JPH11231532A - Photosensitive resin composition, manufacture of pattern and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive resin composition remarkably excellent in transmittance to 'i' line and capable of forming a pattern good in profiles and forming a polyimide film low in dielectric constant, and high in sensitivity and to provide the pattern forming method and the semiconductor device superior in reliability by using this composition. SOLUTION: This photosensitive resin composition contains a polyimide precursor having respecting units represented by the formula in which X is a tetravalent aliphatic or alicyclic group; Y is a divalent organic group having a fluorine atom; and each of R<1> and R<2> is a hydroxyl group or univalent organic group and at least one of them is an organic group having a photosensitive group. The pattern is formed by irradiating a coating film of this composition through a mask having a pattern depicted with activated rays of 365 nm in wavelength and developing it to remove the unexposed parts, and the semiconductor device is manufactured by using the polyimide pattern obtained by this manufacturing method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition using a polyimide precursor having high i-line transparency, a method for producing a pattern using the same, and a semiconductor device.

[0002]

2. Description of the Related Art In recent years, in the semiconductor industry, an organic material having excellent heat resistance, such as a polyimide resin, has been used as an interlayer insulating material which has conventionally used an inorganic material, taking advantage of its characteristics. However, formation of a circuit pattern on a semiconductor integrated circuit or a printed circuit board is complicated and diversified, such as forming a resist material on a substrate surface, exposing a predetermined portion, removing unnecessary portions by etching, and cleaning the substrate surface. Therefore, development of a heat-resistant photosensitive material that can use a necessary portion of a resist as an insulating material as it is even after pattern formation by exposure and development is desired.

[0003] As these materials, for example, heat-resistant light-sensitive materials based on photosensitive polyimide, cyclized polybutadiene and the like have been proposed. In particular, photosensitive polyimide has excellent heat resistance and impurities. Particular attention has been paid to its ease of removal. As such a photosensitive polyimide, a system comprising a polyimide precursor and a dichromate (Japanese Patent Publication No. 49-17374) was first proposed, but this material has practical photosensitivity. In addition, it has advantages such as high film-forming ability, but has disadvantages such as lack of storage stability and chromium ions remaining in polyimide, and thus has not been put to practical use.

[0004] In order to avoid such a problem, for example, a method of mixing a compound having a photosensitive group with a polyimide precursor (Japanese Patent Application Laid-Open No. 54-109828) is proposed. A method of reacting a functional group of a compound having a group with a functional group to provide a photosensitive group
Japanese Patent No. 24343, Japanese Patent Application Laid-Open No. 60-100143, and the like). However, these photosensitive polyimide precursors use a basic skeleton for an aromatic monomer having excellent heat resistance and mechanical properties, and due to the absorption of the polyimide precursor itself, the light transmittance in the ultraviolet region is low, The photochemical reaction in the exposed portion cannot be performed sufficiently effectively, and there is a problem that the sensitivity is low and the pattern shape is deteriorated. In recent years, with the increasing integration of semiconductors, processing rules have become increasingly smaller, and higher resolutions have been required.

For this reason, a 1: 1 projection exposure machine called a mirror projection and a reduction exposure machine called a stepper have been used instead of a conventional contact / proximity exposure machine using parallel rays.
The stepper utilizes a monochromatic light such as an excimer laser and a high-power oscillation line of an ultra-high pressure mercury lamp. Until now, g-line steppers using visible light (wavelength: 435 nm) called g-line of ultra-high pressure mercury lamps have been the mainstream stepper. However, in order to respond to the demand for finer processing rules, use g-line steppers. It is necessary to shorten the wavelength of the stepper to be used. Therefore, the exposure equipment used is from a g-line stepper (wavelength: 435 nm) to an i-line stepper (wavelength: 365 n).
m).

However, conventional photosensitive polyimide base polymers designed for contact / proximity exposure machines, mirror projection projection exposure machines and g-line steppers have low transparency for the reasons mentioned above,
Since there is almost no transmittance at the i-line (wavelength: 365 nm), a proper pattern cannot be obtained with the i-line stepper. In addition, LOC, which is a high-density mounting method for semiconductor elements, is used.
A polyimide film for surface protection is required to have a larger thickness corresponding to (lead-on-chip). However, in the case of a thick film, the problem of low transmittance becomes more serious. Therefore, there is a strong demand for a photosensitive polyimide having a high i-line transmittance and a polyimide pattern having a good pattern shape by an i-line stepper.

