JP2001064579A - Composition and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a low-permittivity uniform film excellent in adhesiveness on a semiconductor substrate by using a composition containing a polyquinoline resin and a silane compound. SOLUTION: A composition comprising a silane compound represented by formula I, II of III (wherein R1 to R8 are each H, methyl, ethyl, propyl, butyl, hexyl, cycolohxyl, phenyl or benzyl; (k) is 1 or 2; (m), (a), (p), (r), (s) and (t) are each an integer of 0 to 10; and (n), (q) and (u) are each 1, 2 or 3) and a polyquinoline resin is used. Preferably, 100 pts.wt. polyquinoline resin is compounded with 0.01 to 15 pts.wt. silane compound and 600 to 2,000 pts.wt. organic solvent (e.g. phenol). Except specified areas of a circuit element, the surface of a semiconductor substrate is covered with a protective film 2; on the uncovered areas of the circuit element, a first conductor layer 3 is formed; and the semiconductor substrate 1 is coated with the composition e.g. by the spinner method and is thermally treated to form an interlayer insulation film layer 4. The process is repeated, and finally a surface protection film layer 8 is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition for forming a film and a semiconductor device.

[0002]

2. Description of the Related Art Conventionally, interlayer insulating films and surface protective films of semiconductors having a multilayer wiring structure have higher flatness than inorganic insulating films such as silicon dioxide formed by a chemical vapor deposition method or the like. And polyimide-based resins are widely used. However, polyimide resins have problems such as low heat resistance, high dielectric constant, and hygroscopicity, and their use has been limited to some elements such as bipolar ICs in terms of reliability.

[0003]

According to the first and second aspects of the present invention, there is provided an interlayer insulating film for a semiconductor substrate, which can easily form a uniform film having a low dielectric constant, low hygroscopicity and excellent adhesiveness. And / or a composition suitable for forming a surface protective film. The third aspect of the present invention provides a semiconductor device having a small signal delay, good moisture resistance, and excellent long-term reliability.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a composition comprising a polyquinoline resin and a silane compound.

In the present invention, the silane compound may be represented by the following general formula (1), general formula (2) or general formula (3):

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R
⁸ is each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group,
A phenyl group or a benzyl group; k is an integer of 1 to 2; m, a, p, r, s and t are each independently 0 to
An integer of 10; n, q and u are each independently 1 to
The compound represented by the formula (1) represents an integer of 3).

Further, the present invention relates to a semiconductor device having a film formed using the above composition as an interlayer insulating film and / or a surface protective film of a semiconductor substrate.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyquinoline resin in the present invention is a polymer having a quinoline ring in a repeating unit. Polyquinoline resins are described, for example, in U.S. Pat.
No. 0,187, U.S. Pat. No. 5,017,677, U.S. Pat. No. 5,247,050, Macromolecules, Vol. 14, (1981),
It is described together with the synthesis method on pages 870 to 880 (JKStille) and the like.

In addition to the polyquinoline resin, a difluoromonomer having a quinoline ring can be used separately from the above-mentioned synthesis method.
The diol monomer and optionally used monofluoromonohydroxy monomer (usually, each monomer is used in a usage ratio such that the fluoro group and the hydroxy group are substantially equivalent) and the base are heated in an anhydrous solvent. Alternatively, it can be produced by azeotropically removing water. Also,
It can also be produced by heating a monofluoromonohydroxy monomer and a base in an anhydrous solvent and azeotropically removing water. The heating conditions at this time are appropriately determined in consideration of the azeotropic temperature / reflux temperature of the solvent to be used, but are usually 100 to 250 ° C. and 1 to 24 hours.

