Kinetics and Growth of Silicon Dioxide

The main ambient parameter used to control oxide growth

during silicon oxidation is temperature. However, it is also
possible to vary the hydrostatic pressure in the reaction chamber.
Whether the oxidation environment is wet (H O) or dry (O )
also plays a role in determining the growth rate, in addition to
the role played by the crystal orientation of the silicon wafer.
2.2.1.1 Dry Oxidation

During dry oxidation, the wafer is placed in a pure oxygen gas

(O ) environment and the chemical reaction which ensues is
between the solid silicon atoms (Si) on the surface of the wafer
and the approaching oxide gas
(29)
 Figure 2.7: Oxide thickness versus oxidation time for dry (O ) oxidation of a (100) oriented
silicon wafer under various temperatures.
Figure 2.7 shows the oxide thickness as a function of oxidation time for dry oxidation.

It can be noted that the oxidation rate does not exceed 150nm h, making it a
relatively slow process which can be accurately controled in order to achieve a desired
thickness. The oxide films resulting from a dry oxidation process have a better quality
than those grown in a wet environment, which makes them more desirable when high
quality oxides are needed. Dry oxidation is generally used to grow films not thicker
than 100nm or as a second step in the growth of thicker films, after wet oxidation has
already been used to obtain a desired thickness. The application of a second step is
only meant to improve the quality of the thick oxide.

2.2.1.2 Wet Oxidation

During wet oxidation, the silicon wafer is placed into an

atmosphere of water vapor (H O) and the ensuing chemical
reaction is between the water vapor molecules and the solid
silicon atoms (Si) on the surface of the wafer, with hydrogen gas
(H ) released as a byproduct
(30)

Figure 2.8 shows the oxide thickness as a function of oxidation time for wet oxidation
processing.
Figure 2.8: Oxide thickness versus oxidation time for wet (H O) oxidation of a (100) oriented
silicon wafer under various temperatures.
It is evident that wet oxidation operates with much higher oxidation rates than dry
oxidation, up to approximately 600nm/h. The reason is the ability of hydroxide (OH
) to diffuse through the already-grown oxide much quicker than O , effectively
widening the oxidation rate bottleneck when growing thick oxides, which is the
diffusion of species. Due to the fast growth rate, wet oxidation is generally used where
thick oxides are required, such as insulation and passivation layers, masking layers,
and for blanket field oxides.

2.2.1.3 Temperature Effects

As the temperature in the oxidation environment is increased,

the oxidation rate can increase significantly, both in wet and dry
processes. The temperature dependence on the oxidation rate
can be observed in Figure 2.7 and Figure 2.8 for dry and wet
oxidation, respectively.
Figure 2.9: Oxide thickness versus process temperature for wet (H O) and dry (O ) oxidation
of a (100) oriented silicon wafer at 1000 C.
In Figure 2.9, the ratio between oxide thickness and temperature is visualized,
suggesting the existence of an exponential relationship between the thickness ( )
and inverse negative temperature
(31)

The dramatic increase in oxide thickness with increasing temperature is not surprising,
since the diffusivity ( ) of oxygen and water through the oxide depends greatly on
temperature,
(32)

where is a parameter independent of temperature . Since the oxidant diffusivity

increases exponentially with increasing temperature, so should the oxidation rates,
because the diffusivity of oxidants is the rate-limiting step when thicker oxides (
30nm) are grown. A higher diffusivity rate means that more oxidants will be allowed
to penetrate through the already grown oxide to reach the silicon surface.
2.2.1.4 Pressure Effects

The effect of hydrostatic pressure on thermally grown oxides in

dry and wet environments is shown in Figure 2.10a and
Figure 2.10b, respectively, while Figure 2.10c shows the direct
relationship between the oxide thickness and the applied
pressure. It is evident that increasing the pressure results in
thicker oxides and a faster oxidation rate.

(a) Dry oxidation (b) Wet oxidation

(c) Effect of pressure

 Figure 2.10: Effects of hydrostatic pressure on thermally grown oxide thickness for a (100)

oriented silicon wafer in a) dry (O ) and b) wet (H O) ambients.

A logarithmic relationship appears to exist between the thickness of oxide grown and
the applied pressure. The main advantage of increasing the pressure during oxidation
is to achieve relatively fast oxidation rates at reduced temperatures [124], [179].
Reducing the processing temperature results in less impurities and minimal movement
of the junction during multiple subsequent oxidation steps required for complex IC
device manufacturing [125]. Oxides grown in a high pressure ambient have also been
found to have significantly reduced stacking faults, leading to an improved device
performance [98].

2.2.1.5 Crystal Orientation Effects

Multiple studies have shown that silicon is not oxidized at the

same rate in each crystalline direction [122]. Therefore, the
crystal orientation of the wafer plays a role in determining the
oxide thickness, as can be seen in Figure 2.11. Oxide growth
appears to be faster on (111) oriented silicon when compared to
(100) oriented silicon. In fact, in [122] it is shown that the (111)
and (100) orientations represent the upper and lower bound for
oxidation rates, respectively. All other silicon orientations lie
between these extrema.
 Figure 2.11: Oxide thickness versus oxidation time for (100) and (111) oriented silicon by wet
oxidation at various temperatures.
Ligenza [126] argued that the crystal orientation effect on the oxidation rate is due to
the differences in the densities of silicon atoms on the various crystal faces. Since
silicon atoms are required in order to generate the oxide, having a larger number of
bondable Si atoms available on the (111) face meant that the oxide would grow faster
in the (111) direction, as is observed experimentally.