VLSI Technology

Lecture 6

Oxidation

Dr. Brajendra Singh Sengar (PhD, IIT Indore)

Assistant Professor
Department of Electronics and Communication Engineering
National Institute of Technology Srinagar
Email id: [email protected]

1
 Oxidation

The ability to grow a high-quality thermal oxide has propelled Si into the forefront of all
semiconductor technology.

Ge allows faster transistors (due to it’s much higher mobility) , dissipates much less heat and was
used first, before Silicon. However, Ge-oxides are much more unstable, much poorer quality, and
difficult to form.

Some present-day efforts are being made to produce SiGe channel transistors to marry the benefits of
Si (good oxides) with the speed of Ge.

High-power devices are being developed in SiC. One key advantage of SiC over other material
alternatives is the ability to grow high-quality oxides on the Si face of SiC. (Note: SiO2 is a low
vapour pressure solid while CO2 is a high vapour pressure gas).

During the oxidation of Si, the Oxidizing Species defuse through the oxide to react with the Si at the
Si/SiO2 interface. In theory, some Si can diffuse back out of the oxide, but this does not occur (due to
Si Interstitial injection into the bulk).
 Thermal Oxidation of Si
• General Properties of SiO2
• Applications of thermal SiO2
• Deal-Grove Model of Oxidation
SiO2

Thermal SiO2 is amorphous.

Weight Density = 2.20 gm/cm3 <Si>
Molecular Density = 2.3E22 molecules/cm3

Crystalline SiO2 [Quartz] = 2.65 gm/cm3

3
 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

SiO2

Thermal
Oxidation

Si Si

44
 Thermal SiO2 Properties – cont.
(5) SiO2 is a good diffusion mask for common dopants
Dsio  Dsi e.g. B, P, As, Sb.
2

*exceptions are Ga
(a p-type dopant) and some
SiO2 metals, e.g. Cu, Au
Si
(6) Very good etching selectivity between Si and SiO2.

SiO2 HF dip

Si Si

55
 Thermal
Oxidation
Equipment

Steam generation
for wet oxidation

66
 Volume change due to thermal oxidation

Molecular Density of SiO2 = 2.3E22 molecules / cm3

Atomic Density of Si = 5.0E22 atoms / cm3
 Volume of SiO2 = 2.16 Volume of Si consumed
Mechanical stress will be generated with confined oxidation

7
 One-dimensional planar oxide growth

1 m
SiO2 2.17 m
Si
Si
•Roughly half of oxide grown
is under original Si surface

1 m Si oxidized 2.17 m SiO2

Suggested exercise:
completely
oxidized 1.3 m
1 m diameter SiO2
Si diameter
Si sphere
SiO2 sphere
8
Thickness of Si consumed (planar oxidation)
original
surface SiO2
Xox
Si Xsi
Si

molecular density of SiO2

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

2.3  10 22 molecules / cm 3
= X ox • = 0.46 X
5  10 atoms / cm
22 3 ox

9
 Kinetics of SiO2 Growth

Oxidant Flow
(O2 or H2O)

Gas Diffusion Gas Flow

Stagnant Layer
Solid-state SiO2
Diffusion

SiO2 Si-Substrate
Formation

10
 Deal-Grove Model
stagnant
CG layer
Cs SiO2 Si

Note
Cs  Co Co
Ci
X0x

F1 F2 F3
gas diffusion reaction
transport flux flux
flux through SiO2 at interface
11
F1 = hG (CG − CS )
Mass transfer coefficient [cm/sec].

C
F2 = −D “Fick’s Law of Solid-state Diffusion”
x
 C o − Ci 
 D  
 X ox 
Diffusivity [cm2/sec]
F3=ksCi
Surface reaction rate constant [cm/sec]

12
 How to solve the oxidant concentrations?

• 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
and C Cii are
are the
the 22 unknown
unknown variables
variables
which can be solved from the steady-state condition:
FF11 == FF22 =F
=F33 (( 22 equations)
equations)

13
 Derivation of Oxidation Growth Rate

C o = H  Ps Henry’s Law

partial pressure of oxidant

Henry’s at surface [in gaseous form].
constant

= H  (kT Cs ) from ideal gas law PV= NkT

Co
 Cs =
HkT

14
 Derivation of Oxidation Growth Rate – cont.
This is a control

Define C *  ( HkT  C G ) process variable.

