cs/ CL , Under partial stirring condition, where CL is the equilibrium

concentration in the melt

The effective segregation coefficient is larger than k (distribution coefficient) =

CS/CL’ , where CL’ is the concentration at the interface.
 R= growth velocity (pull-rate) for crystal (i.e., rate of movement of the
liquid-solid interface.
D=diffusivity for solute atoms in liquid (m2/s).

The equation governing the diffusion of solute atoms in the layer

may now be written. Noting that the amount of solute rejected from
the solid is equal to that gained by the liquid, distribution is given by

d 2c dc
D 2
+R =0
dx dx

Dd2C /dx2 = is a factor which will decide the rate of concentration of impurity
atoms in the stagnant layer or dC/dt due to diffusion of impurity atoms
RdC/dx = will decide the rate of dC/dt due to the rejection of impurity atoms at
interface. For stationary distribution, both should be equal and opposite.
 This the solution of equation given in the previous slide

-Rx/D
c=Ae +B
If we differentiate the above equation , we will get

dc AR -Rx/D
=- e
dx D

Where A and B are constants of integration

How to find the value of constants.

 Use boundary conditions. (a). C = CL’ at x = 0

(b)

As sum of impurity flux at boundary must be zero.

Flux means number of impurity atom diffusing unit area per unit time.

Unit = No of atoms/ area-time.

and noting that C = CL at x =

 We can obtain the following relation:

C L -CS
=e -Rδ/D
C L '-CS

Substituting k and Ke value in the above equation we get:

k
ke =
k+(1-k)e -Rδ/D
Where k = Cs / CL , and CL is the concentration of impurity atoms which is
uniform through out the melt.

Ke = Cs / CL , where CL’ is the concentration at the boundary or interface and

CL is the concentration in the melt. CL and CL’ are different.
Means that under full stirring case, we have only segregation coefficient
But under partial stirring case, we have both segregation coefficient and effective
segregation coefficient.
k
ke =
k+(1-k)e -Rδ/D

Finally, the crystal growth for partial stirring may be derived from the
results for complete stirring by substituting ke in place of k because all
parameters are define wrt to the melt.
The impurity level in the crystal (Cs)

C  C k 1  f 
k O 1

S O O
f = Vs/Vo is the fraction frozen.

ko= Segregation Coefficient

ke= Effective Segregation Coefficient