JP2002311591A - Photosensitive composition used for forming interlayer dielectric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily form a patterned cured film having high heat resistance and a low dielectric constant and suitable for use as the interlayer dielectric of a semiconductor device or as an etching resist without applying etching. SOLUTION: The photosensitive composition contains (A) a hydrolyzate of a compound of the formula R<1> n Si(OR<2> )4-n (where R<1> and R<2> may be the same or different and are each a 1-5C alkyl or a 6-20C aryl and (n) is an integer of 0-2) and/or a partial condensation product of the hydrolyzate, (B) a metallic chelate compound of the formula R<3> t M(OR<4> )s-t (where R<3> is a chelating agent; M is a metallic atom; R<4> is a 2-5C alkyl or a 6-20C aryl; (s) is the valence of M; and (t) is an integer of 1 to (s)), (C) a compound which is decomposed by an acid and generates an acid and (D) a compound which generates an acid when irradiated with light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition suitable for forming an interlayer insulating film, and more particularly, to a photosensitive composition having a uniform thickness which is useful as a material for forming an interlayer insulating film of a semiconductor device or the like. The present invention relates to a photosensitive composition capable of forming a film, having a low dielectric constant, and capable of performing high-resolution fine patterning by light.

[0002]

2. Description of the Related Art In manufacturing a semiconductor device or a liquid crystal display device, an interlayer insulating film is used to electrically separate wiring layers of a multilayer wiring. This interlayer insulating film has a low dielectric constant, a high dielectric breakdown electric field, a low leak current,
It has excellent adhesion to wiring materials, strong mechanical strength, is chemically and thermally stable, does not contain contaminants for LSI, etc., has a high ability to block the entry of moisture and alkali ions from the outside, and It is required to have various characteristics such that the surface can be easily formed flat even if the base has irregularities, and a film having an appropriate thickness can be easily formed as an interlayer insulating film.

Conventionally, various interlayer insulating film forming materials have been developed to obtain such characteristics. As these interlayer insulating film materials, silicon dioxide-based, silicon nitride-based, and organic resin-based materials are widely known. The silicon dioxide-based interlayer insulating film is formed by, for example, a CVD method, a coating method, a high-density plasma method, and the like, and the silicon nitride-based interlayer insulating film is formed by a vapor phase deposition, such as a plasma CVD method. Further, as an organic resin-based interlayer insulating film, a polyimide or an organic siloxane polymer formed by a coating method is known.

[0004] As described above, the interlayer insulating film is generally formed by coating or deposition from a gas phase, followed by etching through an etching mask usually formed of a photoresist to form contact holes and the like. A fine pattern is formed. In order to form this fine etching pattern, a vapor phase etching method is used as an etching method. However, the etching by the vapor phase etching method has a problem that the equipment cost is high and the processing speed is slow.

On the other hand, since the interlayer insulating film is exposed to a high temperature exceeding 400 ° C. during a device manufacturing process, an organic resin used for a general resist cannot withstand such use. From such a viewpoint, silica-based ceramic films are widely used in semiconductor devices, liquid crystal display devices, printed circuit boards, and the like as coatings having excellent heat resistance, abrasion resistance, corrosion resistance, insulation, transparency, and the like. ing. When such a silica-based ceramic film is formed by a coating method,
A method of applying and baking a solution of an alkoxysilane or an alkylalkoxysilane or a hydrolyzate thereof (Japanese Patent Publication No.
JP-A-2-20825, JP-A-55-34258, JP-A-58-28850, JP-A-63-24
Further, a coating liquid for forming an oxide film obtained by hydrolyzing and polymerizing an alkoxysilane or an alkylalkoxysilane compound and an organometallic compound or a metal chelate compound in the presence of an organic solvent is applied, followed by firing. (JP-A-3-20377, JP-A-6-181201, WO96 / 00758, JP-A-2000-256621, etc.) are known. In addition to these polysilane-based materials, polysilazane-based materials are also known.

[0006]

SUMMARY OF THE INVENTION Among the above materials, in particular,
The oxide film obtained by the hydrolysis of the silane compound and the chelate compound, by selecting a specific solvent as the organic solvent of the film forming material, more preferably by specifying the amount used, suitable for the interlayer insulating film It is known that a coating film having a film thickness can be applied and formed with a uniform thickness, and that an interlayer insulating film excellent in dielectric constant characteristics, storage stability and the like can be obtained (Japanese Patent Laid-Open No. 2000-256621). No.). However, this oxide film also has a problem that the apparatus cost is high and the processing speed is slow, as described above, because vapor phase etching via a photoresist is used in the process of forming a fine pattern.

For this reason, when forming the patterned interlayer insulating film, the patterned interlayer insulating film can be formed without using an etching technique including a vapor phase etching. A coating film having an appropriate film thickness can be applied and formed with a uniform thickness.
Further, there is a need for an interlayer insulating film material capable of forming an interlayer insulating film having excellent dielectric constant characteristics, storage stability, and the like, and a method for forming the interlayer insulating film.

As a result of intensive studies, the present inventors have found that a hydrolyzate and / or a partial condensate of a specific silane compound and a specific chelate compound are hydrolyzed and polymerized in the presence of an organic solvent. The composition for film formation contains a compound which decomposes with an acid to generate an acid and a compound which generates an acid upon irradiation with actinic radiation, and is subjected to pattern exposure to provide high resolution and uniformity and dielectric constant of the film. The inventors have found that a patterned interlayer insulating film having excellent characteristics and storage stability can be formed, and have reached the present invention.

[0009]

That is, the present invention provides:
(A) the general formula _{^{(1); R 1 n Si}} (OR 2) 4-n (1) (R 1 and R ² may be the same or different, 1 to 5 carbon atoms each an alkyl group or a C A hydrolyzate and / or a partial condensate thereof of the compound represented by the following formula (2): R ³ _t M (OR ⁴ ) _s-t (2) (R ³ is a chelating agent, M is a metal atom, and R ⁴ is C 2-5
Represents an aryl group having 6 to 20 carbon atoms, s represents a valence of M, and t represents an integer of 1 to s. ), A compound (C) that decomposes with an acid to generate an acid (hereinafter, referred to as a “dissolution inhibitor”), and (D) a compound that generates an acid by irradiation with actinic radiation (hereinafter, “A”). Photo-acid generator ") is provided.