For a given oxidant
pressure, CA is known.
F1 can be re-written as:
hG
F1 = (C * − Co )
HkT
h
Using the steady-state condition:

Conservation
of mass flux
F1 = F2 = F3 2 equations to solve the
2 unknowns: Co & Ci
1 2
15
Derivation of Oxidation Growth Rate – cont.
Therefore

C*
Ci =
ks ks X ox
1+ +
h D

 k s X ox 
C o = C i  1 + 
 D 

(F =F =F )=k ⋅C =
F = ks C *
1 2 3 s i
ks ksXox
1+ +
h D 16
 Lecture 6

Now, convert Flux F into Oxide Thickness Growth Rate

 dX ox 
F = N1  
 dt 
Xox Oxidant molecules/unit volume required
to form a unit volume of SiO2.

SiO2 Si Therefore, we have the oxide growth rate eqn:

 
F dX ox  k sC * 
N1 • = 
dt k s k s X ox 
1 + +
 h D 
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 Initial Condition: At t = 0 , Xox = Xi

SiO2 xox
SiO2

Si
Si

Solution Xox + AX ox = B(t + τ)

2

1 1
A  2D( + ) Note: h >>ks for typical
ks h oxidation condition
2DC *
B
i + AXi
2
N1 τ= X
B
18
Note : “dry” and “wet” oxidation have different
N1 factors

N1 = 2.3  10 22 / cm3 for O2 as oxidant

Si + O2 → SiO2
N1 = 4.6  1022 / cm3
for H2O as oxidant

Si + 2H2 O → SiO2 + 2H2 

19
Xox Summary of Deal-Grove Model

 t

t
t
+ AX = B ( t + τ)
2
X ox 0x

dx ox dx ox
2X ox
+ A = B
dt dt
dxox B
 = Oxide Growth Rate slows
dt A+ 2X ox down with increase of oxide
thickness
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 
A  + τ  
t 
X ox =  1+  2  − 1
2 A 
 4B 

(Case 1) Large t [ large Xox ]

Xox → Bt

(Case 2) Small t [ Small Xox ]

B
X ox → t
A
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Growth dependence on “dry” and “wet” oxidation

Temp (C) Type A (µm) B (µm2 /h) B/A (µm /h)

Wet 0.5 0.203 0.406

920
Dry 0.235 0.005 0.021
1200 Wet 0.05 0.72 14.4
Dry 0.04 0.045 1.12

22
C *= 5.2 10^16 for Dry

3.0 10^19 for Wet

23
010 Lecture6

Deal-Grove Model Parameters

−Q

(1) B  2 D C* De kT
 D
N1 Q = activation energy
for diffusion

−Q'
(2) B
=
1 C* ks e kT
A 1 1
( + ) N 1
Q’ = activation energy
h k s
for interface reaction

For thermal oxidation of Si, h is typically >> ks

B/A is ∝ ks (i.e.
(i.e. FF11 is
is rarely
rarely the
the rate-limiting
rate-limiting step)
step)
24
B = Parabolic Constant
B/A = Linear Constant

25
Oxidation Charts

The charts are

based on
Xi = 0 !

26
 Two Ways to Calculate Oxide Thickness
Grown by Thermal Oxidation

E.g.
1100oC
33min xo
SiO2 xi= SiO2 x
4000A
Si steam
Si

Method 1: Find B & B/A from Charts

Solve Xox + AX
2
= B(t + τ)
ox

27
 Two Ways to Calculate Oxide Thickness
Grown by Thermal Oxidation
Method 2: Use Oxidation Charts
Xox T3
T2 The charts are
6500oA based on
T1
4000oA =0!!
XXi i=0

time(min)
0
24 33 5
7

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

 Total effective oxidation time
(24+ 33) min= 57min if start with Xi =0
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 (3) CVD Oxide
(1) Grown at 1000oC, 5hrs
CVD
SiO2 4000oA xi SiO2 4000oA Oxide

Si Si

(2) Grown at 1100oC, 24min

SiO2 4000oA
For same Xi,
Si is the same for all three
cases shown here
29
Effect of Xi on Wafer Topography

Slower
1 2 3 growth
rate
Faster
growth
SiO2 rate SiO2 Xi more oxide grown
more Si consumed
Si
1 3
2
less oxide grown
less Si consumed

30
Factors Influencing Thermal Oxidation

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

31
 High Pressure Oxidation

B/A = C * / [N1(1/ks+1/h)]  C *  PG

B = 2D C * / N1  C *  PG

When PG increases, both B and B/A will increase.

Therefore oxidation rate increases.

