JP2000284480A - High-polymer compound, photosensitive resin composition using the same, production of relief pattern and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to form patterns having good resolution by i ray exposure by using a high-polymer compound having a specific structural unit, thereby obtaining the photosensitive resin composition of a negative type or position type which attains the compatibility of good i ray permeability with low expandability and is useful as a material for the surface protective films and interlayer insulating films of semiconductor devices, etc., of low residual stress. SOLUTION: The high-polymer compound having the structural unit expressed by formula is provided. In the formula, Z is the group selected from -O-, -CO-, -Si(CH3)2-, -Si(OCH3)2-, -C(CH3)2-, -C(OCF3)2-, -C(OCH3)(CF3)-, -C(OCH3)2-, -C(OCF3)2- and -C(OCH3)(OCF3)-. and R and R' are respectively independently univalent groups and are the groups capable of constituting a ring together with Z by adding or condensing each other by light or heat. The high-polymer compound in which R and R' are both OH is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer compound, a photosensitive resin composition using the same, a method for producing a relief pattern, and an electronic component.

[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 been formed using an inorganic material, taking advantage of its characteristics. Have been. 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 the base material surface, removing unnecessary portions by exposing and etching predetermined portions, 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.

As these materials, for example, heat-resistant photosensitive materials using photosensitive polyimide, cyclized polybutadiene or the like as a base polymer have been proposed. Particularly, photosensitive polyimide has excellent heat resistance and elimination of impurities. Has attracted particular attention because of its ease of use. 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) discloses a method in which a functional group and a photosensitive group in the polyimide precursor are mixed. A method of reacting with a functional group of a compound having a compound to give a photosensitive group (JP-A-56-2
No. 4343, Japanese Unexamined Patent Publication No. 60-100143)
And so on. However, these photosensitive polyimide precursors use a basic skeleton for an aromatic monomer having excellent heat resistance and mechanical properties.Because of the absorption of the polyimide precursor itself, the light transmittance in the ultraviolet region is low and the exposure is low. However, the photochemical reaction in the portion cannot be performed sufficiently effectively, resulting in a problem that the sensitivity is low and the shape of the pattern 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 conventional contact / proximity exposure apparatus using parallel rays has been replaced by a 1: 1 projection exposure apparatus called a mirror projection and a reduction projection exposure apparatus called a stepper. 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 an ultra-high pressure mercury lamp have been the mainstream stepper. Needs to be shortened. Therefore, the exposure equipment used is from a g-line stepper (wavelength: 435 nm) to an i-line stepper (wavelength: 3).
65 nm).

However, conventional photosensitive polyimide base polymers designed for contact / proximity exposure machines, mirror projection projection exposure machines, and g-line steppers have low transparency due to the above-mentioned reasons, especially i-line. (Wavelength: 365 nm) because there is almost no transmittance.
A decent pattern cannot be obtained with an i-line stepper. In addition, a polyimide film for surface protection is required to be a thicker film corresponding to LOC (lead-on-chip), which is a high-density mounting method of a semiconductor element. The problem gets worse. 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 a photosensitive polyimide having a lower thermal expansion property than conventional polyimides. In general, low thermal expansion can be achieved by making the molecular structure rigid. However, in the case of the rigid structure, almost no i-line is transmitted, so that the photosensitive characteristics deteriorate.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a polymer compound which has both good i-line transmittance and low thermal expansion, and is useful as a material for a surface protective film or an interlayer insulating film of a semiconductor device having a low residual stress. Is provided. Further, in addition to the above-mentioned problems, the present invention provides a polymer compound capable of forming a resin film having good heat resistance, in particular, a polyimide precursor and a polybenzoxazole precursor.

Further, the present invention provides a negative or positive photosensitive material which has both good i-line transmittance and low thermal expansion, and is useful as a material for a surface protective film or an interlayer insulating film of a semiconductor device having a low residual stress. The present invention provides a resin composition. The present invention also provides
An object of the present invention is to provide a method for producing a relief pattern which can form a pattern having a good resolution by i-line exposure and gives a resin film having low residual stress. Further, the present invention provides an electronic component having a surface protection film or an interlayer insulating film with low residual stress and excellent in reliability.

