Chapter 6: Thermal Oxidation and the Si/SiO2

Interface
Contents
1. Introduction
2. Structure
3. Manufacturing Methods and Equipment
4. Measurement Methods
5. Growth kinetics
– Deal Grove model
– Influence ambient
6. Trends
7. Summarisation

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 1. Introduction
Thermally grown oxides:
• Si is unique, its oxide (SiO2) and the Si/SiO2 interface are
very stable.
Nothing in this world is perfect:
• When SiO2 is formed, misfit at the interface causes interface
states and some Si atoms in the SiO2 near the interface are
positively ionised (fixed oxide charge)=> shift in MOST Vt
(threshold voltage).
• Sodium (Na) and Potasium (K) are incorporated and form
mobile ions => instabilities of MOST Vt

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 1. Introduction

Thermal oxides are used for:

• Gate oxide 2-10 nm
Dry oxidation (slow) Si + O2 => SiO2
• Pad oxide (20 nm, dry) between Si3N4 and Si for LOCOS (LOCal
Oxidation of Silicon)
• Electrical isolation between devices (lateral);
Field Oxide (0.5-1 mm)
Wet oxidation (fast) Si+2H2O => SiO2+2H2
• Masking layers (0.5-1.0 mm wet) for implantation and diffusion of doping
atoms
• The dielectric between conductors and the protection on top are made by
CVD (Chemical Vapor Deposition)

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 3. Structure
• tetrahedron

• amorphous

• no periodic structure of lattice, density low → diffusion rel.

easy
• quartzite: crystalline structure
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 Si+O2 →SiO2
Si+2 H 2O→SiO2 +2 H 2

• diffusion of oxidant through already grown SiO2-layer

• at Si-SiO2 interface: reaction of oxidant with Si

thickness SiO2 = x 
consumed Si-thickness = 0.44x 6
 molecular weight
volume of 1 mole =
density
volume of 1 mole of Si =
28.09g / mole
3
= 12 . 06cm 3
/ mole
2.33g / cm
• volume of 1 mole of SiO2 =
60.08g / mole
2
= 27 . 18cm 3
/ mole
2.21g / cm
• 1 mole SiO2 uses 1 mole of Si
volume = thickness area
hSi 12.06
= = 0.44
hSiO2 27.18

• To grow 100 Å thick SiO2, 44 Å Si is consumed

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 Field oxide - LOCOS
• Lateral isolation between devices
• Thick : Wet oxidation
• LOCOS: Local oxidation of Silicon
Pad oxide
• bird's beak!

Fully recessed LOCOS:

prior to oxidation
etch trench in Silicon

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 Field Oxide - Shallow Trench Isolation

+ Less area loss ( higher packing density)

+ planar surface
+ easy downscaling

Trenches, reoxidation + B-implant, CVD oxide + CMP,

spacers, etching pad oxide, gate -oxidation + -deposition

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 3. Manufacturing Methods and Equipment

Oxidation Techniques
• Thermal Oxidation
• Rapid Thermal Oxidation

Thermal Oxidation Techniques

• Wet Oxidation
Si (solid) + H20 => SiO2 (solid) + 2H2
• Dry Oxidation
Si (solid) + O2 (gas) => SiO2(solid)

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 3. Manufacturing Methods and Equipment

Furnace:

Temperature: 700C - 1200C

Ambient: oxygen ("dry oxidation")
water vapour or burning hydrogen flame ("wet oxidation")
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Wafers are placed in wafer load station
• Dry nitrogen is introduced into chamber
- Nitrogen prevents oxidation from occurring
• Nitrogen gas flow shut off and oxygen added to chamber
- Occurs when furnace has reached maximum temperature
- Oxygen can be in a dry gas or in a water vapor state
• Nitrogen gas reintroduced into chamber
- Stops oxidation process
• Wafers are removed from furnace and inspected