The diameter of a silicon wafer serving as a substrate is
It has been increasing year by year, and there has been a problem that the warpage of the silicon wafer on which the polyimide as the surface protective film is formed becomes larger than before due to the difference in thermal expansion coefficient between the polyimide and the silicon wafer. Therefore, there is a strong demand for photosensitive polyimides having even lower thermal expansion properties than conventional polyimides. In general, low thermal expansion can be achieved by making the molecular structure rigid, but in the case of the rigid structure, almost no i-line is transmitted, so that there is a problem in that the photosensitive characteristics are deteriorated. As a solution to such a problem, for example, JP-A-9-73172 describes a composition having excellent i-line transmittance. However, those specifically described in this publication have sufficient heat resistance. It did not have properties, photosensitivity and film properties.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a highly sensitive photosensitive resin composition which is remarkably excellent in i-line transmittance, can form a pattern having a good shape, and can form a polyimide film having a low dielectric constant. It is intended to provide a pattern manufacturing method using the same and a semiconductor device excellent in reliability.

[0009]

The present invention provides a compound represented by the general formula (I):

Embedded image [Wherein, X represents a tetravalent aliphatic group or an alicyclic group, Y represents a divalent organic group containing a fluorine atom, R ¹ and R ² represent a hydroxyl group or a monovalent organic group, At least one of which is a monovalent organic group having a photosensitive group].

Further, the present invention provides a polyimide precursor film having a repeating unit represented by the general formula (I) having a light transmittance of 1 μm per 10 μm film thickness at a wavelength of 365 nm.
The present invention relates to the photosensitive resin composition having a content of 0% or more.

Further, the present invention relates to a compound represented by the formula (I):
But

Embedded image And a photosensitive resin composition selected from the group consisting of:

Further, the present invention provides a compound represented by the formula (I)
But

Embedded image

Embedded image And a divalent organic group containing a fluorine atom selected from the group consisting of:

In the present invention, at least one of —COR ¹ and —COR ² in the general formula (I) has a structure in which a photosensitive group is bonded to a carboxyl group via a salt complex. And a photosensitive resin composition. Further, the present invention, at least one of -COR ¹ and -COR ² in the general formula (I) is a structural acrylic or methacrylic compound having an amino group via a salt complex is bound to a carboxyl group It relates to the above-mentioned photosensitive resin composition.

According to the present invention, further, a wavelength of 365 nm is applied from a mask on which a pattern is drawn on the coating film of the photosensitive resin composition.
The present invention relates to a method for producing a pattern, which comprises irradiating an actinic ray of nm and developing and removing an unirradiated portion. Further, the present invention relates to a semiconductor device having a polyimide resin pattern obtained by the above-mentioned manufacturing method.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide precursor used in the present invention is a compound having a repeating unit represented by the general formula (I). The polyimide precursor having a repeating unit represented by the general formula (1) is preferably a polyimide precursor having a light transmittance of 10% or more per 10 μm thickness at a wavelength of 365 nm of the film after coating and drying. , 30% or more, still more preferably 50% or more, particularly preferably 70% or more, and most preferably 90% or more. If the light transmittance is less than 10%, the photosensitive characteristics tend to be reduced, and the resolution and pattern properties tend to be poor.

X in the general formula (I) is a tetravalent aliphatic group or an alicyclic group, which is a tetravalent organic group containing no aromatic ring, and generally reacts with a diamine to form a polyamide. It is a residue of a tetracarboxylic acid capable of forming an acid. X
The total number of carbons contained in is preferably 4 to 40 groups. X
As an alicyclic group, an alicyclic group is more preferable than an aliphatic group (containing no ring structure) because of its excellent heat resistance and pattern forming property. In the case of an alicyclic group, all four binding sites are preferably present on the alicyclic ring, and the four binding sites are divided into two sets of two, and the two binding sites of each set are:
It is preferably present on a carbon atom adjacent to the alicyclic ring.

