Thin film formation III: Thermal oxidation

Thermal oxidation is one of the most basic film growth technologies, but it is limited to
materials that can be oxidised and it can only form oxides of that material. One of the most
important reasons why Si has been widely used in microelectronics is that it can for a stable
good quality oxide which can be used as dielectric layers in transistors and capacitors as well as
passivation layers and isolation. Thermal oxidation stages are employed several times in most
device processing schemes.

4.1 Wet and dry oxidation

Thermal oxidation is carried out in a furnace similar to the schematic shown below. One of the
following two reactions take place during the process:

i) dry oxidation: Si (s) + O2 (g) → SiO2 (s)

ii) wet oxidation: Si (s) + 2H2O (g) → SiO2 (s) + 2H2 (g)

Typical oxidation furnace

The process is carried out at high temperature since Si requires temperatures close to 1000ºC to
oxidise, therefore, thermal oxidation is typically restricted to the early processing stages during
device fabrication.

Dry oxidation delivers a good quality oxide which is often used as gate dielectric in MOS
structures, however, the oxide growth rate is low and long processing times are required. Wet
oxide grows much faster and it is typically used as passivation, isolation and implantation
mask. The growth rate also depends on the temperature, gas pressure and the substrate
orientation. The following figures show the growth rates for dry and wet oxidation.
 Oxide thickness as a function of oxidation time for dry and wet
processes

Since growth depends on the reaction between the gas molecules (either O2 or H2O) with the Si
atoms at the surface, a portion of the original Si layer will get consumed by the oxidation
process, as shown in the following diagram. In general, for an oxide layer of thickness x, the
layer of Si consumed is around 0.44x thick.

Si consumption during oxidation

As the oxide layer grows, the O2 has to travel a longer distance to reach the Si surface, therefore
(diffusion through the already grown oxide!), the oxidation rate slows down. The Deal and
Grove model describes the oxidation rates:

Deal and Grove model:x2 + Ax = Bt

where x is the oxide thickness, t is the oxidation time and A and B are the rate constants.
Typical values for A and B at various temperatures are shown in the tables below. The model
can be simplified for short and long oxidation times resulting in the following approximations:
i) short oxidation time:
B
𝑥 ≈ 𝑡
A

ii) long oxidation time:

𝑥 ≈ √B𝑡

Typical rate constants for wet oxidation:

Temperature (ºC) A (m) B (m2/h)

920 0.5 0.203
1000 0.226 0.287
1100 0.11 0.51
1200 0.05 0.72

Typical rate constants for dry oxidation:

Temperature (ºC) A (m) B (m2/h)

920 0.235 0.005
1000 0.165 0.012
1100 0.09 0.027
1200 0.04 0.045

The Deal and Grove model gives reasonably accurate approximations for thick oxides, however,
for thin oxides (x < 30 nm) grown in O2 the model predicts slower growth rates.

Segregation

Segregation refers to the doping redistribution at the Si/SiO2 interface when a doping species is
already present in the Si prior to the thermal oxidation. Depending on the doping species, the
resulting doping profile shows either a depletion or an accumulation of dopants near the
interface, as shown in the figure. Segregation can affect device operation, for example, in a
MOSFET, if a large concentration of doping atoms are incorporated into the oxide, the channel
doping may have a doping concentration below that of the gate and inversion of the Si doping
type may occur.
 Distribution of boron and phosphorous at the SiO2/Si interface
following thermal oxidation

4.2 Oxide quality

Stress

Oxides grown by thermal oxidation are under compressive stress. This stress is due to the
intrinsic SiO2 stress and the difference in thermal expansion coefficients between SiO2 and Si.
Stress in the oxide layer can induce defects in the underlying Si film and wafer warpage.

Stress may also result in non-uniform oxide thickness. This happens especially in non-planar
surfaces with sharp features. Uneven oxides may cause problems for device reliability.

Oxide charges

Oxides have an electrical defect density. It is often considered that a defect density around 10 10
cm-2 is satisfactory, but higher defect densities can affect the operation of MOS devices. The
different types of oxide charges can be classified as follows:

 Interface trapped charge (Qit): always localised at the Si/SiO2 interface. They arise
primarily from dangling bonds at the Si surface. The density of Qit is lower in <100>
than <111> crystal orientations. Annealing at 450ºC can help to remove these charges.

 Oxide trapped charge (Qot): due to either holes of electrons trapped in the bulk of the
oxide (i.e. Qot can be positive or negative). Qot can arise due to radiation or electron
bombardment (or even during device operation if high electric field is applied to the
oxide or by injecting current through the oxide). These charges can be annealed out at
550ºC.

 Fixed charge (Qf): fixed charges are generally positive and are normally located within 3
nm from the interface, in the transition region between the Si and the SiO 2 structure.
 The Qf density depends on the oxide growth and annealing conditions, but it is generally
lower for <100> than <111> crystal orientations. Qf can be reduced with argon or
nitrogen annealing and adding HCl during oxide growth.

 Mobile ionic charge (Qm): these charges are due to alkali metal contamination. Alkali ions
such as sodium can become incorporated into the oxide. These ions can move within the
oxide when bias is applied. Qm can be reduced by adding HCl during oxide growth.

Interface traps and charges in thermal oxide

4.3 Local oxidation

LOCal Oxidation of Silicon is also known as LOCOS. If a silicon nitride mask is used, it is
possible to selectively oxidise some areas of the silicon surface. The nitride prevents the oxygen
diffusion, therefore, oxide does not grow under the mask. Nevertheless, it is common to begin
the LOCOS process by growing a thin oxide layer by thermal oxidation before the nitride
deposition. The thin oxide helps to relieve the stress between the silicon and the nitride (stress
can induce defects into the silicon, which may affect the device operation). The figure shows the
nitride pad before and after thermal oxidation. LOCOS is typically used to provide isolation
between devices.

LOCOS structure before and after oxidation