OXIDATION- Overview

Process Types
Details of Thermal Oxidation
Models
Relevant Issues
Uses
As a part of a structure
e.g. Gate Oxide
For hard masks
e.g. In Nitride Etch, implant mask ...
Protecting the silicon surface (Passivation )
Insulator (ILD/IMD)
As part of mild etch (oxidation / removal cycles)
Whether useful or not, automatically forms in ambient
Native Oxide ( ~ 20 A thick)
except H-terminated Si (111)
Processes
Thermal Oxidation (Heating)
Dry vs Wet
Electrochemical Oxidation (Anodization)
Oxide (and nitride)
adhere well to the silicon
good insulator
Breakdown voltage 10 MV/cm
==> Can make a very thin gate
Structure
Tetrahedral Structure
each Si to four O
each O to two Si
Single crystal quartz (density 2.6 g/cm
3
)
Fused silica (density 2.2 g/cm
3
)
Reaction with water
Time Domain CVD
2
0 Si O Si H Si OH Si OH + +
Si-OH termination is stable
structure is more porous than Si-O-Si
Thermal Oxidation
Dry oxidation
2 2
Si O SiO +
2 2 2
2 2 Si H O SiO H + +
Dense oxide formed
(good quality, low diffusion)
slow growth rate

NEED TO KEEP
WATER OUT OF THE
SYSTEM
Wet oxidation
Overall reaction
Relatively porous oxide formed
(lower quality, species diffuse faster)
Still good quality compared to
electrochem oxidation, for
example
faster growth rate
Wet oxide for masking Dry oxide for gate ox
Wet Oxidation
Proposed Mechanism
2
Si O Si H O SiOH SiOH + +
2
2 2 Si OH Si Si Si O Si H + +
Hydration near Silicon/ Silicon oxide interface
Oxidation of silicon
Hydrogen rapidly diffuses out
Some hydrogen may form hydroxyl group
2
1
2
Si O H SiOH +
Diffusivities in Oxide
Oxygen diffuses faster (compared to water)
Sodium and Hydrogen diffuse very fast
Water
Oxygen
Hydrogen
Sodium
1/T
D
i
f
f
u
s
i
v
i
t
y

(
l
o
g

s
c
a
l
e
)

Oxide Growth (Thermal)
Si Oxide
Original Si surface
To obtain 1 unit of oxide,
almost half unit of silicon is
consumed (0.44)
Oxidation occurs at the
Si/SiO
2
interface
i.e. Oxidizing species has
to diffuse through already
existing silicon oxide
Oxide Growth (Thermal)
Silicon Oxide Air (BL)
At any point
of time, amount
of oxide is
variable x
Usually,
concentration of
oxidizing species
(H
2
O or O
2
) is
sufficiently high
in gas phase
==> Saturated
in the oxide
interface
x
Distance
C
o
n
c
e
n
t
r
a
t
i
o
n

o
i
Oxidation Kinetics
At steady state
diffusion through oxide = reaction rate at the Si/SiO
2

interface
Oxygen diffuses faster than Water
However, water solubility is very high (1000 times)
==> Effectively water concentration at the interface is
higher
==> wet oxidation faster
dN
J D
dx
=
( )
o i
N N
D
x

~
i
Rate k N =
o
i
N
N D
kx D
=
+
At steady state
Diffusion
Reaction
Oxidation Kinetics
Oxide Growth Rate
o
DN
J
D
x
k
=
+
Flux at
steady state
dx
dt
= Flux/ # oxidizing species per unit volume (of SiO
2
)
n = 2.2 10
22
cm
-3
for O
2
= 4.4 10
22
cm
-3
for H
2
O
J
n
o
DN dx
D
dt
x
k
=
+
0
i
x x at t = =
Eqn
Initial Condition
6.023x10
23
molecules
=1 mol of oxide = x g of
oxide
= y cm3 of oxide (from
density)
2.2 x 10
22
molecules/cm
3

One O
2
per SiO
2

Two H
2
0 per SiO
2

Deal-Grove Model
2
0
2 2
( )
DN D
x x t
k n
t + = +
Solution
( )
2
i i
x x
B
B
A
t = +
2D
A
k
=
2
o
DN
B
n
=
where
( )
2
x x
t
B
B
A
t = +
OR
t is the time needed to grow the initial oxide
A and B depend on diffusivity D, solubility and #
oxidizing species per unit volume n
A and B will be different for Dry and Wet oxidation
Bruce Deal & Andy Grove
Linear & Parabolic Regimes
Linear vs Parabolic Regimes
Kinetic Controlled vs Mass Transfer Controlled
Initially faster growth rate, then slower growth rate
( )
B
x t
A
t = +
Very short Time
2
( ) x B t t = +
Longer Time
If one starts with thin oxide (or bare silicon)
1
2
2
4
0.5 1 ( ) 1
B
x A t
A
t
| |

|
= + +
`
|
)
\ .
2
( )
4
A
t
B
t +
( )
2
4
A
t
B
t +
( )
2
4
A
t
B
t +
Exponential Regime
Hypothesis 1
Charged species forms
holes diffuse faster / set up electrical field
diffusion + drift ==> effective diffusivity high
space charge regime controls
length = 15 nm for oxygen, 0.5 nm for water
==> wet oxidation not affected
For dry oxidation, one finds that t is not zero in the model
fit
A t corresponding to an initial thickness of 25 nm provides
good fit
Initial growth at very high rate
Approximated by exponential curve
If one starts with bare oxide
Exponential Regime
Hypothesis 2
In dry oxidation, many open areas exist
oxygen diffuses fast in silicon
hence more initial growth rate
once covered by silicon di oxide, slow diffusion

Hypothesis 3
Even before reaction (at high temp), oxygen dissolved in
silicon (reasonable diffusion)
once temp is increased, 5 nm quick oxide formation
Temp Variation of
Linear/Parabolic Coeff
Linear [B/A]
Parabolic [B]
Solubility and Diffusion function of temp
May & Sze
Effect of Doping
Doping increases oxidation rate
Segregation
ratio of dopant in silicon / dopant in oxide
e.g. Boron
incorporated in oxide;
more porous oxide
more diffusion
parabolic rate
constant is higher

P not incorporated in
oxide
no significant
change in parabolic
rate constant
May & Sze
Issues
Na diffuses fast in oxide
Use Cl during oxidation
helps trap Na
helps create volatile compounds of heavy metals
(contaminant from furnace etc)
use 3% HCl or Tri chloro ethylene (TCE)

Ref: VLSI Fabrication Principles by S.K. Ghandhi
Electrochemical
Use neutral solution and apply potential
Pt as counter electrode (Hydrogen evolution)
Use Ammonium hydrogen Phosphate or Phosphoric acid or
ammonia solution
Silicon diffuses out and forms oxide
Increase in oxide thickness ==> increase in potential needed
self limiting
Oxide quality poor
Used to oxidize controlled amount and strip
for diagnosis