Oxidation

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Why Wet oxide grows faster than dry oxide ?

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Where N1 is the no. of oxidant molecules incorporated per unit volume of oxide
grown. N1= 2.2x1022cm -3 for O2 oxidation and twice this value for H2O oxidation.
Integrating this equation from an initial oxide thickness xi to a final thickness xo
leads us to our final result describing the oxide growth kinetics:

At 1100*C typical values for C* are = 5x10 cm for dry O2 and = 3x10 19 cm−3
16 -3

for H2O. As a result, both rate constants, B and B/A are much larger for H2O
than for dry O2. Dry O2 oxidations are thus generally useful for producing
oxide films upto 100-200 nm.Films thicker than this would normally be grown
using H2O ambients.

It is also apparent that SiO2 grows much faster in an H2O ambient than it does
in dry O2.

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Effect of Temperature, pressure and crystal orientation on B and B/A

we have seen that the oxidation growth rates are higher for wet oxidation than
for dry oxidation

Now we will see that the growth rates are also higher at higher temperature.
That is if you carry out the oxidation for higher temperature, for a given amount
of time you would expect to grow thicker oxide.

Why?

Diffusivity increase with increase in temperature and also ks .

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Ref: Diffusion in Siliocn Scotten W. Jones

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Ref: Diffusion in Siliocn Scotten W. Jones

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Oxidation is performed at T = 920 oC . Given τ = 50 sec., we monitor x at different times

Time (hour)
0.11 0.3 0.4 0.5 0.6

X (um) 0.041 0.10 0.128 0153 0.177

𝑥 2 +Ax=B(t+τ)

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 (𝑡+𝜏)
𝑥= 𝐵 -A
𝑥

t+τ
Plot x vs
x

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Temperature Dependence of and

Arrhenius relationship

The Arrhenius relationship describes the temperature dependence of

many thermally induced processes, like: chemical reactions, particle
diffusion, evaporation rates, lattice vibrations etc.

The Arrhenius equation says that a given quantity, “α”, has an

exponential dependence on temperature,
𝐸𝐴
𝛼 𝑇 = 𝐴𝑜𝑒𝑥𝑝(− )
𝐾𝐵 𝑇
where
Αo is a pre-factor
EA is the activation energy for the process.

The activation energy represents the energy that must be overcome in

order for a reaction to occur.
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 k = 1.38x10–23 J/K = 8.617x10–5 eV/K.

Oxidation is performed at T = 920 oC . Given τ = 50 sec., we monitor x at different times

Temp. (oC)
920 1000 1100 1200

B/A (um/ H) 0.406 1.27 4.64 14.4

B (um2/ H) 0.203 .287 0.510 0.720

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 −𝐸1 𝐵 𝐶∗ 𝐶∗𝐾𝑠
𝐵= 𝐶1𝑒𝑥𝑝 𝐾𝑇 = =
𝐴 𝑁1( 1 + 1 ) 𝑁1
𝐾𝑠 ℎ
𝐵 −𝐸1
= 𝐶2𝑒𝑥𝑝 𝐾𝑇 2𝐷𝐶∗
𝐴 B is
𝑁1
𝐵
𝑥= ∗ 𝑡+𝜏
𝐴

𝑥 = 𝐵𝑡

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Dependence of and on Crystal Orientation

B/A = Reaction rate limited and thus orientation of silicon wafer

becomes important during initial growth of oxide. As, later process
becomes diffusion limited orientation becomes insignificant

And thus B is not affected by orientation of wafer.

Now surface density of (111) plane is around 1.68 time of (100) wafer.

So, C2 (111) = 1.68C2 (100)

Or
[B/A(111)]o =1.68 [B/A (100)]o
But
B (111) = B (100)

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Pressure Dependence of and

For H2O ambient the pressure dependence of the

parabolic and linear rate constants are:

In contrast to wet oxidation for dry oxidation

the pressure dependence is inconsistent with
the linear parabolic model.

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(100)

(111)

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Limitation of D-G model

Thin Oxide ??

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Dopant Redistribution

As oxidation proceeds, the interface advances into the silicon. A doping

impurities initially presented in the silicon will distribute at the interface. This
results in an abrupt change in the impurities concentration across the
interface.

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Segregation coefficient:

Impurities (dopants) will prefer to go into the oxide or will stay back into
silicon?

This is going to vary from impurity to impurity.

Other factor that influence the redistribution is diffusivity.

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Dopant Redistribution

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When

m <1,

Means the equilibrium concentration of the dopant is less in silicon compared

to in silicon dioxide.

m>1

Means the equilibrium concentration of the dopant in silicon is greater than in

case of silicon dioxide.

