JP2003306639A - Porous film, method for producing the same and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition which has a low dielectric constant, low water-absorbing characteristics, a good mechanical strength and a good adhesion performance and is used for semiconductor devices, and to provide an insulation film comprising the same. <P>SOLUTION: This composition comprising at least a component A and a component B and used for forming insulation films is characterized in that the component A is a silicon-containing resin having at least repeating units represented by the general formula (1) in repeating units and the component B is a compound having a boiling or decomposition point within a range of 220 to 500°C. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel composition for an insulating film of a semiconductor device, a method of manufacturing a porous film using the same, an insulating film, and a semiconductor device including the same, and more particularly to a low dielectric constant. The present invention relates to an insulating film material having a high rate, yet having sufficient mechanical strength and adhesion, and having excellent resistance in a chemical mechanical polishing (CMP) step.

[0002]

2. Description of the Related Art With the progress of higher integration of semiconductor integrated circuits, the problem of signal delay has been an obstacle to higher performance of semiconductor integrated circuits. The signal delay is related to the product of the resistance R of the metal wiring and the capacitance C between the wirings and between the wirings, and in order to minimize the delay, it is necessary to reduce the resistance of the metal wiring as well as the ratio of the interlayer insulating film. Reducing the dielectric constant is an effective means.

Conventionally, a silicon oxide film formed by a CVD method or a spin-on-glass (SOG) method using tetraethoxysilane (TEOS) has been used as an interlayer insulating film. However, the conventional silicon oxide film has a relative dielectric constant of 4.0, and cannot meet the recent demand for miniaturization. Therefore, a method of using a porous material for the interlayer insulating film has been proposed. Porous material is said to be the only material to achieve a dielectric constant of 2.0 or less,
Is expected. There are various porosification methods. For example, after forming an insulating film from an organic material and an inorganic material, heat treatment at high temperature removes the organic material from the inside of the film,
There is a method of making the membrane porous. The method of lowering the density of such a film is an indispensable technique for the next-generation low dielectric constant insulating film, and there is also one having a relative dielectric constant of 1.5. In addition, as a newer technology, an insulating film is formed from a resin material that has an easily decomposable group in a part of the molecule, and then heat treatment is performed at high temperature to form an insulating film with uniformly fine pores. A method for making it happen is also being considered.

However, the porous insulating films that have been proposed so far are generally liable to absorb moisture, and as a result, there is a possibility that the relative dielectric constant is increased and the wiring is corroded. There is a case where a special hydrophobic treatment is required. Further, since only a material having a low mechanical strength is obtained, damage is likely to occur particularly in the CMP process, and, for example, peeling of the film due to the CMP process is a factor that significantly reduces the yield. Furthermore, the low density of the insulating film due to the porosity is a factor that reduces the adhesion to the barrier film, the etch stopper film, etc., and further improvement of the adhesion performance of the material itself is expected.

[0005]

The object of the present invention is to solve the problems of the conventional techniques as described above, to have a low dielectric constant, yet low water absorption characteristics, good mechanical strength and adhesion performance. An insulating film for a semiconductor device having the same is provided.

[0006]

Means for Solving the Problems As a result of intensive studies to overcome the above problems, the present inventors have found that a porous film of a silicon-containing resin having a specific structure is used as an insulating film for a semiconductor device. It was found that the above problems could be solved, and the present invention was completed. That is, the invention of the present application is (1) an insulating film forming composition comprising at least an A component and a B component, wherein the A component is at least a compound represented by the general formula (1) in the repeating unit.

[0007]

[Chemical 2]