[0010]

According to the present invention, there is provided a compound represented by the general formula (1):

Embedded image (Wherein, Z is a single bond, -O-, -CO-, -Si (CH
_{3) 2 -, - Si (} OCH 3) 2 -, - C (CH 3) 2
_{-, - C (CF 3)} 2 -, - C (CH 3) (CF 3)
—, —C (OCH ₃ ) ₂ —, —C (OCF ₃ ) ₂ — and —C (OCH ₃ ) (OCF ₃ ) —, wherein R and R ′ are each independently monovalent Which can be added or condensed to each other by light or heat to form a ring together with Z)).

The present invention also relates to a polymer compound wherein R and R 'are both OH. Further, the present invention provides a compound represented by the general formula (2):

Embedded image (Wherein, X is a tetravalent organic group, Y is a divalent organic group, R ¹ and R ² are each independently OH or a monovalent organic group, and at least one of X and Y is The polymer compound is a polyimide precursor having a repeating unit represented by the general formula (1):

Further, the present invention provides a compound represented by the following general formula (3):

Embedded image (Wherein X ′ is a divalent organic group, Y ′ is a tetravalent organic group, R ³ and R ⁴ are each independently a hydrogen atom or a monovalent organic group, and X ′ and Y At least one is a structural unit represented by the general formula (1)), which is a polybenzoxazole precursor having a repeating unit represented by the general formula (1).

[0013] The present invention also relates to a photosensitive resin composition containing the polymer compound. Further, in the present invention, the polymer compound is a polyimide precursor having a repeating unit represented by the general formula (2) or a polybenzoxazole precursor having a repeating unit represented by the general formula (3), and A photosensitive resin composition having a carbon-carbon unsaturated double bond in its structure and having negative photosensitive properties.

The present invention also relates to the negative photosensitive resin composition further containing a photopolymerization initiator. Further, in the present invention, the polymer compound is a polyimide precursor having a repeating unit represented by the general formula (2) or a polybenzoxazole precursor having a repeating unit represented by the general formula (3). The present invention relates to a photosensitive resin composition containing a compound that generates an acid by light and having positive photosensitive characteristics. The present invention also relates to the positive photosensitive resin composition, wherein the compound that generates an acid by light is an o-quinonediazide compound.

According to the present invention, there is also provided a method for producing a relief pattern, comprising the steps of applying and drying the photosensitive resin composition according to any of the above on a support substrate, exposing, developing, and heating. About. The present invention also relates to a method for producing a relief pattern, wherein the exposing step is performed using i-line as an exposure light source.

Further, according to the present invention, the support substrate preferably has a diameter of 1 mm.
The present invention relates to a method for manufacturing a relief pattern which is a silicon wafer of 2 inches or more. The present invention also relates to an electronic component having a relief pattern layer obtained by the above-mentioned manufacturing method.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer compound of the present invention is characterized by having a structural unit represented by the general formula (1), and is not particularly limited except that it has the structural unit. R and R 'of the structural unit represented by the general formula (1) can be cyclized together with Z and two carbon atoms on each benzene ring by adding or condensing R and R' by light or heat.

Therefore, before the cyclization, the polymer has high i-line permeability and high solubility, and after cyclization, becomes a polymer having excellent film properties, low thermal expansion and low stress. . Examples of the combination of R and R ′, which are monovalent groups that are added or condensed and cyclized by light or heat, include a hydroxyl group and a hydroxyl group, a hydroxyl group and a hydrogen atom, and a carboxyl group and a hydrogen atom. A combination of a hydroxyl group and a hydroxyl group is preferred because of easy cyclization.

When R and R 'in the general formula (1) are a combination of a hydroxyl group and a hydroxyl group, the structure represented by the general formula (1) changes as follows by condensation to form a ring together with Z. .

Embedded image

The type of the high molecular compound having the structural unit represented by the general formula (1) is not particularly limited, but may be used as a surface protective film or an interlayer insulating film of a semiconductor device or a multilayer wiring board. Is preferably a polyimide precursor or a polybenzoxazole precursor which forms a film having excellent heat resistance. The polyimide precursor has the general formula (2)

Embedded image (Wherein, X is a tetravalent organic group, Y is a divalent organic group, R ¹ and R ² are each independently a hydroxyl group or a monovalent organic group, and at least one of X and Y is Which is a structural unit represented by the general formula (1)), and the polybenzoxazole precursor is represented by the general formula (3)

Embedded image (Wherein X ′ is a divalent organic group, Y ′ is a tetravalent organic group, R ³ and R ⁴ are each independently a hydrogen atom or a monovalent organic group, and X ′ and Y At least one is a structural unit represented by the general formula (1)).

