Thermal Oxidation of Si-Lecture Notes

SiO 2 layers are frequently formed by thermal oxidation of Si in the range 900-1200C.

There are two commonly used chemical reactions

(i) dry oxidation Si(solid)+O 2 (gas) SiO 2 (solid)
(ii) wet oxidation Si(solid)+ 2H 2 O(vapor) SiO 2 (solid)+ 2H 2

Wet oxidation generally proceeds much faster than dry oxidation

The SiO 2 grown by thermal oxidation are amorphous (the rate of transformation to the
crystalline form is negligible below 1000C).Thus there is an absence of grain boundary
diffusion of impurities, helping maintain a pure interface with the Si .However, the SiO 2
does have a short range order and consists of a network of Si atoms sitting at the center of
oxygen polyhedra.

In growing the SiO 2 , some of the underlying Si is consumed-a thickness of SiO 2 equal to
x o consumes about 0.45x o thickness of Si. The Si-SiO 2 interface is buried and not
exposed to environmental contamination.

The kinetics of the oxidation follows the Deal-Grove model. For the oxidizing species to
reach the Si surface, there are three steps:
1. The oxidizing species must be transported from the bulk of the gas to the oxide-
gas interface
2. The oxidizing species must diffuse across the oxide layer already present
3. The oxidizing species must react with the Si at the oxide-Si interface.
Step 1 is rarely the rate-limiting step.

If step 2 is the rate-limiting step, the oxidation is said to be diffusion-controlled

If step 3 is rate-limiting, the oxidation is said to be reaction-limited.

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The rate at which the oxide grows yields the following relation

t ox 2 +At ox = B(t+)
where

t ox is the oxide thickness

t is the oxidation time
A,B are rate constants (B is usually called the parabolic rate constant because it is
important in the case of diffusion-controlled oxidation, the ratio B/A is usually called the
linear rate coefficient). A has dimensions of thickness or length, B has dimensions of
thickness or distance squared per unit time, while B/A has dimensions of distance per
unit time
= (t ox 2 + At ox )/B and is a term that accounts for the rapid growth regime in the initial
stages of oxide growth. For wet oxidation, =0.

There are two main limiting cases of importance.

1. For short oxidation times and therefore thin oxides, the oxide thickness is
controlled by the reaction limited case and is given by

t ox = (B/A)(t +)

2. For long oxidation times, the term that dominates is the diffusion-related one in
which the rate-limiting step is the diffusion of O 2 or H 2 O through the existing
oxide, leading to

t ox 2= B(t +)

Some key observations:

1. The orientation of the Si controls the number of Si atoms available for oxidation.
The linear oxidation rate is therefore controlled by orientation. The rate is fastest
for (111) and slowest for (100).There is very little difference in oxidation rate for
different orientations in the diffusion-controlled region.
2. Both linear and diffusion-controlled rate constants increase exponentially with
temperature. In the case of diffusion-controlled, this activation energy represents
the activation energy for diffusion of the oxidizing species.

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 3. The activation energy in the linear case is the same for dry and wet oxidation
because the rate-limiting step is Si bond-breaking in both cases.
4. For large oxide thicknesses, parabolic oxidation relation is accurate, while for
small oxide thicknesses the linear law is accurate. However, at very small
thicknesses, alternative models have to be invoked.
5. Gas flow has no effect on the linear rate constant.
6. The presence of dopants such as B and P in the Si can increase the oxidation rate
for both linear and parabolic cases. The presence of Cl in the oxidation ambient
also increases the oxidation rate due to an increase in diffusivity of O 2 and H 2 O
molecules in SiO 2 containing Cl, the catalytic effect of Cl on reactions at the Si-
SiO 2 interface and the creation of water molecules by reaction of HCl with
oxygen.

Properties of the Si-SiO 2 Interface

There may be present in the thermal oxide several types of charge that affect device
performance, reliability and yield. They are shown schematically below.

Siliconsilicon dioxide structure with mobile, fixed charge, and interface states

The interface trapped charge Q it is located at the Si-SiO 2 interface and originated from
disruption of the lattice periodicity. On clean Si in vacuum, Q it is as high as 1015 cm-2 but

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in the SiO 2 -Si interface, the passivation of defect states by annealing in hydrogen can
lower this value to the 1010 cm-2 range. The charge can be either positive or negative.

The oxide fixed charge Q f is always positive and is located within 3 nm of the interface.
It appears to be related to a transition region of incomplete oxidation. The fixed charge
density ranges from 1010-1012 cm-2 and is minimized by a high temperature dry oxidation
followed by cooling in an inert ambient or by lower temperature wet oxidation followed
by an inert anneal.

The oxide trapped charge Q ot is located within the oxide layer and both electrons and
holes can be trapped in the oxide. These charges are caused by high currents through the
oxide, avalanche of carriers or by ionizing radiation. The trapped charge density is
typically in the range 1010-1013cm-2.

The mobile ionic charge Q m is due to impurities such as Na+ , K+ or Li+ that have
diffused into the oxide. They can often be neutralized or gettered by addition of Cl 2 to
the oxidizing ambient through the formation of volatile metal chlorides and the value of
the mobile ionic charge is typically in the range 1010-1013cm-2.

Effects of Mobile Ionic Charge on MOSFETs.

The presence of mobile ionic charge, fixed charge and interface and trapped charge
causes shifts in capacitance-voltage characteristics of MOS structures and in the
threshold voltages of MOSFETs. The effect of fixed charge is to move the CV curve
laterally, leading to a change in the voltage at which the MOS transistor starts to conduct
current, shown in the figure below. The capacitance C ox of the MOS structure is given by
C ox =( o k ox A)/t ox
where o is the permittivity of free space , k ox is the relative permittivity or dielectric
constant of the oxide, A is the area and t ox is the oxide thickness.