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Case 1:

The segregation coefficient is chosen to be m < 1

This corresponding to a situation where the oxide takes up the

impurity.

In such a case the impurity will be depleted from the silicon.

Rapid diffusion of the impurity through the oxide region will, of

course, increase the degree of depletion.

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Dopant Redistribution

e. g. B (m = 0.3) e. g. B with ambient of H2

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Case 2:

The segregation coefficient is chosen to be m > 1

This corresponding to a situation where the oxide rejects the

impurity.

If the diffusion through the oxide layer is relatively slow, oxidation
will result in a pile-up of the impurity within the silicon.

If diffusion through the oxide is very rapid, so much impurity may
escape from the solid to the gaseous ambient that the over-all effect
will be a depletion of the impurity.

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Dopant Redistribution

Phosphorous (P) Gallium (Ga)

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Masking Property of Silicon Dioxide

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High Doping concentration effect

Dopants in silicon

• Dopants increase oxide growth rate.

• Dopants cause differential oxidation - Results in the formation of

steps - Affects etching process.

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Thermal Oxidation-Poly versus single crystal Si

 Deal-Grove model is not good for Polysilicon

 Oxidant molecules diffuse rapidly along grain boundaries, so that poly-

silicon oxidizes more rapidly than single-crystal silicon

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Thermal Oxidation-Thickness of existing oxide

Native oxide and oxide in previous fabrication steps must be taken into account when
modeling oxidation.

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Graphical Method

Thermal
Oxidation on
<100> Silicon

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Thermal
Oxidation on
<111> Silicon

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(a) According to Fig., it would take
2.8 hr to grow 0.2 μm oxide in dry
oxygen at 1100 C.

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Oxide Quality
In real MOS devices, there is
always some charge in the oxide
and at the Si/oxide interface.
• In the oxide:
– Trapped charge Qot
• High-energy electrons
and/or holes injected into
oxide
– Mobile charge QM
• Alkali-metal ions, which
have sufficient mobility to
drift in oxide under an
applied electric field
• At the interface:
– Fixed charge
– Trapped charge QIT
• Dangling bonds
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Fixed positive charges

Fixed positive charges are there because of incomplete oxidation.

The term fixed oxide charge obviously signifies that these charges are fixed. They
cannot move.

The composition of the oxide is SiOx where x is less than 2.

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Interface trap charges

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One way to reduce this interface trapped charge is to have a post oxidation
annealing in hydrogen at comparatively lower temperature that is at around
4500C. So, what happens in that case? The dangling bonds which are present at
the interface, hydrogen reacts with silicon, satisfies these dangling bonds and
therefore, the interface charge density is reduced.

–Before annealing, Qit ~ 1011

–After annealing, Qit ~ 1010

Qit(100) is lower in than Qit(111)

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Trap charges inside the oxide

Due to hot electrons.

Ion implantation

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Mobile charges

Major source is water. Unless your water is properly deionized, they

contain a lot of dissolved sodium and potassium salts.

As the names imply these charge are mobile in nature and can be find
anywhere in the oxide.

Since these charges are free to move, it is easy to understand

that whenever a gate voltage is applied, depending on the polarity
and magnitude of the gate voltage, these ions will move towards
the metal gate or move inside towards the silicon-silicon dioxide
interface and thus it will affect the device performance.

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 Use Cl during oxidation
 helps trap Na
 helps create volatile compounds of metals (contaminant from furnace etc)
 use 3% HCl or Trichloro ethylene (TCE)

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Oxide thickness Measurements Techniques

1. Thickness determination from the color.

2. Stylus profilometer (mechanical profilometer)

3. Ellipsometry.

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Thickness determination by looking the color

• Our eye can tell the color difference between two films having 10nm thickness
difference.

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• Interference effects can give a thin transparent layer a characteristic color
Color depends on:

film thickness
index of refraction

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Surface profilometry

Oxide etched away by HF over

part of the wafer and a
Stylus
mechanical stylus is dragged
over the resulting step.

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Optical thickness measurement: ellipsometry
Quarter
Light wave plate
source Filter Polarizer Analyzer Detector

Film being
measured
Substrate

• After quarter wave plate, the linear polarized light becomes circular polarized,
which is incident on the oxide covered wafer.
• The polarization of the reflected light, which depends on the thickness and
refractive index (usually known) of the oxide layer, is determined and used to
calculate the oxide thickness.

Very accurate (1nm accuracy)

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Basic Concept of Local Oxidation of Si

Why Locally ? Why not

over the entire wafer?

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