JP2001131469A - Film-forming composition, method for forming film and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film-forming composition having excellent processability and capable of forming a film which is excellent in heat resistance, low in dielectric constant and excellent mechanical strengths, and also a film-forming method and a film. SOLUTION: A film-forming composition comprises (A) a polymer containing not less than 10 mole % of recurring units of the following formula (1), (B) an organic compound whose temperature of reduction by 5 wt.% ranges from 200 to 400 deg.C when measured under conditions of a heating rate of 10 deg.C.min in nitrogen by TG/DTAS, and (C) an organic solvent -[C≡C-Y-C≡C-Ar]- (wherein Y represents a specific type of divalent organic group, and Ar represents a divalent aromatic group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition for forming a film,
The present invention relates to a method for forming a film and a film. More specifically, LS
I, system LSI, DRAM, SDRAM, RDRA
Low dielectric interlayer insulating films for semiconductor devices such as M and D-RDRAMs; protective films such as surface coat films for semiconductor devices; low dielectric interlayer insulating films for multilayer wiring substrates; protective films and insulating films for liquid crystal display devices. The present invention relates to a film-forming composition, a film-forming method, and a film that can form a coating film having excellent workability, heat resistance, low dielectric properties, and mechanical strength, which is suitable as a raw material such as.

[0002]

2. Description of the Related Art In recent years, in the field of electronic materials, with the progress of high integration, multifunctionality, and high performance, circuit resistance and capacitance between wirings have increased, leading to an increase in power consumption and delay time. Have been. Above all, an increase in the delay time is a major factor in lowering the signal speed of the device and generating crosstalk. Therefore, in order to reduce the delay time and increase the speed of the device, it is necessary to reduce the parasitic resistance and the parasitic capacitance. Have been. As one of specific measures for reducing the parasitic capacitance, attempts have been made to cover the periphery of the wiring with a low dielectric interlayer insulating film. In addition, the interlayer insulating film is required to have excellent heat resistance that can withstand post-processes such as a thin film forming step in manufacturing a mounting substrate, chip connection, and pinning, and chemical resistance that can withstand a wet process. Furthermore, in recent years, Al
With the introduction of low-resistance Cu wiring from wiring, flattening by CMP (chemical mechanical polishing) is becoming common, and mechanical strength that can withstand this process is required.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and has been made in consideration of an LSI, a system LSI,
Interlayer insulating film for semiconductor devices such as DRAM, SDRAM, RDRAM, D-RDRAM; protective film such as surface coat film of semiconductor device; interlayer insulating film of multilayer wiring board; protective film for liquid crystal display device, insulating film, gas Suitable for raw materials such as separation membranes, with excellent workability, heat resistance, low dielectric properties,
Another object of the present invention is to provide a composition for forming a film, a method for forming a film, and a film capable of forming a coating film having excellent mechanical strength.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have intensively studied a polymer suitable as a raw material of an insulating film or a protective film, and as a result, have a specific repeating unit in a specific mole% or more. Novel polymers have been found to be suitable. This novel polymer can be cross-linked at a low temperature by heating to cause a specific repeating unit to undergo a Bergman cyclization and to generate an aryl radical. Was applied to a substrate and heated to form a film suitable for an insulating film and a protective film, thereby completing the present invention. That is, the present invention provides the following film-forming composition, cured film, and a method for forming a cured film.

[1] (A) a polymer containing 10 mol% or more of a repeating unit represented by the following formula (1): (B) TG / DTA
5 under a condition of a heating rate of 10 ° C./min under nitrogen
A composition for forming a film, comprising: an organic compound having a% weight loss temperature of 200 to 400 ° C .; and (C) an organic solvent.

[0006]

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In the formula (1), Y represents a divalent organic group represented by the following formula (2) or (3), and Ar represents a divalent aromatic group. ]

[0008]

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[In the formula (2), R ^{1 and} R ² may be the same or different and are located at the cis position, and represent a hydrogen atom, an alkyl group or an aryl group. ]

[0010]

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[In the formula (3), R ^{3 to} R ⁶ may be the same or different, and represent a hydrogen atom, a fluorine atom, an alkyl group,
It represents a halogenated alkyl group or an aryl group. ]

[0012]

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[In the formula (1), Y represents a divalent organic group represented by the following formula (2) or (3), and Ar represents a divalent aromatic group. ]

[0014]

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[In the formula (2), R ^{1 and} R ² may be the same or different and represent a hydrogen atom, an alkyl group or an aryl group. ]

[0016]

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[In the formula (3), R ^{3 to} R ⁶ may be the same or different, and represent a hydrogen atom, a fluorine atom, an alkyl group,
It represents a halogenated alkyl group or an aryl group. ]

[2] The organic compound (B) is a polyalkylene glycol derivative, polystyrene derivative, epoxy derivative, novolak resin, melamine resin, polyester, polycarbonate, (meth) acrylate copolymer, vinylpyrrolidone copolymer, acrylamide The film-forming composition according to [1], which is at least one selected from the group consisting of a copolymer, an aliphatic polyamide, an abietic acid derivative, a cholesterol derivative, and a cyclodextrin derivative.