Examples of difluoromonomers having a quinoline ring include 2- (2-fluorophenyl) -5-fluoro-4-phenylquinoline, 2- (4-fluorophenyl) -5-fluoro-4-phenylquinoline, 4-
(2-fluorophenyl) -5-fluoro-2-phenylquinoline, 2- (4-fluorophenyl) -7-fluoro-4-phenylquinoline, 2,4-difluoroquinoline, 2,7-difluoroquinoline, 2, 5-difluoroquinoline, 2,7-difluoro-6-phenylquinoline, 4- (4-fluorophenyl) -7-fluoroquinoline, 6,6'-bis [2- (4-fluorophenyl)
-4-phenylquinoline], 6,6'-bis [2- (2
-Fluorophenyl) -4-phenylquinoline], 6,
6'-bis [2- (4-fluorophenyl) -4-te
rt-butylquinoline], 6,6'-bis [4- (4-
Fluorophenyl) -2phenylquinoline], 6,6 ′
-Bis-4-fluoroquinoline, 6,6'-bis [4-
(4-fluorophenyl) -2- (2-pyridyl) quinoline], 6,6'-bis-2-fluoroquinoline, 6,
6'-bis [4- (4-fluorophenyl) -2- (methyl) quinoline], 6,6'-bis [2-fluoro-4
-Phenylquinoline], oxy-6,6'-bis [2-
(4-fluorophenyl) -4-phenylquinoline],
1,4-benzene-bis-2,2- [4- (4-fluorophenyl) quinoline], 1,4-benzene-bis-
2,2- [4-fluoroquinoline], 1,4-benzene-bis-4,4- [2- (4-fluorophenyl) quinoline], 1,1,1,3,3,3-hexafluoroisopropyl Ridene-bis-[(4-phenoxy-4-phenyl) -2- (4-fluoroquinoline)] and the like. These are used alone or in combination of two or more.

Examples of the diol monomer include resorcinol, hydroquinone, 4,4'-dihydroxybiphenyl, 1,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 3,4'-dihydroxybiphenyl. , 3,3'-dihydroxybiphenyl, methyl-2,4-dihydroxybenzoate, isopropylidene diphenol (bisphenol A), hexafluoroisopropylidene diphenol (bisphenol AF), trifluoroisopropylidene diphenol, phenolphthalein, phenol Red, 1,2-di (4-hydroxyphenyl) ethane, di (4-hydroxyphenyl) methane, 4,4-
Dihydroxybenzophenone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 3,3'-diamino-
4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl ether,
4,4'-diamino-3,3'-dihydroxydiphenyl ether, etc., which are used alone or in combination of two or more.

Examples of the monofluoromonohydroxy monomer include 2- (4-fluorophenyl) -6-hydroxy-4-phenylquinoline, 2- (2-fluorophenyl) -6-hydroxy-4-phenylquinoline,
-(2-fluorophenyl) -6-hydroxy-2-phenylquinoline, 2,3-diphenyl-4- (2-fluorophenyl) -6-hydroxyquinoline, 2,3-diphenyl-4- (4-fluorophenyl ) -6-Hydroxyquinoline, 2,3-diphenyl-6- (2-fluorophenyl) -4-hydroxyquinoline, 2,3-diphenyl-6- (4-fluorophenyl) -4-hydroxyquinoline, 7-fluoro -2-hydroxyquinoline,
7-fluoro-2-hydroxy-4-phenylquinoline, 7- (4-fluorophenyl) -2-hydroxy-
4-phenylquinoline, 7-fluoro-4-hydroxy-4-phenylquinoline, 7- (4-fluorophenyl) -4-hydroxy-2-phenylquinoline, 2-
(4-fluorophenyl) -4-hydroxy-3-phenylquinoline, 2- (4-fluorophenyl) -6-hydroxy-3-phenylquinoline, 2- (4-fluorophenyl) -8-hydroxy-3-phenyl Quinoline,
2- (4-fluorophenyl) -8-hydroxyquinoline, 2- (2-fluorophenyl) -4- (4-hydroxyphenyl) quinoline and the like can be mentioned. These are used alone or in combination of two or more.

Examples of the solvent used for the synthesis include, for example,
N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, tetramethylurea, dimethylsulfoxide, sulfolane, diphenylsulfone, toluene, dichlorobenzene and the like. These are used alone or in combination of two or more. Examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, metal hydride, metal amide, butyllithium and the like. These are used alone or in combination of two or more.

As the polyquinoline resin, the following general formula (I) or general formula (II) is preferred from the viewpoints of handleability, electric characteristics, low hygroscopicity and the like.

