Microelectronics Processing

Oxidation

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 Content

 Properties of SiO2  Factors affecting

 Oxidation Process oxidation
 Doping
 Functions of SiO2  Substrate
 Equipment for Si Orientation
Oxidation  Pressure
 Mechanism of Si  Chlorine addition
Oxidation  Dopant Redistribution
 Polysilicon Oxidation
 Additional Oxidation
Processes
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 Thermal SiO2 Properties

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 Thermal SiO2 Properties (cont.)

(7) Amorphous material

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 Oxidation Process
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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 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

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 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
Microelectronics / hour
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 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)
- Hydrochloric acid (HCI)
- Trichloroethylene (TCE)
- Trichloroethane (TCA)
• Decreasing pressure slows down oxide growth rate

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 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

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 Goal of Oxidation Process

The goal of oxidation is to grow a high quality

oxide layer on a silicon substrate

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 Functions of Oxide Layers (1)

Passivation
• Physically protects wafers from scratches and particle
..contamination
• Traps mobile ions in oxide layer

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 Function of Oxide Layers (2)
Masking
• During Diffusion, Ion Implantation, and Etching

SiO2

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 Function of Oxide Layers (3)
Insulating Material
• Gate region
- Thin layer of oxide
- Allows an inductive charge to pass between gate
metal and silicon

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 Function of Oxide Layers (4)
Dielectric Material
• Insulating material between metal layers
- Field Oxide

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 Function of Oxide Layers (5)

Dielectric Material
• Tunneling oxide
- Allows electrons to pass through oxide without
resistance

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Functions and Thickness of Oxide Layers

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 Projections for Si Technology
Future projections for silicon technology taken from the SIA NTRS*
Year of First DRAM 1997 1999 2003 2006 2009 2012
ShipmentFeature Size (nm)
Minimum 250 180 130 100 70 50
DRAM Bits/Chip 256M 1G 4G 16G 64G 256G
Minimum Supply Voltage 1.8-2.5 1.5-1.8 1.2-1.5 0.9-1.2 0.6-0.9 0.5-0.6
(volts)
Gate Oxide Tox Equivalent 4-5 3-4 2-3 1.5-2 <1.5 <1.0
(nm)
Thickness Control (% 3 σ) ±4 ±4 ± 4-6 ± 4-8 ± 4-8 ± 4-8
Equivalent Maximum E-field 4-5 5 5 >5 >5 >5
(MV cm-1 )
Gate Oxide Leakage (DRAM) <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
(pA μm-2)
Tunnel Oxide (nm) 8.5 8 7.5 7 6.5 6
Maximum Wiring Levels 6 6-7 7 7-8 8-9 9
Dielectric Constant, K for 3.0-4.1 2.5-3.0 1.5-2.0 1.5-2.0 <1.5 <1.5
Intermetal Insulator
*
NTRS- National Technology Roadmap for Semiconductors

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 Thermal Oxidation Equipment
Oxidation occurs in tube furnace
- Vertical Tube Furnace
- Horizontal Tube Furnace

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Wet Thermal Oxidation Techniques
Bubbler

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Wet Thermal Oxidation Techniques

Flash System

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Wet Thermal Oxidation Techniques

Dryox System

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 Thickness of Si consumed during
oxidation

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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

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 Oxide Growth Mechanism (1)

Linear Parabolic 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

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 Oxide Growth Mechanism (2)

Linear 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

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 Deal-Grove Model (1)

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 Deal-Grove Model (2)

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 Deal-Grove Model (3)

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 Deal-Grove Model (4)

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 Deal-Grove Model (5)

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 Deal-Grove Model (6)

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 Deal-Grove Model (7)

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 Deal-Grove Model (8)

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 Deal-Grove Model (9)

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 Limiting cases in Si oxidation

(a) (b)
a) Interface reaction is the rate limiting step
b) Limited by oxidant transport through the SiO2 rate
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 Deal-Grove Model Parameters

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Deal-Grove model (10) - Effect of temperature on
the rate constants B, and B/A
B(T)=Boexp(-EA/kT)
(B/A)(T)=(B/A)oexp(-EA/kT)

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 Values for the coefficients Do and EA
Each of the coefficients B, and B/A has an Arrhenius relationship
of the type: D=D0exp(-EA/kT)

