Section 4: Thermal Oxidation

Jaeger Chapter 3

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Properties of SiO2
Thermal SiO2 is amorphous. SiO2
Weight Density = 2.20 gm/cm3
Molecular Density = 2.3E22 molecules/cm3

Crystalline SiO2 [Quartz] = 2.65 gm/cm3 <Si>

(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

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 Properties of SiO2 (cont’d)
(4) Conformal oxide growth on exposed Si surface SiO2

Thermal
Oxidation

Si Si

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

Dsio2 << Dsi e.g. B, P, As, Sb.
*exceptions are Ga
(a p-type dopant) and some
SiO2 metals, e.g. Cu, Au

Si
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Properties of SiO2 (cont’d)

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

SiO2 HF dip

Si Si

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 Thermal Oxidation of Silicon

Dry Oxidation

Si + O2 → SiO2

Wet Oxidation

Si + 2 H 2O → SiO2 + 2 H 2

Growth Occurs 54% above and

46% below original surface as
silicon is consumed

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Thermal Oxidation Equipment

Horizontal Furnace

Vertical Furnace

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 Kinetics of SiO2 growth

Oxidant Flow
(O2 or H2O)

Gas Diffusion Gas Flow

Stagnant Layer
Solid-state SiO2
Diffusion

SiO2 Si-Substrate
Formation

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Silicon consumption during oxidation

Si SiO2 2.17 μm
1μm
Si

1μm Si oxidized 2.17 μm SiO2

molecular density of SiO2

N
X si = X ox • ox atomic density of Si
Nsi

2 . 3 × 10 22 molecules / cm 3
= X ox • = 0 . 46 X ox
5 × 10 atoms / cm
22 3

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 The Deal-Grove Model of Oxidation
stagnant
CG layer
Cs SiO2 Si

Note
Note
CCs ≠≠CCo Co
s o
Ci

X0x
F1 F2 F3

gas diffusion reaction

transport flux flux
flux through SiO2 at interface
™ F: oxygen flux – the number of oxygen molecules that crosses a plane of a
certain area in a certain time
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The Deal-Grove Model of Oxidation (cont’d)

stagnant
CG layer
Cs SiO2 Si

Note
Note
CCs ≠≠CCo Co
s o
Ci

X0x

F1 F2 F3

F1 = h G ( C G − C S )
Mass transfer coefficient [cm/sec].
∂C
F2 = −D “Fick’s Law of Solid-state Diffusion”
∂x
⎛ C − Ci ⎞
≅ D ⋅ ⎜⎜ o ⎟⎟
⎝ X ox ⎠
Diffusivity [cm2/sec]
F3 = ks ⋅ Ci
Oxidation reaction rate constant

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 Diffusivity: the diffusion coefficient
⎛ E ⎞
D = DO exp⎜ − A ⎟
⎝ kT ⎠

E A = activation energy
k = Boltzmann's constant = 1.38 x10-23 J/K
T = absolute temperature

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The Deal-Grove Model of Oxidation (cont’d)

stagnant
CG layer
Cs SiO2 Si

Note
Note
CCs ≠≠CCo Co
s o
Ci

X0x

F1 F2 F3

• CS and Co are related by Henry’s Law

• CG is a controlled process variable (proportional to the input

oxidant gas pressure)

Only Co and Ci are the 2 unknown variables

which can be solved from the steady-state condition:
F1 = F2 =F3 ( 2 equations)

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The Deal-Grove Model of Oxidation (cont’d)
stagnant
CG layer
Cs SiO2 Si

Note
Note
CCs ≠≠CCo Co
s o
Ci

X0x

F1 F2 F3

C o = H ⋅ P s Henry’s Law

Henry’s partial pressure of oxidant

constant at surface [in gaseous form].
= H ⋅ (kT ⋅ C s ) from ideal gas law PV= NkT

Co
∴C
s =
HkT
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The Deal-Grove Model of Oxidation (cont’d)

stagnant
CG layer
Cs SiO2 Si

Note
Note
CCs ≠≠CCo Co
s o
Ci

X0x

F1 F2 F3

Define C A ≡ ( HkT ⋅ C G )
h hG
F1 = G (C A − Co ) ≡h
HkT HkT

Similarly, we can set up equations for F2 and F3

Using the steady-state condition:
F1 = F 2 = F 3 We therefore can solve for Co and Ci
1 2
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 The Deal-Grove Model of Oxidation (cont’d)
We have: ⎛ C − Ci ⎞
F2 ≅ D ⋅ ⎜⎜ o ⎟⎟ F3 = ks ⋅ Ci F1 = h(CA − Co )
⎝ X ox ⎠
At equilibrium: F1=F2=F3
Solving, we get:

