1

Oxidization Furnace

2
3
Native and deposited films
Native films are grown out of the semiconductor itself.
Thermal or electrochemical means Eg. SiO
2
.
Films can be deposited by chemical or physical
methods.
Native films have better quality and excellent interface
with the substrate.
But all films cannot be grown .
Thicker films are to be deposited.
Film thickness and quality is determined by growth
/deposition pressure and temperature.
Used as gate oxides and for passivation ,masking,
interconnects etc.
4
Thermal oxidation of Si
Slice of Si is always covered with 15-20A
o
of SiO
2
(upper limit 40
o
A)
when it is exposed to atmosphere.
Patchy in nature and of no technological value.
Thicker and better quality SiO2 layers can be grown if the slice is
subjected to oxidizing ambient at elevated temperature.
SiO
2
helps to reduce the surface state density of Si by tying dangling
bonds.
Dry oxidation
Slice is subjected to dry oxygen. growth rate less, but of good
quality.
wet oxidation
Subjected to water vapor. Thicker films but of poor quality.
5
Thermal oxidation of Si
44% of Si is cosumed.(2.27 times thickness of the Si
consumed).
Oxidizing species should move through the growing
oxide layer for further oxidation of Si.
Growth rate decreases as growth progresses.
Chemistry of oxidation.

2 2 2
2 2
2 2 H SiO O H Si
SiO O Si
+ +
+
6
Kinetics of oxide growth
Assume a Si slice brought in contact with the oxidant
with a gas phase concentration of N
g
.
High mass transfer coefficient is assumed so that
surface concentration N
o
is determined by the solid
solubility of reactants.
Solid solubility of dry oxygen in SiO
2
is 5.2 x 10
16
molecules cm
-3
and the corresponding value for water
vapor is 3 x 10
19
cm
-3.

N
o
N
1
The flux of reactants arriving at
the Si-SiO
2
interface is

( )
x
N N D
x
N
D j
o 1

~
c
c
=
7
Kinetics of oxide growth
Assuming linear reaction, the flux of reaction
products is given by

Equating both fluxes


The growth rate of oxide layer is given by


1
kN j =
k
D
x
DN
j
+
=
0
k
D
x
n DN
n
j
dt
dx
+
= =
/
0
8
Kinetics of oxide growth
Solving this equation with the boundary value that at t=0
at x=0





For small values of t


For large t

t
n
DN
x
k
D
x
0 2
2 2
= +
(
(

|
.
|

\
|
+ = 1
2 0 2
1
2
1
Dn
t k N
k
D
x
t
n
k N
x
0
=
2
1
2
1
0
2
t
n
D N
x
|
.
|

\
|
=
9
Kinetics of oxide growth
In the initial phases the growth is kinetic
controlled and linear.
At later phases the growth is diffusion
limited and proportional to the square root
of time.
10
Linear & Parabolic rate constants




Bt Ax x = +
2
Oxidation of Si can be represented by
For small t
t
A
B
x =
For large t
Bt x =
B/A is the linear rate constant
B is the parabolic rate constant.
11
Linear & Parabolic rate constants
KT
E
KT
E
e C
A
B
e C B
2
2
1
1

=
=
Mathematical relationships for the rate constants.
12
Linear & Parabolic rate constants
.00001
{111} Si
{100} Si
{111} Si
{100} Si
H
2
O

Dry O
2
L
i
n
e
a
r

r
a
t
e

c
o
n
s
t
a
n
t

B
/
A

m
/
h
r

10

1

0.1

0.01

.001

.0001
0.6 0.7 0.8 0.9 1 1.1
1000/T K
-1
E
A
=2.0eV
E
A
=2.05eV
H
2
O
Dry O
2
{111} Si
{111} Si
{100} Si
{100} Si
Log of Linear rate constant falls
off with 1/T, with a slope of
2.0 eV/molecule for
dry oxidation.
2.05eV/molecule for
wet oxidation.
comparable to the
energy required to break Si-Si
bonds (1.83 eV/molecule).
13
Linear & Parabolic rate constants
0.6 0.7 0.8 0.9 1.0
1000/T K
-1
1

0.1

0.01

0.001
Dry O
2
EA=1.23eV

H
2
O EA=0.78eV

Independent of orientation
P
a
r
a
b
o
l
i
c

r
a
t
e

c
o
n
s
t
a
n
t

B

m
2
/
h
r

Log of parabolic rate constant
falls off with 1/T, with a slope of

1.23 eV/molecule for dry
oxidation.
0.78 eV/molecule for wet
oxidation.
comparable to the activation
energy of Dry O
2
(1.18
eV/molecule) and H
2
O (0.79
eV/molecule) in SiO
2

14
Linear & Parabolic rate constants
Orientation dependent effects.
Linear rate constant
Growth rate constant higher for {111} surface.
Greater by 1.68:1 against {100} surface.
Depends on reaction at the surface.
In-turn depends on the surface atomic density.
Atomic density is higher for {111} surface compared to {100}
surface.
Parabolic rate constant.
Depends on diffusivity of species.
Independent of orientation.


15
Linear & Parabolic rate constants
Rate constants (growth rate) higher for wet oxidation
,compared to dry oxidation.

Water vapor has greater solid solubility compared to dry O
2
, in
SiO
2
.