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 Diffusivities of some materials in
silicon glass

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 Examples

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Effect of Xi on Wafer Topography (1)

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Effect of Xi on Wafer Topography (2)

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 Factors that Affect
Oxidation

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 High Doping concentration effect

Dopants in silicon
• Dopants increase oxide growth rate
- During Linear Stage of oxidation N-type dopants
increase growth rate
• Dopants cause differential oxidation
- Results in the formation of steps
- Affects etching process

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 High Doping concentration effect

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 Growth Rate 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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Origin of Substrate Orientation Effect

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Substrate Orientation Effect - Oxidation
Charts

(a) (b)
Growth of SiO2 on <100> and <111> oriented
Si wafers:
(a) dry oxygen; (b) steam.
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 Effect of High Pressure Oxidation
Atmospheric pressure
- Slow oxide growth rate
• An increase in pressure increase oxide growth rate
• Increasing pressure allows temperature to be
..decreased
- Oxide growth rate remains the same
- For every 10atm of pressure the temperature can
be reduced 30°C
•Dry Thermal oxidation
- Pressure in oxidation tube increased
• Wet Thermal oxidation
- Steam pressure introduced into oxidation tube
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 Effect of High Pressure Oxidation

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 High Pressure Oxidation

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 Chlorine added with Oxidants

Chlorine species
- Anhydrous chloride (CI2)
- Anhydrous hydrogen chloride (HCI)
- Trichloroethylene – TCE
- Trichloroethane – TCA
• Oxide growth rate increases
• Oxide cleaner
• Device performance is improved

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 Oxidation With Cl Containing Gas

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 Effect of HCl on Oxidation Rate

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 Local Oxidation of Si (LOCOS)

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 Local Oxidation

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Dopant Redistribution During Thermal
Oxidation (1)
Dopant concentration Dopant concentration

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Dopant Redistribution During Thermal
Oxidation (2)

Dopants affect device performance

- The change in dopant location and concentration
during oxidation can affect the device operation
- N-type dopants move deeper into silicon so high
concentration at the silicon/silicon dioxide interface
- P-type dopants move into the silicon dioxide and
deplete the silicon layer

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Dopant Redistribution During Thermal
Oxidation (3)

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Dopant Redistribution During Thermal
Oxidation (4)

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 Dopant Redistribution During Thermal
Oxidation (5)

) boron
) boron with
ydrogen ambient
Phosphorus
) gallium

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 Thin Oxide Growth

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 Structure of SiO2-Si Interface

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 Thin Oxide Tunneling Current
Comparison

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 Polycrystalline Si Oxidation

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 Polysilicon Oxidation

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 Oxide inspection techniques

Surface Inspection
Oxide Thickness
Oxide Cleanliness

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 Additional (Chemical) Oxidation
Processes
Anodic Oxidation Process
• Wafer is attached to a positive electrode
• Wafer is immersed in bath of potassium nitrate ..
(KNO3)
• Immersion tank contains a negative electrode
• Oxygen produced when current is applied
• Reaction between silicon and oxygen occurs

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 Additional Oxidation Processes

Anodic Oxidation Characteristics

• Oxidation reaction occurs at the surface of the oxide
- Silicon atoms move to top of oxide layer during
oxidation
• Used to grow oxide on wafers that will be tested for
..dopant location and concentration

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 Additional Oxidation Processes
Rapid Thermal Oxidation Equipment

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 Additional Processes - Thermal
Nitridation
Thermal Nitridation Characteristics
• Alternative method to Oxidation
• Oxidant is nitrogen
- Pure ammonia gas (NH3)
- Ammonia plasma
• Reaction produces silicon nitride (Si3N4)
- Reaction occurs at the gas/silicon nitride interface
- Silicon atoms diffuse through silicon nitride layer
during process
• Silicon nitride is a good substitute for silicon dioxide
- Silicon nitride is denser than silicon dioxide
- Silicon nitride has a higher dielectric rating
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 Additional Oxidation Processes

Thermal Nitridation Disadvantage

• Process puts high level of strain on wafer
- Thermal expansion rate of silicon nitride is 2 times
greater than silicon dioxide
- High temperature processing techniques (950-
1200°C) results in wafer strain

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