Embedded image [Wherein, R ⁹ and R ¹⁰ are each independently an alkyl group, an aryl group, an alkoxy group, an allyloxy group, a formyl group (—COH), a ketone group (—COR ¹¹ ), an ester group (—CO ₂ R ¹² or -OCOR ^13), amide group (-
NR ¹⁴ COR ¹⁵ or —CONR ¹⁶ R ¹⁷ ), a heteroaryl group, a cyano group, or a divalent hydrocarbon group which may contain an unsaturated bond formed by connecting two groups, provided that R ^{11 to} R ^{11 17} represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group), b and c are each independently an integer of 0 to 5, X is absent (chemical bond),
-O -, - S -, - CO -, - SO -, - SO 2 -, -
A-,-(OA) _q -O- or -Q- (where q is 1 to
And A is -Ar ^1- (arylene group);
-Hr ¹ - (heteroarylene ^{group), - Ar 1 -O-Ar} 1
-, -Ar ¹ -CO-Ar ^1- , -Ar ¹ -S-Ar ^1- ,
-Ar ¹ -SO-Ar ^1- , Ar ¹ -SO ₂ -Ar ¹ -or -Ar ¹ -Q-Ar ¹ , wherein Q is

Embedded image (L ¹ and L ² are a methyl group, a trifluoromethyl group or 2
Z ¹ and Z ² each independently represent absent (chemical bond) or an arylene group; Represents -O- or -O-A-O-]], and is preferably a polyquinoline resin having a repeating unit represented by the following formula:

In the definition of the above formula (I) or (II), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group and a tert-butyl group. Groups, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, decyl, undecyl, dodecyl, docosyl and the like. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a diphenylphenyl group and the like. Examples of the heteroaryl group include a pyridyl group, a quinolinidyl group, and a pyrazyl group.

Two R ⁹ , two R ¹⁰ , and L ¹ and L
Examples of the divalent hydrocarbon group which may include an unsaturated bond and are formed by connecting two of ² each include, for example, a 1,3-propylene group, a 1,4-butylene group,
Alkylene group such as 5-pentylene group, -CH = CH-C
H = CH-,

Embedded image And the like.

The molecular weight of the polyquinoline resin is not particularly limited as long as the composition of the present invention can be applied to a substrate as a uniform film, but the weight-average molecular weight is determined by gel permeation chromatography (GPC). Measurement), but 10,000 to 1,
20,000, preferably 20,000 to
More preferably, it is 200,000. The molecular weight of the resin can be appropriately selected according to the purpose and conditions of the coating film formation, such as the thickness of the cured coating film to be formed and the coating method. Number average molecular weight (gel permeation chromatography (G
PC) using a standard polystyrene calibration curve), preferably from 1,000 to 400,000, more preferably from 5,000 to 200,000.

In the present invention, the composition containing the polyquinoline resin and the silane compound may contain an organic solvent. As the organic solvent, for example, phenol,
Aromatic solvents such as cresol, benzene, toluene, and mesitylene; ketone solvents such as cyclopentanone and cyclohexanone; ether solvents such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; and ester solvents such as γ-butyrolactone. Amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, and N-cyclohexylpyrrolidone. These are used alone or in combination of two or more. Among these solvents, ketone solvents and amide solvents are preferred.

When an organic solvent is used, its compounding amount is
From the viewpoints of coatability, obtaining a predetermined thickness, uniformity of the film, and the like, the amount is preferably 100 to 3500 parts by weight, more preferably 200 to 2500 parts by weight, and more preferably 600 to 2500 parts by weight based on 100 parts by weight of the polyquinoline resin. It is particularly preferred that the amount is 2,000 parts by weight.

As the silane compound in the present invention, the following general formula (1), general formula (2) or general formula (3)

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R
⁸ is each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group,
A phenyl group or a benzyl group; k is an integer of 1 to 2; m, a, p, r, s and t are each independently 0 to
An integer of 10; n, q and u are each independently 1 to
And an integer of 3).