Ci =
CA ⎛ k X ⎞
k kX C o = C i ⋅ ⎜ 1 + s ox ⎟
1 + s + s ox ⎝ D ⎠
h D

F (= F1 = F2 = F3 ) = ks ⋅ Ci =
ksCA
ks ksXox
1+ +
Where h=h /HkT g h D
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The Deal-Grove Model of Oxidation (cont’d)

We can convert flux into growth thickness from:

F ⎛ dX ox ⎞
= ⎜ ⎟
N1 ⎝ dt ⎠
Oxidant molecules/unit volume required
ΔX ox to form a unit volume of SiO2.

SiO2 Si

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The Deal-Grove Model of Oxidation (cont’d)
Initial Condition: At t = 0 , Xox = Xi

SiO2 xox
SiO2

Si
Si
Solution Xox 2 + AX ox = B (t + τ )
1 1
A ≡ 2D( + ) Note: hg >>ks for typical
k s hg oxidation condition

X i + AXi
2
2 DC A
B≡ τ=
N1
B
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Dry / Wet Oxidation

Note : “dry” and “wet” oxidation have different N1 factors

N1 = 2.3 × 1022 / cm3 for O2 as oxidant

Si + O2 → SiO2

N1 = 4.6 × 1022 / cm3 for H2O as oxidant

Si + 2 H2 O → SiO2 + 2 H2 ↑

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Xox Summary: Deal-Grove Model

∝ t

∝t
t
X ox + AX = B (t + τ )
2
0x

dx ox dx
2 X ox + A ox = B
dt dt
dxox B
∴ = Oxide Growth Rate slows
dt A + 2 X ox down with increase of oxide thickness

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Solution: Oxide Thickness Regimes

⎧ ⎛ ⎞ ⎫
A⎪ ⎜ t +τ ⎟ ⎪
X ox = ⎨ 1+ ⎜ 2 ⎟ − 1⎬
2⎪ ⎜ A ⎟ ⎪
⎩ ⎝ 4 B ⎠ ⎭

(Case 1) Large t [ large Xox ]

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

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 Thermal
Oxidation on
<100> Silicon

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Thermal
Oxidation on
<111> Silicon

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Thermal Oxidation Example
A <100> silicon wafer has a 2000-Å oxide on its surface

(a) How long did it take to grow this oxide at 1100o C in

dry oxygen?

(b)The wafer is put back in the furnace in wet oxygen at

1000o C. How long will it take to grow an additional 3000
Å of oxide?

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Thermal Oxidation Example

Graphical Solution

(a) According to Fig. 3.6, it would take

2.8 hr to grow 0.2 μm oxide in dry
oxygen at 1100o C.

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Thermal Oxidation Example
Graphical Solution

(b) The total oxide thickness at the end

of the oxidation would be 0.5 μm
which would require 1.5 hr to grow
if there was no oxide on the surface
to begin with. However, the wafer
“thinks” it has already been in the
furnace 0.4 hr. Thus the additional
time needed to grow the 0.3 μm
oxide is 1.5-0.4 = 1.1 hr.

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Thermal Oxidation Example

Mathematical Solution
(a) From Table 3.1,
⎛ − 1.23 ⎞ μm ⎛ − 2.00 ⎞ μm
2
B
B = 7.72 x10 exp⎜
2
⎟ = 3.71x106 exp⎜ ⎟ X i = 25nm
⎝ kT ⎠ hr A ⎝ kT ⎠ hr
μm 2 B μm
For T = 1373 K, B = 0.0236 and = 0.169
hr A hr

τ=
(0.025μm ) + 0.025μm = 0.174 hr
2

μm 2 0.169 μm
0.0236
hr hr

t=
(0.2μm )2 +
0.2μm
− 0.174hr = 2.70 hr
μm 2
μm
0.0236 0.169
hr hr

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Thermal Oxidation Example
Mathematical Solution
(b) From Table 3.1,
⎛ − 0.78 ⎞ μm ⎛ − 2.05 ⎞ μm
2
B
B = 3.86 x10 2 exp⎜ ⎟ = 9.70 x107 exp⎜ ⎟ Xi = 0
⎝ kT ⎠ hr A ⎝ kT ⎠ hr
μm 2 B μm
For T = 1273 K, B = 0.314 and = 0.742
hr A hr