Specifically,

Embedded image Wherein n is an integer of 0 to 10; an aliphatic group represented by the following formulas: a monocyclic ring such as a cyclohexyl ring;
A group in which an individual is bonded via a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a sulfinyl group, a methylene group, a 2,2-propylene group, a carbonyl group, a dimethylsilyl group, a siloxane structure, etc., bicyclo [2. 2.1] alicyclic groups such as a condensed ring such as a heptane ring and a bicyclo [4.4.0] decane ring;

Among these, X is preferred in terms of pattern formability and the like.

Embedded image Is preferably selected from

Embedded image More preferably, it is selected from

In the general formula (I), Y is a divalent organic group containing a fluorine atom, which is generally a diamine residue capable of reacting with a tetracarboxylic acid to form a polyamic acid. As the divalent organic group containing a fluorine atom, a group containing an aromatic ring is preferable, and as the aromatic ring, a benzene ring, a naphthalene ring or the like can be mentioned, and the total number of carbon atoms contained in Y is preferably a group of 6 to 40. . Further, it is preferable that both of the two binding sites are present on the aromatic ring. Fluorine atoms are those directly bonded to the aromatic ring, those in which a perfluoroalkyl group (trifluoromethyl group or the like), a fluoroalkyl group, a fluoroalkyloxy group or the like are bonded to an aromatic ring, and those in which the fluoroalkyl group is Perfluoro-2,2- existing between the rings and connecting them
It is preferably present in a form such as that present in the form of a propenyl group. There is no particular limitation on the number of fluorine atoms,
It is preferable to have two or more, and more preferably three or more, per one Y.

Specifically, a benzene ring or a benzene ring to which a fluorine atom, a perfluoroalkyl group, another fluoroalkyl group, a fluoroalkyloxy group (for example, a group having 1 to 30 carbon atoms) is directly or indirectly bonded. Naphthalene ring, 2 to 6 of those aromatic rings are a single bond, oxygen atom, sulfur atom, sulfonyl group, sulfinyl group, methylene group, 2,2-propylene group, carbonyl group, dimethylsilyl group, siloxane structure, etc. And a group in which a plurality of aromatic rings are bonded via a perfluoro-2,2-propenyl group.

Above all, in terms of light transmittance, pattern forming property, dielectric constant and the like,

Embedded image

Embedded image It is preferable to be selected from among

Embedded image

Embedded image More preferably, it is selected from

Further, R ¹ and R ² are a hydroxyl group or a monovalent organic group, at least one of which is required to contain a photosensitive group, and it is preferable that both contain a photosensitive group. As the monovalent organic group, those containing a photosensitive group are preferable, and specific examples of the photosensitive group include a group having a carbon-carbon double bond polymerizable by light. General formula (a), general formula (b) and general formula (c)

Embedded image ^{Wherein, R 3, R 4, R} 5, R 7, R 8 and R ⁹ is hydrogen, an alkyl group, a phenyl group, groups each independently selected from a vinyl group and propenyl group, R ⁶ is Which represents a divalent organic group]. The alkyl group preferably has 1 to 4 carbon atoms. Examples of the divalent organic group represented by R ⁶ include a methylene group, an ethylene group, and a propylene group having 1 to 1 carbon atoms.
An alkylene group of 4 is preferred.

Among the monovalent organic groups represented by the general formulas (a), (b) and (c), R ⁶
Is an alkylene group having 1 to 4 carbon atoms, R ⁷ is hydrogen or a methyl group, and organic groups in which R ⁸ and R ⁹ are hydrogen realize not only high sensitivity but also easy synthesis. It is suitable for the photosensitive resin composition of the present invention.

Among these, -COR ¹ and -COR ²
Is preferably a structure in which a photosensitive group is bonded to a carboxyl group via a salt complex. Particularly, as shown in the general formula (a), an acrylic or methacrylic compound having an amino group via a salt complex Those having a structure in which the compound is bonded to a carboxyl group are preferred.

