JPH11231533A - Photosensitive resin composition, manufacture of pattern and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive resin composition high in light transmittance, especially, to KrF laser beams and capable of forming a pattern good in profiles and forming a film superior in heat resistance and mechanical characteristics and high in sensitivity and to provide the pattern forming method and the semiconductor device by using this composition. SOLUTION: This photosensitive resin composition contains a polyimide precursor having repeating 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 248.8 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 highly light-transmitting polyimide precursor, a pattern manufacturing method 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), and further to a KrF stepper (wavelength: 248.8 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,
i-line (wavelength: 365 nm) or KrF laser (wavelength: 24
(8.8 nm), the i-line stepper or the KrF stepper cannot obtain a proper pattern. 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 KrF laser transmittance and capable of obtaining a polyimide pattern having a good pattern shape by a KrF 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. Generally, low thermal expansion can be achieved by making the molecular structure rigid. However, in the case of the rigid structure, since a KrF laser is hardly transmitted, there is a problem that the photosensitive characteristics are deteriorated.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a film having high light transmittance, particularly good KrF laser wavelength transmittance, capable of forming a pattern having a good shape, and further having excellent heat resistance and mechanical properties. Formable, high-sensitivity photosensitive resin composition,
It is intended to provide a pattern manufacturing method and a semiconductor device using the same.

[0009]

The present invention relates to a compound of the formula (I)

Embedded image [Wherein, X represents a tetravalent aliphatic group or an alicyclic group, Y represents a divalent aliphatic group or an alicyclic group, and R ¹ and R ² represent a hydroxyl group or a monovalent organic group. And 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:

Further, the present invention provides the above-mentioned photosensitive composition, wherein the polyimide precursor film having the repeating unit represented by the general formula (I) has a light transmittance of 10% or more per 10 μm thickness at a wavelength of 248.8 nm. The present invention relates to a conductive resin composition. The present invention also relates to the photosensitive resin composition, wherein X in the general formula (I) is an alicyclic group. Further, the present invention relates to the photosensitive resin composition, wherein Y in the general formula (I) is an alicyclic group containing an alicyclic ring which is a condensed ring.
Further, the present invention provides the above-mentioned photosensitive resin, wherein 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. 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.

[0011] The present invention further relates to a photosensitive resin composition coated film having a wavelength of 24
The present invention relates to a method for producing a pattern, which comprises irradiating an 8.8 nm actinic ray 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 manufacturing method.

[0012]

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 a polyimide precursor having a light transmittance of 10% or more per 10 μm of film thickness at a wavelength of 248.8 nm after coating and drying. Is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% 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 above 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. It is a residue of a tetracarboxylic acid capable of forming a polyamic acid.
The total number of carbon atoms contained in X is preferably from 4 to 40. X
As the alicyclic group, an alicyclic group is more preferable than an aliphatic group (having no ring structure) because of its excellent heat resistance and pattern formability. In the case of an alicyclic group, all four bonding positions are preferably present on the alicyclic ring, and the four bonding sites are 2
Each is preferably divided into two sets, and the two binding sites in each set are preferably present on adjacent carbon atoms on the alicyclic ring.

Specifically,

Embedded image (N is an integer of 0 to 10) an aliphatic group, a monocyclic ring such as a cyclohexyl ring, and 2 to 6 of those monocyclic rings are 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 group bonded via a siloxane structure, a bicyclo [2.2.1] heptane ring, a bicyclo [4.4.0] decane ring And an alicyclic group such as a condensed ring. Further, a tetravalent aliphatic group or an alicyclic group having a fluorine atom can also be used, and these are suitable when low dielectric properties are required. For example,

Embedded image And the like.

Of these, X is

Embedded image Those having a repeating unit of the general formula (I) selected from the alicyclic group consisting of

Embedded image Those having a repeating unit of the general formula (I) selected from the alicyclic group consisting of

In the general formula (I), Y is a divalent aliphatic group or an alicyclic group, which can generally react with an aromatic tetracarboxylic acid to form a polyamic acid.
It is a residue of a diamine containing no aromatic ring, and the total number of carbons contained is preferably 1 to 30 groups.

Specifically,

Embedded image An alicyclic group consisting of

Embedded image An alicyclic group having a fluorine atom, such as-(CH ₂ ) _n-
(N represents an integer of 1 to 15). Among these, those having an alicyclic ring which is a condensed ring are preferable because of having good heat resistance, pattern forming property and the like,

Embedded image Are more preferable. Further, those containing a fluorine atom are preferred from the viewpoint of low dielectric properties.

Further, R ¹ and R ² are a hydroxyl group or a monovalent organic group, at least one of which needs to contain a photosensitive group, and it is preferable that both of them 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 has 1 to 1 carbon atoms.
Four are preferred. The divalent organic group represented by R ⁶ is preferably an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, and a propylene group. Among the monovalent organic groups represented by the general formulas (a), (b) and (c), particularly, R ⁶ has 1 to 4 carbon atoms.
Is an alkylene group; R ⁷ is hydrogen or a methyl group; and R ⁸ and R ⁹ are hydrogen. The organic group not only realizes high sensitivity but also is easy to synthesize, and the photosensitive resin of the present invention Suitable for the composition.

Of these, -COR ¹ and -COR ²
However, those having a structure in which a photosensitive group is bonded to a carboxyl group via a salt complex are preferable. In particular, as shown in the general formula (a), an acrylic compound having an amino group via a salt complex is preferable. Those having a structure 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, X represents the same as above], or a derivative thereof as an essential component. Those containing a fluorine atom can be obtained by hydrogenating a compound whose cyclohexyl ring is a benzene ring. In addition to the above essential components, other tetracarboxylic acids or derivatives thereof can be used to the extent that the KrF laser wavelength transmittance, heat resistance and the like are not reduced.

