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Thermal Oxidation of Si

General Properties of SiO2


Applications of thermal SiO2
Deal-Grove Model of Oxidation
Thermal SiO2 is amorphous.
Weight Density = 2.2 gm/cm3
Molecular Density = 2.3E22 molecules / cm3
Crystalline SiO2 [Quartz] = 2.65 gm/cm3
Professor Nathan Cheung, U.C. Berkeley

EE143 Lecture # 5

Thermal SiO2 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/SiO2 Interface
(4) Conformal oxide growth on exposed Si surface
Si
SiO2

Substrate
Professor Nathan Cheung, U.C. Berkeley

Thermal
Oxidation

SiO2

Si
SiO2

Substrate
EE143 Lecture # 5

(5) SiO2 is a good diffusion mask for common dopants

Dsio 2 << Dsi

e.g. B, P, As, Sb.

SiO2

*exceptions are Ga
(a p-type dopant) and some
metals, e.g. Cu, Au

Si

(6) Very good etching selectivity between Si and SiO2.


SiO2

HF dip

Si

Si

Professor Nathan Cheung, U.C. Berkeley

EE143 Lecture # 5

Thickness of Si consumed during oxidation


original
surface

Si

SiO2
Xsi

Xox

Si

Nox
X si = X ox
Nsi

molecular density of SiO2


atomic density of Si

2.3 10 22 molecules / cm 3
= X ox
= 0.46 X ox
22
3
5 10 atoms / cm
Professor Nathan Cheung, U.C. Berkeley

EE143 Lecture # 5

1m Si oxidized

2.17 m SiO2

Professor Nathan Cheung, U.C. Berkeley

EE143 Lecture # 5

Kinetics of SiO2 Growth


Oxidant Flow
(e.g. O2, or H2O)
Gas Diffusion

Gas Flow
Stagnant Layer

Solid-state
Diffusion

SiO2

SiO2
Formation

Si-Substrate

Professor Nathan Cheung, U.C. Berkeley

EE143 Lecture # 5

Deal-Grove Model
stagnant
layer

CG

SiO2

Si

Cs
Note
Cs > Co

Co
Ci
X0x

F1
gas
transport
flux
Professor Nathan Cheung, U.C. Berkeley

F2
diffusion
flux
through SiO2

F3
reaction
flux
at interface
EE143 Lecture # 5

F1 = hG ( CG CS )
mass transfer coefficient [cm/sec].

C
F2 = D
x

Ficks Law of Solid-state Diffusion.

Co Ci

D
X

ox

Diffusivity [cm2/sec]

F3 =ks Ci
surface reaction rate constant [cm/sec]
Professor Nathan Cheung, U.C. Berkeley

EE143 Lecture # 5

We use Henrys Law to relate Co and Cs

C o = H Ps
Henrys
constant

partial pressure of oxidant


at surface [in gaseous form].

= H (kTCs )
Professor Nathan Cheung, U.C. Berkeley

N
use Cs =
V

PV = NkT

EE143 Lecture # 5

Co
Cs =
HkT
Define C A ( HkT C G )

hG
(C A Co )
F1 =
HkT
h

At steady-state:

F1 = F2 = F3
1
Professor Nathan Cheung, U.C. Berkeley

2 equations:
2 unknown: Co & Ci

2
EE143 Lecture # 5

CA
Ci =
ks ks X ox
1+ +
h
D

k s X ox
Co = Ci 1 +

ksC A
F (= F1 = F2 = F3 ) = k s Ci =
k s k s X ox
1+ +
h
D
Professor Nathan Cheung, U.C. Berkeley

EE143 Lecture # 5

Now, to convert F into Oxide Thickness Growth Rate

dX ox
F = N 1

dt
X ox

SiO2

oxidant molecules/unit volume required


to form a unit volume of SiO2.
Si

{t }
Professor Nathan Cheung, U.C. Berkeley

ksC A
k s k s X ox
1+ +
h
D
EE143 Lecture # 5

dX ox
N1
dt

k sC A
=
k s k s X ox
1 +
+
h
D

[Comment]

N1 = 2.3 1022 / cm3


Si + O2 SiO2
N1 = 4.6 10 / cm
22

for O2 as oxidant

for H2O as oxidant

Si + 2 H2 O SiO2 + 2 H2
Professor Nathan Cheung, U.C. Berkeley

EE143 Lecture # 5

Boundary Condition: At

xi

after
time t

SiO2

t = 0 , Xox = Xi
xox

SiO2

Si

Solution

Si

Xox + AX ox = B(t + )
2

1 1
A 2D( + )
ks h
2 DC A
B
N1
Professor Nathan Cheung, U.C. Berkeley

X i + AXi
=
B
2

EE143 Lecture # 5

A
t +

X ox = 1 + 2
1
A

2
4 B

(Case 1) Large t [large Xox]

Xox

Bt

(Case 2) Small t [Small Xox]

X ox
Professor Nathan Cheung, U.C. Berkeley

B
t

A
EE143 Lecture # 5

Deal-Grove Model

Xox

t
X

ox

2X

ox

+ AX

t
0x

= B (t + )

dx ox
dx ox
+ A
= B
dt
dt

dxox
B

=
dt
A + 2 X ox
Professor Nathan Cheung, U.C. Berkeley

Oxide Growth Rate slows


down with increase oxide thickness
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
Xi=0 !

Professor Nathan Cheung, U.C. Berkeley

EE143 Lecture # 5

Two Ways to Calculate Oxide Thickness


Grown by Thermal Oxidation
E.g.
SiO2
Si

xi=
4000oA

1100oC
33min
steam

SiO2

xox

Si

Method 1: Find B & B/A from Charts


Solve

X ox + AX ox = B ( t + )
2

Professor Nathan Cheung, U.C. Berkeley

EE143 Lecture # 5

Method 2: Use Oxidation Charts


Xox

oC

0
110

T3

6500oA

T2

The charts are


based on
Xi =0 !

T1

4000oA

time(min)
24

33 57

X i = 4000 A = 24 min at 1100oC from chart


Total effective oxidation time
(24 + 33) min = 57 min
Professor Nathan Cheung, U.C. Berkeley

if start with Xi = 0
EE143 Lecture # 5

(3) CVD Oxide

(1) Grown at 1000oC, t=5hrs


xi
SiO2

SiO2

4000oA

4000oA

CVD
Oxide

Si

Si

(2) Grown at 1100oC, 24min


SiO2

4000oA

Si

Professor Nathan Cheung, U.C. Berkeley

is the same for all three


cases shown here

EE143 Lecture # 5

Effect of Xi on Wafer Topography


1

SiO2

3
SiO2

Xi

more oxide grown


more Si consumed

Si
1
less oxide grown
less Si consumed

Professor Nathan Cheung, U.C. Berkeley

EE143 Lecture # 5