[0010] The present invention also provides a photosensitive composition as described above, wherein a part of R ^{1 in} the formula (1) is an acid-decomposable group. is there.

Further, the present invention provides a photosensitive composition, characterized in that any one of the above photosensitive compositions is a photosensitive composition for forming an interlayer insulating film.

The present invention also provides a method for forming an interlayer insulating film, which comprises applying the photosensitive composition to a semiconductor substrate, developing after exposure, and sintering.

Further, the present invention provides a semiconductor device having an interlayer insulating film formed by the above-mentioned method for forming an interlayer insulating film.

Preferred embodiments of the photosensitive composition for forming an interlayer insulating film of the present invention are listed below. However, this preferred embodiment does not limit the scope of the present invention.

[1] In the above-described photosensitive composition for forming an interlayer insulating film, the acid-decomposable group constituting a part of R ¹ in the general formula (1) is an aliphatic alkyl carboxylic acid derivative or an alicyclic group. A composition for forming an interlayer insulating film, which is a carboxylic acid derivative or an aromatic carboxylic acid derivative residue.

[2] The photosensitive composition for forming an interlayer insulating film as described above, further comprising a water-soluble compound as a shape stabilizer.

[3] In the above-described photosensitive composition for forming an interlayer insulating film, M in the metal chelate compound represented by the general formula (2) is at least one selected from titanium, zirconium and aluminum. A photosensitive composition for forming an interlayer insulating film, comprising:

[4] The photosensitive composition for forming an interlayer insulating film as described above, wherein the water-soluble compound as a shape stabilizer is a compound containing a nitro group. Composition.

[5] The photosensitive composition for forming an interlayer insulating film described above, wherein the photosensitive composition further comprises (E) a propylene glycol monoalkyl ether and / or (F) a β-diketone. For a photosensitive interlayer insulating film.

[6] The photosensitive composition for forming an interlayer insulating film as described above, wherein the propylene glycol monoalkyl ether is propylene glycol monomethyl ether,
A composition for a photosensitive interlayer insulating film, which is at least one selected from propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

Hereinafter, the present invention will be described in more detail. First, as the compound represented by the general formula (1) used in the photosensitive composition of the present invention, specifically, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxy Silane, tetra-n-butoxysilane, tetra-s-butoxysilane, tetra-t-butoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriiso Propoxysilane, methyltri-n-butoxysilane, methyltri-s-butoxysilane, methyltri-
t-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,
Ethyl tri-n-propoxy silane, ethyl triisopropoxy silane, ethyl tri-n-butoxy silane, ethyl tri-s-butoxy silane, ethyl tri-t-butoxy silane, ethyl triphenoxy silane, n-propyl trimethoxy silane, n-propyl tri Ethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n-propyltri-
n-butoxysilane, n-propyltri-s-butoxysilane, n-propyltri-t-butoxysilane, n-
Propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltri-s-butoxysilane, isopropyltri-t- Butoxysilane, isopropyltriphenoxysilane, n-butyltrimethoxysilane,
n-butyltriethoxysilane, n-butyltri-n-
Propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, n-butyltri-s-butoxysilane, n-butyltri-t-butoxysilane, n-butyltriphenoxysilane, s-butyltrimethoxy Silane, s-butylisotriethoxysilane, s-butyltri-n-propoxysilane, s-
Butyltriisopropoxysilane, s-butyltri-n
-Butoxysilane, s-butyltri-s-butoxysilane, s-butyltri-t-butoxysilane, s-butyltriphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butylto-n
-Propoxysilane, t-butyltriisopropoxysilane, t-butyltri-n-butoxysilane, t-butyltri-s-butoxysilane, t-butyltri-t-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane , Phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-s-butoxysilane, phenyltri-t-butoxysilane, phenyltriphenoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-s-butoxysilane, dimethyldi-
t-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane,
Diethyl di-n-propoxy silane, diethyl diisopropoxy silane, diethyl di-n-butoxy silane, diethyl di-s-butoxy silane, diethyl di-t-butoxy silane, diethyl diphenoxy silane, di-n-propyl dimethoxy silane, di-n -Propyldiethoxysilane, di-n-propyldi-n-propoxysilane,
Di-n-propyldiisopropoxysilane, di-n-propyldi-n-butoxysilane, di-n-propyldi-
s-butoxysilane, di-n-propyldi-t-butoxysilane, di-n-propyldi-phenoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi -N-butoxysilane, diisopropyldi-s
-Butoxysilane, diisopropyldi-t-butoxysilane, diisopropyldiphenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n
-Butyldiisopropoxysilane, di-n-butyldi-
n-butoxysilane, di-n-butyldi-s-butoxysilane, di-n-butyldi-t-butoxysilane, di-
n-butyldi-phenoxysilane, di-s-butyldimethoxysilane, di-s-butyldiethoxysilane, di-
s-butyldi-n-propoxysilane, di-s-butyldiisopropoxysilane, di-s-butyldi-n-butoxysilane, di-s-butyldi-s-butoxysilane,
Di-s-butyldi-tert-butoxysilane, di-s-butyldi-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di- t-butyldiisopropoxysilane, di-t-butyldi-n-butoxysilane, di-t-butyldi-s-butoxysilane, di-t-
Butyldi-t-butoxysilane, di-t-butyldi-phenoxysilane, diphenyldimethoxysilane, diphenyldi-ethoxysilane, diphenyldi-n-propoxysilane, diphenyldiisopropoxysilane, diphenyldi-n-butoxysilane, diphenyldi -S-butoxysilane, diphenyldi-t-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, One or more of γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane and the like can be mentioned.