[3] The composition for film formation according to [1] or [2] is applied on a substrate and heated at a temperature lower than the thermal decomposition temperature of the organic compound (B) to form the diyne-containing ( Both)
A method for forming a film, comprising partially curing the polymer (A) and then heating the film at a temperature equal to or higher than the thermal decomposition temperature of the compound (B).

[4] The method for forming a film according to the above [3], wherein the film is formed in a vacuum or an atmosphere of an inert gas.

[5] A film formed by the method for forming a film according to [3] or [4].

[6] It is an insulating film [5]
A membrane according to claim 1.

The film-forming composition of the present invention comprises, as a base polymer for forming a film, (A) a diyne-containing (co) polymer (A) having a specific repeating unit in a specific mol% or more and a specific weight average molecular weight. Hereinafter, as a material that contains a “polymer (A)” and forms a porous material, (B) a specific organic compound (hereinafter, referred to as “polymer (A)”)
(Sometimes referred to as “compound (B)”), and as a solvent for the polymer (A) and the compound (B), (C)
Since an organic solvent (hereinafter, sometimes referred to as “solvent (C)”) is used, a coating film having excellent heat resistance, low dielectric properties, and mechanical strength can be formed. Further, the method for forming a film of the present invention comprises applying the above-described composition to a substrate such as a silicon wafer, and heating under a specific temperature condition to remove the compound (B) and the solvent (C); The polymer (A) is heat-cured. By this forming method, a macromolecular film of the polymer (A) can be formed, and the compound (B) is decomposed and removed to form a film. Micropores can be formed. Therefore, a film formed by the method for forming a film of the present invention has a low density, is excellent in heat resistance, low dielectric property, and mechanical strength, and can be suitably used as an interlayer insulating film material in a semiconductor element or the like. .

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. I. Film-forming composition The film-forming composition of the present invention comprises (A) a polymer containing at least 10 mol% of the repeating unit represented by the above formula (1), (B) TG
It is characterized by comprising an organic compound having a 5% weight loss temperature of 200 to 400 ° C. measured by a / DTA under nitrogen at a temperature increasing rate of 10 ° C./min, and (C) an organic solvent.

The total solid content of the film-forming composition of the present invention is preferably 2 to 30% by weight and can be appropriately adjusted according to the purpose of use. When the total solid content of the composition is 2 to 30% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent.

Hereinafter, the film forming composition of the present invention will be described more specifically for each component.

1. Polymer (A) (1) Repeating unit represented by the formula (1) The polymer (A) used in the present invention has a repeating unit represented by the formula (1) in an amount of 10 mol% or more.
Equation (1) is again shown below for convenience of explanation.

[0028]

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[In the formula (1), Y represents a divalent organic group represented by the following formula (2) or (3), and Ar represents a divalent aromatic group. ]

[0030]

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[In the formula (2), R ^{1 and} R ² may be the same or different and are at a cis position and represent a hydrogen atom, an alkyl group or an aryl group. ]

[0032]

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[In the formula (3), R ^{3 to} R ⁶ may be the same or different, and represent a hydrogen atom, a fluorine atom, an alkyl group,
It represents a halogenated alkyl group or an aryl group. ]

In the formula (2), the alkyl group represented by R ^{1 to} R ² includes a methyl group, an ethyl group, an isopropyl group, an n-propyl group and the like; and the aryl group includes a phenyl group and the like. it can.

The alkyl groups represented by R ^{3 to} R ⁶ in the formula (3) include a methyl group, an ethyl group, an isopropyl group, an n-propyl group and the like; a halogenated alkyl group includes a trifluoromethyl group, Pentafluoroethyl group and the like; Examples of the aryl group include a phenyl group and a pentafluorophenyl group.

Examples of the divalent organic group represented by Y in the above formula (1) include a cis-vinylene group and a 1,2-phenylene group.

Examples of the divalent aromatic group represented by Ar in the above formula (1) include a 1,2-phenylene group,
Examples thereof include a 3-phenylene group, a 1,4-phenylene group, and groups (a) to (f) shown below.

[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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[0043]

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Among them, 1,3-phenylene group, 1,4-
Phenylene groups, the groups (a) and (d) are preferred.

The polymer (A) used in the present invention contains the repeating unit represented by the formula (1) in an amount of at least 10 mol%, preferably at least 20 mol%, more preferably at least 30 mol%, particularly preferably at least 50 mol%. It has at least mol%. If it is less than 10 mol%, the solvent resistance becomes insufficient.

