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/cm3)
Fused silica (density 2.2 g/cm3)
Time Domain CVD
Reaction with water

Si O Si H 2 0 Si OH Si OH
Si-OH termination is stable
structure is more porous than Si-O-Si

Thermal Oxidation
Dry oxidation

Si O2 SiO2
Dense oxide formed
(good quality, low diffusion)
slow growth rate

Wet oxidation

Si 2 H 2O SiO2 2 H 2

NEED TO KEEP
WATER OUT OF THE
SYSTEM

Overall reaction
Relatively porous oxide formed
(lower quality, species diffuse faster)
Still good quality compared to
electrochem oxidation, for
example
faster growth rate

Dry oxide for gate ox

Wet oxide for masking

Wet Oxidation
Proposed Mechanism
Hydration near Silicon/ Silicon oxide interface

Si O Si H 2O SiOH SiOH
Oxidation of silicon

2Si OH Si Si 2Si O Si H 2
Hydrogen rapidly diffuses out
Some hydrogen may form hydroxyl group

Si O 1 H 2 SiOH
2

Diffusivities in Oxide

Diffusivity (log scale)

Oxygen diffuses faster (compared to water)

Sodium and Hydrogen diffuse very fast

Hydrogen
Oxygen

Sodium

Water

1/T

Oxide Growth (Thermal)

Original Si surface

Oxide

Si

To obtain 1 unit of oxide,

almost half unit of silicon is
consumed (0.44)
Oxidation occurs at the
Si/SiO2 interface
i.e. Oxidizing species has
to diffuse through already
existing silicon oxide

Oxide Growth (Thermal)

Air (BL) Oxide

Concentration

At any point
of time, amount
of oxide is
variable x
Usually,
concentration of
oxidizing species
(H2O or O2) is
sufficiently high
in gas phase
==> Saturated
in the oxide
interface

Silicon

o
i

Distance

Oxidation Kinetics
At steady state
diffusion through oxide = reaction rate at the Si/SiO2
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
( No Ni )
dN
Diffusion J D
D

dx

Reaction

Rate k N i

At steady state

No
Ni D
kx D

Oxidation Kinetics
6.023x1023 molecules
=1 mol of oxide = x g of
DN o
Flux at
J
oxide
xD
steady state
= y cm3 of oxide (from
k
density)
Oxide Growth Rate dx
2.2 x 1022 molecules/cm3
One O2 per SiO2
dt
Two H20 per SiO2
= Flux/ # oxidizing species per unit volume (of SiO2)
n = 2.2 1022 cm-3 for O2
= 4.4 1022 cm-3 for H2O
Eqn

DN o
dx

dt x D

J
n

Initial Condition

x xi at t 0

Bruce Deal & Andy Grove

Deal-Grove Model

Solution

2 DN 0
2D
x
x
(t )
k
n
2

OR
2

x
x
t

B
B

where
2
i

x
xi

B
B
A

2D
A
k

2 DN o
B
n

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

Linear & Parabolic Regimes

4B

x 0.5 A 1 2 (t )

A

If one starts with thin oxide (or bare silicon)

Very short Time

B
x (t )
A
Longer Time

x B (t )
2

A
(t ) =
4B

A2
t ?
4B

Linear vs Parabolic Regimes

Kinetic Controlled vs Mass Transfer Controlled

A2
t ?
4B

Exponential Regime

If one starts with bare oxide

For dry oxidation, one finds that is not zero in the model
fit
A corresponding to an initial thickness of 25 nm provides
good fit
Initial growth at very high rate
Approximated by exponential curve
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

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
SolubilityLinear/Parabolic
and Diffusion function of temp Coeff
Parabolic [B]

Linear [B/A]

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

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