The metal in the metal chelate compound represented by the general formula (2) is preferably titanium, aluminum or zirconium. Specific examples of the metal chelate compound represented by the general formula (2) include triethoxy.
Mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, triisopropoxy mono (acetylacetonato) titanium,
Tri-n-butoxy mono (acetylacetonate) titanium, tri-s-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy bis (acetylacetonate) Titanium, di-n-propoxybis (acetylacetonato) titanium, diisopropoxybis (acetylacetonato) titanium, di-n-butoxybis (acetylacetonato) titanium, di-s-butoxy.
Bis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, mono-n
-Propoxy-tris (acetylacetonato) titanium, monoisopropoxy-tris (acetylacetonate) titanium, mono-n-butoxy-tris (acetylacetonate) titanium, mono-s-butoxy-tris (acetylacetonate) titanium , Mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, triisopropoxy・ Mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-s-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) tita , Diethoxybis (ethylacetoacetate) titanium, di-n-propoxybis (ethylacetoacetate) titanium, diisopropoxybis (ethylacetoacetate) titanium, di-n-butoxybis (ethylacetoacetate) titanium , Di-s-
Butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate)
Titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, monoisopropoxy tris (ethylacetoacetate) titanium, mono-n-butoxy.
Tris (ethylacetoacetate) titanium, mono-s-
Butoxy-tris (ethylacetoacetate) titanium,
Mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl acetoacetate) titanium, bis (acetylacetonate) bis (ethyl acetoacetate) titanium, Titanium chelate compounds such as tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxy mono (acetylacetonato) zirconium, tri-
n-propoxy mono (acetylacetonate) zirconium, triisopropoxy mono (acetylacetonate) zirconium, tri-n-butoxy mono (acetylacetonate) zirconium, tri-s-butoxy mono (acetylacetonate) Zirconium, tri-
t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, diisopropoxybis (acetylacetonato) zirconium, di- n-butoxy
Bis (acetylacetonate) zirconium, di-s-
Butoxy bis (acetylacetonate) zirconium, di-t-butoxybis (acetylacetonate)
Zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris (acetylacetonate) zirconium, monoisopropoxy tris (acetylacetonate) zirconium, mono-n-butoxy tris (acetylacetonate) ) Zirconium, mono-s-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri -N-propoxy mono (ethylacetoacetate) zirconium, triisopropoxy mono (ethylacetoacetate) zirconium, tri-n-butoxymono (ethylacetate) (Acetate) zirconium, tri-s-butoxymono (ethylacetoacetate) zirconium, tri-t-butoxymono (ethylacetoacetate) zirconium, diethoxybis (ethylacetoacetate) zirconium, di-n-propoxybis ( Ethyl acetoacetate) zirconium, diisopropoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-s-butoxy bis (ethyl acetoacetate) zirconium, di-t- Butoxy
Bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, monoisopropoxy tris (ethyl acetoacetate) zirconium, mono-n-
Butoxy tris (ethyl acetoacetate) zirconium, mono-s-butoxy tris (ethyl acetoacetate) zirconium, mono-t-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium, mono (acetyl acetoacetate) Natto) tris (ethyl acetoacetate)
Zirconium chelate compounds such as zirconium, bis (acetylacetonate) bis (ethylacetoacetate) zirconium, tris (acetylacetonate) mono (ethylacetoacetate) zirconium; triethoxymono (acetylacetonate) aluminum, tri-n- Aluminum propoxy mono (acetylacetonate), triisopropoxy mono (acetylacetonate) aluminum, tri-n-butoxy mono (acetylacetonate) aluminum, tri-s-butoxy mono (acetylacetonate) aluminum,
Tri-t-butoxy mono (acetylacetonato) aluminum, diethoxybis (acetylacetonato) aluminum, di-n-propoxybis (acetylacetonato) aluminum, diisopropoxybis (acetylacetonato) aluminum, Di-n-butoxybis (acetylacetonato) aluminum,
Di-s-butoxybis (acetylacetonato) aluminum, di-t-butoxybis (acetylacetonato) aluminum, monoethoxytris (acetylacetonato) aluminum, mono-n-propoxy.
Tris (acetylacetonate) aluminum, monoisopropoxytris (acetylacetonate) aluminum, mono-n-butoxytris (acetylacetonate) aluminum, mono-s-butoxytris (acetylacetonate) aluminum, mono- t-butoxy tris (acetylacetonate) aluminum, tetrakis (acetylacetonate) aluminum, triethoxy mono (ethyl acetoacetate) aluminum, tri-n-propoxy mono (ethyl acetoacetate) aluminum, triisopropoxy mono ( Ethyl acetoacetate) aluminum, tri-n
-Butoxy mono (ethyl acetoacetate) aluminum, tri-s-butoxy mono (ethyl acetoacetate) aluminum, tri-t-butoxy mono (ethyl acetoacetate) aluminum, diethoxy bis (ethyl acetoacetate) aluminum, di -N-propoxybis (ethylacetoacetate) aluminum, diisopropoxybis (ethylacetoacetate) aluminum, di-n-butoxybis (ethylacetoacetate) aluminum, di-s-butoxybis (ethylacetoacetate) ) Aluminum, di-t-
Butoxy bis (ethyl acetoacetate) aluminum, monoethoxy tris (ethyl acetoacetate)
Aluminum, mono-n-propoxy tris (ethyl acetoacetate) aluminum, monoisopropoxy tris (ethyl acetoacetate) aluminum, mono-n-butoxy tris (ethyl acetoacetate)
Aluminum, mono-s-butoxy tris (ethylacetoacetate) aluminum, mono-t-butoxy
Tris (ethylacetoacetate) aluminum, tetrakis (ethylacetoacetate) aluminum, mono (acetylacetonate) tris (ethylacetoacetate) aluminum, bis (acetylacetonate) bis (ethylacetoacetate) aluminum, tris (acetylacetonate) Aluminum chelate compounds such as aluminum mono (ethylacetoacetate);
And one or more of these.

The amount of the metal chelate compound represented by the general formula (2) is based on 100 parts by weight of the hydrolyzate of the alkylalkoxysilane represented by the general formula (1) and / or its partial condensate. Usually, the value is in the range of 0.5 to 300 parts by weight, more preferably 1 to 100 parts by weight.