(2) Weight Average Molecular Weight The weight average molecular weight of the polymer (A) used in the present invention is as follows:
500-1,000,000, preferably 1,000-
200,000. If it is less than 500, the coating properties will be insufficient, and if it exceeds 1,000,000, the organic solvent solubility will be insufficient or the viscosity will be high, and the coating film (cured film) will lack smoothness. Become something.

(3) Blending Amount The blending amount of the polymer (A) is relative to the blending amounts of the compound (B) and the solvent (C) as the other blending components. When the amount is 100 parts by weight,
The compounding amount of the compound (B) is 1 to 400 parts by weight, and the compounding amount of the solvent (C) is 50 to 10,000 parts by weight. That is, the weight ratio of the polymer (A), the compound (B) and the solvent (C) is (A) :( B) :( C) = 1: 0.
01 to 4: 0.5 to 100.

2. Compound (B) By using the compound (B) in the film-forming composition of the present invention, the density of the obtained coating film can be reduced and low dielectric properties can be achieved. Therefore, the obtained film is useful as an interlayer low dielectric insulating film in a semiconductor device or the like.

The compound (B) used in the present invention includes a 5% weight measured by TG (thermogravimetry) / DTA (differential thermal analysis) under nitrogen at a heating rate of 10 ° C./min. There is no particular limitation as long as the decrease temperature is 200 to 400 ° C., for example, polyalkylene glycol derivative, polystyrene derivative, epoxy derivative, novolak resin, melamine resin, polyester, polycarbonate, (meth) acrylate copolymer, vinyl At least one selected from the group consisting of pyrrolidone copolymers, acrylamide copolymers, aliphatic polyamides, abietic acid derivatives, cholesterol derivatives and cyclodextrin derivatives can be mentioned.

(1) Specific Examples of Compound (B) Polyalkylene Glycol Derivatives Examples of the polyalkylene glycol derivatives used in the present invention include polyalkylene glycol compounds having 2 to 12 carbon atoms. Specifically, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol, polyethylene glycol-polypropylene glycol block copolymer, polyethylene glycol-polytetramethylene glycol block copolymer, polyethylene Glycol-polypropylene glycol-polyethylene glycol block copolymer and its methyl ether, ethyl ether, propyl ether, trimethoxysilyl ether, triethoxysilyl ether, tripropoxysilyl ether, trimethoxysilylmethyl ether, triethoxysilylmethyl ether, Trimethoxysilyl ethyl ether, 2-
In addition to triethoxysilylethyl ether, 3-trimethoxysilylpropyl ether, 3-triethoxysilylpropyl ether, etc., polyethylene glycol monopentyl ether, polyethylene glycol monohexyl ether, polyethylene glycol monoheptyl ether, polyethylene glycol monooctyl ether, polyethylene Glycol monononyl ether, polyethylene glycol monodecanyl ether, polyethylene glycol monoundecanyl ether, polyethylene glycol monododecanyl ether, polyethylene glycol monotridecanyl ether, polyethylene glycol monotetradecanyl ether, polyethylene glycol monopentadecanyl ether, polyethylene Glycol monohexadecanyl , Polyethylene glycol monoheptadecyl ether, polyethylene glycol monooctadecanyl ether, polyethylene glycol monononadecanyl ether, polyethylene glycol monoicosanyl ether, polyethylene glycol monohenicosanyl ether, polyethylene glycol monodocosanyl ether, polyethylene glycol mono Tricosanyl ether, polyethylene glycol monotetracosanyl ether, polyethylene glycol monopentacosanyl ether, polyethylene glycol monohexacosanyl ether, polyethylene glycol monoheptacosanyl ether, polyethylene glycol monooctacosanyl ether, polyethylene glycol monononacosanyl ether , Polyethylene glycol Polyethylene glycol alkyl ethers such as notriacontanyl ether and its methyl ether, ethyl ether, propyl ether, trimethoxysilyl ether, triethoxysilyl ether, tripropoxysilyl ether, trimethoxysilyl methyl ether, triethoxysilyl methyl ether, Polyethylene glycol alkyl ether derivatives such as 2-trimethoxysilylethyl ether, 2-triethoxysilylethyl ether, 3-trimethoxysilylpropyl ether, and 3-triethoxysilylpropyl ether;