When the polyimide precursor having a repeating unit represented by the general formula (I) has a structure in which a photosensitive group is bonded to a carboxyl group via a salt complex, the polyimide precursor includes, for example, It is obtained by introducing an acrylic or methacrylic compound having an amino group into a polyimide precursor solution generated by reacting a tetracarboxylic dianhydride with a diamine. In addition, a polyimide precursor having a structure in which a photosensitive group is bonded through a covalent bond such as an ester bond is, for example, a reaction between a tetracarboxylic dianhydride and a hydroxyl group-containing acrylic compound, and the like. Known methods such as a method of amidation using a condensing agent such as dicyclohexylcarbodiimide, and a method of reacting a carboxyl group of a polyamic acid with a hydroxyl group-containing acrylic compound or the like by a covalent bond are exemplified.

The tetracarboxylic acid or a derivative thereof is represented by the general formula (II)

Embedded image Wherein, in the formula, X represents the above-mentioned one), a tetracarboxylic acid or a derivative thereof as an essential component, but i-ray transmittance, to the extent that heat resistance and the like are not reduced, other tetracarboxylic acids or a derivative thereof. Derivative components can be used.

Examples of the tetracarboxylic acid or its derivative other than the tetracarboxylic acid or its derivative represented by the above general formula (II) include, for example, oxydiphthalic acid, pyromellitic acid, 3,3 ', 4,4'-benzophenone Tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid,
1,4,5,8-naphthalenetetracarboxylic acid, 2,
3,5,6-pyridinetetracarboxylic acid, 3,4,9,
10-perylenetetracarboxylic acid, sulfonyldiphthalic acid, m-terphenyl-3,3 ', 4,4'-tetracarboxylic acid, p-terphenyl-3,3', 4,4'-tetracarboxylic acid, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis (2,3- or 3,4 -Dicarboxyphenyl) propane, 2,2-bis [4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane, 1,1,1,3,3,3-
Hexafluoro-2,2-bis [4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane, the following general formula (III)

Embedded image [Wherein, R ¹¹ and R ¹² each independently represent a carbon number of 1 to 1
0 represents a monovalent hydrocarbon group, and s represents an integer of 1 to 10], such as an aromatic tetracarboxylic acid such as a tetracarboxylic anhydride, which may be used alone or in combination of two or more. They can be used in combination.

Examples of the tetracarboxylic acid derivative include tetracarboxylic dianhydride and tetracarboxylic acid chloride. As a reaction partner of the diamine, tetracarboxylic dianhydride is preferable from the viewpoint of reactivity.

The diamine is represented by the general formula (IV)

Embedded image [Wherein, Y represents the above], the diamine represented by the essential component is used, but other diamines are used as the amine component to such an extent that the i-line transmittance, heat resistance and low dielectric property are not reduced. be able to.

The diamine component other than the diamine of the general formula (IV) is not particularly limited. For example, 4,4'- (or 3,4'-, 3,3'-, 2,4'- or 2 , 2 '
-) Diaminodiphenyl ether, 4,4'- (or 3,4'-, 3,3'-, 2,4'- or 2,2'-)
Diaminodiphenylmethane, 4,4 '-(or 3,4'
-, 3,3'-, 2,4'- or 2,2'-) diaminodiphenyl sulfone, 4,4'- (or 3,4'-,
3,3'-, 2,4'- or 2,2 '-) diaminodiphenyl sulfide, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o- Trizine sulfone,
4,4'-methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5
-Diaminonaphthalene, 4,4'-benzophenonediamine, bis [4- (4'-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4'-aminophenoxy) phenyl] propane, 3,3 ' -Dimethyl-
4,4'-diaminodiphenylmethane, 3,3 ', 5
5'-tetramethyl-4,4'-diaminodiphenylmethane, bis [4- (3'-aminophenoxy) phenyl] sulfone, 2,2-bis (4-aminophenyl) propane, etc., which are used alone Alternatively, two or more types are used in combination.

The general formula (V)

Embedded image [Wherein, R ¹³ and R ¹⁴ each independently have 1 to 10 carbon atoms.
Wherein R ¹⁵ and R ¹⁶ each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, and t represents 1
Diamine such as diaminopolysiloxane represented by the following formula:

The amount of the diamine represented by the above general formula (IV) is preferably in the range of 10 to 100 mol%, more preferably 30 to 100 mol%, and more preferably 50 to 100 mol% of the total amount of the diamine. It is particularly preferred to be 100 mol%. If the amount is less than 10 mol%, the transmittance tends to decrease, and the mechanical and thermal properties of the polyimide film tend to decrease.

