OXIDATION

Thermal Oxidation
Oxidation is a process used in wafer fabrication. The goal of oxidation is to grow a high quality oxide layer on a silicon substrate. During oxidation a chemical reaction between the oxidants and the silicon atoms produces a layer of oxide on the silicon surface of the wafer. It is often the first step in wafer fabrication Oxidation takes place in an oxidation tube. During the reaction silicon reacts with oxidants to form silicon oxide layers. Typical operating temperature is between 900C and 1,200C. The oxide growth rate increases with temperature.

Generally, this technique is used to grow oxides between 60 and 100,000 thick.

Thermal oxidation of silicon is divided into two classes dry and wet. Dry Oxidation Si (s) + O2 (g) SiO2 (s) Wet Oxidation Si (s) + 2 H2O (g) SiO2 (s) + 2 H2 (g)

Dry Oxidation
1. During dry oxidation, dry oxygen is introduced into the process tube where it reacts with silicon.

2. Dry oxidation is a slow process that grows films at a rate between 140 and 250/hour. 3. It is only used in industry to grow thin oxides (<1000).

Si (s) + O2 (g) SiO2 (s)

Wet Oxidation During wet oxidation, water vapour is introduced into the heated oxidation tube. Because water molecules are smaller in size than oxygen molecules, they diffuse faster in silicon dioxide and the oxide growth rate increases.

The wet oxidation growth rate is 1000 to 1200 /hour, so wet oxidation is the preferred method to grow thick oxides.
Si (s) + 2 H2O (g) SiO2 (s) + 2 H2 (g)

 As a general principle, the amount of silicon consumed in the oxidation reaction is 45% of the final oxide thickness. For example, growing 10,000 of oxide consumes 4,400 of silicon.

Oxide quality
Wet oxidation is preferred to dry oxidation for growing thick oxides, because of the higher growth rate.

Fast oxidation leaves more dangling bonds at the silicon interface, which allow current to leak along the interface.
Wet oxidation also yields a lower-density oxide, with lower dielectric strength.

KINETICS OF OXIDE GROWTH

Linear Parabolic Model

The Linear Parabolic Model developed by Deal and Grove demonstrates how silicon dioxide is grown on a silicon substrate during oxidation under wet and dry conditions. Was published in 1965 by Bruce Deal and Andrew Grove, of Fairchild Semiconductor The model identifies and defines two different stages in the oxidation of silicon: 1. Linear 2. Parabolic

Linear (first) Stage of Oxidation

As the first phase in oxide growth, the Linear Stage refers to the chemical reaction resulting from the direct contact between the silicon and the oxidants at the surface of the wafer. The reaction is limited by the number of silicon atoms available to react with the oxidants. For approximately the first 500 , the oxide grows linearly with time. From that point on, the reaction rate begins to slow down as a direct result of the silicon dioxide layer covering the silicon atoms. As the silicon dioxide layer grows, it eventually prevents the oxidants from coming in direct contact with the silicon atoms . The reaction of the oxygen at the silicon/silicon dioxide interface limits the oxide growth in this stage.

Parabolic (second) Stage

The Parabolic Stage of oxidation begins when approximately 1,000 of silicon dioxide has been grown on the silicon substrate. At this point, the silicon atoms are no longer exposed to the oxidants and the oxidants begin to diffuse through the silicon dioxide in order to reach the Si. 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. The oxide growth rate is limited by the diffusion of the oxidants through silicon dioxide.

KINETICS OF SILICON DIOXIDE GROWTH

The kinetics of SiO2 growth are three step:

1. First, the oxidant (H2O or O2) reacts with silicon atoms; 2.Then silicon atoms are consumed by the reaction; 3.and finally a layer of oxide forms on silicon surface.