Polyethylene glycol mono-p-methylphenyl ether, polyethylene glycol mono-p-
Ethyl phenyl ether, polyethylene glycol mono-p-propyl phenyl ether, polyethylene glycol mono-p-butyl phenyl ether, polyethylene glycol mono-p-pentyl phenyl ether, polyethylene glycol mono-p-hexyl phenyl ether, polyethylene glycol mono-p- Peptyl phenyl ether, polyethylene glycol mono-p-octyl phenyl ether, polyethylene glycol mono-p
-Nonylphenyl ether, polyethylene glycol mono-p-decanylphenyl ether, polyethylene glycol mono-p-undecanylphenyl ether, polyethylene glycol mono-p-dodecanylphenyl ether, polyethylene glycol mono-p-tridecanylphenyl ether , Polyethylene glycol mono-p-
Tetradecanyl phenyl ether, polyethylene glycol mono-p-pentadecanyl phenyl ether, polyethylene glycol mono-p-hexadecanyl phenyl ether, polyethylene glycol mono-p-heptadecanyl phenyl ether, polyethylene glycol mono-p-octadeca Nyl phenyl ether, polyethylene glycol mono-p-nonadecanyl phenyl ether,
Polyethylene glycol mono-p-icosanyl phenyl ether, polyethylene glycol mono-p-henicosanyl phenyl ether, polyethylene glycol mono-
polyethylene glycol-p-alkylphenyl ethers such as p-docosanyl phenyl ether, polyethylene glycol mono-p-tricosanyl phenyl ether, polyethylene glycol mono-p-tetracosanyl phenyl ether, and methyl ether, ethyl ether and propyl thereof; Ether, trimethoxysilyl ether,
Triethoxysilyl ether, tripropoxysilyl ether, trimethoxysilylmethyl ether, triethoxysilylmethyl ether, 2-trimethoxysilylethyl ether, 2-triethoxysilylethyl ether, 3-trimethoxysilylpropyl ether, 3-triethoxy Polyethylene glycol-p-alkylphenyl ether derivatives such as silylpropyl ether;

Polyethylene glycol monopentanoate, polyethylene glycol monohexanoate, polyethylene glycol monoheptanoate,
Polyethylene glycol monooctanoate, polyethylene glycol monononanoate, polyethylene glycol monodecanoate, polyethylene glycol monoundecanoate, polyethylene glycol monododecanoate, polyethylene glycol monotridecanoate, polyethylene glycol monotetradecanoate, Polyethylene glycol monopentadecanoate, polyethylene glycol monohexadecanoate, polyethylene glycol monoheptadecanoate, polyethylene glycol monooctadecanoate, polyethylene glycol monononadecanoate, polyethylene glycol monoicosanoate, polyethylene glycol monohexanoate Sanate ester Polyethylene glycol monodocosanoate, polyethylene glycol monotricosanoate, polyethylene glycol monotetracosanoate, polyethylene glycol monopentacosanoate, polyethylene glycol monohexacosanoate, polyethylene glycol monoheptacosanoate, polyethylene glycol Monooctacosanoic acid esters, polyethylene glycol monononaconic acid esters, polyethylene glycol alkyl acid esters such as polyethylene glycol monotricontanic acid ester and its methyl ether, ethyl ether, propyl ether, trimethoxysilyl ether, triethoxysilyl ether, Tripropoxysilyl ether,
Polyethylene glycol alkyl esters such as trimethoxysilyl methyl ether, triethoxysilyl methyl ether, 2-trimethoxysilylethyl ether, 2-triethoxysilylethyl ether, 3-trimethoxysilylpropyl ether and 3-triethoxysilylpropyl ether Derivatives and the like can be mentioned.

The weight average molecular weight of the polyalkylene glycol derivative in terms of polystyrene is preferably from 300 to 300.
300,000, more preferably 300 to 200,0
00, particularly preferably 300 to 100,000.

Polystyrene Derivatives Examples of the polystyrene derivatives used in the present invention include polystyrene, polyα-methylstyrene, polyhydroxystyrene, and styrene- (meth) acrylate copolymer.