In the polyimide precursor and the polybenzoxazole precursor, the repeating unit represented by the general formula (2) or the repeating unit represented by the general formula (3)
The ratio to all repeating units is preferably 5 to 100 mol%, more preferably 50 to 100 mol%. When the amount is less than 5 mol%, the photosensitive characteristics such as i-line transmittance and the solubility tend to decrease.

Here, the polyimide precursor having the repeating unit represented by the general formula (2) will be described in detail. The polyimide precursor having a repeating unit represented by the general formula (2) is a tetracarboxylic acid having a structure represented by the general formula (1) or a derivative thereof or a diamine having a structure represented by the general formula (1) As an essential component, if necessary, in combination with other tetracarboxylic acids or derivatives thereof or diamines, and if necessary, other compounds which form side chains can be produced as a raw material. The reaction of these raw materials can be performed in an organic solvent.

Examples of the tetracarboxylic acid having a structural unit represented by the general formula (1) or a derivative thereof or a diamine compound include, for example,

Embedded image And the like.

Examples of the tetracarboxylic acid containing no structural unit of the general formula (1) or a derivative thereof include oxydiphthalic acid, pyromellitic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 3 ', 4,4'-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid 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-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

Embedded image (Wherein, R ¹¹ and R ¹² represent a monovalent hydrocarbon group,
Each of which may be the same or different, and s is an integer of 1 or more), and an aromatic tetracarboxylic acid such as a tetracarboxylic acid represented by the formula (I), and these may be used alone or in combination of two or more. You. Examples of the derivative of tetracarboxylic acid include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid chloride and the like. As a reaction partner of the diamine, tetracarboxylic dianhydride is preferable from the viewpoint of reactivity and the like.

Examples of the diamine which does not contain the structure of the general formula (1) include 4,4 '-(or 3,4'-,
3'-, 2,4'-, 2,2'-) diaminodiphenyl ether, 4,4'- (or 3,4'-, 3,3'-,
2,4 '-, 2,2'-) diaminodiphenylmethane,
4,4'- (or 3,4'-, 3,3'-, 2,4 '
-, 2,2 '-) diaminodiphenylsulfone, 4,
4'- (or 3,4'-, 3,3'-, 2,4'-,
2,2 '-) diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidinesulfone, 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-bis (4-aminophenyl) propane and the like, which are used alone or in combination of two or more.

The following general formula

Embedded image (Wherein, R ¹³ and R ¹⁴ represent a divalent hydrocarbon group,
R ¹⁵ and R may be the same or different.
¹⁶ represents a monovalent hydrocarbon group, which may be the same or different, and t is an integer of 1 or more.) It is also possible to use an aliphatic diamine such as diaminopolysiloxane.

In the polyimide precursor of the general formula (2), the groups represented by R ¹ and R ² are OH or a monovalent organic group. The monovalent organic group is not particularly limited, and examples thereof include a hydrocarbon group and a monovalent organic group having a carbon-carbon unsaturated double bond. The groups represented by R ¹ and R ² are different depending on whether the intended photosensitive resin composition is a positive type or a negative type, a solvent development type, an alkali development type, and the like. For example, in the case of using an alkali-developable photosensitive resin composition, there is a method in which at least one of the groups represented by R ¹ and R ² is OH. R ¹ and R
It is preferable that 50 to 100 mol% of the group represented by ² be OH.

When a negative photosensitive resin composition is used, R
¹ and at least a part of R ² , preferably 20 to 100
It is preferable that mol% be a monovalent organic group having a carbon-carbon unsaturated double bond. Preferred examples of such a monovalent organic group include the following groups having a carbon-carbon unsaturated double bond group through an ionic bond, an ester bond, an amide bond, or the like.

Embedded image (Wherein, A is a divalent hydrocarbon group, R is a hydrogen atom or a methyl group, and Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group. A) As A, an alkylene group having 1 to 10 carbon atoms is preferable, and among Z ¹ , Z ² and Z ³ , the monovalent organic group is an alkyl group having 1 to 5 carbon atoms. Are preferred.