(In the formula, R ¹ and R ² each independently have a hydrogen atom, an alkyl group having 1 to 30 carbon atoms and a substituent, and a substituent having 1 to 30 carbon atoms. Is an alkenyl group having 1 to 30 carbon atoms, an alkynyl group optionally having a substituent, or an aromatic group optionally having a substituent, and R ³ is —C≡C—, at least one -C≡C-
Linked may have a substituent -CH ₂ and - at least one -C≡C- and linked alkylene group which may have a substituent group having 2 to 30, at least one -C
Alkenylene group which may have a substituent having 2 to 30 carbon atoms linked to ≡C-, and alkynylene group which may have a substituent having 2 to 30 carbon atoms linked to at least one -C≡C-. , A silicon-containing resin having a repeating unit represented by a divalent aromatic group which may have a substituent linked to at least one —C≡C—, and the component B has a boiling point or a decomposition point. A composition characterized in that it is a compound in the range of 220 to 500 ° C. (2) The composition according to (1), wherein the amount of the component B compound used is in the range of 50 to 200 parts by weight relative to 100 parts by weight of the silicon-containing resin (component A). (3) The composition according to (1) or (2), wherein the compound of the component B is a thermally decomposable polymer compound. (4) The compound of the component B is a compound containing a polyalkylene glycol chain (1) to
(3) The composition according to any one of the above. (5) A method for producing a porous membrane, which comprises applying the composition according to any one of (1) to (4) to a substrate and then removing the component B compound by heating. (6) An insulating film manufactured by the method according to (5). (7) A semiconductor device comprising the insulating film according to (6).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1) of the present invention,
Examples of the alkyl group of R ¹ and R ² which may have a substituent having 1 to 30 carbon atoms include a methyl group, an ethyl group, a propyl group,
Hexyl group, cyclohexyl group, octyl group, dodecanyl group, trifluoromethyl group, 3,3,3-trifluoropropyl group, chloromethyl group, aminomethyl group, hydroxymethyl group, silylmethyl group, 2-methoxyethyl group, etc. Examples of the alkenyl group which may have a substituent having 1 to 30 carbon atoms include vinyl group, 2-propenyl group,
Examples include isopropenyl group, 3-butenyl group, 5-hexenyl group, 1,3-butadienyl group, 3,3,3-trifluoro-1-propenyl group, and the like, having a substituent having 1 to 30 carbon atoms. Examples of the alkynyl group that may be, include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a trimethylsilylethynyl group, a phenylethynyl group, and the like, or an aromatic group that may have a substituent is phenyl. Group, naphthyl group, pyrazinyl group, 4-methylphenyl group, 4-vinylphenyl group, 4-ethynylphenyl group, 4-aminophenyl group, 4-chlorophenyl group, 4-hydroxyphenyl group, 4-carboxyphenyl group, 4 - methoxyphenyl group, 4-silyl phenyl group and the like, have at least one substituent linked with -C≡C- of R ³ There Examples -CH2- methylene group, a fluoromethylene group -C≡C- is 1 or 2
And a group in which at least one —C≡C— is present.
As the alkylene group which may have a substituent having 2 to 30 carbon atoms and which is linked to, an ethylene group, a propylene group, a tetramethylene group, a tetrafluoroethylene group or the like, in which one or two -C≡C- are bonded As the alkenylene group which may have a substituent having 2 to 30 carbon atoms and which is linked to at least one —C≡C—, vinylene group, propenylene group, butadienylene group and the like have —C≡C— of 1 Alternatively, two bonded groups may be mentioned, and the alkynylene group which may have a substituent having 2 to 30 carbon atoms and which is linked to at least one —C≡C— is, for example, an ethynylene group, a propynylene group or a butynylene group. Examples of the divalent aromatic group which may have a substituent linked to at least one -C≡C- include a phenylene group,
Naphthylene group, biphenylene group, anthracenedyl group, pyridinedyl group, thiophenedilyl group, fluorophenylene group, chlorophenylene group, methylphenylene group, silylphenylene group, hydroxyphenylene group,
Examples thereof include groups in which one or two -C≡C- are bonded to an aminophenylene group, a phenylenemethylenephenylene group, a phenyleneoxyphenylene group, a phenylenepropylidenephenylene group, a phenylene (hexafluoropropylidene) phenylene group and the like.

Specific examples of the repeating unit represented by the general formula (1) in the silicon-containing resin used in the present invention include those shown below. For example, silyleneethynylene, methylsilyleneethynylene, phenylsilyleneethynylene, silyleneethynylene-1,3-phenyleneethynylene (chemical formula (2))

[0011]

[Chemical 3]

, Silyleneethynylene-1,4-phenyleneethynylene, silyleneethynylene-1,2-phenyleneethynylene, methylsilyleneethynylene-1,3-phenyleneethynylene (chemical formula (3))

[0013]

[Chemical 4]

Methylsilyleneethynylene-1,4-phenyleneethynylene, methylsilyleneethynylene-1,
2-phenyleneethynylene, dimethylsilyleneethynylene-1,3-phenyleneethynylene, dimethylsilyleneethynylene-1,4-phenyleneethynylene, dimethylsilyleneethynylene-1,2-phenyleneethynylene,
Diethyl silylene ethynylene-1,3-phenylene ethynylene, phenyl silylene ethynylene-1,3-phenylene ethynylene (chemical formula (4))