Polyester Examples of the polyester used in the present invention include a compound containing an aliphatic chain having 2 to 12 carbon atoms and an ester bond in a repeating unit. In particular,
Polycaprolactone, polypivalolactone, polyethylene oxalate, polyethylene malonate, polyethylene succinate, polyethylene glylate, polyethylene adipate, polyethylene pimerate, polyethylene suberate, polyethylene azelate, polyethylene sebacate, polypropylene oxalate, polypropylene Malonate, polypropylene succinate, polypropylene glulate, polypropylene adipate, polypropylene pimerate, polypropylene suberate,
Polypropylene azelate, polypropylene sebacate, polybutylene oxalate, polybutylene malonate, polybutylene succinate, polybutylene glulate, polybutylene adipate, polybutylene pimerate, polybutylene belate, polybutylene azelate, poly Butylene sebacate, polyoxydiethylene oxalate, polyoxydiethylene malonate, polyoxydiethylene succinate, polyoxydiethylene glutarate, polyoxydiethylene adipate, polyoxydiethylene pimerate, polyoxydiethylene suberate, polyoxydiethylene Aliphatic polyesters such as azelate, polyoxydiethylene sebacate, etc., and their methyl ether, ethyl ether, propyl ether, trimethoxy Ethers, triethoxysilyl ethers, tripropoxysilyl ethers, trimethoxysilylmethyl ethers, triethoxysilylmethyl ethers, 2-trimethoxysilyl ethyl ether, 2
-Triethoxysilyl ethyl ether, 3-trimethoxysilylpropyl ether, 3-triethoxysilylpropyl ether, methyl ester, ethyl ester, propyl ester, trimethoxysilyl ester, triethoxysilyl ester, tripropoxysilyl ester, trimethoxysilyl Methyl ester, triethoxysilyl methyl ester, 2-trimethoxysilylethyl ester, 2-triethoxysilylethyl ester, 3
Examples thereof include aliphatic polyester alkyl ether derivatives such as -trimethoxysilylpropyl ester and 3-triethoxysilylpropyl ester, and aliphatic polyester alkyl ester derivatives.

The weight average molecular weight of the polyester in terms of polystyrene is preferably 300 to 300,000, more preferably 300 to 200,000, and particularly preferably 300 to 100,000.

Polycarbonate Examples of the polycarbonate used in the present invention include aliphatic polycarbonates having 2 to 12 carbon atoms. Specifically, polyethylene carbonate, polypropylene carbonate, polytrimethylene carbonate, polytetramethylene carbonate, polypentamethylene carbonate, polyhexamethylene carbonate, polyheptamethylene carbonate, polyoctamethylene carbonate, polynonamethylene carbonate, polydecamethylene carbonate , Polyoxydiethylene carbonate, poly-3,6-dioxyoctane carbonate, poly-3,6,9-trioxyundecane carbonate, polyoxydipropylene carbonate,
Aliphatic polycarbonates such as polycyclopentane carbonate, polycyclohexane carbonate, and the like, and methyl esters, ethyl esters, propyl esters thereof,
Trimethoxysilyl ester, triethoxysilyl ester, tripropoxysilyl ester, trimethoxysilylmethyl ester, triethoxysilylmethyl ester, 2-trimethoxysilylethyl ester, 2-triethoxysilylethyl ester, 3-trimethoxysilylpropyl ester And aliphatic polycarbonate alkyl ester derivatives such as 3-triethoxysilylpropyl ester.

The weight average molecular weight of the polycarbonate in terms of polystyrene is preferably from 300 to 300,000.
0, more preferably 300 to 200,000, particularly preferably 300 to 100,000.

(Meth) acrylate copolymer Examples of the (meth) acrylate copolymer used in the present invention include polymethyl (meth) acrylate and trimethoxysilylpropyl (meth) acrylate-methyl (meth) acrylate copolymer. And the like.

Abietic acid derivative Examples of the abietic acid derivative used in the present invention include abietic acid and methyl abietic acid.

Cyclodextrin Derivatives Examples of the cyclodextrin derivatives used in the present invention include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and methyltrimethoxysilyl-modified cyclodextrin.

The above compounds as specific examples of the compound (B) can be used alone or in combination of two or more.

(2) 5% Weight Loss Temperature The compound (B) had a 5% weight loss temperature of 200 measured under TG / DTA under nitrogen at a temperature rising rate of 10 ° C./min.
To 400 ° C, preferably 200 to 350 ° C. If the temperature is lower than 200 ° C., decomposition occurs before cross-linking of the matrix, voids cannot be formed, and 400 ° C.
If the number exceeds the limit, the semiconductor manufacturing process becomes inconvenient.

(3) Compounding Amount The compound (B) is used in an amount of 1 to 400 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the diyne-containing (co) polymer (A). It is. That is,
The weight ratio of the polymer (A) and the compound (B) is (A):
(B) = 1: 0.01 to 4, preferably 1: 0.05
~ 1. If the amount is less than 1 part by weight, the effect of lowering the dielectric constant is small, and if it exceeds 400 parts by weight, the mechanical strength decreases.

3. Solvent (C) In the film forming composition of the present invention, the solvent (C) is used for dissolving or dispersing the polymer (A) and the compound (B). Therefore, the solvent (C) used in the present invention is:
There is no particular limitation as long as it can dissolve or disperse the polymer (A) and the compound (B). Examples thereof include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, and ketone solvents. At least one selected from the group consisting of: By using these solvents, a composition having good coatability (processability) and excellent storage stability can be obtained.

(1) Specific Examples Ether Solvents Examples of ether solvents include ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolan,
4-methyldioxolan, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene Glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether,
Diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Examples thereof include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran (THF), and 2-methyltetrahydrofuran.

