Oxidation

Uses of dielectric films in

Semiconductor technology
What is oxidation?
Formation of oxide layer on wafer
High temperature
O2 environment

Principle uses of Si dioxide (SiO2) layer

in Si wafer devices
Surface passivation
Doping barrier
Surface dielectric
Device dielectric
 Applied Materials low-
pressure chemical-vapor
deposition (CVD) chamber

ASM A412
batch
oxidation
furnace
 Bulk Micromachining: Structures are formed on a semiconductor
Micromachining to make MEMS devices
surface and then the underlying semi-
conductor is etched away (usually etching
Semiconductor
of much semiconductor material).
(typically silicon) An example of a micromachined part –
Heavily doped
region
the world’s smallest guitar. The strings
are only 5 nm wide and they actually
Orientation-
Etch-resistant can be made to vibrate when touched
dependent
layer etching
(carefully) with a fine probe. Guitar
made by SURFACE
MICROMACHING (below).
Surface Micromachining: Structures are formed on a sacrificial
layer on a substrate and then the
sacrificial layer is etched away (usually
etching very little material, such as
a glass doped for rapid etching).
Semiconductor
Easily etched layer
(e.g., phosphorous doped glass, PSG)

Pattern sacrificial
layer (PSG)

Deposit and pattern

structural material
Freestanding (e.g., polysilicon)
beam

Etch away
sacrificial
layer
Figure 0.1 Bulk and surface micromachining step s. These include deep
1. Surface passivation
SiO2 layer protect semiconductor
devices from contamination:
i. Physical protection of the sample and
underlying devices
Dense and hard SiO2 layer act as
contamination barrier Hardness of the
SiO2 layer protect the surface from
scratches during fabrication process

SiO2 passivation
layer

Si Si
Cont..
ii. Chemical in nature
Avoid contamination from electrically
active contaminants (mobile ionic
contaminants) of the electrically active
surface

e.g. early days, MOS device fabrication

was performed on oxidised Si
remove oxide layer to get rid of the
unwanted ionic contamination surface
before further processing
2. Doping barrier
In doping  need to create holes in a
surface layer in which specific
dopants are introduced into the
exposed wafer surface through
diffusion or ion implantation
SiO2 on Si wafer block the dopants
from reaching Si surface
All dopants have slower rate of
movement in SiO2 compared to Si
Relatively thin layer of SiO2 is required
to block the dopants from reaching SiO 2
Cont..
SiO2 possesses a similar thermal
expansion coefficient with Si
At high temperature oxidation process,
diffusion doping etc, wafer expands and
contracts when it is heated and cooled
 close thermal expansion coefficient, wafer
does not warp
Dopants

Si

SiO2 layer as dopant barrier

3. Surface dielectric
SiO2 is a dielectric  does not
conduct electricity under normal
circumstances
SiO2 layer prevents shorting of metal
layer to underlying metal
Oxide layer
MUST BE continuous; no holes or voids
Thick enough to prevent induction
If too thin SiO2 layer, electrical charge in
metal layer cause a build-up charge in the
wafer surface  cause shorting!!
Thick enough oxide layer to avoid induction
called ‘field oxide’
Metal layer

Oxide layer

Wafer

Dielectric use of SiO2 layer

source Drain

S D

Field oxide MOS gate

4. Device dielectric
• In MOS application
– Grow thin layer SiO2 in the gate region
– Oxide function as dielectric in which the
thickness is chosen specifically to allow
induction of a charge in the gate region
under the oxide
• Thermally grown oxides is also used
as dielectric layer in capacitors
– Between Si wafer and conduction layer
Types of oxidation
1. Thermal oxidation
2. High pressure oxidation
3. Anodic oxidation
Device oxide thicknesses
•Most applications of semiconductor are
dependent on their oxide thicknesses
Silicon dioxide Applications
thickness, Å
60-100 Tunneling gates

150-500 Gates oxides, capacitor

dielectrics
200-500 LOCOS pad oxide

2000-5000 Masking oxides, surface

passivation
3000-10000 Field oxides
Thermal oxidation
mechanisms
• Chemical reaction of thermal oxide
growth
Si (solid) + O2 (gas)  SiO2 (solid)

• Oxidation temperature 900-1200C
• Oxidation: Si wafer  placed in a
heated chamber  exposed to
oxygen gas
SiO 2 growth stages

Initial In a furnace with O2 gas environment

Si wafer

Oxygen atoms combine readily with Si

atoms
Linear Si wafer Linear- oxide grows in equal amounts for
each time
Around 500Å thick