[0015]

[Chemical 5]

Phenylsilyleneethynylene-1,4-
Phenyleneethynylene, Phenylsilyleneethynylene-
1,2-phenyleneethynylene, diphenylsilyleneethynylene-1,3-phenyleneethynylene, hexylsilyleneethynylene-1,3-phenyleneethynylene, vinylsilyleneethynylene-1,3-phenyleneethynylene (chemical formula (5 ))

[0017]

[Chemical 6]

Ethynylsilylene ethynylene-1,3-
Phenyleneethynylene, 2-propenylsilyleneethynylene-1,3-phenyleneethynylene, 2-propynylsilyleneethynylene-1,3-phenyleneethynylene,
Trifluoromethylrosyrryleneethynylene-1,3-phenyleneethynylene, 3,3,3-trifluoropropylsilyleneethynylene-1,3-phenyleneethynylene, 4
-Methylphenylsilyleneethynylene-1,3-phenyleneethynylene, 4-vinylphenylsilyleneethynylene-1,3-phenyleneethynylene, 4-ethynylphenylsilyleneethynylene-1,3-phenyleneethynylene, phenylethynylsilylene Ethynylene-1,3-phenyleneethynylene, silyleneethynylene (5-methyl-1,3-phenylene) ethynylene, phenylsilyleneethynylene (5-methyl-1,3-phenylene) ethynylene, phenylsilyleneethynylene (5 -Cyril-1,
3-phenylene) ethynylene, phenylsilyleneethynylene (5-hydroxy-1,3-phenylene) ethynylene, phenylsilyleneethynylene-2,7-naphthyleneethynylene, silyleneethynylene-5,10-anthracenediylethynylene , Phenylsilyleneethynylene-
4,4'-biphenyleneethynylene (chemical formula (6))

[0019]

[Chemical 7]

Phenylsilyleneethynylene-1,4-
Phenylenemethylene-1 ', 4'-phenyleneethynylene, phenylsilyleneethynylene-1,4-phenylene-2,2-propylidene-1', 4'-phenyleneethynylene, phenylsilyleneethynylene-1,4-phenylene -2,2- (1,1,1,3,3,3-hexafluoropropylidene) -1 ', 4'-phenyleneethynylene, (chemical formula (7))

[0021]

[Chemical 8]

Phenylsilyleneethynylene-1,4-
Phenyleneoxy-1 ', 4'-phenyleneethynylene (chemical formula (8))

[0023]

[Chemical 9]

Phenylsilyleneethynylene-2,5-
Pyridynediethylethynylene, Phenylsilyleneethynylene-2,5-thiophenedylylethynylene, Methylsilyleneethynylenemethyleneethynylene, Phenylsilylene-1,4-phenylene (phenylsilylene) ethynylene-1 ', 3'- Phenylene ethynylene (chemical formula (9))

[0025]

[Chemical 10]

Phenylsilyleneoxy (phenylsilylene) ethynylene-1 ', 3'-phenyleneethynylene (chemical formula (10))

[0027]

[Chemical 11]

Phenylsilyleneoxy (phenylsilylene) ethynylene-1 ', 4'-phenyleneethynylene,
Phenylsilyleneimino (phenylsilylene) ethynylene-1 ', 3'-phenyleneethynylene (Chemical formula (1
1))

[0029]

[Chemical 12]

Phenylsilyleneimino (phenylsilylene) ethynylene-1 ', 4'-phenyleneethynylene,
Chemical formula (12)

[0031]

[Chemical 13]

Chemical formula (13)

[0033]

[Chemical 14]

Chemical formula (14)

[0035]

[Chemical 15]

Chemical formula (15)

[0037]

[Chemical 16]

Chemical formula (16)

[0039]

[Chemical 17]

Chemical formula (17)

[0041]

[Chemical 18]

Chemical formula (18)

[0043]

[Chemical 19]

Silylene-1,3-phenyleneethynylene (chemical formula (19))

[0045]

[Chemical 20]

, Silylene-1,4-phenyleneethynylene, silylene-1,2-phenyleneethynylene, phenylsilylene-1,3-phenyleneethynylene (chemical formula (20))

[0047]