Of the above-mentioned structures, in order to obtain a structure in which a carbon-carbon unsaturated double bond is introduced through an ionic bond, a derivative having an amino group of acrylic acid or methacrylic acid (hereinafter referred to as an acrylic compound having an amino group) Is preferred. Such compounds include, for example,
N, N-dimethylaminoethyl methacrylate, N, N
-Diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, N, N-dimethylaminopropyl acrylate N-diethylaminopropyl acrylate, N, N-dimethylaminoethyl acrylamide,
N, N-dimethylaminoethylacrylamide and the like. These are used alone or in combination of two or more.

The amount of the acrylic compound having an amino group to be used is 1 to 1 with respect to the amount of the polyamic acid before introduction (that is, the compound in which R ¹ and R ² are both OH in the general formula (2)). Preferably, the content is 200% by weight.
More preferably, it is 150% by weight. If the amount is less than 1% by weight, the light sensitivity tends to be poor,
If it exceeds 200% by weight, heat resistance and mechanical properties of the film tend to be inferior. According to this method, when an ion-bonding type polyimide precursor is produced, the tetracarboxylic dianhydride and the diamine are mixed, a ring-opening polyaddition reaction is performed, and the polyamic acid is mixed. Then, the acrylic compound having an amino group is mixed. I just need.

The compound having a carbon-carbon unsaturated double bond introduced through an ester bond is a polyamic acid ester,
In this production, first, a tetracarboxylic acid diester compound is synthesized. As a method for synthesizing the tetracarboxylic acid diester compound, for example, the compound can be obtained by mixing the tetracarboxylic dianhydride and the unsaturated alcohol compound in an organic solvent in the presence of a base. Examples of the unsaturated alcohol compound include hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and the like. The hydroxyalkyl acrylate or methacrylate is preferably used.

In the case of producing a positive photosensitive resin composition, as the polyimide precursor, a polyamic acid or a polyamic acid ester is preferable. In particular, as R ¹ and R ² , a monovalent hydrocarbon group via an oxygen atom ( It is preferably a form in which an alkyl group having 1 to 10 carbon atoms is bonded. This polyamic acid ester can be produced by the same synthesis method as described above, using a different alcohol compound instead of the unsaturated alcohol compound.
The alcohol compound used in this case includes methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol,
Preferred are alkyl alcohols having 1 to 10 carbon atoms such as -pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol and 3-hexanol, and these may be used alone or in combination of two or more. Can be.

In the synthesis of the tetracarboxylic diester, the ratio (molar ratio) of the tetracarboxylic dianhydride to the alcohol compound is preferably in the range of 1/2 to 1 / 2.5 for the former / the latter. / 2 is most preferable. Further, the ratio (molar ratio) of the tetracarboxylic dianhydride and the base is preferably in the range of 1 / 0.001 to 1/3 in the former / latter, and is preferably 1 / 0.005 to 1/2. Is more preferable. The reaction temperature is preferably from 10 to 60C, and the reaction time is preferably from 3 to 24 hours.

Next, a tetracarboxylic diester dihalide is synthesized, and this method is known. For example, it can be obtained by reacting a tetracarboxylic diester dissolved in an organic solvent by dropwise addition of thionyl chloride. The ratio (molar ratio) of the tetracarboxylic acid diester to thionyl chloride is preferably in the range of 1 / 1.1 to 1 / 2.5 for the former / latter, and is preferably in the range of 1 / 1.5 to 1 / 2.2. It is more preferable to set the range. The reaction temperature is preferably -20 to 40C, and the reaction time is preferably 1 to 10 hours.

The polyamic acid ester is prepared by, for example, dissolving a diamine and a dehalogenating agent such as pyridine in an organic solvent, and reacting the solution by dropping the tetracarboxylic diester dihalide dissolved in the organic solvent. Thereafter, it is obtained by pouring into a poor solvent such as water, filtering and drying the precipitate. The ratio (molar ratio) of the total amount of the diamine and the tetracarboxylic diester dihalide was 0.1 in the former / the latter.
The range of 6/1 to 1 / 0.6 is preferable, and 0.7 / 1 to 1 / 0.6.
The range of /0.7 is more preferable. Reaction temperature is -20 to 4
0 ° C. is preferable, and the reaction time is preferably 1 to 10 hours.
The ratio between the dehalogenating agent and the tetracarboxylic diester dihalide is such that the former / latter (molar ratio) is 1.8 / 1 to
The range of 2.2 / 1 is preferred, and 1.9 / 1 to 2.1 / 1
Is more preferable.