Above 500Å, in order for oxide layer to

Parabolic keep growing, oxygen and Si atoms must be
Si wafer in contact
SiO2 layer separate the oxygen in the
chamber from the wafer surface
Si must migrate through the grown
oxide layer to the oxygen in the vapor
oxygen must migrate to the wafer
surface
Three dimension view of
SiO 2 growth by thermal
oxidation
SiO2 surface
Original SiO2
surface

SiO2

Si substrate
 Linear oxidation
B
X  t
A

Parabolic oxidation of silicon

X  Bt
where X = oxide thickness, B = parabolic rate constant, B/A =
linear rate constant, t = oxidation time
Parabolic relationship of SiO2 growth parameters
2
X
R
t

where R = SiO2 growth rate, X = oxide thickness, t = oxidation

time
Cont..
• Implication of parabolic relationship:
– Thicker oxides need longer time to grow
than thinner oxides
• 2000Å, 1200C in dry O2 = 6 minutes
• 4000Å, 1200C in dry O2 = 220 minutes (36
times longer)
• Long oxidation time required:
– Dry O2
– Low temperature
Dependence of silicon oxidation rate constants on temperature
Oxide thickness vs oxidation time for silicon oxidation in
dry oxygen at various temperatures
Oxide thickness vs oxidation time for silicon oxidation in
pyrogenic steam (~ 640 Torr) at various temperatures
Kinetics of growth
• Si is oxidised by oxygen or steam at high
temperature according to the following chemical
reactions:
Si (solid) + O2 (gas)  SiO2 (solid) (dry oxidation)
Or
Si (solid) + 2H2O (gas)  SiO2 (solid) + 2H2(gas)
(wet oxidation)
Also called steam oxidation, wet oxidation, pyrogenic
steam
Faster oxidation – OH- hydroxyl ions diffuses faster in
oxide layer than dry oxygen
2H2 on the right side of the equation shows H 2 are
trapped in SiO2 layer
Layer less dense than oxide layer in dry oxidation
Can be eliminated by heat treatment in an inert
atmosphere e.g. N2
• 2 mechanisms influence the growth rate of the oxide
1. Actual chemical reaction rate between Si and O2
2. Diffusion rate of the oxidising species through an
already grown oxide layer
• No or little oxide on Si the oxidising agent easily reach the
Si surface
– Factor that determine the growth rate is kinetics of the
silicon-oxide chemical reaction
• Si is already covered by a sufficiently thick layer of oxide
– Oxidation process is mass-transport limited
– Diffusion rate of O2 and H2O through the oxide limit the
growth rate is diffusion of O 2 and H2O through the oxide
• A steam ambient is preferred for the growth of thick oxides:
H2O molecules smaller than O2 thus, easier diffuse through
SiO2 that cause high oxidation rates
Si oxidation

Oxygen concentration profile during oxidation

•Mass transport of O2 molecules from gas ambient
towards the Si through a layer of already grown oxide
•Flux of O2 molecules is proportional to the
differential in O2 concentration between the ambient
(C*) and oxide surface (C0)
F1  h (C *  C0 )..............5.1
Where h is the mass transport coefficient for O2 in the gas
phase
•Diffusion of O2 through the oxide is proportional to
the difference of oxygen concentration between the
oxide surface and the Si/SiO2 interface. The flux of
oxygen through the oxide, F2 becomes
C0  Ci
F2  D ...................5.2
tox
Where,
Ci = oxygen concentration at theSi/SiO2 interface
D = diffusion coefficient of O2 or H2O in oxide
tox = oxide thickness
•Kinetics of the chemical reaction between
silicon and oxygen is characterised by
reaction constant, k:
F3  k sCi .................5.3
In steady state, all flux terms are equal: F 1 =
F2 = F3. Eliminating C0 from the flux
equations, we can obtain:
C*
Ci  ...................5.4
k kt
1  s  s ox
h D
•If N0x is a constant representing the
number of oxidising gas molecules
necessary to grow a unit thickness of
oxide, one can write:
dtox N ox k sC *
 N ox F  N ox k sCi  .......5.5
dt k s k s tox
1 
h D

•The solution to this differential equation

is:
k s k s tox
tox 1  t
h D dt  dt..........5.6

0
N ox k sC *
ox 0
•If tox=0 when t=0, th eintegration yields:
tox2  D D 
   tox  N oxC *dt  0........5.7
2  ks h 
Or
 1 1
tox2  2 D   tox  2 DN oxC *t............5.8
 ks h 
Defining new constant A and B in terms of D, k s, Nox and
C*:  1 1
A  2 D   ............5.9
 ks h 
and
B  2 DC * N ox ................5.10

We can obtain:
t 2  Atox  Bt.....................5.11
From which we find t ox :
A (t   ) 
tox   1 2 .................5.12