[Chemical 21]

Phenylsilylene-1,4-phenyleneethynylene, phenylsilylene-1,2-phenyleneethynylene, diphenylsilylene-1,3-phenyleneethynylene, methylsilylene-1,3-phenyleneethynylene (chemical formula ( 21))

[0049]

[Chemical formula 22]

Methylsilylene-1,4-phenyleneethynylene, methylsilylene-1,2-phenyleneethynylene, dimethylsilylene-1,3-phenyleneethynylene, diethylsilylene-1,3-phenyleneethynylene, phenylsilylene -1,3-butadiynylene, diphenylsilylene-1,3-butadiynylene, phenylsilylenemethyleneethynylene, diphenylsilylenemethyleneethynylenemethylene, phenylsilylenemethyleneethynylenemethylene, silylene-1,4-phenyleneethynylene-1 ', 4 '-Phenylene, methylsilylene-1,4-
Phenyleneethynylene-1 ', 4'-phenylene, dimethylsilylene-1,4-phenyleneethynylene-1', 4'-
Examples thereof include phenylene and phenylsilylene-1,4-phenyleneethynylene-1 ′, 4′-phenylene. The weight average molecular weight of the silicon-containing resin is not particularly limited, but is preferably 500 to 500,000. The form of these silicon-containing resins is solid or liquid at room temperature.

As the method for producing the silicon-containing resin of the present invention, a method for dehydrogenative copolymerization of a diethynyl compound and a silane compound using a basic oxide, a metal hydride, or a metal compound as a catalyst (JP-A-7-90085, Japanese Patent Laid-Open No. 10-12
0689, JP-A-11-158187), a method of dehydrogenatively polymerizing an ethynylsilane compound with a basic oxide as a catalyst (JP-A-9-143721), and a method of reacting an organomagnesium reagent with dichlorosilanes (JP-A-7-18787). −
102069, JP-A-11-029579), a method of dehydrogenative copolymerization of a diethynyl compound and a silane compound using cuprous chloride and a tertiary amine as a catalyst (Hua Qin Liu and Jo).
hn F. Harrod, The Canadian Journal of Chemistry, Vo
l. 68, 1100-1105 (1990)) can be used, but the method is not particularly limited to these.

The compound used as the component B is a compound having a boiling point or a decomposition point of 220 to 500 ° C., preferably in the range of 220 to 400 ° C. There is no particular limitation within this range, but 220 Examples of the compound having a boiling point of ℃ or more include quinoline, 2,4-tolylene diisocyanate, hexamethylphosphoric triamide, acetamide, diethylene glycol, glycerin, and the like. Polymer compounds such as polystyrene-based resins, poly (meth) acrylate-based resins, polyurethane-based resins, polyethylene-based resins and polypropylene-based resins are known resin compounds. Compounds containing polyalkylene glycol chains are preferred compounds. There is no particular limitation as long as it is a compound containing a polyalkylene glycol chain, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol,
Polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmylate, polyoxyethylene sorbitan stearate, polyoxyethylene oleate , Polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, (polyethylene glycol-polypropylene glycol) diblock copolymer Coalescence, (polyethylene glycol-polypropylene glycol-poly Such as Chi glycol) tri-block copolymers. Of these, preferred are polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, (polyethylene glycol-polypropylene glycol) diblock copolymer, and (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymer. To be The amount of these used is silicon-containing resin 1
1 to 500 parts by weight, preferably 50 to 100 parts by weight
~ 200 parts by weight. Usually, one kind is used, but several kinds of compounds can be mixed and used. The silicon-containing resin and these compounds can be mixed by a generally known method. For example, the compound is previously dissolved in an organic solvent, the silicon-containing resin is added to this solution, and the solution is uniformly dissolved to obtain a precursor for the porous membrane. It can be body fluid. Examples of usable organic solvents include aromatic solvents such as benzene, toluene and xylene, tetrahydrofuran, dioxane, ether solvents such as monoglyme, diglyme and anisole, ketone solvents such as acetone and cyclohexanone, methanol, ethanol, propanol and full solvent. Examples thereof include aliphatic alcohol solvents such as furyl alcohol, halogen-containing solvents such as dichloromethane, chloroform and freon, and organic polar solvents such as N, N-dimethylimidazolidinone, dimethylformamide, dimethylacetamide and N-methylpyrrolidone. The amount of these used depends on the film forming conditions, but usually when the precursor liquid for the film forming method by the spin coating method is used, the concentration is adjusted so as to obtain a desired film thickness. The solvent is preferably used so that the silicon-containing resin is used in an amount of 1% by weight to 50% by weight.