Dry Thermal Oxidation Characteristics

• Oxidant is dry oxygen
• Used to grow oxides less than 1000Å thick
• Slow process
- 140 - 250Å / hour 12
Thin Oxide Growth
• Thin oxides grown (<150Å) for features smaller than 1mm
- MOS transistors, MOS gates, and dielectric components
• Additional of chemical species to oxygen decreases oxide
growth rate (only in special cases)
- Hydrochloric acid (HCI)
- Trichloroethylene (TCE)
- Trichloroethane (TCA)
• Decreasing pressure slows down oxide growth rate

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Wet Thermal Oxidation Characteristics
• Oxidant is water vapor
• Fast oxidation rate
- Oxide growth rate is 1000-1200Å / hour
• Preferred oxidation process for growth of thick oxides

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 Modern Equipments

Oxidation occurs in tube furnace

- Vertical Tube Furnace
- Horizontal Tube Furnace

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 4.Measurement Methods
Physical Measurements
Step measurements:
--step SiO2
-SEM Si
-AFM
-TEM

SiO2

Si

SEM image TEM image

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 4.Measurement Methods

Optical Characterisation

n1/n0 = sinf/sinb => lmin,max = 2 n1x0 cosb/m

m= 1,2,3… for maximum, 0.5, 1.5, 2.5… for minimum
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 4.Measurement Methods

Ellipsometer Method
• The instrument relies on the fact that the reflection at a dielectric
interface depends on the polarization of the light while the transmission of
light through a transparent layer changes the phase of the incoming wave
depending on the refractive index of the material.

• An ellipsometer can be used

to measure layers as thin as 1
nm up to layers which are
several microns thick.

Schematic drawing of an ellipsometer

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 4.Measurement Methods
Electrical characterisation
Charges in oxide

potassium
sodium
incomplete Si-Si
/ Si-O bonds;
3 nm from interface

• Mobile charges Qm :1010 -1012 cm-2

clean furnace tube, clean chemicals , do not ever touch wafers with bare hands
Trapped oxide charge Qot : 109 -1013 cm-2
low-T anneal
• Fixed oxide charge (+) Of : 1010 -1012 cm-2
rapid cooling or N2-anneal Qf<100> < Qf<111>
• Interface states (E in gap) Qit  1010 cm-2
low T (450ºC) hydrogen anneal  neutralisation 19
C-V Measurements 4.Measurement Methods

• There are a number of

measurement techniques used to
characterize SiO2 and the
Si/SiO2 interface.
• The most powerful of these is
the C-V method which is
described in the text in detail.

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 4.Measurement Methods
• Electric field lines pass through the “perfect” insulator and Si/SiO2
interface, into the substrate where they control charge carriers.
• Accumulation, depletion and inversion result.

• HF curve - inversion layer

carriers cannot be generated
fast enough to follow the AC
signal so Cinv is Cox + CD
• LF curve - inversion layer
carriers follow the AC signal
so Cinv is just Cox.

• Deep depletion - “DC” voltage is applied fast enough that inversion layer
carriers cannot follow it, so CD must expand to balance the charge on the gate.
• C-V measurements can be used to extract quantitative values for:
• tox - oxide thickness
• NA - the substrate doping profile
• Qf, Qit, Qm, and Qot - oxide & interface charges.
• See text for more details on these measurements. 21
 5. Growth kinetics
Deal-Grove model

• The basic model for oxidation was developed in 1965 by Deal and Grove.
Si+O2 => SiO2
Si+2H2O => SiO2+2H2 )
• Three first order flux equations describe the three series parts of the process. 22
 5. Growth kinetics

(1)
• Three first order flux equations
describe the three series parts of (2)
the process.
(3)

(4)
• Under steady state conditions,
F1 = F2 = F3, so

• Note that the simplifications are

made by neglecting F1 which is a (5)
very good approximation.

• Combining (3) and (4), we have (6)

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• Integrating this equation (6) (see text), results in the
linear parabolic model.
(7)

Where ( parabolic rate constant)

(linear rate constant)

• (7) can also be written with oxide thickness as a function of time.

where

t>>A2/4B (long time) t+ τ <<A2/4B (short time)

xo2=B(t+τ) Parabolic rate xo=(B/A)(t+τ) Linear rate
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• The rate constants B and B/A have physical meaning (oxidant diffusion and
interface reaction rate respectively).