2 A / 4B  1 
• is introduced to take into account the possible presence of an
oxide layer on the Si before thermal oxide growth being carry out
–Oxide layer can be a native oxide layer due to oxidation of bare Si by
ambient air or thermally grown oxide produced during a prior oxidation
step
–=0 if the thickness of the initial oxide is equal to zero
•When thin oxides are formed the growth rate is limited by the
kinetics of chemical reaction between Si and O 2.
Eq. 5.12 becomes:
B
tox  t   ...........5.13
A
Which is linear with time.
B
•The A ratio is called “linear growth coefficient”, and is dependent
on crystal orientation of Si
•When thick oxides are formed, the growth rate is limited by the
diffusion rate of oxygen through the oxide. Eq 5.12 becomes:

tox  B (t   )  Bt ..............5.14
• The coefficient B is called “parabolic growth coefficient” and is
independent on crystal orientation of Si.
• The parabolic growth coefficient can be increased:
– Increase the pressure of the ambient oxygen up to 10-20 atm (high
pressure oxidation)
•The linear growth coefficient can be increased:
– Si consists of high concentration of impurities e.g. phosphorous:
increase point defects in the crystal which increase the oxidation reaction
rate at the Si/SiO 2 interface
– Oxidation process also generate point defects in Si which enhance
diffusion of dopants. Some dopants diffuse faster when annealed in
oxidising ambient than in neutral gas such at N 2
Oxidation rate
Controlled by:
1. Wafer orientation
2. Wafer dopant
3. Impurities
4. Oxidation of polysilicon layers
1. Wafer orientation
Large no of atoms allows faster oxide growth
<111> plane have more Si atoms than <100>
plane
• Faster oxide growth in <111> Si
• More obvious in linear growth stage and at low
temperature
Crystal structure of
silicon

<100> plane

<111> plane
Dependence of oxidation linear rate constant and oxide fixed
charge density on silicon orientation
2. Wafer dopant(s) distribution
Oxidised Si surface always has dopants; N-type
or P-type
Dopant may also present on the Si surface from
diffusion or ion implantation
Oxidation growth rate is influenced by dopant
element used and their concentration e.g.
• Phosphorus-doped oxide: less dense and etch faster
• Higher doped region oxidise faster than lesser doped
region e.g. high P doping can oxidise 2-5 times the
undoped oxidation region
• Doping induced oxidation effects are more obvious in
the linear stage oxidation
Schematic illustration of dopant distribution as a function of position
is the SiO2/Si structure indicating the redistribution and segregation
of dopants during silicon thermal oxidation
Distribution of dopant atoms in Si
after oxidation is completed
During thermal oxidation, oxide layer
grows down into Si wafer- behavior
depends on conductivity type of dopant
N-type: higher solubility in Si than SiO2,
move down to wafer. Interface consists of
high concentration N-type doping
P-type: opposite effect occurs e.g Boron
doping in Si move to SiO2 surface causes B
pile up in SiO2 layer and depletion in Si
wafer  change electrical properties
3. Oxide impurities
Certain impurities may influence
oxidation rate
e.g. chlorine from HCl from
oxidation atmosphere  increase
growth rate 1-5%
4. Oxidation of polysilicon
Oxidation of polysilicon is essential
for polysilicon conductors and
gates in MOS devices and circuits
Oxidation of polysilicon is
dependent on
Polisilicon deposition method
Deposition temperature
Deposition pressure
The type and concentration of doping
Grain structure of polysilicon
Thermal oxidation method
Thermal oxidation  energy is
supplied by heating a wafer
SiO2 layer are grown:
Atmospheric pressure oxidation 
oxidation without intentional pressure control
(auto-generated pressure); also called
atmospheric technique
High pressure oxidation  high pressure is
applied during oxidation
2 atmospheric techniques
1.Tube furnace
2.Rapid thermal system
Oxidation methods
Thermal oxidation
Atmospheric Tube furnace Dry oxygen
pressure Wet oxygen

Rapid thermal Dry oxygen

High pressure Tube furnace Dry or wet
oxygen
Chemical oxidation
Anodic Electrolytic cell Chemical
oxidation
Horizontal tube furnace
• Quartz reaction tube – reaction
chamber for oxidation
• Muffle – heat sink, more even
heat distributing along quartz
tube
• Thermocouple – placed close
to quartz tube. Send temp to
band controller
• Controller – send power to coil
to heat the reaction tube by
radiation/conduction
• Source zone- heating zone