The method of removing the compound used as the component B is not particularly limited, but usually a composition comprising a silicon-containing resin and the compound is decomposed by heating, and the decomposed product is a silicon-containing resin. It is removed by discharging it from the inside by vaporization. The heating temperature is determined by the boiling point or the decomposition temperature of the compound used, but it is preferably carried out at a temperature below the temperature at which the silicon-containing resin deteriorates.

In order to use the porous film of the present invention as an insulating film of a semiconductor device, a coating such as a spin coating method is applied to an insulating film forming portion on a substrate, for example, a substrate on which a wiring pattern is already formed. The precursor liquid is applied by a method, and then a firing process is performed to form the precursor liquid. The thickness of the coating film is not particularly limited, but is usually 0.5 to 2 microns. The conditions in the firing step must be equal to or higher than the curing temperature of the silicon resin and the boiling point or decomposition temperature of the compound used as the B component. Regarding the method for curing the silicon resin, curing by heat is preferable, but a general thermosetting resin such as curing by reaction with a metal-free radical initiator such as azobisisobutyronitrile or benzoyl peroxide is used. A method similar to the above can also be used. When curing with heat, it may be carried out in an air atmosphere, but it is preferably carried out in an inert gas such as nitrogen, helium or argon, or under reduced pressure. The heating time is not particularly limited, but 1 minute to 100 hours is suitable. The temperature and time vary depending on the type of silicon-containing resin, the type of compound used as the mixed B component, and the type of solvent.

The fact that the insulating film is made porous can be easily observed by a transmission electron microscope photograph of a thin film obtained by vertically cutting the obtained film. In addition, as another example of the measuring method, it is also possible to obtain a pseudo pore diameter distribution by measuring scattering obtained by irradiating X-rays at a low angle, and to calculate the average pore diameter. You can Porosification can be confirmed by these measurements.

The insulating film of the semiconductor device of the present invention is characterized by having extremely high heat resistance while maintaining a low relative dielectric constant as compared with the conventional organic insulating film. The decomposition point of 5% by weight or more, which is an index as heat resistance, usually indicates 500 ° C. or higher, however, the relative dielectric constant and the mechanical strength are usually in a trade-off relationship. There is no particular limitation on the preferred mechanical strength and relative permittivity, but normally, when the relative permittivity is 4 or less, the elastic modulus is 2 GPa or more and the strength is 0.1 or less.
GPa or more is preferable.

[0057]

EXAMPLES The present invention will be described below with reference to synthesis examples, examples and comparative examples. The film was evaluated by the following method.

(Film Evaluation Method) (1) Porosity (%): The density of a film formed by coating a silicon-containing resin containing no thermally decomposable compound on a silicon wafer was measured in advance, From the comparison with the density, it was calculated by the following formula. Porosity (%) = (1- (density of film / density of silicon-containing resin without addition of thermally decomposable compound)) × 100 (2) Adhesion: Cross-cut test (tape peeling) according to JIS K5400 Test) was carried out. The same test was repeated 3 times, and an average value (n) of the number of crosses that did not cause peeling from the substrate out of 100 crosses was calculated, and this was evaluated as adhesion. The evaluation results are as follows: ○: n = 100, △
Is n = 50 or more, and x is n <50. (3) Heat resistance: Argon 100 ml / min was measured using powders scraped from a coating film formed on a silicon wafer using a differential thermogravimetric simultaneous analysis analyzer (TG / DTA-200) manufactured by Seiko Denshi Kogyo. 10 ° C under circulation
It was heated to 500 ° C. at a heating rate of / min, and it was judged whether or not the weight loss rate at 500 ° C. was within 5%. (4) Mechanical strength: The coating film formed on the silicon wafer was measured as it was without pretreatment, using an ultra light load thin film hardness tester manufactured by Hysitron. Berkovich type was used as the indenter. (5) Relative permittivity: An Al electrode having a diameter of 1 mm was attached as an upper electrode, and the value at 1 MHz was measured by an impedance analyzer. (6) Film thickness measurement: A spectroscopic ellipsometry apparatus M-150 manufactured by JASCO Corporation was used. (7) Pore diameter: An average pore diameter was calculated from the data obtained by small-angle X-ray scattering measurement using an X-ray generator manufactured by Rigaku Denki Co., Ltd.

