Introduction to Microfabrication Technology

(24B11EC111)
Unit-2
Lecture-9-11
(Oxidation: Growth mechanism & kinetics, Silicon oxidation model, interface
considerations, orientation dependence of oxidation rates thin oxides. Oxidation
technique & systems dry & wet oxidation. Masking properties of SiO2, Device
Isolation techniques)

1
 Thermal Oxidation
• When silicon dioxide is formed by deposition, both silicon and oxygen are conveyed to the wafer surface
and reacted there .
• In thermal oxidation, however, there is a direct reaction between atoms near the surface of the wafer and
oxygen supplied in a high-temperature furnace ( structure is amorphous).
• The interface between silicon and thermally grown SiO2 has stable and controllable electrical properties.
• In addition, the quartz furnace tube and other fixtures start to soften and degrade above 1150°C.
• The oxidizing ambient can be dry oxygen, water vapor,
 Conceptual Si Oxidation System
Thermal Oxidation
•Heat is added to the oxidation tube during the reaction between
oxidants and silicon
- 900-1,200C temperature range
- Oxide growth rate increases as a result of heat
• Used to grow oxides between 60-10,000Å
 Thermal Oxidation Equipment
Oxidation occurs in tube furnace
- Vertical Tube Furnace
- Horizontal Tube Furnace

Bubbler

Wet Thermal Oxidation Techniques

 Oxidation Process

Thermal Oxidation Techniques

• Wet Oxidation
Si (solid) + H2O SiO2 (solid) + 2H2
• Dry Oxidation
Si (solid) + O2 (gas) SiO2(solid)
 Thermal Oxidation Process
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
 Dry Thermal Oxidation Process
Thin Oxide Growth : Thin oxides grown (<150Å) for features
smaller than 1 micrometer
- MOS transistors, MOS gates, and dielectric components
•Additional of chemical species to oxygen decreases oxide growth
rate (only in special cases)
The goal of oxidation is to grow a
- Hydrochloric acid (HCI)
high quality oxide layer on a silicon
- Trichloroethylene (TCE)
substrate
- Trichloroethane (TCA)
• Decreasing pressure slows down oxide growth rate

Wet Thermal Oxidation

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
Thickness of Si consumed during oxidation
 Kinetics of Si02 Growth ‐ Oxide Growth Mechanism

1. Oxidant (O2) reacts with silicon atoms

2. Silicon atoms are consumed by reaction
3. Layer of oxide forms on silicon surface
 Oxide Growth Mechanism (1)

Linear Model :
• Linear (first) Stage of Oxidation
‐ Chemical reaction between silicon and oxidants at wafer surface.
‐ Reaction limited by number of silicon atoms available to react with oxidants.
‐ During the first 500Å of oxide growth, the oxide grows linearly with time.
‐ Growth rate begins to slow down as oxide layer grows.

Oxide Growth Mechanism (2)

Parabolic Model :

Parabolic Stage
‐ Begins when 1,000Å of oxide has been grown on silicon
‐ Silicon atoms are no longer exposed directly to oxidants
‐ Oxidants diffuse through oxide to reach silicon
‐ Reaction limited by diffusion rate of oxidant
 SiO2 Growth Kinetics: (Deal Grove Model)

• The basic model for oxidation (linear parabolic model) was developed in
1965 by Deal and Grove.

Si + O 2 → SiO 2 (1)

Si + 2H 2 O → SiO 2 + 2H 2 (2)
Deal‐Grove Model (1)
 Deal Grove Model
0.01 - 1 µm 500 µm
xO

CG

CS
CO

CI
C
I
Gas Oxide Silicon

F1 F2 F3

Where, (CG - CS) is oxidant concentration difference between main

gas flow and oxide surface.
CO and CI are the oxidant concentration at just inside the
oxide surface and SiO2/Si interface respectively.
 Deal Grove Model
The flux representing the transport of oxidant in the gas phase to the
oxide surface,

F1 = h G (C G − C S ) (3)
Where, hG is mass transfer coefficient

CO is given as by Henry’s Law

CO = HPS (4)
Where, PS is the partial pressure of species at the solid surface

The oxidant concentration in the oxide, C* is given as

C* = HPG (5)
Where, PG is the bulk gas pressure
 Deal Grove Model
From the ideal gas law,

CG = PG / kT and CS = PS / kT (6)
By substituting equations 4, 5 and 6 in equation 3, we get

F1 = h (C* - CO) (7)

Where, h = hG / HkT

The flux representing the diffusion of oxidant through the oxide to the
SiO2/Si interface is given by Fick’s law,
N  CO − CI 
F2 = D = D  (8)
x  xO 
Where, D is the oxidant diffusivity in the oxide

The flux representing the reaction at SiO2/Si interface is given as

F3 = k S C I (9)
Where, kS is the interface reaction rate constant
 Deal Grove Model

• Under steady state conditions, F1 = F2 = F3 = F so

C* C*
CI =  (10)
k k x k x
1+ S + S O 1+ S O
h D D

* k S xO 
C 1 + 
 D
CO =  C* (11)
k S k S x O
1+ +
h D

• Note that the simplifications are made by considering h very

large as compared to kS which is a very good approximation.
 Deal Grove Model
• Combining (9) and (10), we have the growth rate,
dx = F = k S C*
 k k x  (12)
N 1 1 + S + S O 
dt N 1
 h D 
Where, N1 is the number of oxidant molecules incorporated per unit
volume of oxide grown.
• Integrating this equation, results in the linear parabolic model.
x2O − x2i x O − x i
+ =t (13)
B B/ A
2DC*
where B = (parabolic rate constant) (14)
N1
B= C* C*kS
and  (linear rate constant) (15)
A 1 1  N1
N1 + 
kS h
 Deal Grove Model
• (13) can also be written with oxide thickness as a function of time.

A t + −1
xO = 1+ (16)
2 A2 / 4B 
x2i +Axi
where = (17)
B
• The rate constants B and B/A have physical meaning (oxidant
diffusion and interface reaction rate respectively).
These can be described by Arrhenius expressions as

B = C 1 exp (−E1 / kT) (18)

= C 2 exp (−E2 / kT)

B
(19)
A
 Deal Grove Model
Ambient B B/A

Dry O2 C1 = 7.72 x 102 µ2 C2 = 6.23 x 106 µ

hr-1 E1 = 1.23 hr-1 E2 = 2.0
eV eV

Wet O2 C1 = 2.14 x 102 µ2 C2 = 8.95 x 107 µ

hr-1 E1 = 0.71 hr-1 E2 = 2.05
eV eV

H2O C1 = 3.86 x 102 µ2 C2 = 1.63 x 108 µ

hr-1 E1 = 0.78 hr-1 E2 = 2.05
eV eV

• Numbers are for (111) silicon, for (100) divide C2 by 1.68.

Oxidation Techniques and Systems

• .
Dry OXIDATION
WET OXIDATION
Oxide Growth Rate
 Summary of Key Ideas
• Thermal oxidation has been a key element of silicon
technology since its inception.
• Thermally, chemically, mechanically and electrically
stable SiO2 layers on silicon distinguish silicon from
other possible semiconductors.
• The basic growth kinetics of SiO2 on silicon are
controlled by oxidant diffusion and Si/SiO2 interface
chemical reaction (Deal-Grove model).
• This simple Deal-Grove model has been extended to
thin oxides and to incorporate the effect of some
other growth parameters.
•
Making Properties of Silicon dioxide