In the present invention, examples of the dissolution inhibitor include
For example, a compound represented by the following general formula (3) may be mentioned.
You. R¹¹-Y¹¹-R¹² (3) In the general formula (3), R¹¹Is a substituted or unsubstituted fat
Group consisting of an aromatic group and a substituted or unsubstituted aromatic group
Selected from Y¹¹Means COO, OCO, OSO _Two, S
O_Two, OCOO, OCH_TwoCOO or O, R
¹²Is a substituted or unsubstituted aliphatic group,
Represents a group obtained by substituting hydrogen for hydrogen. Can be used in the present invention
Specific examples of the dissolution inhibitor include the compounds shown below.
Things.

[0025]

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[0026]

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[0027]

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In the composition of the present invention, not only the compound capable of decomposing with an acid to generate an acid as described above is added as a dissolution inhibitor, but also the compound represented by the general formula (1)
A part of ¹ may be a group that is decomposed by an acid to generate an acid.

In the present invention, examples of the photoacid generator include onium salts, halogen-containing compounds, quinonediazides, sulfone compounds, sulfonic acid compounds and nitrobenzyl compounds. Onium salts include sulfonium salts, iodonium salts, and diazonium salts. More specifically, 3, 3 ',
4,4'-tetra (t-butylperoxycarbonyl)
Examples include benzophenone and compounds as shown below.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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In the formula, NA represents naphthoquinonediazide.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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The amount of the photoacid generator is 0.1 to 30% by weight, preferably 1 to 10% by weight, based on the total weight of the composition.
It is preferable to set the weight%. The photoacid generator is 0.1
If the amount is less than% by weight, the amount of acid generated at the time of exposure is small, and the reaction may not sufficiently occur. On the other hand, when the photoacid generator exceeds 30% by weight, film properties such as strength and flatness are deteriorated.

The photosensitive composition according to the present invention may further contain a shape stabilizer. Here, the shape stabilizer is
A compound capable of sharpening the side wall of a pattern section formed by removing a light irradiation part. Examples of the shape stabilizer include a water-soluble compound. When a water-soluble compound is added to the photosensitive composition, the hydrophobicity of the photosensitive coating is reduced, and access of moisture from the coating surface in contact with the water-containing atmosphere to the inside of the coating is promoted. For this reason, the difference in the generation rate of the silanol bond between the vicinity of the surface of the coating film and the vicinity of the interface with the substrate, that is, the difference in sensitivity is reduced. Then, the irradiation light energy required to sufficiently dissolve and remove the coating film portion corresponding to the mask opening to the vicinity of the substrate interface can be reduced, and the amount of “exuding light” to the mask shielding portion can be reduced. Can be done.
The portion where the amount of “exuding light” is reduced is not dissolved and removed at the time of development because no silanol bond is generated even in a portion indirectly irradiated by the “exuding light”. As a result, the dissolution-removed portion in the mask shielding portion is reduced, so that the side wall of the pattern section is sharpened.

Such a water-soluble compound is useful as long as it is soluble in acidic water or basic water even if it is insoluble in neutral water. This is because, if soluble in acidic water, the radiation-irradiated part becomes acidic due to the acid generated from the photoacid generator,
Further, if it is soluble in basic water, the permeability of the developing solution is promoted at the time of development with an alkaline aqueous solution. In any case, access of moisture from the surface of the coating film to the inside of the coating film is promoted, whereby the sensitivity difference between the vicinity of the coating surface and the vicinity of the substrate interface is reduced.

The water-soluble compound according to the present invention may be a monomer or a polymer. The degree of water solubility of the water-soluble compound may be about 0.01 g / 100 mL or more in any of neutral water, acidic water, and basic water, and does not necessarily have to be easily soluble. . In addition, since it is preferable that the water-soluble compound is uniformly mixed with the photosensitive composition, a hydrolyzate of the compound represented by the general formula (1) and / or a partial condensate thereof and a solvent thereof are also used. It is necessary to show sufficient miscibility.

Specific examples of such a water-soluble compound include 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-nitro-4-aminotoluene, and 4-nitroaniline.
Nitro-2-aminotoluene, 5-nitro-2-aminotoluene, 6-nitro-2-aminotoluene, 4-nitrobenzene-azo-ortinol, 1- (4-nitrobenzenesulfonyl) -1H-1,2,4- Triazole, 5-nitrobenzimidazole, 4-nitrobenzene acetate, 2-nitrobenzyl alcohol, 3-nitrobenzyl alcohol, 4-nitrobenzyl alcohol, nitrocyclohexane, 1-nitropropane, 2-nitrobenzyl alcohol
Nitropropane, nifedipine, 2,7-dinitrofluone, 2,7-dinitro-9-fluorenone, 3,3 '
-Amide compounds such as dinitro-9-fluorenone, 3,3'-dinitrobenzophenone, 3,4'-dinitrobenzophenone, propylene carbonate, ethylene carbonate, trifluoroacetamide, ammonium trifluoroacetate, water-soluble acrylic polymer, water-soluble Epoxy polymers, water-soluble melamine polymers, and the like. Particularly suitable water-soluble compounds are 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-nitro-4-aminotoluene, propylene carbonate, ethylene carbonate and water-soluble acrylic polymers.

The water-soluble compound as a shape stabilizer is preferably added in an amount of 0.01 to 50% by weight based on the total weight of the composition. The optimum mixing ratio varies depending on the characteristics of the individual water-soluble compounds. However, if the content of the water-soluble compound is less than 0.01% by weight, the effect of improving the inclination of the pattern side wall is small. This causes problems such as defects and insufficient strength in later film properties.
The amount of the water-soluble compound based on the hydrolyzate of the compound represented by the general formula (1) and / or its partial condensate is preferably 0.05 to 40% by weight, more preferably 0.1 to 40% by weight.
30% by weight.

As a solvent used in the photosensitive composition for an interlayer insulating film of the present invention, propylene glycol monoalkyl ether is preferable. Examples of the propylene glycol monoalkyl ether include one or more of propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, and the like, Particularly, propylene glycol monopropyl ether is preferred.

In addition, a small amount of a solvent such as an ester or an amide can be used together with the propylene glycol monoalkyl ether. The amount of the solvent used in the present invention is, for example, in the case of propylene glycol monoalkyl ether, the hydrolyzate of alkylalkoxysilane represented by the general formula (1) and / or its partial condensate 10
The value is preferably in the range of 20 to 4000 parts by weight, more preferably 100 to 2000 parts by weight with respect to 0 parts by weight.