As the organic solvent used for the synthesis of the polyimide precursor, a polar solvent that completely dissolves the produced polyimide precursor is preferable. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylacetamide N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone and the like can be mentioned. In addition to these polar solvents, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like can also be used, for example, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone ,
Methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane,
Examples thereof include 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, oxane, benzene, toluene, and xylene. These organic solvents are
Used alone or in combination of two or more.

Among the polyimide precursors having a repeating unit represented by the general formula (I), those having a photosensitive group bonded via a salt complex include, as described above, the tetracarboxylic acid of the general formula (II) or Reacting the derivative with a diamine,
The obtained general formula (Ia)

Embedded image Wherein, in the formula, X and Y represent the same as described above, a photosensitive group is introduced by reacting at least one of the carboxyl groups of the polyimide precursor having a repeating unit with an amine compound having a photosensitive group. Thus obtained.

The amine having a photosensitive group in the present invention is preferably an acryl or methacryl compound having an amino group, and examples thereof include N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, and the like. N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminopropyl acrylate, N, N-dimethylaminoethyl acrylamide,
N, N-dimethylaminoethylacrylamide and the like. These can be used alone or in combination of two or more. The amount of the acrylic or methacrylic compound having an amino group is from 1 to 200 with respect to the amount of the compound having a repeating unit represented by the general formula (I).
% By weight, and more preferably 5 to 150% by weight. If the amount is less than 1% by weight, the photosensitivity tends to be inferior, and if it exceeds 200% by weight, the heat resistance and the mechanical properties of the film tend to be inferior.

It is necessary that the polyimide precursor used in the present invention has a repeating unit represented by the above general formula (I), and the content of the repeating unit is preferably at least 10 mol%. , 30 mol% or more, more preferably 50 mol% or more, and particularly preferably 70 mol% or more.
If the content is less than 10 mol%, low dielectric properties, transparency, mechanical strength, and the like tend to be poor.

The polyimide film can be synthesized by subjecting a polyimide precursor having a repeating unit represented by the above general formula (I) to imide ring closure. The imide ring closure can be usually performed by heating. The heating conditions are not particularly limited, but the heating temperature is preferably from 80 to 450 ° C. When the heating temperature is lower than 80 ° C., the ring closure reaction tends to be slow,
If it exceeds 450 ° C., the produced polyimide tends to deteriorate. The heating time is preferably set to 10 to 100 minutes. If the heating time is less than 10 minutes,
The ring closure reaction tends to be slow, and if it exceeds 100 minutes,
The resulting polyimide tends to deteriorate, and the workability tends to decrease. The dielectric constant of the polyimide film is
It is preferably 3.0 or less. This dielectric constant is 3.0
When the ratio exceeds, the processing capability of the semiconductor element tends to be slow.

The photosensitive resin composition of the present invention contains a polyimide precursor having a repeating unit represented by the above general formula (I) as an essential component. If necessary, a photoinitiator may be used. Can be contained. Michler's ketone, benzoin methyl ether,
Benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4-bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxy Cyclohexyl phenyl ketone,
2-methyl-4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl, diphenylsulfide, phenanthrenequinone, 2-isopropylthioxanthone, riboflavin tetrabutyrate, 2,6-bis (p-diethylaminoben Monkey) -4-methyl-4-
Azacyclohexanone, N-ethyl-N- (p-chlorophenyl) glycine, N-phenyldiethanolamine, 2- (o-ethoxycarbonyl) oxyimino-
1,3-diphenylpropanedione, 1-phenyl-2
-(O-ethoxycarbonyl) oxyiminopropane-
1-one, 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone, 3,3-carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) -bis- [2,6 -Difluoro-3-
(Pyri-1-yl) phenyl] titanium and the like. These can be used alone or in combination of two or more.

The amount of the photoinitiator to be used is preferably 0.01 to 30% by weight based on the amount of the polyimide precursor having a repeating unit represented by the general formula (I).
More preferably, the content is set to 05 to 10% by weight. If the amount is less than 0.01% by weight, the photosensitivity tends to be inferior, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

Further, the photosensitive resin composition of the present invention may further contain an addition polymerizable compound, if necessary. Examples of the addition polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane. Triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate , Pentaerythritol triacrylate, pentaerythritol tetraacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyl toluene, 4-vinyl pyridine, N- vinylpyrrolidone, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2
-Hydroxypropane, methylenebisacrylamide,
N, N-dimethylacrylamide, N-methylolacrylamide and the like can be mentioned. These can be used alone or
More than one type can be used in combination.