A rapid initial growth phase is found in the case of dry O
2
compared to wet oxidation.
The molecular oxygen reaching the oxide surface dissociates
into O
2

-
and O
2

2-
and one or two holes. These holes have higher
mobility compared to the oxygen ions. This creates a space
charge at the gas oxide interface which enhances the transport
of oxygen into the silicon surface by providing an additional drift
component.
16
Rapid initial growth phase
Deal Grove model is found to be applicable for
thicknesses involving more than 20-25nm.
In order to include this rapid initial growth ,the model is
re-written as
x
2
+Ax =B (t + t
i
)
Where t
i
is the parameter for accounting the initial
thickness x
i
.


B
Ax x
t
i
i
i
+
=
2
17
Dependence on doping
Heavily doped Si oxidizes faster.
Surface reaction rate more due to increased defects.
Diffusion through the oxide increases as segregation
of the impurities into the oxide will weaken its
structure.
Growth behavior of phosphorous doped Silicon
Has large segregation constant and it is a slow diffuser in the
oxide. Hence it piles up at the interface on Si side.
Reaction rate at the interface is enhanced ,so linear rate
constant increases with doping.
Since only a small amount of phosphorous is incorporated
into the oxide its structure is not much affected. Parabolic
rate constant is not affected by doping.
18
Dependence on doping
Boron doping.

Large amount of boron is incorporated into the oxide,
weakening its structure. Hence diffusion is enhanced
and parabolic rate constant increases with doping.

There is a depletion of boron at the surface, so
reaction rate and linear rate constant is not affected.
19
Behavior of rate constants with doping
phosphorous doping
Significant change
No significant change
20
Oxidization Graph
21
Chemical properties of SiO
2
Amorphous or vitreous state at lower
temperatures.
At high temperatures returns to its crystalline
form.
Rate of devitrification can be neglected below
1000
o
C.
Can cause cracks in the oxide film, thus quality is
degraded.
Melting point 1732
o
C.
22
Pure (Intrinsic) Silica
Polyhedra of oxygen ions with centers
occupied by Si ions.
Crystalline quartz
amorphous
23
Pure (Intrinsic) Silica
Bridging and non bridging oxygen ions.
Bridging
oxygen atom
24
Extrinsic Silica glass
Presence of impurities greatly modifies the
structure and properties of SiO
2.
Impurities can be substitutional.
Substitutes for a Si ion.
Eg. B
3+
and P
5+
These are called network formers since they can exist in
vitreous state like SiO
2
.
Interstitial impurities.
Weakens the network.
Na
+
, K
+
Called network modifiers, as they do not form glasses by
themselves.
Na is a very important contaminant.
+
+ + = + Na Si O O Si Si O Si O Na 2
2
25
Extrinsic Silica glass
26
Oxygen and water vapor in SiO
2
Oxygen is more free to move in the network.
The water vapor enters into reaction with
Bridging oxygen ions to form pairs of stable non-
bridging hydroxyl groups.
Weaken the structure.
Si OH OH Si Si O Si O H + +
2
OH Si Si O H
H Si O Si Si OH Si
+
+ +
2
2
2
1
2
1
27
Impurity redistribution during Oxide
growth
Oxidation of doped Si.
Impurities will redistribute at the interface.
Determined by
Segregation of impurities into the oxide.
Diffusion of impurities in the oxide.
Rate at which the interface moves with respect to the
diffusion rate.
Segregation constant m.
Ratio of equilibrium concentration of the impurity in Si
to that in SiO
2.
Function of temperature and orientation.

28
Impurity redistribution during Oxide
growth
C
SI
= concentration in Si
C= concentration in the oxide at the interface
Diffusion in oxide
slow (boron)
m<1
C/C
SI
x
SiO
2
Si

m<1
C/C
B
x
SiO
2
Si

Diffusion in oxide fast
(boron H
2
ambient)
29
Impurity redistribution during Oxide
growth
Diffusion in oxide slow
(phosphorous)
m>1
C/C
SI
x
SiO
2
Si

Diffusion in oxide fast
(Gallium)
m>1
C/C
SI
x
SiO
2
Si

C
SI
= concentration in Si
C= concentration in the oxide at the interface
30
Oxide Charges
Si-SiO
2
is a transition layer between crystalline Silicon
and amorphous silica.
Charges and traps are present in thermally oxidized Si.
Most of the charges are at the interface.
A charge at the interface can induce a charge of
opposite polarity in the underlying Silicon
Affect the threshold voltage of a MOS.
Interface charge is represented by
N = Q/q N = number of charges per unit area.
Q = net effective charge per unit area.
q = electronic charge
31
Interface charge
Mobile ions Q
m -
Interface trapped charges (interface states) sudden termination of
semiconductor lattice at the interface Q
it
Fixed oxide charge Q
f
un completed bonds (SiO
x
) as well as ionic Si.
Oxide trapped charges due to imperfections in SiO
2
and radiations
Q
ot.
Net oxide charge is taken as positive
Negative voltage is to be applied to get flat band conditions.


m ot it f ox
Q Q Q Q Q + + + =
ox
ox
ms FB
C
Q
V u =