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Oxidation

Thermal SiO2 Properties

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 - 900-1,200C temperature range - Oxide growth rate increases as a result of heat Used to grow oxides between 60-10,000

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 1000 thick Slow process - 140 - 250 / hour
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Dry Thermal Oxidation Process


Thin Oxide Growth Thin oxides grown (<150) 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 1000-1200 / hour Preferred oxidation process for growth of thick oxides

Goal of Oxidation Process

The goal of oxidation is to grow a high quality oxide layer on a silicon substrate

Functions of Oxide Layers (1)


Passivation

Physically protects wafers from scratches and particle ..contamination


Traps mobile ions in oxide layer

The oxide layer isolates these ions from the silicon and prevents them from disrupting the performance of the device.

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Function of Oxide Layers (2)


Masking: A layer of oxide grown on wafer prior to the diffusion and ion implantation process steps will act as mask.

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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Thermal Oxidation Equipment


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

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Bubbler
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Wet Thermal Oxidation Techniques

glass flask, referred to as a bubbler contains deionized water and is attached to the oxidation tube. The water is heated (9099 C), and water vapor forms above the deionized water level.
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Bubbler
A carrier gas, nitrogen, is bubbled through the deionized water. As it passes through the vapor it becomes saturated with water. The vapor travels into the oxidation tube, where with additional heating it turns into steam and oxidation occurs. A consistent oxide growth rate is hard to maintain with the bubbler method because of the difficulties involved in controlling both the amount of water vapor entering the oxidation tube and the temperature of the water. The risk of contamination is also high.

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Wet Thermal Oxidation Techniques


Flash System

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Flash System.
A small amount of deionized water is dropped onto a heated quartz surface where it instantly turns into steam. A carrier gas moves the steam into the heated oxidation chamber. As with the bubbler, it is very difficult to achieve a constant rate of oxide growth. Unlike a bubbler, however, the flask is never opened in a flash system so the risk of contamination is low. 20

Wet Thermal Oxidation Techniques


Dryox System

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Dryox System
In a dryox system, oxygen and hydrogen directly enter a heated oxidation tube. In the heated oxidation tube, the two gases mix and form water as steam. The dryox system is preferred oxidation method for advanced devices because the oxide growth rate can be precisely controlled. Mass Flow Controllers regulate the gas flow into the tube, insuring uniform oxide growth. Contamination of the oxide is limited since these gases are clean. One major disadvantage of dryox system is the explosive nature of hydrogen at high temperatures. Safety precautions must be taken to minimize the risk of a hydrogen explosion.
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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 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 500 of oxide growth, the oxide grows linearly with time - Growth rate begins to slow down as oxide layer grows

Oxide Growth Mechanism (2)


Parabolic Stage - Begins when 1,000 of oxide has been grown on silicon - Silicon atoms are no longer exposed directly to oxidants - Oxidants diffuse through oxide to reach silicon The oxidation of silicon during this stage occurs at the silicon/silicon dioxide interface. As oxidation continues, the silicon dioxide layer thickens, and the distance the oxidants must travel to reach the silicon increases. - Reaction limited by diffusion rate of oxidant
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Deal-Grove Model (1)

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F1 CG O2 concentration in the gas (bulk) Cs - O2 concentration in the gas-SiO2 interface C0 - O2 concentration in the SiO2 surface (in the solid) Ci - O2 concentration in the Si-SiO2 interface At equillibrium we will have F1 =F2 = F3 Temperature Range-700-1300 celcius. Pressure- 0.2-1.0 atm Oxide Thicknes-300-20000 Angstrom. F1 in the linear approximation can be assumed to be proportional to the concentration difference between bulk gas and surface. F2 the diffussion flux through the oxide layer, will also be written as a difference equation.
F3 is the chemical reaction flux = (rate)X(concentration)
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Deal-Grove Model (1) - Gas transport from the bulk

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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Factors that Affect Oxidation

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High Doping concentration effect


When high concentrations of dopants are present in silicon wafers, they tend to increase the oxide growth rate. - During Linear Stage of oxidation N-type dopants increase growth rate. For example, throughout the Linear Stage of oxidation, doped phosphorous continually moves from within the silicon to the silicon surface of the wafer. This constant supply of phosphorous on the silicon surface increases the oxide growth rate.