Such compounds include, for example, 3-
Aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3
-Aminopropyldimethylmethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropyldiethylmethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldiethylethoxysilane, 3-aminopropyltripropoxysilane, 3
-Aminopropylmethyldipropoxysilane, 3-aminopropyldimethylpropoxysilane, 3-aminopropyltributoxysilane, 3-aminopropylmethyldibutoxysilane, 3-aminopropyldimethylbutoxysilane, 3-aminopropyltrihexylsilane, 3 −
Aminopropylmethyldihexylsilane, 3-aminopropyldimethylhexylsilane, 3-cyclohexylaminopropyltriethoxysilane, 3-cyclohexylaminopropylmethyldiethoxysilane, 3-cyclohexylaminopropyldimethylethoxysilane, 3-cyclohexylaminopropyltrimethoxysilane , 3-
Cyclohexylaminopropylmethyldimethoxysilane, 3-cyclohexylaminopropyldimethylmethoxysilane, 3-cyclohexylaminopropylethyldimethoxysilane, 3-cyclohexylaminopropyldiethylmethoxysilane, 3-cyclohexylaminopropylethyldiethoxysilane, 3-cyclohexylaminopropyldiethyl Ethoxysilane, 3-cyclohexylaminopropyltripropoxysilane, 3-cyclohexylaminopropylmethyldipropoxysilane, 3-
Cyclohexylaminopropyldimethylpropoxysilane, 3-cyclohexylaminopropyltributoxysilane, 3-cyclohexylaminopropylmethyldibutoxysilane, 3-cyclohexylaminopropyldimethylbutoxysilane, 3-cyclohexylaminopropyltrihexylsilane, 3-cyclohexylaminopropylmethyl Dihexylsilane, 3-cyclohexylaminopropyldimethylhexylsilane, 3-benzylaminopropyltriethoxysilane, 3-benzylaminopropylmethyldiethoxysilane, 3-benzylaminopropyldimethylethoxysilane, 3-benzylaminopropyltrimethoxysilane, 3 -Benzylaminopropylmethyldimethoxysilane, 3-benzylaminopropyldimethylmethoxy Orchid, 3-benzylaminopropylethyldimethoxysilane, 3-benzylaminopropyldiethylmethoxysilane, 3-benzylaminopropylethyldiethoxysilane, 3-benzylaminopropyldiethylethoxysilane, 3-benzylaminopropyltripropoxysilane, 3- Benzylaminopropylmethyldipropoxysilane, 3-benzylaminopropyldimethylpropoxysilane, 3-benzylaminopropyltributoxysilane, 3-benzylaminopropylmethyldibutoxysilane, 3-benzylaminopropyldimethylbutoxysilane, 3-benzylaminopropyl Trihexylsilane, 3-benzylaminopropylmethyldihexylsilane, 3-benzylaminopropyldimethylhexylsilane, 2-aminoethyl Aminomethyltrimethoxysilane, 2-aminoethylaminomethyltriethoxysilane, 2-aminoethylaminomethyltripropoxysilane, 2-aminoethylaminomethyltributoxysilane, 2-aminoethylaminomethyltrihexylsilane, 3- (2 -Aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 3- (2-aminoethylaminopropyl) tripropoxysilane, 3- (2-aminoethylaminopropyl) tributoxy Silane, 3-
(2-aminoethylaminopropyl) trihexylsilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, 3- (2-aminoethylaminopropyl) diethoxymethylsilane, 3- (2-aminoethylaminopropyl ) Dipropoxymethylsilane, 3- (2
-Aminoethylaminopropyl) dibutoxymethylsilane, 3- (2-aminoethylaminopropyl) dihexylmethylsilane, 3- (2- (2-aminoethylaminoethylamino) propyl) trimethoxysilane, 3-
(2- (2-aminoethylaminoethylamino) propyl) triethoxysilane, 3- (2- (2-aminoethylaminoethylamino) propyl) tripropoxysilane, 3- (2- (2-aminoethylamino) Ethylamino) propyl) tributoxysilane, 3- (2- (2-
Aminoethylaminoethylamino) propyl) trihexyloxysilane and the like.

Among them, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane,
Aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropyldiethylmethoxysilane, 3-aminopropylethyldiethoxysilane, 3-
Aminopropyldiethylethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropylmethyldipropoxysilane, 3-aminopropyldimethylpropoxysilane, 3-aminopropyltributoxysilane, 3-aminopropylmethyldibutoxysilane, 3-
Aminopropyldimethylbutoxysilane, 3-aminopropyltrihexylsilane, 3-aminopropylmethyldihexylsilane, 3-aminopropyldimethylhexylsilane and the like are preferable, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 3-
Aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropyldiethylmethoxysilane, 3-aminopropylethyldiethoxysilane, 3-
Aminopropyldiethylethoxysilane and the like are more preferred. These are used alone or in combination of two or more.

The amount of the silane compound used is preferably 0.001 to 50 parts by weight, more preferably 0.01 to 25 parts by weight, and more preferably 0.01 to 15 parts by weight, based on 100 parts by weight of the polyquinoline resin. It is particularly preferred that the amount is by weight. If the amount of the silane compound is less than 0.001 part by weight, the target adhesiveness tends not to be obtained. If the amount of the silane compound exceeds 50 parts by weight, it tends to be difficult to obtain a stable coating film.
It should be noted that the addition of other resins, additives, and the like to the composition of the present invention is not limited as long as the effects of the present invention are not impaired.

