Professor Nathan Cheung, U.C.

Berkeley EE143 Lecture # 5

Thermal Oxidation of Si
General Properties of SiO
2
Applications of thermal SiO
2
Deal-Grove Model of Oxidation
Thermal SiO
2
is amorphous.
Weight Density = 2.2 gm/cm
3
Molecular Density = 2.3E22 molecules / cm
3
Crystalline SiO
2
[Quartz] = 2.65 gm/cm
3
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
Thermal SiO
2
Properties
(1) Excellent Electrical Insulator
Resistivity > 1E20 ohm-cm
Energy Gap ~ 9 eV
(2) High Breakdown Electric Field
> 10MV/cm
(3) Stable and Reproducible Si/SiO
2
Interface
(4) Conformal oxide growth on exposed Si surface
Si
SiO2
Substrate
Si
SiO2
Substrate
SiO2
Thermal
Oxidation
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
(5) SiO
2
is a good diffusion mask for common dopants
D D
sio si
2
<<
e.g. B, P, As, Sb.
(6) Very good etching selectivity between Si and SiO
2
.
SiO
2
Si
Si
SiO
2
Si
HF dip
*exceptions are Ga
(a p-type dopant) and some
metals, e.g. Cu, Au
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
Thickness of Si consumed during oxidation
si
ox
ox si
N
N
X X
ox ox
X
cm atoms
cm molecules
X 46 . 0
/ 10 5
/ 10 3 . 2
3 22
3 22

X
si
Si
Si
SiO
2
original
surface
X
ox
molecular density of SiO2
atomic density of Si
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
1m Si oxidized
2.17 m SiO
2
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
Kinetics of SiO
2
Growth
Gas Diffusion
Solid-state
Diffusion
SiO
2
Formation
Si-Substrate
SiO
2
Oxidant Flow
(e.g. O
2
, or H
2
O)
Gas Flow
Stagnant Layer
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
Deal-Grove Model
C
G
C
s
C
o
C
i
X
0x
stagnant
layer
SiO
2
Si
F
1
F
2
F
3
gas
transport
flux
diffusion
flux
through SiO
2
reaction
flux
at interface
Note
C
s
> C
o
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
( ) F h C C
G G S 1

x
C
D F

,
_

ox
i o
X
C C
D
i s
C k F
3
Diffusivity [cm
2
/sec]
mass transfer coefficient [cm/sec].
Ficks Law of Solid-state Diffusion.
surface reaction rate constant [cm/sec]
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
We use Henrys Law to relate C
o
and C
s
s o
P H C
( )
s
C kT H

'

use C
N
V
s

PV NkT
partial pressure of oxidant
at surface [in gaseous form].
Henrys
constant
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
HkT
C
C
o
s

) (
G A
C HkT C
F
h
HkT
C C
G
A o 1
( )
3 2 1
F F F
Define
At steady-state:
2 equations:
2 unknown: C
o
&C
i
1 2
h
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
C
C
k
h
k X
D
i
A
s s ox

+ + 1

,
_

+
D
X k
C C
ox s
i o
1
( )
D
X k
h
k
C k
C k F F F F
ox s s
A s
i s
+ +

1
3 2 1
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
Now, to convert F into Oxide Thickness Growth Rate

,
_

dt
dX
N F
ox
1
D
X k
h
k
C k
ox s s
A s
+ + 1
oxidant molecules/unit volume required
to form a unit volume of SiO
2
.
SiO
2
Si
F
X
ox
{ } t
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
1
1
1
]
1

+ +

D
X k
h
k
C k
dt
dX
N
ox s s
A s ox
1
1
[Comment]
N cm
1
22 3
2 3 10 . / for O
2
as oxidant
Si O SiO +
2 2
Si H O SiO H + + 2 2
2 2 2
N cm
1
22 3
4 6 10 . /
for H
2
O as oxidant
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
1
2
)
1 1
( 2
N
DC
B
h k
D A
A
s

+
SiO
2
SiO
2
Si
Si
x
i
x
ox
after
time t
B
AX X
i i
+

Boundary Condition: At t = 0 , X
ox
= X
i
) (
2
+ + t B AX X
ox
ox
Solution
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
X
A t
A
B
ox
+
+

_
,

'

2
1
4
1
2

(Case 1) Large t [large X

ox
]
Bt X
ox

(Case 2) Small t [Small X
ox
]
t
A
B
X
ox

Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
B
dt
dx
A
dt
dx
X
t B AX X
ox ox
ox
x ox
+
+ +
2
) (
0
2

Deal-Grove Model
t
t
X
ox
t
ox
ox
X A
B
dt
dx
2 +

Oxide Growth Rate slows
down with increase oxide thickness
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
B = Parabolic Constant
B/A = Linear Constant
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
Oxidation
Charts
The charts are
based on
X
i
=0 !
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
Two Ways to Calculate Oxide Thickness
Grown by Thermal Oxidation
E.g.
SiO
2
Si
4000
o
A
x
i=
1100
o
C
33min
steam
SiO
2
Si
x
ox
Method 1: Find B & B/A from Charts
Solve
X AX B t
ox ox
2
+ + ( )
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
Method 2: Use Oxidation Charts
The charts are
based on
X
i
=0 !
min 24 4000 A X
i
at 1100
o
C from chart
Total effective oxidation time
min 57 min ) 33 24 ( +
if start with
0
i
X

Xox
T
3
T
2
T
1
1
1
0
0
o
C
6500
o
A
4000
o
A
24 33
57
time(min)
0
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
SiO
2
Si
4000
o
A
SiO
2
Si
4000
o
A
SiO
2
Si
4000
o
A x
i
CVD
Oxide
(1) Grown at 1000
o
C, t=5hrs
(2) Grown at 1100
o
C, 24min
(3) CVD Oxide
is the same for all three
cases shown here
Professor Nathan Cheung, U.C. Berkeley EE143 Lecture # 5
Effect of X
i
on Wafer Topography
SiO
2
SiO
2
X
i
1 3 2
Si
less oxide grown
less Si consumed
more oxide grown
more Si consumed
3
2
1