Ester Solvents Ester solvents include, for example, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ
Valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol mono-acetate
n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, acetic acid Methoxy triglycol, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, Examples thereof include dimethyl phthalate, diethyl phthalate, methoxymethyl propionate, and ethoxyethyl propionate.

Aromatic hydrocarbon solvents Examples of the aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, and the like.
Examples thereof include isobutylbenzene, triethylbenzene, di-isopropylbenzene, n-amylnaphthalene, and trimethylbenzene.

Amide solvents Examples of the amide solvents include N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methyl Propionamide, N-methylpyrrolidone and the like can be mentioned.

Ketone-based solvents Examples of ketone-based solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl Ketone, diisobutyl ketone, trimethyl nonanone,
Examples thereof include cyclohexanone, methylcyclohexanone, 2-hexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone.

The above compound which is a specific example of the solvent (C) is
Can be used alone or in combination of two or more.

(2) Compounding Amount The solvent (C) is used in an amount of 50 to 10,000 parts by weight, preferably 100 to 2,000 parts by weight, based on 100 parts by weight of the polymer (A). It is. That is, the weight ratio of the polymer (A) and the solvent (C) is (A) :( C) =
1: 0.5 to 100, preferably 1: 1 to 20. If it is less than 50 parts by weight, it may not be uniformly dissolved, and if it exceeds 10,000 parts by weight, a desired film thickness may not be obtained.

4. Other Compounding Components The film-forming composition of the present invention further comprises another compounding component (D) such as a surfactant and a compounding amount of the polymer (A) of 10%.
Preferably, 0.001 to 10 parts by weight may be blended with respect to 0 parts by weight.

Examples of the surfactant include, in terms of ionic species, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. From the aspect of the species, a silicone-based surfactant, a polyalkylene oxide-based surfactant, a fluorinated surfactant, and the like can be given.

II. Method for Forming Film The method for forming a film according to the present invention comprises applying the above-described film-forming composition on a substrate and heating the composition at a temperature lower than the thermal decomposition temperature of the compound (B) to partially convert the polymer (A). Curing, and then heating at a temperature equal to or higher than the thermal decomposition temperature of the compound (B) to form a film. In the above formation method, the film is preferably formed at a heating temperature of 200 to 600 ° C. and in an atmosphere of a vacuum or an inert gas.

1. Coating on Substrate In order to form a film using the above-described composition for forming a film, the composition is first applied to a substrate. Examples of a substrate on which the composition can be applied include a semiconductor, glass, ceramics, and metal. The above-mentioned composition is suitable for being applied on a semiconductor chip such as a silicon wafer, a SiO ₂ wafer, and a SiN wafer among the above-mentioned substrates to form an insulating film. Also, as the application method,
For example, spin coating, dipping, a roller blade method and the like can be mentioned.

2. Heating method Examples of the heating method include a method using a hot plate, an oven, a furnace, and the like. Examples of the heating atmosphere include a nitrogen atmosphere, an argon atmosphere, a vacuum, and a reduced pressure in which the oxygen concentration is controlled. As this heating method, the formed coating film is heated at a temperature lower than the thermal decomposition temperature of the compound (B) to partially cure the polymer (A), and then heated at a temperature higher than the thermal decomposition temperature of the compound (B). A method of heating from a temperature to a final curing temperature to obtain a low-density cured product is preferred. That is, by partially curing the polymer (A) and decomposing the compound (B) in a state where the fluidity of the matrix is sufficiently reduced, a film is formed while maintaining the shape of the pores formed by the decomposition. be able to.

The thermal decomposition temperature of compound (B) is usually 20
Since the temperature is in the range of 0 to 400 ° C., and more often in the range of 200 to 350 ° C., the coating ultimately exceeds this temperature, ie 2
It is preferable to heat at 00 to 600 ° C, and it is preferable to heat under reduced pressure (vacuum) or under an inert gas.

III. Film The film of the present invention can be formed by the above-described forming method. Since this film is porous, it has a low density and a low dielectric property. That is, the film of the present invention (hereinafter sometimes referred to as a “low-density film”) preferably has a film density of 0.35 to 1.2 g / cm ³ , more preferably 0.4 to 1. 1 g / cm ³ , particularly preferably 0.5 to
It is in the range of 1.0 g / cm ³ . 0.35
If it is less than g / cm ³ , the mechanical strength of the coating film may decrease, and if it exceeds 1.2 g / cm ³ , it may not be possible to obtain low dielectric properties. This adjustment of film density
It can be easily performed depending on the content of the compound (B) in the film-forming composition of the present invention.

The dielectric constant of the low-density film of the present invention is a low dielectric constant, preferably 2.6 to 1.2, more preferably 2.5 to 1.2, and particularly preferably 2.4 to 1.2. 1.2. The adjustment of the dielectric constant can be easily performed by adjusting the content of the compound (B) in the film forming composition.