Concept and Formulation

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If one assumes that the oxidation process is dominated by the inward movement of the oxidant species, the transported species must go through the following stages:

(1) It is transported from the bulk of the oxidizing gas to the outer surface of oxide, where it is adsorbed. (2) It is transported across the oxide film towards silicon.
(3) It reacts at the interface with silicon and form a new layer of SiO2

 Each of these steps can be described as independent flux equation. The adsorption of oxidants is written as

Where h is the gas-phase transport coefficient, C* is the equilibrium concentration of the oxidants in the surrounding gas atmosphere, and Co is the concentration of oxidants at the gas-oxide surface at any given time.

Henrys Law
It states that in equilibrium the concentration of a species within a solid is proportional to the partial pressure in the surrounding gas.

C* = concentration of a species within a solid

p = partial pressure of the oxidant in the gas

 The flux F2 represents the diffusion of the oxidants through the oxide layer to the Si-SiO2 interface , which can be expressed as

Where D is the oxidant diffusivity in oxide Cs is the oxidant concentration at oxide-Si interface Xo represents oxide thickness

NOTE PROCESS IS STEADY-STATE

The third part of the oxidation process is the flux of the oxidants consumed by the oxidation reaction at the oxide-silicon interface given by

with ks as the surface rate constant Cs is oxidant concentration at the interface The rate at which this reaction takes place should proportional to the oxidant concentration at the interface.

One-dimensional model for the oxidation of silicon.

Deal and Grove assumed that in the steady state condition these three fluxes are equal, which allows to express them as :

The rate of oxide growth is proportional to the flux of oxidant molecules,

where N is the NUMBER of oxidant molecules incorporated per unit volume. The differential equation can be simplified as :

The physical parameters A an B are:-

where,

B/A = Linear Rate Constant B = Parabolic Rate Constant

Temperature Dependence of B and B/A

In order to model the corresponding growth rate for different temperatures, the values for B and B/A must change with temperature. The oxidation rate increases with higher temperature, and so the values of B and B/A must also increase. It was found experimentally that both and are well described by Arrhenius expressions of the form :

E1 and E2 are the activation energies C1 and C2 are the pre- exponential constants

B and B/A versus temperature for (111) oriented silicon for wet and dry oxidation.

Pressure Dependence of B and B/A

Oxide growth rate should be directly proportional to the oxidant pressure . If Henrys law holds and C* is proportional to the pressure, both B and B/A are proportional to p. Therefore oxide rate should be proportional to p.

 Where Pressure dependence of comes exclusively from C*, because C* as determined in Henrys law must be Thus diffusion constant D for the oxidants in the solid phase can be assumed constant.

Dependence of B and B/A on Crystal Orientation

Except in the region very near the Si/SiO2 interface, the oxide grows on silicon in an amorphous way.

So it does not incorporate any information about the underlying silicon crystal structure.
Therefore, the parabolic rate constant B should not be orientation dependent, since B represents the oxidant diffusion through the SiO2 .

 On the other hand B/A should be orientation dependent, because it involves the reaction at the Si/SiO2 interface. This reaction surely involves silicon atoms and should be affected by the number of available reaction sites. It was found experimentally, that there are two extremes of the linear rate constant B/A. The minimum was found for (100) oriented silicon whereas the maximum is at (111) orientation, and all other orientation are normally between these two extremes.

Drawbacks with Deal-Grove Model It has been observed in many experiments that there is a fast and non-linear oxide growth in the initial stage of dry oxidation . One weakness of the model is the impossibility to predict the initial stage of the oxidation growth. Even with the best fit, the approximately first 30 nm of the oxide thickness can not be forecasted with the linear parabolic model, because the oxide growth is fast and non-linear .

PLASMA OXIDATION
There are basically 3 different techniques for the plasma oxidation of silicon and other semiconductors. Some systems use a DC glow discharge to sustain the plasma , while in other systems the plasma is excited via capacitively couple electrodes .

 An electric glow discharge tube showing the different regions in the gas that appear when a high DC voltage is applied between the electrodes

When a DC bias is superimposed across the discharge this latter method is then known as plasma anodization.