τ=
(0.2μm ) + 0.2μm = 0.398 hr
2

μm 2 0.742 μm
0.314
hr hr

t=
(0.5μm )2 +
0.5μm
− 0.398hr = 1.07 hr
μm 2
μm
0.314 0.742
hr hr

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Effect of Xi on Wafer Topography

1 2 3

SiO2 SiO2 Xi

Si

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 Effect of Xi on Wafer Topography

1 2 3

SiO2 SiO2 Xi more

moreoxide
oxidegrown
grown
more
moreSi
Siconsumed
consumed
Si
1 3
2
less
lessoxide
oxidegrown
grown
less
lessSi
Siconsumed
consumed

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Factors Influencing Thermal Oxidation

– Temperature
– Ambient Type (Dry O2, Steam, HCl)
– Ambient Pressure
– Substrate Crystallographic Orientation
– Substrate Doping

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 High Doping Concentration Effect
Coefficients for dry oxidation at 900oC
as function of surface Phosphorus concentration

Dry oxidation, 900oC

SiO2
n+ n+
n n
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Transmission Electron Micrograph of Si/SiO2

Interface

Amorphous
SiO2

Crystalline
Si

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 Thermal Oxide Charges

potassium
potassium

sodium
sodium

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Oxide Quality Improvement

To minimize Interface Charges Qf and Qit

•Use inert gas ambient (Ar or N2) when cooling down at

end of oxidation step

•A final annealing step at 400-450oC is performed with

10%H2+90%N2 ambient (“forming gas”) after the IC
metallization step.

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 Oxidation with Chlorine-containing Gas
• Introduction of halogen species during oxidation
e.g. add ~1- 5% HCl or TCE (trichloroethylene) to O2
→ reduction in metallic contamination
→ improved SiO2/Si interface properties

SiO2

Na+ K+
Si M + Cl → MCl
Cl2

Na+ or K+ in SiO2 are mobile!

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Effect of HCl on Oxidation Rate

HCl + O2 → H 2O + Cl 2

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 Local Oxidation of Si [LOCOS]

~100 A SiO2 (thermal) - pad oxide

to release mechanical stress
between nitride and Si.
Oxidation

Nitride Etch

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Local Oxidation of Silicon (LOCOS)

Standard process suffers for Fully recessed process attempts
significant bird’s beak to minimize bird’s beak

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 Dopant Redistribution during Thermal Oxidation
conc. e. g. B, P, As, Sb.
Si SiO2 Si
C1
CB (uniform)
CB
x C2

Segregation Coefficient
equilibrium dopant conc. in Si
m≡
equilibrium dopant conc. in SiO2
Fixed ratio
C1
= (can be>1 or <1)
C2
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Four Cases of Interest

(A) m < 1 and dopant diffuses slowly in SiO2

SiO2 Si
C2
CB e. g. B (m = 0.3)
D
C1

flux loss through SiO2 surface not considered here.

⇒ B will be depleted near

Si interface.

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 Four Cases of Interest
(B) m > 1, slow diffusion in SiO2.
SiO2 Si
C1

e.g. P, As, Sb
CB
C2

⇒ dopant piling up near Si interface

for P, As & Sb
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Four Cases of Interest

(C) m < 1, fast diffusion in SiO2

SiO2 Si e. g.
B,
oxidize with
C2 presence of H2
CB
C1

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 Four Cases of Interest
(D) m > 1, fast diffusion in SiO2

SiO2 Si
CB
e. g. Ga (m=20)
C1
C2

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Polycrystalline Si Oxidation
poly-Si
SiO2
grain boundaries (have lots of defects).

fast slower
SiO2

a roughness
with Xox

b
Overall growth rate
is higher than
single-crystal Si
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 2-Dimensional oxidation effects
(100)
(110) Thinner oxide
Thicker
(100)
oxide
(100)
(110)
Si
cylinder
Top
view

Mechanical stress created by SiO2 volume expansion also affects oxide

growth rate

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