One example of the manufacturing process of the semiconductor device of the present invention will be described below with reference to the drawings. FIG. 1 is an example of a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In FIG. 1, a semiconductor substrate 1 such as a Si substrate, a glass plate, or a metal plate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element. One conductor layer 3 is formed. The composition of the present invention is applied on the semiconductor substrate by a spinner method or the like, and the solvent is removed by heat treatment to form an interlayer insulating film 4 (step (a)).

Next, for example, a photosensitive resin layer 5 of a chlorinated rubber type or a phenol novolak type is formed on the interlayer insulating film 4 by a spinner method, and a predetermined portion of the interlayer insulating film 4 is exposed by a photolithography technique. Is provided with a window 6A (step (b)). The interlayer insulating film 4 of the window 6A is made of oxygen,
The window 6B is selectively etched by dry etching using a gas such as carbon tetrafluoride.
Next, an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B, for example, when the photosensitive resin layer 5 is the above-described one, is exposed to light using n-butyl acetate or the like. The resin layer 5 is completely removed (step (c)).

Further, the second conductor layer 7 is formed by using a known metal film forming method and a photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (step (d)).

When a multilayer wiring structure having three or more layers is formed, each of the above steps is repeated to form each layer. That is, a step (a) of forming an interlayer insulating film to be an insulating layer on the conductor layer, and a step (b) of selectively removing a predetermined portion of the coating and opening a window to expose a lower conductor layer.
And (c) and step (d) of forming an upper conductor extending over the coating and connected to a predetermined portion of the lower conductor layer.

Next, a surface protection film 8 is formed. The protective film 8 is formed by applying the composition of the present invention on the uppermost conductive layer of a semiconductor device having a multilayer wiring structure in the same manner, and then forming a window 6C on a predetermined portion.
Is formed (step (e)). The conductor layer can be protected from external moisture, foreign matter, and the like by the surface protection film 8.

In the semiconductor device of the present invention, even if a film formed by using the composition of the present invention is used only as an interlayer insulating film or a surface protective film of the semiconductor device, It may be used for both the film and the surface protective film. Further, the film may be used as a buffer coat film of a semiconductor device. For example, the film is formed on the surface protective film 8, and the film is formed by the same method as the formation of the surface protective film 8. You.

[0029]

The present invention will be described below in more detail with reference to examples. Synthesis Example 1 (Synthesis of polyquinoline resin) 6,6'-bis (2- (4 "-fluorophenyl) -4
-Phenylquinoline) 74.3 g (0.124 mol,
1.03 equivalents), 4,4 '-(1,1,1,3,3,3
-Hexafluoro-2,2-propylidene) bisphenol 46.9 g (0.121 mol, 1.00 equivalent), anhydrous potassium carbonate 25 g (0.181 mol, 1.5 equivalent)
Was added to a 1-liter stainless steel flask, and 450 ml of N-methyl-2-pyrrolidone and 90 ml of toluene were used as solvents.
Was added. A water-cooled cooling tube equipped with a calcium chloride tube and a Dean-Stark tube for removing water, a dry nitrogen introduction tube, a mechanical stirrer, and a thermometer were installed. The mixture was heated under reflux for 24 hours using an oil bath, and water in the system was distilled off together with toluene for 24 hours. The solution was initially yellow, but gradually turned brown and black at this stage. Further, the reaction temperature was raised to 200 ° C., and the reaction was performed for 6 hours. The reaction solution changed from black to deep blue as the viscosity increased. N-methyl-2-pyrrolidone 6
The reaction was stopped by adding 50 ml and diluting and cooling.

In order to purify the obtained polymer solution,
It was poured into water and precipitated. Subsequently, after repeating the washing and stirring three times in water at 50 ° C. for 2 hours, the polymer was separated by filtration and dried overnight in a vacuum dryer at 60 ° C. The yield of the polymer was 101.1 g (89.0%). Its weight average molecular weight was 87,000 in terms of polystyrene.