Place the
sample
Horizontal tube furnace
Integrated system of a tube furnace
consists of several sections:
1. Reaction chamber
2. Temperature control system
3. Furnace section
4. Source cabinet
5. Wafer cleaning station
6. Wafer load station
7. Process automation
Vertical tube furnaces
Small footprint
Maybe placed outside
the cleanroom with
only a load station
door opening into the
cleanroom
Disadvantage:
expensive
Rapid Thermal Processing
Based on radiation principle heating
Useful for thin oxides used in MOS
gates
Trend in device miniaturisation
requires reduction in thickness of
thermally grown gate oxides
< 100Å thin gate oxide
Hard to control thin film in
conventional tube furnace
Problem: quick supply and remove O2
from the system
RTP system: able to heat and cool the
wafer temperature VERY rapidly
RTP used for oxidation is known as Rapid
Thermal Oxidation (RTO)
Have O2 atmosphere
Other processes use RTP system:
Wet oxide (steam) growth
Localised oxide growth
Source/ drain activation after ion implantation
LPCVD polysilicon, amorphous silicon, tungsten, silicide
contacts
LPCVD nitrides
LPCVD oxides
 RTP design

e.g. RTP time/temperature

curve
High Pressure Oxidation
Problems in high temperature
oxidation
Growth of dislocations in the bulk of the
wafer  dislocations cause device performance
problems
Growth of hydrogen-induced
dislocations along the edge of opening
 surface dislocations cause electrical leakage along
the surface or the degradation of silicon layers grown on
the wafer for bipolar circuits

Solve: low temperature oxidation

BUT require a longer oxidation time
High pressure system  similar to
conventional horizontal tube furnace with
several features:
Sealed tube
Oxidant is pumped into the tube at pressure 10-25 atm
The use of a high pressure requires encasing the quartz
tube in a stainless steel jacket to prevent it from cracking
High pressure oxidation results in faster
oxidation rate
Rule of thumb: 1 atm causes temperature drop of 30C
In high pressure system, temperature drop of 300-750C
 This reduction is sufficient to minimise the growth of
dislocations in and on the wafers
 Advantage of high pressure oxidation
Drop the oxidation temperature
Reduce oxidation time

• Thin oxide produced using high

pressure oxidation  higher dielectric
strength than oxides grown at atmospheric pressure

High pressure
oxidation
Oxidant sources
1. Dry oxygen
2. Water vapor sources
a) Bubblers/ flash
b) Dry oxidation
c) Chlorine added oxidation
1. Dry oxygen
• Oxygen gas must dry  not
contaminated by water vapor
• If water present in the oxygen:
– Increase oxidation rate
– Oxide layer out of specification
• Dry oxygen is preferred for growing
very thin gate oxides ~ 1000Å
2a. Bubblers
• Bubbler liquid – DI water heated close to boiling
point 98-99C
– create a water vapor in the space above liquid
• When carrier gas is bubbled through the water
and passes through the vapor  saturated with
water
• Influence of elevated temp inside tube  water
vapor becomes steam and results in oxidation of
Si surface
• Problem: contamination of tube and oxide layer
from dirty water and flask
2b. Dry oxidation (dryox)
• O2 and H2 are introduced directly into oxidation
tube  mixes
• High temperature in tube forms steam  wet
oxidation in steam
• Advantage:
– Controllable: gas flow can be controlled by
flow controllers
– Clean: can purchase gases in a very clean and
dry state
• Disadvantage: explosive property of H2 
overcome by flow in excess O2
2c. Chlorine added
oxidation
• Chlorine addition:
– Reduce mobile ionic charges in the oxide layer
– Reduce structural defects in oxide and Si
surface
– Reduce charges at Si-SiO2 interface
• Chlorine sources:
– Gas: anhydrous chlorine (Cl2), anhydrous
hydrogen chloride
– Liquid: trichloroethylene (TCE), trichloroethane
(TCA)
• TCA is preferred source for safety and
ease of delivery
Post-oxidation evaluation
• Surface inspection
– quick check of the wafer surface using UV light (surface
particulates, irregularities, stains)
• Oxide thickness
– several techniques such as color comparison, fringe counting,
interference, ellipsometers, stylus apparatus, scanning
electron microscope
• Oxide and furnace cleanliness
– Ensure oxide consists of minimum number of mobile ionic
contaminants. Use capacitance/voltage (C/V) evaluation: detect
total number of mobile ionic contaminants NOT the origin of
contaminants
Thermal nitridation
• < 100Å SiO2 film possesses poor
quality and difficult to control
• Silicon nitride (Si3N4)
– Denser than SiO2  less pin holes in
thin film ranges
– Good diffusion barrier
• Growth control of thin film is
enhanced by a flat growth
mechanism (after an initial rapid
growth)
Nitridation of <100> silicon