Synthesis Example 1 JP-A-7-90085 and JP-A-10-204181
Poly (phenylsilyleneethynylene-1,3-phenyleneethynylene) was synthesized based on the method described in (1). In a 50 liter stainless steel reaction vessel, place Mg (O
H) 2 Mg burned at 400 ° C for 7 hours under nitrogen stream
3.39 kg of O, 2.16 kg of phenylsilane, m-
2.82 kg of diethynylbenzene and 27.4 liters of toluene as a solvent were charged. Next, in a nitrogen atmosphere, the reaction was carried out at 30 ° C. for 1 hour, 40 ° C. for 1 hour, 50 ° C. for 1 hour, 60 ° C. for 1 hour, and 80 ° C. for 2 hours, for a total of 6 hours. The reaction solution was filtered to separate and remove MgO.
The filtered reaction solution was concentrated under reduced pressure to 9.44 kg (polymer concentration 43% by weight). The weight average molecular weight of the concentrate is 34
00, the number average molecular weight was 1500. To this concentrated solution, 9.45 kg of n-heptane was added, stirred at room temperature for 30 minutes, and allowed to stand for 2 hours. An upper phase containing a cloudy low molecular weight component and a brown lower phase containing a high molecular weight component were separated. 3.91 kg of lower phase was taken out from the bottom, and then 4.42 kg of upper phase
Took out. The solvent of the upper phase was distilled off under reduced pressure to obtain 1.32 kg of an orange viscous liquid having a weight average molecular weight of 1460 and a number average molecular weight of 850 (yield 27%). Further, the lower phase was concentrated under reduced pressure and dried under reduced pressure at 60 ° C. for 23 hours to obtain 2.74 kg of a pale yellow powder having a weight average molecular weight (Mw) of 4890 and a number average molecular weight (Mn) of 2130 (yield 56%). Liquid and powdery poly (phenylsilylene ethynylene-
The structure of (1,3-phenyleneethynylene) is IR, NMR.
Confirmed by spectrum.

Example 1 In a 200 ml round bottom flask under a nitrogen stream, the powdery poly (phenylsilylene ethynylene) obtained in Synthesis Example 1 was used.
10.0 g of 1,3-phenyleneethynylene) and 10.0 g of polystyrene (Mn772, Aldrich reagent) were added to 80.0 g of mesitylene and stirred for 1 hour to obtain a yellow uniform solution. The liquid thus prepared was formed into a film on a silicon wafer by a spin coater, and then heated at 420 ° C. for 30 minutes in an argon atmosphere. The evaluation results of the obtained film are shown in Table 1.

Example 2 The procedure of Example 1 was repeated except that 8.0 g of the powdery poly (phenylsilylene ethynylene-1,3-phenylene ethynylene) obtained in Synthesis Example 1 and 12.0 g of polystyrene were used. Completely the same as in Example 1. The evaluation results of the obtained film are shown in Table 1 together with the results of Example 1.

Example 3 13.4 g of the powdery poly (phenylsilylene ethynylene-1,3-phenylene ethynylene) obtained in Synthesis Example 1 and 6.6 g of polystyrene were used in the same manner as in Example 1. Completely the same as in Example 1. The evaluation results of the obtained film are shown in Table 1 together with the results of Example 1.

Examples 4 and 5 In Example 1, instead of polystyrene, polytetramethylene glycol (Mn250, reagent from Aldrich, Example 4), N, N'-dimethylimidazolidinone (boiling point 225 ° C, Tokyo Kasei Co., Ltd. Example 1 was repeated except that the reagents and Example 5) were used. The evaluation results of the obtained film are shown in Table 1 together with the results of Example 1.

[0064]

[Table 1]

Example 6 The relative permittivity was measured again after leaving the porous film obtained in Example 1 in the atmosphere for 40 hours. During this time, the humidity of the atmosphere was controlled within the range of RH 45 to 55%.
As a result of the measurement, the relative dielectric constant was slightly increased from 2.5 to 2.7. From this result, in the porous membrane of the present invention,
It was found that the porous film has low water absorption characteristics with almost no increase in relative permittivity due to water absorption.

