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 Wet oxidation
Si 2 H 2O SiO2 2 H 2
Si O2 SiO2
Dense oxide formed (good quality, Overall reaction
low diffusion) Relatively porous oxide formed (lower quality
slow growth rate species diffuse faster)
Still good quality compared to
NEED TO KEEP WATER OUT OF electrochem oxidation, for example
THE SYSTEM 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
2 Si 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
Oxygen diffuses faster (compared to water)
Sodium and Hydrogen diffuse very fast
Diffusivity (log scale) Hydrogen
Oxygen Sodium
Water
1/T
Oxide Growth (Thermal)
Original Si surface
To obtain 1 unit of oxide, almost half
unit of silicon is consumed (0.44)
Oxidation occurs at the Si/SiO2
interface
Oxide Si
i.e. Oxidizing species has to diffuse
through ‘already existing’ silicon oxide
Oxide Growth (Thermal)
Air (BL) Oxide Silicon
At any point of time,
amount of oxide is variable ‘x’
Usually, concentration of
oxidizing species (H2O or O2) is No
Concentration
sufficiently high in gas phase
Ni
==> Saturated in the oxide
interface
x
Distance
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 ( No Ni )
Diffusion Flux JJ1= D dx D x
Reaction
J2= k N i
Rate
No
At steady state J1= J2=J N i D
kx D
Oxidation Kinetics 6.023x1023 molecules
=1 mol of oxide = x g of oxide
Flux at DN o
steady state
J = y cm3 of oxide (from density)
xD 2.2 x 1022 molecules/cm3
k
One O2 per SiO2
dx Two H2O per SiO2
Oxide Growth Rate =
dt
= Flux/ # oxidizing species per unit volume (of SiO2)
=
J n = 2.2 × 1022 cm-3 for O2
= 4.4 × 1022 cm-3 for H2O
n
dx DN o /n
dt x D
k
Initial Condition x xi at t 0
Deal-Grove Model Bruce Deal & Andy Grove
Solution
OR
2D 2 DN 0 x2 x
t
2
x x (t ) B B A
k n
N0
n
where
xi2 xi
2D 2 DN o
B B
A A
k
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 2
1
x 0.5 A 1 2 (t ) 1
A
If one starts with thin oxide (or bare silicon)
Very short Time
B
x (t )
A
Longer Time
A2
x B (t )
2
t =
4B
Linear vs Parabolic Regimes
Kinetic Controlled vs Mass Transfer Controlled
Initially faster growth rate, then slower growth rate
Experimental results for silicon dioxide thickness as a function
of reaction time and temperature for two substrate
orientations
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 dioxide, 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
Solubility and Diffusion function of temp
Linear [B/A] Parabolic [B]
© 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