The amount of the addition polymerizable compound used is preferably 1 to 200% by weight based on the amount of the polyimide precursor having a repeating unit represented by the general formula (I). If the amount is less than 1% by weight, the photosensitive characteristics including solubility in a developing solution tend to be inferior, and if it exceeds 200% by weight, the mechanical characteristics of the film tend to be inferior.

Further, an azide compound can be added to the photosensitive resin composition of the present invention, if necessary. The azide compound includes, for example, compounds of the following formulas, which can be used alone or in combination of two or more.

[0043]

Embedded image

[0044]

Embedded image

The amount of the azide compound used is preferably 0.01 to 30% by weight based on the polyimide precursor having a repeating unit represented by the general formula (I).
More preferably, the content is set to 05 to 10% by weight. If the amount is less than 0.01% by weight, the photosensitivity tends to be inferior, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

Further, a radical polymerization inhibitor or a radical polymerization inhibitor can be added to the photosensitive resin composition of the present invention in order to enhance the stability during storage. As the radical polymerization inhibitor or the radical polymerization inhibitor, for example,
p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthraquinone, N-phenyl-1-naphthylamine, N -Phenyl-2-naphthylamine, cupron,
Examples include 2,5-toluquinone, tannic acid, p-benzylaminophenol, and nitrosamines. These can be used alone or in combination of two or more.

The amount of the radical polymerization inhibitor or the radical polymerization inhibitor is preferably 0.01 to 30% by weight based on the weight of the polyimide precursor having the repeating unit represented by the general formula (I). More preferably, the content is 0.05 to 10% by weight. If the amount is less than 0.01% by weight, the storage stability tends to be poor, and if it exceeds 30% by weight, the photosensitivity and the mechanical properties of the film tend to be inferior.

The photosensitive resin composition of the present invention is applied to a substrate such as a silicon wafer, a metal substrate, a ceramic substrate or the like by a method such as an immersion method, a spray method, a screen printing method, a spin coating method and the like. By removing the portion by heating, a coating film having no tackiness can be obtained. The thickness of the coating film is not particularly limited, but may be 4 to 4 in terms of circuit characteristics and the like.
It is preferably 50 μm, more preferably 6 to 40 μm, particularly preferably 10 to 40 μm, and most preferably 20 to 35 μm. On this coating film, after exposing in a pattern by a method such as irradiating actinic rays or actinic rays through a mask on which a desired pattern is drawn, the unexposed portion is developed and dissolved with an appropriate developing solution, and removed. By doing so, a desired relief pattern can be obtained.

The photosensitive resin composition of the present invention is suitable for exposure to i-rays (wavelength: 365 nm). As the actinic rays or actinic rays to be irradiated, besides the i-rays, for example, an ultra-high pressure mercury lamp may be used. A contact / proximity exposure machine, a mirror projection exposure machine, a g-ray stepper, and other ultraviolet, visible, X-ray, and electron beams can be used.

Examples of the developing solution include, for example, good solvents (such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, and dimethylsulfoxide); Examples thereof include a mixed solvent with a poor solvent (lower alcohol, ketone, water, aromatic hydrocarbon, etc.) and a basic solution (tetramethylammonium hydroxide aqueous solution, triethanolamine aqueous solution, etc.). After development, rinsing with water or a poor solvent, if necessary, and drying at about 100 ° C. are preferable to make the pattern stable.

By heating this relief pattern, a patterned high heat-resistant polyimide film can be formed. The heating temperature at this time is 150 to 5
The temperature is preferably set to 00 ° C, more preferably 200 to 400 ° C. If the heating temperature is lower than 150 ° C., the mechanical properties and thermal properties of the polyimide film tend to decrease, and if it exceeds 500 ° C., the mechanical properties and thermal properties of the polyimide film tend to decrease. Further, the heating time at this time is preferably 0.05 to 10 hours. If the heating time is less than 0.05 hours, the mechanical and thermal properties of the polyimide film tend to decrease, and
If the time exceeds 0 hours, the mechanical properties and thermal properties of the polyimide film tend to decrease.

