Semiconductor device manufacturing: process – Coating of substrate containing semiconductor region or of... – Insulative material deposited upon semiconductive substrate
Reexamination Certificate
2000-08-24
2003-05-20
Chen, Bret (Department: 1762)
Semiconductor device manufacturing: process
Coating of substrate containing semiconductor region or of...
Insulative material deposited upon semiconductive substrate
C438S788000, C438S789000, C438S790000, C427S553000, C427S558000
Reexamination Certificate
active
06566278
ABSTRACT:
BACKGROUND OF THE INVENTION
Silicon oxide (SiO
2
) finds extremely widespread use in the fabrication of semiconductor devices. Important applications for SiO
2
films include providing gate dielectric structures for MOS transistor devices, and providing electrical isolation between electrically conducting metal lines in an integrated circuit.
One approach for forming silicon oxide films on a semiconductor substrate is through the process of chemical vapor deposition (CVD). Specifically, chemical reaction between a silicon supplying material and an oxygen supplying material results in deposition of solid phase silicon oxide on top of a semiconductor substrate.
Organosilane silicon supplying materials including at least one Si—C bond are often utilized during CVD of silicon oxide. As a result of the carbon present in such a silicon supplying material, carbon-doped silicon carbon oxide (SiC
x
O
y
) can be formed, for example, through the following chemical reactions:
SiH(CH
3
)
3
(gas)+O
3
(gas)+(heat or UV)→SiC
x
O
y
(solid)+H
2
O+CO
2
SiH(CH
3
)
3
(gas)+O
2
(gas)+RF(plasma)→SiC
x
O
y
(solid)+H
2
O+CO
2
The reactant species SiH(CH
3
)
3
is trimethylsilane (“TMS”). Other organosilane compounds include dimethylsilane, diethylsilane, diacetoxyditertiarybutoxysilane, and 2,4,6,8-tetramethyltetrasiloxane.
As a result of CVD chemical reactions involving organosilane process gases, carbon at concentrations of at least about 8 atomic percent and greater may be incorporated into the silicon oxide film. Incorporation of carbon at these quantities into the silicon oxide during deposition has several effects. First, carbon favorably enhances the dielectric properties of the resulting film. Second, the presence of carbon softens the freshly deposited film, rendering the it more sensitive to handling stress.
Water is one by-product of the CVD reaction to form carbon-doped silicon oxide. Water can be incorporated into the deposited film as an Si—OH chemical bond, or physically absorbed into the film as moisture. This Si—OH bond or moisture is not part of stable carbon-doped silicon oxide film, and may later cause failure of dielectric material during device operation.
Accordingly, undesirable chemical bonds such as Si—OH are typically removed from a deposited carbon-doped silicon oxide film through the process of densification. Conventional densification steps subject the deposited carbon-doped silicon oxide film to a high temperature anneal. The energy from this anneal replaces unstable, undesirable chemical bonds with more stable bonds characteristic of an ordered silicon oxide film, increasing the density of the film.
The conventional thermal anneal step is of relatively long duration (approx. 30 min-2 hrs.) This thermal anneal thus consumes significant processing time and slows down the overall fabrication process.
In order to maintain high throughput, thermal annealing steps of long duration are performed in batch-type furnace devices having a high wafer capacity, wherein a large number of wafers are supported by their edges in slots in the walls of the furnace. However, as stated above carbon-doped silicon oxide films are soft and easily damaged by insertion and removal from conventional batch-type furnaces. This prevents wafers coated with the films from being annealed in large quantities.
Therefore, there is a need in the art for a process for densifying CVD carbon-doped silicon oxide films which requires a minimum of water handling and which consumes a minimum of processing time.
It has been suggested to utilize ultraviolet radiation to aid in the densification of deposited silicon oxide films. However, conventional ultraviolet radiation sources typically emit radiation at a single wavelength corresponding to the excited energy state of electrons from a single excited gas species. However, it may be useful to utilize ultraviolet radiation having a plurality of wavelengths.
Therefore, there is a need in the art for a radiation source which simultaneously emits ultraviolet radiation of a combination of different intensities and energies.
SUMMARY OF THE INVENTION
One embodiment of the present invention relates to the use of ultraviolet radiation to anneal and densify a CVD carbon-doped silicon oxide film. Specifically, a freshly deposited carbon-doped silicon oxide film is exposed to ultraviolet radiation calculated to disrupt undesirable chemical bonds, replacing these bonds with more stable bonds characteristic of an ordered silicon oxide film. As a result of this UV radiation exposure, undesirable chemical bonds in the film such as Si—OH are broken, and gas is evolved. This gas is then removed to leave a densified and stable deposited carbon-doped silicon dioxide film.
Another embodiment of the present invention relates to a source of UV radiation useful for optimizing densification of carbon-doped silicon oxide films. Specifically, the composition and relative concentration of stimulated gases is controlled to produce radiation having a desired combination of energies and intensities. The energy and intensity of the radiation is a result of the identity and concentration, respectively, of the excited gases. The energy and intensity of the radiation is dictated by the identity and population of undesirable bonds expected to be present in the silicon oxide film.
A first embodiment of a method in accordance with the present invention for forming a silicon oxide film comprises the steps of flowing into a substrate processing chamber an oxygen supplying material and an organosilane silicon supplying material including at least one carbon-silicon bond, causing a reaction between the oxygen supplying material and the organosilane silicon supplying material to form carbon-doped silicon oxide, and exposing the carbon-doped silicon oxide to ultraviolet radiation.
A first embodiment of a substrate processing system in accordance with the present invention comprises a housing defining a process chamber; a substrate holder adapted to hold a substrate during substrate processing, and a gas delivery system configured to introduce gases into said process chamber. An ultraviolet radiation source is configured to introduce ultraviolet radiation into said process chamber, and a controller controls said gas delivery system and said ultraviolet radiation source. A memory is coupled to said controller comprising a computer-readable medium having a computer-readable program embodied therein for directing operation of said controller, said computer readable program including instructions to control said gas delivery system to flow a process gas comprising a silicon supplying gas and an oxygen supplying gas into the substrate processing chamber, and to control said ultraviolet radiation source to irradiate at least one of the process chamber and the substrate holder.
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“Critic
Harvey Keith R.
Lim Tian-Hoe
Xia Li-Qun
Applied Materials Inc.
Chen Bret
Townsend and Townsend and Crew
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