Examples of the tetracarboxylic acid or its derivative other than the tetracarboxylic acid or its derivative represented by the 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
Represents a monovalent hydrocarbon group of 0, s represents an integer of 1 to 10], and an aromatic tetracarboxylic acid such as a tetracarboxylic anhydride represented by They can be used in combination.

The tetracarboxylic acid derivatives include tetracarboxylic dianhydride, tetracarboxylic acid chloride and the like. 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 [In the formula, Y represents the above-mentioned one] as an essential component. Those containing a fluorine atom can be obtained by hydrogenating a compound whose cyclohexyl ring is a benzene ring. In addition to the above essential components, K
Other diamines can be used as the amine component to the extent that the rF laser wavelength transmittance and heat resistance are not reduced.

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, 1,1,1,3,3,3-hexafluoro-2,2-bis (4- Aminophenyl) propane,
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 and the like are used, and these are used alone or in combination of two or more.

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. The content is more preferably 100 mol%, particularly preferably 70 to 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 polyimide precursor to be formed 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, octane, 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 in which the photosensitive group is bonded via a salt complex are, as described above, tetracarboxylic acids of the general formula (II) or The derivative is reacted with a diamine of the general formula (IV), and 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.

As the amine compound having a photosensitive group in the present invention, an acryl or methacryl compound having an amino group is preferable.
-Dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminopropyl acrylate, N-dimethylaminoethylacrylamide, N, N-dimethylaminoethylacrylamide and the like can be mentioned. These can be used alone or in combination of two or more. The amount of the acrylic or methacrylic compound having an amino group to be used is 1 to 2 with respect to the amount of the compound having a repeating unit represented by the general formula (I).
It is preferably set to 00% by weight, 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 this content is less than 10 mol%, the transparency and mechanical strength tend to be poor.

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 may 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.

[0038]

Embedded image

[0039]

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 onto 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 use with a KrF laser, but the actinic rays or actinic rays to be irradiated may be, for example, a contact / proximity using an ultra-high pressure mercury lamp in addition to the KrF laser. An exposure machine, a mirror projection exposure machine, a g-ray stepper, an i-ray stepper, and other ultraviolet, visible, X-ray, and electron beams can also be used.

Examples of the developing solution include, for example, good solvents (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylsulfoxide, etc.) 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.

Further, by heating the 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.

[0048]

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-dicarboxycyclohexyl) dianhydride NBDA: norbornanediamine [2,5-bis (aminomethyl) bicyclo [2.2.1] heptane and 2,6
-Bis (aminomethyl) bicyclo [2.2.1] heptane mixture (trade name: NBDA, manufactured by Mitsui Chemicals, Inc.)] LS7430: 1,3-bis (3-aminopropyl) tetramethyldisiloxane ODPA: Oxydiphthalic dianhydride s-BPDA: biphenyltetracarboxylic dianhydride o-TD: o-tolidine PPD: p-phenylenediamine NMP: N-methyl-2-pyrrolidone

[0051]

[Table 1]

Examples 1 and 2 and Comparative Examples 1 and 2 Each of the polyimide precursor solutions (PA
A-1 to PAA-4) 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.

[0053]

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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, the film was irradiated with a KrF laser with a pattern mask. This one more
The mixture was heated at 00 ° C. for 60 seconds, and paddle-developed using a mixed solution of N-methyl-2-pyrrolidone / water (75/25 (weight ratio)).
After heating at 350 ° C. for 60 minutes for 60 seconds, a polyimide relief pattern was obtained. 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 and the resolution of the relief pattern obtained above were evaluated by the following methods. The results are shown in Table 2. The transmittance was determined by spin-coating the resin solution of each of the obtained polyimide precursors (PAA-1 to PAA-4) at 85 ° C. for 3 minutes, and further for 1 minute.
The coating film (10 μm) obtained by drying at 05 ° C. for 3 minutes was measured with a spectrophotometer. 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 the resolution was good. In Comparative Examples 1 and 2, no pattern was obtained.

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[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.

[0060]

The photosensitive resin composition of the present invention has a good K
It has rF wavelength transmittance, is highly sensitive, can form a film having excellent heat resistance and mechanical properties, can form a polyimide film having a good shape pattern, and has a surface protection film for semiconductors and multilayers. It is suitable for forming an interlayer insulating film of a wiring board. Further, according to the pattern manufacturing method of the present invention, a film having high sensitivity, excellent heat resistance and excellent mechanical properties can be formed, and a polyimide film having a good shape pattern can be formed. Further, the semiconductor device of the present invention has a polyimide film of a good shape pattern excellent in mechanical properties, heat resistance and the like, 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 aliphatic group or an alicyclic group, and R ¹ and R ² represent a hydroxyl group or a monovalent organic group. And 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. A wavelength of 248.8 nm of a polyimide precursor film having a repeating unit represented by the general formula (I).
The photosensitive resin composition according to claim 1, wherein the light transmittance per 10 µm of film thickness is 10% or more. 3. The photosensitive resin composition according to claim 1, wherein X in the general formula (I) is an alicyclic group. 4. The photosensitive resin composition according to claim 1, wherein Y in the general formula (I) is an alicyclic group containing an alicyclic ring which is a condensed ring. 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
5. 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. An actinic ray having a wavelength of 248.8 nm is irradiated from a mask on which a pattern is formed on a coating film of the photosensitive resin composition according to any one of claims 1 to 6, and an unirradiated portion is removed by development. A method for producing a pattern. 8. A semiconductor device having a polyimide resin pattern obtained by the method according to claim 7.