The photosensitive resin composition of the present invention thus obtained can be used for forming a surface protective film and an interlayer insulating film of a semiconductor device, an interlayer insulating film of a multilayer wiring board, and the like. The semiconductor device of the present invention obtained using the composition has a polyimide resin pattern obtained from the composition as a surface protective film or an interlayer insulating film, but other than that, there is no particular limitation, and various structures are taken. be able to. Since the polyimide resin pattern can have a dielectric constant of 3.0 or less, the processing capability of the semiconductor is fast and the reliability is excellent.

[0053]

Next, the present invention will be described in more detail with reference to examples. Synthesis Examples 1 to 4 In a 100 ml flask equipped with a stirrer and a thermometer, Table 1 was prepared.
And the N-methyl-2-pyrrolidone shown in (1) was added, and the mixture was stirred and dissolved at room temperature. The acid component shown in Table 1 was added to this solution, and the mixture was stirred for 30 hours. A solution of a viscous polyimide precursor having units was obtained. The solution was heated at 50 ° C. for 3 hours to obtain a viscosity of 8
0 poise (solid content 25% by weight), and the obtained polyimide precursor solution (PAA-1 to PAA-4 in the table).
Abbreviated). In addition, diamine component, acid component and N-
Table 1 also shows the amounts of methyl-2-pyrrolidone used.

The viscosity was measured using an E-type viscometer (Toki Sangyo Co., Ltd.)
, EHD type) at a temperature of 25 ° C and a rotation speed of 2.
It was measured as 5 rpm. Further, an infrared absorption spectrum (manufactured by JEOL Ltd., JIR-100 type) of the dried solution of the obtained polyimide precursor (PAA-1 to PAA-4) was measured by the KBr method. In each case, the absorption of C = O of the amide group near 1600 cm ^-1 ,
The absorption of NH was confirmed at around 3300 cm ^-1 .

The symbols in the table mean the following. HBPDA: bis (3,4-dicarboxylcyclohexyl) dianhydride ODPA: oxydiphthalic dianhydride s-BPDA: biphenyltetracarboxylic dianhydride TFDB: bis (4-amino-2-trifluoromethylphenyl) LS7430: 1,3-bis (3-aminopropyl) tetramethyldisiloxane o-TD: o-tolidine PPD: p-phenylenediamine NMP: N-methyl-2-pyrrolidone

[0056]

[Table 1]

Examples 1-2 and Comparative Examples 1-2 Solutions (P) of the respective polyimide precursors obtained in Synthesis Examples 1-4
AA-1 to PAA4) per 10 g of 2,6-bis (4'-azidobenzal) -4-carboxycyclohexanone (hereinafter sometimes abbreviated as CA) 0.027
g, 0.027 g of 4,4'-bis (diethylamino) benzophenone (hereinafter may be abbreviated as EAB) and 1-phenyl-2- (O-ethoxycarbonyl) oxyiminopropan-1-one (hereinafter, PDO) 0.054 g), dimethylaminopropyl methacrylate equivalent to the carboxyl group of the polyimide precursor (hereinafter sometimes abbreviated as MDAP) was added, and the mixture was stirred and mixed. ~ 2 and Comparative Example 1
~ 2 uniform photosensitive resin composition solutions were obtained. The structural formulas of the above CA, EAB, PDO and MDAP are shown below.

[0058]

Embedded image

The obtained photosensitive resin composition was filtered with a filter, and each was spin-coated on a silicon wafer by dropping. Then, at 100 ° C. for 150 hours using a hot plate.
After heating for 2 seconds to form a coating film of 23 μm, it was exposed with an i-line stepper using a pattern mask. Add 10 more
Heat at 0 ° C. for 60 seconds and add N-methyl-2-pyrrolidone /
Paddle development was performed using a mixed solution of water (75/25 (weight ratio)), and this was heated at 100 ° C. for 30 minutes, 200 ° C. for 30 seconds, and 350 ° C. for 60 minutes to obtain a polyimide relief pattern. An infrared absorption spectrum of a part of the obtained polyimide relief pattern was measured by the KBr method. As a result, characteristic absorption of the imide was confirmed at around 1780 cm ^-1 .