Example 7 The powdery poly (phenylsilyleneethynylene) obtained in Synthesis Example 1 was placed in a 200 ml round bottom flask under a nitrogen stream.
1,3-phenyleneethynylene) 10.0 g and Plur
onicP123 (manufactured by BASF (ethylene oxide-
co-propylene oxide block copolymer) 10.
0 g and 80.0 g of mesitylene were added and stirred for 1 hour to obtain a yellow uniform solution. The liquid thus prepared was formed on a silicon wafer by a spin coater under the condition of 2000 rpm, and then heated at 420 ° C. for 30 minutes in an argon atmosphere. The evaluation results of the obtained film are shown in Table 2.

Example 8 In Example 7, 8.0 g of the powdery poly (phenylsilyleneethynylene-1,3-phenyleneethynylene) obtained in Synthesis Example 1 and 1 of Pluronic P123 were used.
The same procedure as in Example 1 was carried out except that 2.0 g was used. The evaluation results of the obtained film are shown in Table 2 together with the result of Example 1.

Example 9 In Example 7, except that 13.4 g of the powdery poly (phenylsilyleneethynylene-1,3-phenyleneethynylene) obtained in Synthesis Example 1 and 6.6 g of Pluronic P123 were used. Completely the same as in Example 1. The evaluation results of the obtained film are shown in Table 2 together with the result of Example 7.

Example 10 Example 10 was carried out in the same manner as in Example 7 except that polyethylene oxide nonylphenyl ether (reagent of Aldrich Co.) was used instead of Pluronic P123. The evaluation results of the obtained film are shown in Table 2 together with the result of Example 7.

[0070]

[Table 2] Example 11 The relative permittivity was measured again after leaving the porous film obtained in Example 7 in the atmosphere for 40 hours. During this time, the humidity of the atmosphere was controlled within the range of RH 45 to 55%.
As a result of the measurement, the relative dielectric constant was slightly increased from 2.0 to 2.1. From this result, in the porous membrane of the present invention,
It was found that the porous film has low water absorption properties with almost no increase in relative permittivity due to water absorption.

[0071]

INDUSTRIAL APPLICABILITY The porous film of the present invention has excellent characteristics as an insulating film of a semiconductor device such as good mechanical strength and adhesion performance while having a low dielectric constant and a low water absorption property. Can be an excellent insulating film material that improves the reliability of

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 171/02 C09D 171/02 201/00 201/00 H01L 21/312 H01L 21/312 C F term (reference) ) 4J002 CH022 CP211 EC046 EC056 EP016 ER006 EW156 GQ01 4J035 HA01 HA02 HA06 JA00 LB20 4J038 DF012 DL171 NA04 NA12 NA21 PA19 PB09 5F058 AA04 AA08 AA10 AC03 AC10 AF04 AG01 AH02

Claims (7)

[Claims] 1. A composition for forming an insulating film comprising at least an A component and a B component, wherein the A component has at least one of the general formula (1): (In the formula, R ¹ and R ² are, independently of each other, a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an alkenyl which may have a substituent having 1 to 30 carbon atoms. A group, an alkynyl group having 1 to 30 carbon atoms which may have a substituent, or an aromatic group which may have a substituent, and R ³ represents
C≡C-, optionally substituted with at least one -C≡C-, -CH _2- , at least one -C≡
An alkylene group which may have a substituent having 2 to 30 carbon atoms linked to C-, an alkenylene group which may have a substituent having 2 to 30 carbon atoms linked to at least one -C≡C-, 2 carbon atoms linked to at least one -C≡C-
To 30 alkynylene groups optionally having substituents, divalent aromatic groups optionally having substituents linked to at least one -C [identical to] C-). It is a resin and the component B has a boiling point or decomposition point of 22.
A composition which is a compound in the range of 0 to 500 ° C. 2. The amount of the component B compound used is 50 to 200 with respect to 100 parts by weight of the silicon-containing resin (component A).
The composition of claim 1 in the range of parts by weight. 3. The composition according to claim 1, wherein the compound of the component B is a thermally decomposable polymer compound. 4. The composition according to claim 1, wherein the compound of the component B is a compound containing a polyalkylene glycol chain. 5. A method for producing a porous film, which comprises applying the composition according to any one of claims 1 to 4 to a substrate and then removing the compound of the component B by heating. 6. An insulating film manufactured by the method according to claim 5. 7. A semiconductor device comprising the insulating film according to claim 6.