Synthesis Example 2 (Synthesis of polyquinoline resin) 6,6'-bis (2) was placed in a 2 liter round bottom three-necked flask equipped with a mechanical stirrer, a Dean-Stark tube equipped with a condenser and a nitrogen inlet tube, and a thermometer. -(4 "-fluorophenyl) -4-phenylquinoline) 114.7
5 g (0.1941 mol, 1.03 equivalent), 9,9-bis (4-hydroxyphenyl) fluorene 66.05 g
(0.1885 mol, 1.00 equivalent), potassium carbonate 3
9.1 g (0.28 mol, 1.5 equivalents), N-methyl-
705 ml of pyrrolidone and 421 ml of toluene were charged. The reaction mixture was heated under a nitrogen atmosphere for 15 hours. The toluene was removed via a Dean-Stark tube and the reaction mixture was further heated at 200 ° C. for 12 hours. Then the reaction mixture was diluted with N-methyl-pyrrolidone and cooled to room temperature. The polymer was condensed by slowly pouring the resulting polymer solution into three volumes of acetone. The polymer was collected by filtration, dissolved in N-methyl-pyrrolidone and condensed with three volumes of water. Also, the polymer was collected and dried at 130 ° C. under vacuum for 12 hours. The polymer yield was 170 g (99%). Its number average molecular weight was 46,900 in terms of polystyrene.

Example 1 To 100 parts by weight of the polyquinoline resin obtained in Synthesis Example 1, 900 parts by weight of cyclopentanone was added, and the mixture was mixed uniformly at room temperature. As a silane compound, 5 parts by weight of 3-aminopropyltriethoxysilane was added. Was added to obtain a polyquinoline resin solution.

Example 2 To 100 parts by weight of the polyquinoline resin obtained in Synthesis Example 2, 900 parts by weight of N-methylpyrrolidone was added, and the mixture was homogenized at room temperature, and 5 parts by weight of 3-aminopropyltriethoxysilane was used as a silane compound. Was added to obtain a polyquinoline resin solution.

Example 3 To 100 parts by weight of the polyquinoline resin obtained in Synthesis Example 1, 900 parts by weight of cyclopentanone was added, and the mixture was uniformly mixed at room temperature. Further, 2-aminoethylaminomethyltrimethoxysilane was used as a silane compound. 5 parts by weight were added to obtain a polyquinoline resin solution.

Example 4 To 100 parts by weight of the polyquinoline resin obtained in Synthesis Example 2, 900 parts by weight of N-methylpyrrolidone was added, and the mixture was homogenized at room temperature and further treated with 2-aminoethylaminomethyltrimethoxysilane 5 as a silane compound. By weight, a polyquinoline resin solution was obtained.

Comparative Example 1 A polyquinoline resin solution was prepared in Example 1 to which no silane compound was added.

Comparative Example 2 A polyquinoline resin solution prepared in Example 2 without adding a silane compound was prepared.

Adhesion Evaluation Method The polyquinoline resin solutions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were spin-coated on various substrates described in Tables 1 to 5 using a polyquinoline resin solution, and then subjected to a diffusion furnace. A film was formed by heat treatment at 400 ° C. for 1 hour. A pressure cooker test (PCT) was performed on the obtained substrate with a film. Thereafter, the adhesiveness was evaluated by a grid test. The results are shown in Tables 1 to 5. Here, it was described as 0 when the adhesion was good and it did not peel. In addition, when all were peeled, it was described as 100.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

[Table 5]

[0044]

The composition according to the first and second aspects of the present invention has a low dielectric constant, low hygroscopicity, and can easily form a uniform film excellent in adhesiveness. It is suitable for forming a surface protective film. The semiconductor device according to claim 3 has a small signal delay, good moisture resistance, and excellent long-term reliability.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a manufacturing process of a semiconductor device having a multilayer wiring structure, which is an example of the semiconductor device of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 semiconductor substrate 2 protective film 3 first conductive layer 4 interlayer insulating film layer 5 photosensitive resin layer 6A, 6B, 6C window 7 second conductive layer 8 surface protective film layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Koichi Abe 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside Hitachi Chemical Co., Ltd. F-term in Kasei Kogyo R & D Co., Ltd.

Claims (3)

[Claims] 1. A composition comprising a polyquinoline resin and a silane compound. 2. A silane compound represented by the following general formula (1), general formula (2) or general formula (3): (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R
⁸ is each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group,
A phenyl group or a benzyl group; k is an integer of 1 to 2; m, a, p, r, s and t are each independently 0 to
An integer of 10; n, q and u are each independently 1 to
The composition according to claim 1, which is a compound represented by the formula: 3. A semiconductor device comprising a film formed using the composition according to claim 1 as an interlayer insulating film and / or a surface protective film of a semiconductor substrate.