Nanoporous silicone resins having low dielectric constants...

Details Nanoporous silicone resins having low dielectric constants... Nanoporous silicone resins having low dielectric constants...

1999-12-13

2001-11-06

Everhart, Caridad (Department: 2825)

Semiconductor device manufacturing: process

Coating of substrate containing semiconductor region or of...

C427S255400, C438S781000, C438S782000

Reexamination Certificate

active

06313045

ABSTRACT:

BACKGROUND OF INVENTION
The present invention is nanoporous silicone resin compositions having low dielectric constants, substrates coated with such compositions, and methods for making such nanoporous silicone resins compositions.
Semiconductor devices often have one or more arrays of patterned interconnect levels that serve to electrically couple the individual circuit elements forming an integrated circuit (IC). These interconnect levels are typically separated by an insulating or dielectric film. Previously, a silicon oxide film formed using chemical vapor deposition (CVD) or plasma enhanced techniques (PECVD) was the most commonly used material for such dielectric films. However, as the size of circuit elements and the spaces between such elements decreases, the relatively high dielectric constant of such silicon oxide films is inadequate to provide adequate electrical insulation.
In order to provide a lower dielectric constant than that of silicon oxide, dielectric films formed from siloxane-based resins have found use. An example of such films are those formed from poly(hydrogen)silsesquioxane resins as described for example in Collins et al., U.S. Pat. No. 3,615,272 and Haluska et al. U.S. Pat. No. 4,756,977. While such films provide lower dielectric constants than CVD or PECVD silicon oxide films and also provide other benefits such as enhanced gap filling and surface planarization, typically the dielectric constants of such films are limited to approximately 3 or greater.
It is well known that the dielectric constant of the above discussed insulating films is an important factor where IC's with low power consumption, cross-talk, and signal delay are required. As IC dimensions continue to shrink, this factor increases in importance. As a result, siloxane based resin materials and methods for making such materials that can provide electrically insulating films with dielectric constants below 3 are desirable. In addition, it is desirable to have siloxane-based resins and method for making such resins that provide low dielectric constant films which have a high resistance to cracking. Also, it is desirable for such siloxane-based resins to provide low dielectric constant films by standard processing techniques.
It is known that the dielectric constant of solid films decrease with a decrease in density of the film material. Therefore considerable work is being conduct to develop microporous insulating films for use on semiconductor devices.
Kapoor, U.S. Pat. No. 5,494,859, describes a low dielectric constant insulating layer for an integrated circuit structure and a method of making the layer. A porous layer is formed by depositing on a structure a composite layer comprising an insulating matrix material and a material which can be converted to a gas upon subjection to a converting process. Release of the gas leaves behind a porous matrix of the insulating material which has a lower dielectric constant than the composite layer. The matrix forming material is typically silicon oxide and the material which can be converted to a gas upon subjection to a converting process is exemplified by carbon.
Hedrick et al., U.S. Pat. No. 5,776,990, describe an insulating foamed polymer having a pore size less than about 100 nm made from a copolymer comprising a matrix polymer and a thermally decomposable polymer by heating the copolymer above the decomposition temperature of the decomposable polymer. The copolymers described are organic polymers that do not contain silicon atoms.
Smith et al., WO 98/49721, describe a process for forming a nanoporous dielectric coating on a substrate. The process comprises the steps of blending an alkoxysilane with a solvent composition and optional water; depositing the mixture onto a substrate while evaporating at least a portion of the solvent; placing the substrate in a sealed chamber and evacuating the chamber to a pressure below atmospheric pressure; exposing the substrate to water vapor at a pressure below atmospheric pressure and then exposing the substrate to base vapor.
Mikoshiba et al., Japanese Laid-Open Patent (HEI) 10-287746, describe the preparation of porous films from siloxane-based resins having organic substituents which are oxidized at a temperature of 250° C. or higher. The useful organic substituents which can be oxidized at a temperature of 250° C. or higher given in this document include substituted and unsubstituted groups as exemplified by 3,3,3-trifluoropropyl, &bgr;-phenethyl group, t-butyl group, 2-cyanoethyl group, benzyl group, and vinyl group.
Mikoskiba et al.,
J. Mat. Chem
., 1999, 9, 591-598, report a method to fabricate angstrom size pores in poly(methylsilsesquioxane)films in order to decrease the density and the dielectric constant of the films. Copolymers bearing methyl(trisiloxysilyl) units and alkyl(trisiloxysilyl) units are spin-coated on to a substrate and heated at 250°C. to provide rigid siloxane matrices. The films are then heated at 450° C. to 500° C. to remove thermally labile groups and holes are left corresponding to the sized of the substituents. Trifluoropropyl, cyanoethyl, phenylethyl, and propyl groups were investigated as the thermally labile substituents.
Hacker et al., WO 98/47945, teach a method for reacting trichlorosilane and organotrichlorosilane to form organohydridosiloxane polymer having a cage conformation and between approximately 0.1 to 40 mole percent carbon-containing substituents. Resin formed from the polymers are reported to have a dielectric constant of less than about 3.
The objectives of the present invention is to provide nanoporous silicone resins suitable for forming crack-free electrically insulating films on electronic devices that have low dielectric constants and a method for forming such porous resins. Such low-dielectric constant films can be formed on electrical components such as semiconductor devices by conventional methods to form nanoporous crack-free films having a dielectric constant less than about 2.
SUMMARY OF INVENTION
The present invention is nanoporous films having low dielectric constants prepared from soluble silicone resin compositions and a method for preparing such nanoporous films. The silicone resin comprises the reaction product of a mixture comprising
(A) 15-70 mol % of a tetraalkoxysilane described by formula
 Si(OR
1
)
4
,
 where each R
1
is an independently selected alkyl group comprising 1 to about 6 carbon atoms,
(B) 12 to 60 mol % of an organosilane described by formula
R
4
SiX
3
,
 where R4 is selected from the group consisting of alkyl groups comprising 1 to about 6 carbon atoms and phenyl and each X is an independently selected hydrolyzable substituent,
(C) 15 to 70 mole percent of an organotrialkoxysilane described by formula
R
2
Si(OR
3
)
3
,
 where R
2
is a hydrocarbon group comprising about 8 to 24 carbon atoms or a substituted hydrocarbon group comprising a hydrocarbon chain having about 8 to 24 carbon atoms and each R
3
is an independently selected alkyl group comprising 1 to about 6 carbon atoms; in the presence of
(D) water,
(E) hydrolysis catalyst, and
(F) organic solvent for the reaction product.
The silicone resin is cured and heated preferably in an inert atmosphere at a temperature sufficient to effect thermolysis of carbon-carbon bonds of the R
2
groups thereby forming a nanoporous silicone resin.


REFERENCES:
patent: 3615272 (1971-10-01), Collins
patent: 4017528 (1977-04-01), Unger et al.
patent: 4756977 (1988-07-01), Haluska
patent: 5494859 (1996-02-01), Kapoor
patent: 5776990 (1998-07-01), Hedrick
patent: 6022814 (2000-02-01), Mikoshiba et al.
patent: 6090448 (2000-07-01), Wallace et al.
patent: 686680 (1995-12-01), None
patent: 775669 (1997-05-01), None
patent: 10-287746 (1998-10-01), None
patent: 9-286533 (1998-10-01), None
patent: WO 98/47945 (1998-10-01), None
patent: WO 98/49721 (1998-11-01), None
J. Mat. Chem., 1999, 9, pp. 591-598.

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