The transmittance of each of the polyimide precursors (PAA-1 to PAA-4) obtained in Synthesis Examples 1 to 4, the dielectric constant of the polyimide film obtained above and the resolution of the relief pattern were determined by the following methods. The evaluation was performed, and the evaluation results are shown in Table 2. The transmittance was determined by spin-coating the obtained resin solution of each of the polyimide precursors (PAA-1 to PAA-4) and drying at 85 ° C. for 3 minutes and further at 105 ° C. for 3 minutes to obtain a coating film (10 μm ) Was measured with a spectrophotometer. The dielectric constant is determined by depositing aluminum on a polyimide film and using an LCR meter (HP
4284A). The resolution was evaluated as the minimum size of a developable through hole using a through hole test pattern.

Next, the above Examples 1 and 2 and Comparative Examples 1 and 2
The relief pattern obtained in Step 2 was heated at 100 ° C. for 30 minutes,
The polyimide pattern was obtained by heating at 00 ° C. for 30 minutes and under a nitrogen atmosphere at 350 ° C. for 60 minutes. The polyimide pattern obtained from the relief patterns of Examples 1 and 2 had a good trapezoidal pattern shape reflecting that the pattern shape of the relief pattern was rectangular and had good resolution. The polyimide pattern obtained from the relief patterns of Examples 1 and 2 had an undesired inverted trapezoidal pattern shape reflecting that the pattern shape of the relief pattern was inverted trapezoidal and the resolution was poor.

[0062]

[Table 2]

Example 3 Example 1 except that 2,6-bis (4'-azidobenzal) -4-carboxycyclohexanone was not used.
The same operation as in Example 1 was evaluated, and a good result almost equivalent to that of Example 1 was obtained.

Example 4 Example 2 except that 2,6-bis (4'-azidobenzal) -4-carboxycyclohexanone was not used.
The same operation as in Example 2 was evaluated, and a good result almost equivalent to that of Example 2 was obtained.

[0065]

The photosensitive resin composition of the present invention has a good i
It can form a polyimide film that has high transmittance, high sensitivity, good shape pattern and low dielectric constant at the same time, and is suitable for forming a surface protection film for semiconductors and an interlayer insulating film of a multilayer wiring board. is there. Further, according to the pattern manufacturing method of the present invention, it is possible to form a polyimide film having both high sensitivity, a good shape pattern and a low dielectric constant. Further, the semiconductor device of the present invention has a polyimide film having both a good shape pattern and a low dielectric constant, and is excellent in reliability.

Claims (8)

[Claims] 1. A compound of the general formula (I) [Wherein, X represents a tetravalent aliphatic group or an alicyclic group, Y represents a divalent organic group containing a fluorine atom, R ¹ and R ² represent a hydroxyl group or a monovalent organic group, At least one of them is a monovalent organic group having a photosensitive group.] A polyimide resin having a repeating unit represented by the following formula: 2. The photosensitive resin composition according to claim 1, wherein the polyimide precursor film having a repeating unit represented by the general formula (I) has a light transmittance of 10% or more per 10 μm thickness at a wavelength of 365 nm. . (3) X in the general formula (I) is The photosensitive resin composition according to claim 1, which is selected from the group consisting of: (4) Y in the general formula (I) is Embedded image 4. The photosensitive resin composition according to claim 1, which is a divalent organic group containing a fluorine atom selected from the group consisting of: Wherein -COR ¹ and -CO in the general formula (I)
At least one of R ² has a structure in which a photosensitive group is bonded to a carboxyl group via a salt complex.
5. The photosensitive resin composition according to 3 or 4. 6. A compound represented by the formula (I) wherein —COR ¹ and —CO
6. The photosensitive resin composition according to claim 1, wherein at least one of R ² has a structure in which an acrylic or methacrylic compound having an amino group is bonded to a carboxyl group via a salt complex. 7. Irradiating an actinic ray having a wavelength of 365 nm from a mask on which a pattern is drawn on a coating film of the photosensitive resin composition according to any one of claims 1 to 6, and developing and removing an unirradiated portion. A pattern manufacturing method characterized by the above-mentioned. 8. A semiconductor device having a polyimide resin pattern obtained by the method according to claim 7.