Further, in the photosensitive composition for an interlayer insulating film of the present invention, it is preferable to use β-diketone together with the above-mentioned propylene glycol monoalkyl ether as a solvent. Preferred specific examples of β-diketone include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4 -Nonanedione, 5-methyl-2,4-hexanedione, 2,
2,6,6-tetramethyl-3,5-heptanedione,
1,1,1,5,5,5-hexafluoro-2,4-heptanedione and the like. These β-diketones are used alone or in combination of two or more. The amount of the β-diketone is not particularly limited, but is preferably 1 to 50% by weight, particularly 3 to 30% by weight of the total solvent. If β-diketone is added in such a range,
A certain storage stability is obtained for the composition,
There is little possibility that the properties such as coating uniformity of the photosensitive composition are deteriorated.

The photosensitive composition for an interlayer insulating film of the present invention includes:
A sensitizing dye may be added. For example, 3,3 ', 4
Some photoacid generators, such as 4'-tetra (t-butylperoxycarbonyl) benzophenone, have excitation wavelengths shorter than about 330 nm. In such a photoacid generator, light irradiation is performed using a KrF system (248 nm), Ar
In the case of using an excimer laser such as an F type (193 nm), a sensitizing dye is not necessary because the photoacid generator is directly excited. However, high pressure mercury lamps (360-4
When an inexpensive light source such as 30 nm) is used, the photoacid generator can be indirectly excited by combining a sensitizing dye that is excited in the wavelength region. Thus, by combining a sensitizing dye, the photosensitive composition of the present invention can be patterned using a commonly used inexpensive light source.

Examples of sensitizing dyes that can be used in the photosensitive composition for an interlayer insulating film of the present invention include coumarin, ketocoumarin and derivatives thereof, thiopyrylium salts, and more specifically, p-bis (o-methyl). Styryl) benzene, 7
-Dimethylamino-4-methylquinolone-2,7-amino-4-methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 2- (p-dimethylaminostyryl) -pyridylmethyliodide, 7-diethylamino Coumarin, 7-diethylamino-4-methylcoumarin,
2,3,5,6-1H, 4H-tetrahydro-8-methylquinolizino- <9,9a, 1-gh> coumarin, 7-
Diethylamino-4-trifluoromethylcoumarin, 7
-Dimethylamino-4-trifluoromethylcoumarin,
7-ethylamino-4-trifluoromethylcoumarin,
2,3,5,6-1H, 4H-tetrahydro-9-carbethoxyquinolizino- <9,9a, 1-gh> coumarin, 3- (2'-N-methylbenzimidazolyl) -7
-N, N-diethylaminocoumarin, N-methyl-4-
Trifluoromethylpiperidino- <3,2-g> coumarin, 2- (p-dimethylaminostyryl) -benzothiazolylethyl iodide, 3- (2'-benzimidazolyl) -7-N, N- Diethylaminocoumarin, 3-
(2′-benzothiazolyl) -7-N, N-diethylaminocoumarin, and pyrylium salts and thiopyrylium salts represented by the following formula.

[0063]

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Further specific examples of the sensitizing dye include the following compounds.

[0065]

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Particularly preferred sensitizing dyes are 7-diethylamino-4-methylcoumarin and 7-diethylamino-4-methylcoumarin.
It is trifluoromethyl coumarin. When a sensitizing dye is added, in the photosensitive composition according to the present invention, the sensitizing dye is generally used with respect to the weight of the hydrolyzate of the compound represented by the general formula (1) and / or the partial condensate thereof. 0.05
It may be contained in an amount of up to 50% by weight, preferably 1 to 20% by weight.

When a sensitizing dye is mixed with the photosensitive composition according to the present invention, the resulting film may be colored.
However, when an interlayer insulating film patterned using the photosensitive composition of the present invention is manufactured and applied to a display device or the like, the fired interlayer insulating film must be transparent to visible light. May be required. Even in such a case, the photoacid generator contained in the photosensitive composition of the present invention can decompose the sensitizing dye at the time of film baking to make the interlayer insulating film after baking transparent.

Further, by adding separately to the photosensitive composition of the present invention an oxidation catalyst which is not directly involved in the photoreaction, but which can decompose the sensitizing dye at the time of film baking, a more transparent interlayer insulating film can be obtained. it can. Examples of such an oxidation catalyst include palladium propionate, platinum acetylacetonate, platinum ethylacetonate, fine palladium particles,
Organic compounds of metal such as platinum fine particles, fine particles and the like can be mentioned. In the case where an oxidation catalyst is added, the amount of the compound represented by the general formula (1) in the photosensitive composition according to the present invention is generally 0.0
It may be contained in an amount of 5 to 10% by weight, preferably 0.1 to 5% by weight. In addition, by adding such an oxidation catalyst, unnecessary dyes are decomposed and decolorized, and the formation of ceramics of a hydrolyzate of the compound represented by the general formula (1) and / or a partial condensate thereof is promoted. You can also.

Further, a suitable filler and / or extender can be added to the photosensitive composition according to the present invention, if necessary. Examples of the filler include fine particles of an oxide-based inorganic substance such as silica, alumina, zirconia, and mica, or non-oxide-based inorganic substances such as silicon carbide and silicon nitride. Depending on the application, metal powder such as aluminum, zinc, and copper can be added. These fillers may be of various shapes such as needles (including whiskers), granules, and scales, or may be used alone or in combination of two or more.
Further, it is desirable that the size of the particles of these fillers is smaller than the film thickness that can be applied at one time. The amount of the filler is 0.05 parts by weight to 1 part by weight of the hydrolyzate of the compound represented by the general formula (1) and / or its partial condensate.
10 parts by weight, and a particularly preferred addition amount is 0.2 parts by weight.
The range is from 3 parts by weight to 3 parts by weight.

The photosensitive composition of the present invention may contain various pigments, leveling agents, defoamers, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, surface modifiers, plasticizers, if necessary. , A drying accelerator and a flow stopper.

The present invention also provides a method for forming a patterned interlayer insulating film using the photosensitive composition. That is, first, the photosensitive composition for an interlayer insulating film is applied to a substrate to form a photosensitive composition film, developed after pattern exposure, and baked to form a patterned interlayer insulating film.

