Chapter 4

Oxidation (I)

Semester: Fall 2019

Professor: Sung-Jin Choi
School of EE, Kookmin University
Class Notes, IC fabrication
1
Prof. S.-J. Choi (All rights reserved)
 Thermal oxidation of Si

Thermal SiO2 is amorphous

Weight density = 2.20 g/cm3
Molecular density = 2.3E22 molecules/cm3

Amorphous

Single crystal
cf) Si case = 5E22 atoms/cm3

Transmission electron microscope image

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 Thermal SiO2 properties
1) Excellent Electrical Insulator
– Resistivity > 1E20 ohm-cm
– Energy gap ~ 9 eV (insulator)
2) High Breakdown Electric Field > 10 MV/cm
3) Stable and Reproducible Si/SiO2 Interface
4) Conformal oxide growth on exposed Si surface

Conformal growth

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 Thermal SiO2 properties – cont’d
5) SiO2 is a good diffusion mask for common dopants

6) Very good etching selectivity between Si and SiO2

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 Thermal oxidation
1 Dry oxidation Si + O2 SiO2

2 Wet oxidation Si + 2H2O SiO2 + 2H2

Steam or water vapor

Furnace

Si wafer
• Oxidation (growth)
• Deposition
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 Thickness of Si consumed during oxidation

[#/cm3]
[#/cm3]

46% silicon consumed

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 Thickness of Si consumed during oxidation
• For 1 μm Si oxidized
– 0.46 : 1 = 0.54 : x, x = 0.54/0.46 = 1.17 μm
– That is, 2.17 μm SiO2

• Suggested calculation exercise:

Completely
oxidized

1 μm diameter ? μm diameter
Si sphere SiO2 sphere
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 Kinetics of SiO2 growth

dry wet

First grown

Last grown

Oxidation proceeds by the diffusion of the oxidizing species

(oxidant) through the oxide to the Si-SiO2 interface, where the
oxidation reaction occurs
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 Kinetics of SiO2 growth

In order for oxidation to occur, oxygen must reach the silicon

interface. As the oxide grows, oxygen must pass through more and
more oxide, and the growth rate decreases as time goes on
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 Thermal oxidation modeling
• Deal-Grove model [#/cm2sec]

Fick’s first law of solid-state diffusion

SiO2 Si
No N ( x, t ) ( Ni  No )
J  D  D
확산 x Xo
J Ni Related to Diffusivity
O2 or H2O flux oxidation growth Diffusion constant
Xo rate [cm2/sec]

J: particle flux [number of particles/cm2sec]

- assumed to be constant
N: particle concentration (oxidizing species)
Xo: oxide thickness at a given time

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 Thermal oxidation modeling
N ( x, t ) ( Ni  No )
J  D  D
• At the SiO2-Si interface x Xo
– The oxidation rate is proportional to the
concentration of the oxidizing species
ks is called the reaction rate constant at
J  ks Ni the Si-SiO2 interface.
Interface의 oxygen의 농도가 높을수록 flux가 크다. 많이 들어온다는 뜻이므로

From two equations, one can get

DN o
J Oxide내에서 O2, H2O molecules의 flux
X o  DX o / K s

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 Converting J into oxide thickness growth rate
Number of particles/cm2sec

ΔXO 𝑱∆𝒕𝑨 = 𝑴𝑨∆𝑿𝑶 O2, H2O

molecules 개수

SiO2 Si
A Number of molecules of the oxidizing
J
species per unit volume: [#/cm3]

{Δt}
Δt 동안 ΔXo 두께의 SiO2 growth
𝒅𝑿𝑶
𝑴 = 𝟐. 𝟑 × 𝟏𝟎𝟐𝟐 /𝒄𝒎𝟑 for O2 𝑱=𝑴
𝑴 = 𝟒. 𝟔 × 𝟏𝟎𝟐𝟐 /𝒄𝒎𝟑 for H2O 𝒅𝒕
Class Notes, IC fabrication, Prof. S.-J. Choi
12
(All rights reserved)
 Oxidation rate
• The rate of change of thickness of the oxide layer with
time (dX0/dt)
Oxidation 속도
dX o J ( DN o / M ) Boundary condition
  Xo(t=0) = Xi (initial thickness)
dt M ( X o  DX o / K s ) That is, native oxide (1-2nm)

Growth rate slows down with X0

Solution
τ represents the time which would have
4B been required to grow the initial oxide
X o (t )  0.5 A[{1  2 (t   )}1/ 2  1]
A   X i 2 / B  X i / ( B / A)

t  X o 2 / B  X o / ( B / A)   A = 2D / ks
B = 2DNo / M
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 Linear-parabolic relationship
4B
Oxide X o (t )  0.5 A[{1  2 (t   )}1/ 2  1]
A
thickness

Bt
B
(t   )
A Time
For short time
B
t    A / 4 B 2
 X o (t )  (t   )
A
( B/A = Noks/M : The linear growth rate constant)
For long time
t    A2 / 4 B  X o (t )  Bt
( B = 2DNo/M : The parabolic rate constant)
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 Model parameters
For short time (B/A, linear rate constant)
Growth rate is limited by the reaction at the silicon interface
For long time (B, parabolic rate constant) Limited by diffusion
through oxide
Growth rate is diffusion limited

B/A = Noks/M
B = 2DNo/M

Limited by reaction at
Professor S.-J. Choi Kookmin University the silicon interface 15