The low-density film of the present invention is excellent in heat resistance, low dielectric property and mechanical strength as well as insulating properties.
Interlayer insulating films for semiconductor devices such as RDRAM and D-RDRAM, protective films such as surface coat films for semiconductor devices, interlayer insulating films for multilayer wiring boards, protective films for liquid crystal display devices, insulating films, gas separation films, etc. Useful for applications.

[0082]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited by these examples. In Examples,% and parts are by weight unless otherwise specified. Various measurement items in the examples were measured as described below.

(1) Weight average molecular weight It was determined by gel permeation chromatography (GPC) in terms of polystyrene. (2) Relative Dielectric Constant A composition sample was applied on an 8-inch silicon wafer by a spin coating method, and the substrate was baked on a hot plate at 80 ° C. for 5 minutes, and further at 325 ° C. or 350 ° C. for 5 minutes. Aluminum was deposited as an upper electrode on the obtained substrate to prepare a substrate for dielectric constant evaluation. The dielectric constant is
1 using a Hewlett-Packard HP16451B electrode and HP4284A precision LCR meter.
The capacitance value at 00 kHz was measured, and from the following equation,
The relative permittivity was determined. ε = C · d / ε ₀ · S Here, ε denotes a relative dielectric constant, C denotes a capacitance, ε ₀ denotes a dielectric constant in a vacuum, and S denotes an upper electrode area. (3) Heat resistance The amount of weight loss (% by weight) after holding at 425 ° C. in a nitrogen atmosphere for 2 hours was measured by TG / DTA. (4) Modulus of elasticity (GPa) The obtained film was measured by a continuous rigidity measuring method using Nanodenter XP (manufactured by Nano Instruments).

Synthesis Example 1 100 equipped with a thermometer, an argon gas inlet tube and a stirrer
In a 0 ml three-necked flask, 150 ml of diethylamine (1.
45 mol), dichlorobis (triphenylphosphine)
2.1 g (3 mmol) of palladium, 0.28 of copper iodide
6 g (1.50 mmol), 1,2-dichloroethane 3
50 ml and 99 g of 1,2-diiodobenzene were added.
Next, 18.9 g (150 mmol) of 1,4-diethynylbenzene and 26.5 g (2,1) of 1,3-diethynylbenzene
10 mmol) and reacted at 50 ° C. for 20 hours.
G of ethynylbenzene was added and the mixture was further reacted for 6 hours.
The reaction mixture was reprecipitated twice with 5 l of acetic acid, then dissolved in chloroform and washed twice with water.
Then, the precipitate was filtered and dried to obtain a brown powder (polymer A1) having a weight average molecular weight of 3,600.

Synthesis Example 2 In Synthesis Example 1, 32.7% of 4,4′-diethynyldiphenyl ether was used instead of 1,4-diethynylbenzene.
Polymer A2 was obtained in the same manner as in Synthesis Example 1 except that g (150 mmol) was used.

Synthesis Example 3 100 equipped with a thermometer, an argon gas inlet tube and a stirrer
50 g (43.3 mmol) of tetrakis (triphenylphosphene) palladium (0) in a 0 ml three-necked flask,
16.5 g (86.5 mmol) of copper iodide, 290.0 g (3.96 mol) of n-butylamine, cis-1,2
-83.8 g (0.864 mol) of dichloroethylene were added. Next, 109.0 g of 1,4-diethynylbenzene
(0.865 mol) in 870 ml of benzene,
The mixture was added with a syringe and reacted at room temperature for 6 hours to obtain a dark red reaction solution. The reaction solution was reprecipitated twice with 5 l of acetic acid, dissolved in chloroform, washed twice with water, reprecipitated with 5 l of cyclohexane, and the precipitate was filtered and dried to obtain a brown powder having a weight average molecular weight of 5000 (polymer A3). ) Got.

Synthesis Example 4 In a reactor similar to that of Synthesis Example 1, 2.11 g (3 mmol) of dichlorobis (triphenylphosphine) palladium and 1.14 g (6 mmol) of copper iodide were added, and the system was purged with argon. Under an argon atmosphere, 99 g (300 mmol) of o-diiodobenzene, 150 ml (1.52 mol) of piperidine deoxygenated by bubbling with argon, and T
350 ml of HF was added and the reaction was cooled to 10 ° C.
While stirring the system, 18.9 g (150 mmol) of 1,3-diethynylbenzene and 18.9 g (15 mmol) of 1,4-diethynylbenzene dissolved in 100 ml of THF were further added.
0 mmol) and the reaction was warmed to room temperature. Precipitation of piperidinium iodide began to form, but for two more
The mixture was stirred for 0 hours and the reaction was continued. After the polymerization reaction, the reaction mixture solution was poured into 3 liters of acetic acid to precipitate the produced polymer, and the polymer was recovered and separated by filtration. The obtained polymer was redissolved in chloroform and washed three times with water. Next, the washed polymer solution was poured into a large excess of methanol to cause coagulation and precipitation. The polymer (A4) having a yellow-orange color and a weight average molecular weight of 38,000 was obtained by filtration and vacuum drying.