The formation of the coating film of the photosensitive composition in the present invention can be performed by coating the photosensitive composition on a suitable substrate such as a silicon substrate or a glass substrate by a conventionally known general coating method, that is,
The coating can be performed by dip coating, roll coating, bar coating, brush coating, spray coating, flow coating, spin coating, or the like. When the substrate material is a film, gravure coating is also possible. If desired, drying of the coating film can be a separate step.

A desired film thickness can be obtained by repeatedly applying the coating once or twice or more as necessary. The preferred thickness of the interlayer insulating film is in the range of 0.5 to 4 μm.

After forming the coating film of the photosensitive composition of the present invention, it is preferable to pre-bake (heat-treat) the coating film in order to dry the coating film and reduce the amount of degassing thereafter. The pre-bake step is generally performed at a temperature of 40 to 200 ° C., preferably 60 to 120 ° C., for 10 to 180 seconds, preferably 30 to 90 seconds when using a hot plate, and 1 to 30 minutes when using a clean oven. Can be carried out for 5 to 15 minutes.

After forming a coating film of the photosensitive composition of the present invention and pre-baking as required, the coating film is irradiated with light in a pattern. As such a light source, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an excimer laser, or the like can be used. 25 as irradiation light
It is common to use light of up to 430 nm (high pressure mercury lamp). Above all, in the case of a liquid crystal display device, 430 nm
Often used light. As described above, in such a case, it is advantageous to combine a sensitizing dye with the photosensitive composition of the present invention.

The energy of the irradiation light depends on the light source and the initial film thickness, but is generally 5 to 4000 mJ / cm ² .
If it is less than 5 mJ / cm ² , the photoacid generator will not be sufficiently decomposed, while if it is more than 4000 mJ / cm ² , excessive exposure will occur, which may cause halation.

For irradiation in a pattern, a general photomask may be used, and such a photomask is well known to those skilled in the art. In general, the irradiation environment may be an ambient atmosphere (in the air) or a nitrogen atmosphere.
An atmosphere enriched in oxygen content may be employed to promote the decomposition of the photoacid generator. In the exposed portion of the photosensitive composition that has been irradiated in a pattern, an acid is generated from the photoacid generator, and the dissolution inhibitor is further cleaved by the catalytic action of the acid to form an acid. After the exposure, a post-exposure bake (PEB) is performed if necessary.

In removing the exposed portion of the photosensitive composition, that is, in developing, an aqueous alkali solution can be used as a developing solution. Examples of such an alkaline aqueous solution include aqueous solutions of tetramethylammonium hydroxide (TMAH), sodium silicate, sodium hydroxide, potassium hydroxide, and the like. In the development in the present invention, it is convenient to use an approximately 2% aqueous TMAH solution which is an industry standard alkaline developer. The time required for development depends on the film thickness and the solvent, but is generally 0.1 to 5 minutes, preferably 0.5 to 5 minutes.
~ 3 minutes. The developing temperature is generally 20 to 5
0 ° C, preferably 20-30 ° C. In the case where the patterned photosensitive composition film is used as an interlayer insulating film, it is preferable that metal ions do not exist in the coating film. Therefore, as a developing solution, an organic ammonium salt such as TMAH is used. Aqueous solutions are preferred.

By the development, the exposed portions of the photosensitive composition are removed, and the patterning is completed. The patterned photosensitive composition film can be used as a photoresist having strong chemical resistance as it is. The photoresist according to the present invention has high resolution and high dry etching resistance due to the shape improving agent. In particular, since the photoresist according to the present invention has high oxygen plasma resistance, it is very useful as a substitute for a silicon-containing resist in a two-layer resist method. After the lower layer or the substrate is etched using the photoresist according to the present invention as a protective film, the used photoresist is removed. The photoresist of the present invention may be removed by dissolution using the above-mentioned solvent.

In the present invention, the patterned photosensitive composition is baked to cure the coating film. This makes it possible to form an interlayer insulating film such as a semiconductor device having heat resistance and a low dielectric constant. Firing is generally 250-
It is performed at a temperature of 550 ° C.

[0081]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 203 parts of methyltrimethoxysilane as an alkylalkoxysilane and diisopropoxytitanium bisethylacetyl acetate (purity of 78) as a metal chelate compound
%) And 250 parts of propylene glycol monopropyl ether as an organic solvent, and then heated to 60 ° C. While stirring the reaction solution with a stirrer, a mixture of 40 parts of ion-exchanged water and 50 parts of propylene glycol monopropyl ether was added at 60 ° C. for 1 hour. The reaction was further performed at 60 ° C. for 10 hours. Then, 27 parts of acetylacetone was added, and the mixture was reduced to 40 ° C under reduced pressure.
And then diluted with propylene glycol monopropyl ether to prepare a solid content concentration of 15%. To this solution, triphenylsulfonium triflate was added as a photoacid generator so as to be 5% by weight based on the solid content of the solution. Next, a compound represented by the following structural formula was added as a dissolution inhibitor so as to be 10 wt% with respect to the solid content.

[0083]

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This solution was applied onto a silicon wafer by a spin coating method at 1500 revolutions / minute. The thickness was about 0.3 μm. Followed by 90 on a hot plate
Prebaking was performed at 60 ° C. for 60 seconds. The thus-obtained coating film on the wafer was exposed at a dose of 200 mJ / cm ² by a KrF excimer stepper, and then subjected to PEB at 90 ° C. for 60 seconds. Subsequently, 2.3 which is an alkaline aqueous solution
It was developed with an 8% TMAH aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. As a result, a 0.3 μm line and space pattern was formed. The profile of this pattern was rectangular and had a good pattern shape. The obtained patterned film is heated at 450 ° C.
The coating was cured by heating and baking for 60 minutes in a vacuum oven maintained at the above temperature. The surface of the cured coating film was smooth, and no repelling or unevenness was observed in the coating film. The heat resistance of the cured film is 600 ° C. or higher, and the relative dielectric constant is 2.7.
Met.