 The oxidation rate for the plasma oxide is more than double that for the thermal oxide at approximately half the oxidation temperature. The form of the curves is very similar in both cases and may be modelled by an initial region in which the growth rate is linear with time, followed by a region in which growth is parabolic with time.

MECHANISM OF GROWTH
Various ideas have been advanced to explain the mechanism of the growth of silicon dioxide upon silicon in an oxygen plasma. Since oxidation proceeds most rapidly when the silicon is biased positively, i.e. when it collects negative charges, it has been concluded that a negative oxygen species is responsible for the oxidation process . One theory proposes field-assisted cation (Si+) and anion (0-) diffusion through the growing oxide film.

 As oxidation progresses there is a build-up of charge in the oxide film which inhibits the transport of oxygen ions. In the later stages of oxide growth, therefore, the growth rate falls with time.

COMPARISON B/W DRY,WET &PLASMA OXIDATION

INFLUENCE OF TEMPERATURE: The oxidation rate increases significantly with the temperature in the furnace for dry as well as for wet oxidation. Plasma oxidation is a promising low-temperature alternative for the formation of high-quality insulating layers on semiconductors. The rapid oxidation rate coupled with the marked reduction in lateral oxidation make the technique attractive for novel MOS isolation structures.

INFLUENCE OF PRESSURE
The oxidation rate increases with the pressure in the furnace for dry and wet oxidation in nearly the same way. The principal advantages of higher pressure oxidation over conventional atmospheric oxidation are the faster oxidation rate and the lower processing temperature generally employed . Both lead to less impurity diffusion and minimum junction movement during the several oxidation steps which are necessary in the manufacturing of highdensity multilayer IC devices.

INFLUENCE OF CRYSTAL ORIENTATION

The studies of oxidation have shown that the oxidation rate also depends on the crystal orientation of the silicon substrate. Experiments have demonstrated many times that the oxide growth is faster on (111) oriented surfaces than on (100) oriented at any temperature for dry as well as wet oxidation. Furthermore, for wet oxidation, it was found that the (111) and (100) orientation represent the upper and the lower bound for oxidation rates, respectively. Therefore, the growth rate for all other orientations lies between these two extremal values .

 The effects of silicon crystal orientation on the rate of growth and oxide charge of layers grown in a plasma of oxygen with and without chlorine in the gas stream are described. It is shown that plasma oxide growth rate in the initial linear region is orientation-independent and is not, therefore, surface-reaction-rate-limited as with thermal oxidation. Strong orientation effects are seen, however, in the oxide charge, the results being qualitatively similar to those associated with thermal oxidation. The (111) surface is found to have higher oxide charge levels than (100).

EFFECT OF IMPURITIES
The following impurities affect the oxidation rate: Sodium,group III & V elements,halogen. High concentrations of sodium influence the oxidation rate by changing the bond structure in the oxide,thereby enhancing the diffusion and concentration of the oxygen molecules in the oxide.

 During thermal oxidation process,an interface is formed,which separates the silicon from silicon dioxide. The redistribution of dopants(group III or V elements)at the interface influences the oxidation behaviour .If the dopant segregates into the oxide and remains there(such as boron) ,the bond structure in the silica weakens.This weakend strucure permits an inc. incorporation and diffusivity of the oxidizing species through the oxide,thus enhancing the oxidation rate.

 Phosphorous impurity shows opposite effect to that of boron,i.e, an impurity segregation occurs in silicon rather than sio2. Halogen (such as chlorine) impurities are intentionally introduced into the oxidation ambient to improve both the oxide and the underlying silicon properties. Oxide improvement occurs because there is a reduction in sodium ion contamination,increase in oxide breakdown strength,and a reduction in interface trap density .

APPLICATIONS
Good Electrical properties Birds beak region is much reduced, hence finds much application in LOCOS process. Improved time-dependent dielectric breakdown (TDDB) reliability

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