High frequency CV traces showing the effects of interface states and fixed charge.

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The figure above shows the effect of interface states and trapped charge on the CV
characteristics. The fixed charge created after bias stressing leads to a shift of the
characteristic to the left, while the interface states reduce the slope of the CV curve in
depletion. The CV shows recovery through annealing CV measurements are the most
popular method for measuring the interface state density.

The shift in threshold voltage is related to the fixed charge density through the equation
V g = (-Q f )/C ox A
Other sources of lateral shift of the CV trace include mobile ionic charge. These ionic
species have high and drift diffusion coefficients in SiO 2 even at the device operating
temperature. Mobile ionic charges are detected by temperature bias stressing, as shown in
the figure below. After an initial CV scan, the device is heated to 100C and a positive
field applied to the gate for a fixed period after which the device is cooled to room
temperature for recording of the CV characteristic. Then the device is again heated to
100C and a negative bias applied for a fixed period before cooling and re-measuring of
the CV. The positive bias causes the mobile positive ions to move to the Si-SiO 2
interface where they strongly affect C ox . Under negative bias they are moved to the gate-
SiO 2 interface where they have little affect.

Typical C-V traces from temperature bias stress measurements of an oxide contaminated
with a positive ion impurity.

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Redistribution of Impurities During Thermal Oxidation

Dopants in the Si near the growing thermal oxide will redistribute according to their
segregation coefficient and some will be incorporated into the oxide. The concentration
in the Si near the interface may increase or decrease depending on the segregation
coefficient, m. This is defined as the ratio of dopants in the Si divided by the
concentration in the SiO 2 .When m>1, the oxide rejects the dopant and when m<1 the
oxide takes up the dopant. The redistribution behavior also depends on the diffusivity of
the dopant in the oxide. The figure below shows four possibilities. B has an m value <1
whereas donor dopants have m>1.

The effect of thermal oxidation on the impurity distribution in silicon and silicon dioxide.
(A) Slow diffusion in oxide, m < 1 (boron in neutral or oxidizing ambient); (B) fast
diffusion in oxide, m < 1 (boron in hydrogen ambient); (C) slow diffuser in oxide, m > 1
(phosphorus, arsenic); (D) fast diffuser in oxide, m > 1 (gallium) (after Grove et al.).

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Example Problems
1. (i)A 1000 thick gate oxide is needed for a MOS transistor and is to be carried out at
1000C in dry oxygen. If there is no initial oxide, for how long should the oxidation be
carried out? At this temperature in dry O 2 , A= 0.165 m, B=0.0117 m2/hr and =0.37 hr.

Answer: the oxide thickness is given by

t ox 2 +At ox = B(t+)
so that the oxidation time is
t= [(t ox 2+At ox )/B]-
In this case, t=2.26-0.37=1.89 hours.

(ii) Is the oxidation in the linear regime, the parabolic regime or between the two?

Answer: Since A~tox, this process in not in either the linear or the parabolic regime.

(iii) Repeat this problem for wet O 2 ambient. In this case, A=0.226 m, B= 0.287
m2/hr.What is the oxidation time and which regime is the oxidation
occurring in?
Answer: in this case, =0, so that
t= [(t ox 2+At ox )/B]

=[(0.1)2 +0.1x0.226]/0.287
=0.114 hr or 6.8 mins

This solution is closer to linear than parabolic, but is still in the transition regime.

2. Oxidation of a bare Si wafer is to be done in 1 atm of dry O 2 at 1100C. The desired

thickness of the oxide is 40 nm. Under these conditions, A=0.165 m, B= 0.0117 m2/hr
and =0.37 m.
(a) find the time needed for this oxidation if one ignores rapid growth effects.

Answer:
Ignoring rapid growth, then t= [(t ox 2+At ox )/B]
= [(0.04)2 + 0.165x0.04]/0.0117
= 0.7 hr

(b) find the time needed taking into account rapid growth effects.

Answer:
Including rapid growth effects, then t= [(t ox 2+At ox )/B]-
= {[(0.04)2+0.165x0.04]/0.0117} -0.37
= 0.33 hr

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 (c) for submicron MOSFETs, it is often necessary to grow gate oxides of order 100.
Although process control is very difficult due to the short oxidation time required,
it is preferable to grow these oxides at high temperatures. Explain why.

Answer: It is preferred to grow the oxide at higher temperature to minimize the fixed
oxide charge, the interface state density, and the interface roughness. This produces the
highest inversion layer mobility for the MOSFET. It is likely that these oxides are more
robust (i.e. more resistant to damage) than lower temperature thermal oxides.

(d) A thermal oxide thickness is measured using a film thickness monitor and by
measuring the accumulated capacitance. The results are found to differ by 20%
on the same wafer. Give 3 possible errors that could account for the
discrepancy.

Answer: a) The film is not stoichiometric SiO 2 . This would affect both the dielectric
constant and the refractive index. This is very unusual for thermal oxide which is almost
always very close to perfectly stoichiometric.
b) If the oxide is very thin, one must take into account the finite accumulation layer
thickness in the silicon, and in the gate (unless one uses a metal gate electrode). The
substrate depletion layer typically adds about 0.4 nm to the measured oxide thickness.
c) If the oxide is thin, it may be leaky. Leaky oxides often make for erroneous
capacitance measurements.
d) There may be an error in the area of the capacitor.
e) There may be a poor substrate contact.