Surface treatment of c-doped SiO2 film to enhance film...

Active solid-state devices (e.g. – transistors – solid-state diode – With means to control surface effects – Insulating coating

Reexamination Certificate

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Reexamination Certificate

active

06583497

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to the formation of dielectric layers during fabrication of integrated circuits on semiconductor wafers. More particularly, the present invention relates to a method for providing a dielectric film having a low dielectric constant that is particularly useful as a premetal or intermetal dielectric layer.
One of the primary steps in the fabrication of modern semiconductor devices is the formation of a thin film on a semiconductor substrate by chemical reaction of gases. Such a deposition process is referred to as chemical vapor deposition or “CVD.” Conventional thermal CVD processes supply reactive gases to the substrate surface where heat-induced chemical reactions take place to produce a desired film. Plasma enhanced CVD techniques, on the other hand, promote excitation and/or dissociation of the reactant gases by the application of radio frequency (RF) or microwave energy. The high reactivity of the released species reduces the energy required for a chemical reaction to take place, and thus lowers the required temperature for such PECVD processes.
Semiconductor device geometries have dramatically decreased in size since such devices were first introduced several decades ago. Today's fabrication plants are routinely producing devices having 0.25 &mgr;m and even 0.18 &mgr;m feature sizes, and tomorrow's plants soon will be producing devices having even smaller geometries. In order to further reduce the size of devices on integrated circuits, it has become necessary to use conductive materials having low resistivity and insulators having a low dielectric constant. Low dielectric constant films are particularly desirable for premetal dielectric (PMD) layers and intermetal dielectric (IMD) layers to reduce the RC time delay of the interconnect metalization, to prevent cross-talk between the different levels of metalization, and to reduce device power consumption. Undoped silicon oxide films deposited using conventional CVD techniques may have a dielectric constant (k) as low as about 4.0 or 4.2. One approach to obtaining a lower dielectric constant is to incorporate fluorine in the silicon oxide film. Fluorine-doped silicon oxide films (also referred to as fluorine silicate glass or—“FSG” films) may have a dielectric constant as low as about 3.4 or 3.6. Despite this improvement, films having even lower dielectric constants are highly desirable for the manufacture of integrated circuits using geometries of 0.18 &mgr;m and smaller. Numerous films have been developed in attempts to meet these needs including: a spin-on glass called HSQ (hydrogen silsesqui-oxane, HSiO
1.5
) and various carbon-based dielectric layers, such as parylene and amorphous fluorinated carbon. Other low-k films have been deposited by CVD using an organosilane precursor and oxygen to form a silicon-oxygen-carbon (Si—O—C) layer.
While the above types of dielectric films are useful for some applications, manufacturers are always seeking new and improved methods of depositing low-k materials for use as IMD and other types of dielectric layers. For example, in some applications, Si—O—C low-k films that have been deposited in accordance with the pre-deposition, deposition, post deposition, and curing processes described above are often subject to oxidizing environments in the course of subsequent processing. Such oxidizing processes include, but are not limited to, etching, photoresist strip and oxide capping processes. The low-k film is typically a silicon-oxy-carbon structure. In an oxidizing environment the low-k film can react with oxygen and hydrogen to form carbon dioxide (CO
2
) and water vapor (H
2
O). The reaction removes carbon from the film leading to shrinkage and increase in k-value.
SUMMARY OF THE INVENTION
The present invention provides a new and improved method for enhancing stability of thin films. In the method of the present invention a carbon-doped silicon oxide layer after is densified after deposition and curing. In one embodiment, the cured film is densified in a nitrogen-containing plasma. The substrate can be heated during plasma densification. The carbon-doped silicon oxide layer is generally deposited using a thermal, as opposed to plasma, CVD process. The method is particularly suitable for deposition of low dielectric constant films using methylsilane or di-, tri-, tetra-, or phenylmethylsilane and ozone. In one embodiment, the layer is deposited from a process gas of ozone and an organosilane precursor having at least one silicon-carbon (Si—C) bond. During deposition, the substrate is heated to a temperature less than about 250° C.
In some embodiments, the organosilane precursor has a formula of Si(CH
3
)
x
H
4−x
where x is either 3 or 4 making the organosilane precursor either trimethylsilane (TMS) or tetramethylsilane (T4MS). In other embodiments, the substrate over which the carbon-doped oxide layer is deposited is heated to a temperature of between about 100-200° C. and the deposition is carried out in a vacuum chamber at a pressure of between 1-760 Torr. In still other embodiments, the carbon-doped silicon oxide layer is cured after it is deposited to minimize subsequent moisture absorption. Curing can be done in either a vacuum or conventional furnace environment.
The method is particularly useful in the manufacture of sub-0.2 micron circuits as it can form a PMD or IMD film with a dielectric constant below 3.0. Films prepared in accordance with this process have good gap fill capabilities, high film stability and etch uniformly and controllably when subject to a chemical mechanical polishing (CMP) step.
The above method can be carried out in a substrate processing system having a process chamber; a substrate holder, a heater, a gas delivery system, and a power supply, all of which are coupled to a controller that operates under the direction of a computer program.
These and other embodiments of the present invention, as well as its advantages and features, are described in more detail in conjunction with the text below and attached figures.


REFERENCES:
patent: 5314845 (1994-05-01), Lee et al.
patent: 5338362 (1994-08-01), Imahashi
patent: 5532191 (1996-07-01), Nakano et al.
patent: 5605867 (1997-02-01), Sato et al.
patent: 5610105 (1997-03-01), Vines et al.
patent: 5741740 (1998-04-01), Jang et al.
patent: 5872065 (1999-02-01), Sivaramakrishnan
patent: 5900290 (1999-05-01), Yang et al.

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