Dopants cause differential oxidation - Results in the formation of steps - Affects etching process
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High Doping concentration effect Once the Parabolic Stage begins, the presence of phosphorous at the
silicon/oxide interface no longer impacts the growth rate. Instead, it is the presence of P-type dopants in the silicon dioxide layer that influences the growth rate. During the Parabolic Stage of oxidation a dopant, such as boron, moves from the silicon into the silicon dioxide layer where it weakens the bond structures. The weakened bonds allow oxygen and water to diffuse faster through the silicon dioxide resulting in a faster oxide growth rate. Since oxide grows faster in doped regions of the wafer, the oxide will not be of uniform thickness across the wafer. This results in differential oxidation and produces unwanted steps on the wafer as oxidation occurs at unequal rates across the wafer. As the thicker oxide layers consume more silicon, steps are formed which may affect the operation of the device. The variation in oxide thickness across the wafer must also be taken into consideration during future etching. The etch process must be designed to remove the thicker oxide layers, without overetching the areas with thinner oxide layers.
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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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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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Oxidation Techniques and System


1. Pre-oxidation Cleaning. 2. Dry, Wet Oxidation.

3. High Pressure Oxidation.


4. Plasma Oxidation.
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Pre-oxidation Cleaning
Wafer must be cleaned to eliminate both organic & inorganic contamination. Chemical cleaning involves removing organic contaminates, followed by inorganic ion and atom removal. Common cleaning procedurewater+H2O2+NH4OH For removing heavy metals:-water+H2O2+HCl
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Dry Oxidation- With O2 or HCl.

Dry, Wet Oxidation

Wet Oxidation- using H2 and O2 to form water vapor and then oxidation.

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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 30C

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High Pressure Oxidation


The graphs illustrate both pressure and crystal orientation effects. The graph on the right is for a reaction time of 1 hour., the oxide thickness increases with both pressure and temperature.

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Dopant Redistribution During Thermal Oxidation


Dopant concentration Dopant concentration

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Oxidation affects the electrical performance of the semiconductor device as well. N-type dopants have a higher solubility in silicon (Si) than in silicon dioxide (SiO2). Therefore as the silicon dioxide (SiO2) layer grows during oxidation, the N-type dopants (phosphorous, arsenic, antimony) move into the silicon (Si) layer and away from the oxide layer. This results in a higher concentration level of N-dopants in the silicon (Si) layer, and a build up of N-dopants between the silicon (Si) and silicon dioxide (SiO2) layer. On the other hand, P -type dopants (boron (B)) are drawn into the silicon dioxide layer and actually deplete the silicon (Si) layer of P-dopants. Since the location and concentrations of dopants can affect the performance of a device, the movement of dopants during oxidation must be monitored. Upon completion of the oxidation process, wafers undergo inspection techniques that evaluate the location and concentration of dopants to 46 ensure that the functioning of the device will not be disrupted.

Dopant Redistribution During Thermal Oxidation

Oxide inspection techniques


Surface inspection:-A high-intensity ultraviolet (UV) light is used to evaluate the surface for stains, particulates, and irregularities. Oxide thickness:- The techniques that determine oxide thickness use scanning electron microscopes (SEMs), fringe counting, interference, stylus apparatus, ellipsometers, and color comparison. The wafer is also tested for the number of mobile ionic contaminants (minimal number desired), dielectric strength (non- conducting property of the oxide), and refraction of the oxide (which tests for impurities). Oxide thickness is one of the most important inspection steps in wafer fabrication. Oxide cleanliness:- Capacitance-voltage techniques are used to detect the total number of mobile ionic contaminates present in the oxide. A low level of ionic contaminates indicates that the entire oxidation system is clean. If the level of ionic contaminates is high, then technicians must determine where the contamination is coming from and inspect the tubes, gases, and wafers as well as the cleaning process. Dielectric strength, and index refraction values both are indicators of oxide cleanliness.

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Oxides as Dopant Masks


SiO2 can provide a selective mask against diffusion at high temperatures. Oxides used for masking are ~ 0.5-1 mm thick.
Dopants
B Ga P As Sb

Diffusion Constants at 1100 oC (cm2/s)


3.4 10-17 2.0 10-14 5.3 10-11 2.9 10-16 2.0 10-13 1.2 10-16 3.5 10-15 9.9 10-17

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Dry vs. Wet Oxides


Wet oxides are usually used for masking SiO2 growth rate is much higher when water is the oxidant. Dry oxidation results in a higher quality oxide that is denser and has a higher breakdown voltage (5 10 MV/cm). Thin gate oxides in MOS devices are usually formed using dry oxidation.
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Oxide Charge Locations

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Oxide Charge Definitions


1. Interface trapped charge (Qit): located at Si/SiO2 interface 2. Fixed oxide charge (Qf): positive charge located within 3nm of Si/SiO2 interface

3. Oxide trapped charges (Qot): associated with defects in the SiO2


4. Mobile ionic charges (Qm): result from contamination from Na or other alkali ions
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Methods for measuring thickness of oxide layer


1. Profilometry. 2. Ellipsometry.

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