Example 1 A coating solution comprising 100 parts of the polymer A1 obtained in Synthesis Example 1, 43 parts of polystyrene (weight average molecular weight 4000), 0.02 part of a silicon surfactant, and 400 parts of cyclohexanone was prepared. . This coating solution is spin-coated at 80 ° C.
Calcination was performed in an oven under nitrogen for 30 minutes to ２００200 ° C., and calcination was performed at 425 ° C. for 1 hour in vacuum. Table 1 shows the physical properties of the obtained coating film.

Examples 2 to 4 and Comparative Example 1 Example 1 was repeated except that a coating solution having the composition shown in Table 1 was prepared.
The same was done. Table 1 shows the physical properties of the obtained coating film.

Example 5 A coating solution comprising 100 parts of the polymer A4 obtained in Synthesis Example 4, 43 parts of polystyrene (weight average molecular weight 1500), 0.02 part of a silicon surfactant, and 600 parts of cyclohexanone was prepared. . Coating in the same manner as in Example 1, 80 ° C to 2
Hardening and firing were performed in an oven under nitrogen for 30 minutes up to 00 ° C, and hardening and firing were completed at 425 ° C for 30 minutes under nitrogen. As shown in Table 1, the physical properties of the obtained coating film were heat resistance of 0.3%, relative dielectric constant of 2.4, and elastic modulus of 3.8 GPa.

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[Table 1]

[0092]

As described above, according to the present invention, an LSI, a system LSI, a DRAM, an SDRAM,
Low dielectric interlayer insulating film for semiconductor devices such as RDRAM and D-RDRAM; protective film such as surface coat film of semiconductor device; low dielectric interlayer insulating film of multilayer wiring board; protective film for liquid crystal display device and insulation preventing film Suitable for raw materials such as gas separation membranes, and excellent in processability, heat resistance, low dielectric properties, and a film forming composition capable of forming a coating film excellent in mechanical strength,
A method for forming a film and a film can be provided.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Masayuki Takahashi 2-J-24, Tsukiji, Chuo-ku, Tokyo Inside JAE S.R. In-house F term (reference) 4J032 CA02 CA03 CA04 CB04 CB12 4J038 BA192 CD022 CG142 CG172 CK032 CR071 DA062 DA162 DB002 DD002 DE002 DF012 DH002 GA01 KA06 MA07 MA12 MA14 NA11 NA14 NA17 NA21 NA23 PA15 PA19 PB09 AG01A01A

Claims (6)

[Claims] 1. A polymer containing 10 mol% or more of a repeating unit represented by the following formula (1): (B) 5% measured by TG / DTA under nitrogen at a temperature rising rate of 10 ° C./minute An organic compound having a weight loss temperature of 200 to 400 ° C, and (C)
A composition for forming a film, comprising an organic solvent. Embedded image [In the formula (1), Y represents a divalent organic group represented by the following formula (2) or the following formula (3), and Ar represents a divalent aromatic group. ] [In the formula (2), R ^{1 and} R ² may be the same or different and are at a cis position, and represent a hydrogen atom, an alkyl group, or an aryl group. ] [In the formula (3), R ^{3 to} R ⁶ may be the same or different and represent a hydrogen atom, a fluorine atom, an alkyl group, a halogenated alkyl group, or an aryl group. ] (2) The organic compound (B) is a polyalkylene glycol derivative, polystyrene derivative, epoxy derivative, novolak resin, melamine resin, polyester, polycarbonate, (meth) acrylate copolymer, vinylpyrrolidone copolymer, acrylamide copolymer. The film-forming composition according to claim 1, wherein the composition is at least one selected from the group consisting of a polymer, an aliphatic polyamide, an abietic acid derivative, a cholesterol derivative, and a cyclodextrin derivative. 3. The diyne-containing (co) polymer obtained by applying the film-forming composition according to claim 1 or 2 on a substrate and heating the composition at a temperature lower than the thermal decomposition temperature of the organic compound (B). (A) is partially cured, and then heated at a temperature not lower than the thermal decomposition temperature of the compound (B) to form a film. 4. The method according to claim 3, wherein the film is formed in a vacuum or in an atmosphere of an inert gas. 5. A film formed by the film forming method according to claim 3. 6. The film according to claim 5, wherein the film is an insulating film.