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26
• Calculated dry O2 oxidation rates using Deal Grove.

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• Calculated H2O oxidation rates using Deal Grove.

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 Thin Oxide Growth Kinetics
• A major problem with the Deal Grove model was recognized when it was first
proposed - it does not correctly model thin O2 growth kinetics.
• Experimentally O2 oxides grow much faster for ~ 200 Å than Deal Grove
predicts.
• MANY suggestions have been made in the literature about why. None have
been widely accepted.

1. Reisman e t. a l. Model

• Simple power law “fits the data” over the whole range of oxide thicknesses.
• a and b are experimentally extracted parameters.
• Physically - interface reaction controlled, volume expansion and viscous
flow of SiO2 control growth.

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2. Han and Helms Model

• Second parallel reaction added - “fits the data” ” over the whole range
of oxide thicknesses.
• Three parameters (one of the A values is 0).
• Physically - second process may be outdiffusion of OV and reaction at
the gas/SiO2 interface.

3. M assoud e t. a l. Model

• Second term added to Deal Grove model which gives a higher dx/dt during
initial growth.
• L ~ 70 Å so the second term disappears for thicker oxides.
• Because it is simply implemented along with the Deal
Grove model, this model has been used in process simulators.
• Experimental data agrees with the Reisman, Han and Massoud models. (800°C
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dry O2 model comparison below.)
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Pressure Dependence

i
A  A
=  P B = ( B) i P for HO
B B 2

i
A  A n
=  P B = ( B) i P for O
B B 2

B and B/A  C0 and thus also  P :

P   growth rate 
 enables oxide growth at lower
temperatures

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Dependence on Si Substrate Orientation

Wafer Orientation
• Oxide grows faster on <111>
wafers
- more silicon atoms available
to react with oxidant
• Affects oxide growth rate during
Linear Stage
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 Influence of impurities

• H2O impurity in O2-gas: hydroxyl groups are formed →

more open oxide structure → R
• HCl gas: is able to react with impurities and form volatile
chlorides
→ quality of oxide and Si-SiO2 interface improves
• high concentrations of P and B change fermi level and
vacancy concentration:
– B segregates into oxide →
weakens the Si-O2 bond →
enlarges the diffusion
– P segregates into Si →
surface concentration of P →
B/A
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 Influence Halogens (Chlorine)

increase of growth rate

0-5% HCl
Is often added to improve gate oxide quality
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 Oxidation of doped Si

Phosphorus doped Si Boron doped Si

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 2D SiO2 Growth Kinetics

• 950 °C oxidation (left), 1100 °C oxidation right

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• These effects were investigated in detail experimentally by Kao et. al. about
10 years ago.

• Typical experimental
results (from Kao et.al.)
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 Trends
• Improve Si/SiO2 interface properties
– non-stoichometric monolayer due to incomplete oxidation - dangling
bonds
– strained region (1-4 nm) due to lattice mismatch
Solve by
– Fluorine incorporation (Si-F)
– Nitridation of oxides N2O, NH3 (Si-N)

Further: Si-N: improved barrier to B penetration

Optimum: N2O; 0.5 - 1 at% N at interface
• Ultra thin dielectrics
down to 2 nm (<0.1 mm MOS)
• Deposited gate dielectrics (less strain, less defects)
• Ultra clean technology (reduce defect density)
• Cluster tools (more clean process) 39
 Summarisation

• Furnace oxidation is very well controlled process and is

widely used in IC fabrication
• Model of Deal-Grove widely accepted, except for thin oxide
growth in dry O2
• Oxide growth rate depends on crystal orientation, mechanical
stress, ambient (dry, wet, pressure, impurities, …)
• Si(100) most used material
• LOCOS - STI
• Electrical characterisation of quality of oxide
• Trends to improve quality

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