Example 2 7-diethylamino-4-methylcoumarin was added to the composition prepared in Example 1 as a sensitizing dye in an amount of 5 wt.
%. This solution was applied on a silicon wafer by a spin coating method at 1500 revolutions / minute. The thickness was about 0.3 μm. Subsequently, prebaking was performed on a hot plate at 90 ° C. for 60 seconds. After exposing the coating film on the wafer thus obtained by i-line contact exposure at an irradiation dose of 200 mJ / cm ² , 90
PEB was performed at 60 ° C. for 60 seconds. Subsequently, development was performed for 60 seconds using a 2.38% TMAH aqueous solution as an alkaline aqueous solution, followed by rinsing with pure water for 30 seconds. As a result, a 0.5 μm line and space pattern could be formed. The profile of this pattern was rectangular and had a good pattern shape. The obtained patterned film was heated and baked in a vacuum oven maintained at a temperature of 450 ° C. for 60 minutes to cure the coating film. The surface of the cured coating film was smooth, and no repelling or unevenness was observed in the coating film. The heat resistance of the cured film was 600 ° C. or higher, and the relative dielectric constant was 2.7.

Example 3 As an alkoxysilane having a group capable of decomposing in the presence of an acid to generate an acid (hereinafter referred to as a dissolution inhibiting group), 142 parts of a compound represented by the following structural formula and methyltrimethoxysilane 61 parts and diisopropoxytitanium bisethylacetyl acetate (purity 78) as a metal chelate compound
%) And 250 parts of propylene glycol monopropyl ether as an organic solvent were mixed and then heated to 60 ° C.

[0087]

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While stirring the reaction solution with a stirrer, a mixture of 40 parts of ion-exchanged water and 50 parts of propylene glycol monopropyl ether was added at 60 ° C. for 1 hour. The reaction was further performed at 60 ° C. for 10 hours. Then, after adding 27 parts of acetylacetone, the mixture was concentrated at 40 ° C. under reduced pressure, diluted with propylene glycol monopropyl ether, and adjusted to a solid concentration of 15%. Triphenylsulfonium triflate was added as a photoacid generator so as to be 5% by weight based on the solid content of the solution. Next, a compound represented by the following structural formula was added as a dissolution inhibitor so as to be 10 wt% with respect to the solid content.

[0089]

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This solution was applied onto a silicon wafer at 1500 revolutions / minute by spin coating. The thickness was about 0.3 μm. Followed by 90 on a hot plate
Prebaking was performed at 60 ° C. for 60 seconds. The thus-obtained coating film on the wafer was exposed at a dose of 200 mJ / cm ² by KrF excimer stepper exposure.
A 0 second PEB was performed. Subsequently, an alkaline aqueous solution is used.2.
The film was developed using a 38% TMAH aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. As a result, a 0.3 μm line and space pattern could be formed. The profile of this pattern was rectangular and had a good pattern shape. The obtained patterned film was heated and baked in a vacuum oven maintained at a temperature of 450 ° C. for 60 minutes to cure the coating film. The surface of the cured coating is smooth,
No repelling or unevenness was observed in the coating film. The heat resistance of the cured film was 600 ° C. or higher, and the relative dielectric constant was 2.8.

Example 4 To the composition prepared in Example 3, 7-diethylamino-4-methylcoumarin was added as a sensitizing dye in an amount of 5 wt.
%. This solution was applied on a silicon wafer by a spin coating method at 1500 revolutions / minute. The thickness was about 0.3 μm. Subsequently, prebaking was performed on a hot plate at 90 ° C. for 60 seconds. After exposing the coating film on the wafer thus obtained by i-line contact exposure at an irradiation dose of 200 mJ / cm ² , 90
PEB was performed at 60 ° C. for 60 seconds. Subsequently, development was performed for 60 seconds using a 2.38% TMAH aqueous solution which is an alkaline aqueous solution, and rinsed with pure water for 30 seconds. As a result, a 0.5 μm line and space pattern could be formed. The profile of this pattern was rectangular and had a good pattern shape. The obtained patterned film was heated and baked in a vacuum oven maintained at a temperature of 450 ° C. for 60 minutes to cure the coating film. The surface of the cured coating film was smooth, and no repelling or unevenness was observed in the coating film. The heat resistance of the cured film was 600 ° C. or higher, and the relative dielectric constant was 2.8.

Example 5 142 parts of a compound represented by the following structural formula as an alkoxysilane having a dissolution inhibiting group, 61 parts of methyltrimethoxysilane, and diisopropoxytitanium bisethylacetyl acetate (purity: 78%) as a metal chelate compound.
After mixing 7 parts and 250 parts of propylene glycol monopropyl ether as an organic solvent, the mixture was heated to 60 ° C.

[0093]

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While stirring the reaction solution with a stirrer, a mixture of 40 parts of ion-exchanged water and 50 parts of propylene glycol monopropyl ether was added at 60 ° C. for 1 hour. The reaction was further performed at 60 ° C. for 10 hours. Then, after adding 27 parts of acetylacetone, the mixture was concentrated at 40 ° C. under reduced pressure, diluted with propylene glycol monopropyl ether, and adjusted to a solid concentration of 15%. Triphenylsulfonium triflate was added as a photoacid generator so as to be 5% by weight based on the solid content of the solution. Next, a compound represented by the following structural formula was added as a dissolution inhibitor so as to be 10 wt% with respect to the solid content.

[0095]

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This solution was applied onto a silicon wafer by spin coating at 1500 revolutions / minute. The thickness was about 0.3 μm. Followed by 90 on a hot plate
Prebaking was performed at 60 ° C. for 60 seconds. The thus-obtained coating film on the wafer was exposed at a dose of 200 mJ / cm ² by a KrF excimer stepper, and then exposed at 90 ° C. and 60 ° C.
PEB was performed for 2 seconds. Subsequently, an alkaline solution of 2.
The film was developed using a 38% TMAH aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. As a result, a 0.3 μm line and space pattern could be formed. The profile of this pattern was rectangular and had a good pattern shape. The obtained patterned film was heated and baked in a vacuum oven maintained at a temperature of 450 ° C. for 60 minutes to cure the coating film. The surface of the cured coating is smooth,
No repelling or unevenness was observed in the coating film. The heat resistance of the cured film was 600 ° C. or higher, and the relative dielectric constant was 2.8.