1)The oxidation temperature can be reduced if the pressure

is increased, to achieve a given oxidation rate
2)To grow a given oxide thickness at same temperature,
time can be reduced
32
 High Doping Concentration Effect
Coefficients for dry oxidation at 900oC
as function of surface Phosphorus concentration

Dry oxidation, 900oC SiO2 Si

ks
vacancies
* highly doped Si has more vacancies

SiO2
n+ n+
n n

33
 Substrate Orientation Effect
log Xox
(111) Reason:
(111) surface has more
(100) Si bonds than (100) Surface

Xox SiO2 Si
(111)
* difference more
(110) obvious for thin F1 F2 F3
oxides

(100)
orientation
most IC’s made with (100) Si ks
ks(111) > (ks(100)
34
 Transmission Electron
Micrograph of Si/SiO2 Interface
Amorphous
SiO2

Crystalline
Si

35
 Oxide Charges

potassium

sodium

36
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 400-450o

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

37
 Oxidation with Chlorine-containing Gas

• Introduction of halogen species during oxidation

e.g. add ~1- 5% HCl or TCE (trichloroethylene) to O2

→ Immobilize alkaline(e.g. Na+,K+) ions in oxide

→ improved SiO2/Si interface properties

SiO2

Na+ K+
Si M + Cl → MCl
Cl2

38
 Effect of HCl on Oxidation Rate

HCl + O2 → H 2O + Cl 2

39
 SUMMARY of Deal Grove Model

Xox2 (t) + A Xox(t) = B (t + )

dXox B
The growth rate dt = A+2X slows down as Xox increases
ox

Dependence of B/A and B on Processing Parameters

Linear Constant B/A Parabolic Constant B
Oxidation Pressure linear with oxygen pressure linear with oxygen pressure
(actually  P 0.8 )
Steam versus O2 larger for steam oxidation larger for steam oxidation
Si crystal orientation B/A(111):B/A(100) = 1.68:1 independent of orientation
Dopant type and concentration increases with dopant insensitive
in Si concentration
Addition of Cl-containing gas insensitive increases
in oxidation ambient

40
 Local Oxidation of Si [LOCOS]

Si3N4 (CVD)

~100A SiO2 (thermal) - pad oxide

to release mechanical stress
Si between nitride and Si.

 Thermal oxidation
“bird’s beak”

Xox SiO2

  1.1 - 1.5 Xox Si

41
Fully Recessed LOCOS

Si substrate is etched
to a depth of ~1/2
the intended grown
oxide thickness

Grown oxide surface

is approximately
planar with substrate surface

42
Dopant Redistribution during Thermal Oxidation

conc.
Si e. g. B, P, As, Sb.
SiO2 Si
C1
CB (uniform)
C2 CB
x

Segregation Coefficient at interface

equilibrium dopant conc. in Si
m
equilibrium dopant conc. in SiO2
Fixed ratio
C1
= (can be>1 or <1)
C2
43
 Four Cases of Interest

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

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

Flux loss through SiO2 surface not considered here.

 B will be depleted near

Si interface.

44
(B) m > 1, dopant diffuses slowly in SiO2.
SiO2 Si
C1
C2 e.g. P, As, Sb
CB

 dopant piling up near Si interface

for P, As & Sb

45
(C) m < 1, dopant diffuses fast in SiO2

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

46
(D) m > 1, dopant diffuses fast in SiO2

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

47
 Thin Oxide Growth
The Deal-Grove model provides excellent agreement with
experimental data except for thin (<20 nm) SiO2 grown in O2

Xox When Xox

becomes large,
additional term becomes zero

 t 1/ 2 d Xo x B −Xo x
= +C e L
t d t A+2Xox
25 nm
t
L ~ 7nm

=> For thick oxides grown in O2 on bare Si,

assume Xi =25 nm when using the Deal-Grove equations
48
 Polycrystalline Si Oxidation
poly-Si
SiO
2 grain boundaries (have lots of defects).

fast slower
SiO2

a roughness
with Xox

b
Overall growth rate
is higher than
single-crystal Si

49
Thermal Oxidation of Si-containing Thin Films

* SiO2 is
the final
reaction
product

50
 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
(if interested, see Kao et al, International Electron Devices Meeting Digest, 1985, p.388)

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 Summary of Thermal Oxidation Module
• Volume change with thermal oxidation.
• Deal-Grove Oxidation Model : Linear (B/A) and
Parabolic (B) Constants.
• Calculate oxide grown using: (i) Oxidation charts ,
and (ii) D-G Model.
• Factors influencing oxidation: Temp, Ambients,
Doping Conc, Pressure, Substrate Orientation.
• Oxide Charges.
• LOCOS.
• Qualitative understanding of : dopant redistribution
during oxidation, Thin Oxide Growth, Oxidation of
Poly-Si and Si-containing films.

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