Example 6 To the composition prepared in Example 1 was added 0.5% by weight of 2-nitroaniline as a water-soluble compound based on the solid.
This solution was applied on a silicon wafer by a spin coating method at 1500 revolutions / minute. The thickness was about 0.3 μm. Subsequently, prebaking was performed on a hot plate at 90 ° C. for 60 seconds. The coating film on the wafer thus obtained was irradiated with a dose of 200 mJ by a KrF excimer stepper.
After exposure at / cm ² , PEB was performed at 90 ° C. for 60 seconds. Subsequently, development was performed for 60 seconds using a 2.38% TMAH aqueous solution which is an alkaline aqueous solution, and rinsed with pure water for 30 seconds. As a result, a 0.3 μm line and space pattern could be formed. 450 ° C
The coating was cured by heating and baking for 60 minutes in a vacuum oven maintained at the above temperature. The surface of the cured coating film was smooth, and no repelling or unevenness was observed in the coating film. The heat resistance of the cured film is 600 ° C. or higher, and the relative dielectric constant is 2.8.
Met. In addition, the preservability of the photosensitive compositions of Examples 1 to 6 was all good.

Comparative Example 1 203 parts of methyltrimethoxysilane as alkylalkoxysilane and diisopropoxytitanium bisethylacetyl acetate (purity of 78) as metal chelate compound
%) And 250 parts of propylene glycol monopropyl ether as an organic solvent were mixed and then heated to 60 ° C. While stirring the reaction solution with a stirrer, a mixture of 40 parts of ion-exchanged water and 50 parts of propylene glycol monopropyl ether was added at 60 ° C. for 1 hour. The reaction was further performed at 60 ° C. for 10 hours. Then, 27 parts of acetylacetone was added, and the mixture was reduced to 40 ° C under reduced pressure.
Then, the mixture was diluted with propylene glycol monopropyl ether and adjusted to a solid concentration of 15%. This solution is applied onto a silicon wafer by spin coating.
Coating was performed at 00 revolutions / minute. The thickness was about 0.3 μm. Subsequently, prebaking was performed on a hot plate at 90 ° C. for 60 seconds. The coating film on the wafer thus obtained was irradiated with a KrF excimer stepper at an irradiation dose of 200 mJ /
After exposure at cm ² , PEB was performed at 90 ° C. for 60 seconds. Subsequently, development was carried out using a 2.38% TMAH aqueous solution as an alkaline aqueous solution for 60 seconds, and rinsing was performed with pure water for 80 seconds. However, development did not proceed, and no pattern was obtained at all.

[0099]

As described in detail above, by using the photosensitive composition of the present invention, a coating film having a uniform thickness without repelling or unevenness can be formed on a substrate such as a semiconductor substrate having thin film transistors or wiring. By exposing and developing this coating film, it is possible to form a superfine pattern with a good pattern shape at a high resolution,
By baking the obtained ultrafine pattern, a cured film having high heat resistance and low dielectric constant and suitable as an interlayer insulating film of a semiconductor device or suitable as an etching resist can be formed. Therefore, a pattern-shaped film such as a high heat resistant interlayer insulating film can be easily formed without using an etching technique including a vapor phase etching. Further, the photosensitive composition of the present invention was excellent in storage stability and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 85/00 C08L 85/00 G03F 7/11 G03F 7/11 H01L 21/312 H01L 21/312 CDF Terms (Reference) 2H025 AA02 AA18 AB16 AC04 AC08 AD03 BE00 BE10 BG00 CB41 DA40 FA17 4J002 CP03W CQ03X ED027 EE047 EQ018 ES008 EU028 EU038 EU188 EV048 EV248 EV288 EV298 FD146 FD148 FD208 GP03 5F058 AC03 AF04 AD01 AD05 AD03

Claims (11)

[Claims] (A) a hydrolyzate of a compound represented by the following general formula (1) and / or a partial condensate thereof: R ¹ _n Si (OR ² ) _4-n (1) (R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms, and n represents an integer of 0 to 2.) (B) The following general formula ( A metal chelate compound represented by 2), R ³ _t M (OR ⁴ ) _s-t (2) (R ³ is a chelating agent, M is a metal atom, and R ⁴ is a carbon atom having 2 to 5 carbon atoms.
Represents an aryl group having 6 to 20 carbon atoms, s represents a valence of M, and t represents an integer of 1 to s. (C) a compound which is decomposed by an acid to generate an acid, and (D)
A photosensitive composition comprising a compound that generates an acid upon irradiation with light. 2. The photosensitive composition according to claim 1,
And R in the general formula (1) ¹Part of is an acid-decomposable group
A photosensitive composition comprising: 3. The photosensitive composition according to claim 2, wherein the acid-decomposable group represented by R ¹ is a residue of an aliphatic alkylcarboxylic acid derivative, an alicyclic carboxylic acid derivative or an aromatic carboxylic acid derivative. A photosensitive composition, comprising: 4. The photosensitive composition according to claim 1, wherein the photosensitive composition further comprises a water-soluble compound as a shape stabilizer. 5. The photosensitive composition according to claim 1, wherein M in the metal chelate compound represented by the general formula (2) is at least one selected from titanium, zirconium and aluminum. A photosensitive composition, comprising: 6. The photosensitive composition according to claim 4, wherein the water-soluble compound as a shape stabilizer is a compound containing a nitro group. 7. The photosensitive composition according to claim 1, wherein said photosensitive composition further comprises (E) a propylene glycol monoalkyl ether and / or (F) a β-diketone. A photosensitive composition comprising: 8. The photosensitive composition according to claim 7, wherein
A photosensitive composition, wherein the propylene glycol monoalkyl ether is at least one selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. 9. The photosensitive composition according to claim 1, wherein the photosensitive composition is a photosensitive composition for forming an interlayer insulating film. 10. A method for forming an interlayer insulating film, comprising applying the photosensitive composition according to claim 1 on a substrate such as a semiconductor substrate, developing after exposure, and firing. 11. A semiconductor device having an interlayer insulating film formed by the method according to claim 10.