As the polyimide precursor, R ¹ and R ²
May be a polyamide acid amide in which a hydrocarbon group is bonded via a nitrogen atom. In the production of the polyamic acid ester, a monoamine compound, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n
-Butylamine, sec-butylamine, tert-butylamine, isobutylamine, 1-pentylamine,
2-pentylamine, 3-pentylamine, isoamylamine, 1-hexylamine, 2-hexylamine, 3
-Hexylamine, morpholine, aniline, benzylamine and the like.

Next, the polybenzoxazole precursor represented by the general formula (3) will be described in detail. The polybenzoxazole precursor contains, as an essential component, a dicarboxylic acid having a structural unit represented by the general formula (1) or a diamine having a structure represented by the general formula (1).
It can be produced using other dicarboxylic acids or diamines. These reactions can be performed in an organic solvent.

The dicarboxylic acid or diamine having a structural unit represented by the general formula (1), which is an essential component, includes, for example,

Embedded image And the like.

The dicarboxylic acid containing no structural unit of the general formula (1) is not particularly limited, and is isophthalic acid, terephthalic acid, 4,4'-hexafluoroisopropylidene dibenzoic acid, 4,4'-biphenyldicarboxylic acid , 4,
4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5- Aromatic dicarboxylic acids such as bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3 -Cyclopentanedicarboxylic acid, oxalic acid,
Examples thereof include aliphatic dicarboxylic acids such as malonic acid and succinic acid, and these can be used alone or in combination of two or more. Among these, aromatic dicarboxylic acids are preferred in terms of heat resistance and the like.

The diamine containing no structural unit of the general formula (1) includes 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis ( 3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, Bis (3-amino-4-
Aromatic dihydroxydiamines such as (hydroxyphenyl) hexafluoropropane and bis (4-amino-3-hydroxyphenyl) hexafluoropropane are preferred. By using an aromatic dihydroxydiamine, a polybenzoxazole precursor having good heat resistance can be obtained.

The polybenzoxazole precursor can be obtained, for example, by reacting a dicarboxylic acid dihalide (chloride, bromide, etc.) with a diamine.
In this case, the reaction is preferably performed in an organic solvent in the presence of a dehaloacid catalyst. As the dicarboxylic dihalide, dicarboxylic dichloride is preferable. Dicarboxylic acid dichloride can be obtained by reacting dicarboxylic acid with thionyl chloride.

In the general formula (3), the groups represented by R ³ and R ⁴ may be monovalent organic groups other than a hydrogen atom. Such a monovalent organic group is not particularly limited, and may be a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group having 1 to 10 carbon atoms or a carbon atom having 1 to 2 carbon atoms having a carbon-carbon unsaturated double bond. To 20 monovalent organic groups and the like, similar to the polyimide precursor, the desired photosensitive resin composition is a positive type or a negative type, a preferred group depending on whether a solvent development type or an alkali development type, and the like. The ratios are different and are not particularly limited.

In the present invention, the organic solvent used for producing the polyimide precursor or polybenzoxazole precursor is preferably a polar solvent which completely dissolves the produced polyimide precursor or polybenzoxazole precursor. N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide,
Dimethyl sulfoxide, tetramethyl urea, hexamethyl phosphoric acid triamide, γ-butyrolactone and the like can be mentioned.

In addition to the polar solvent, 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,
Examples include tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like. These organic solvents can be used alone or
Used in combination of more than one type.

Although the molecular weight of the polymer compound of the present invention is not particularly limited, the weight average molecular weight is 20,000 to 100,0.
00 is preferred. The molecular weight can be measured by an E-type viscometer or a gel permeation chromatography method and converted into standard polystyrene. The polymer compound, by light or heat,
R and R ′ in the general formula (1) can be closed. When the polymer compound is a polyimide precursor or a polybenzoxazole precursor, the amide bond portion is also closed at the same time, so that a polyimide or polybenzoxazole having excellent heat resistance can be obtained. Heat is generally used for this ring closure, and the heating conditions include:
Although there is no particular limitation, the heating temperature is preferably from 80 to 450 ° C. If the heating temperature is lower than 80 ° C., the ring closure reaction tends to be slow, and if it exceeds 450 ° C., the produced polymer 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-closing reaction tends to be slow, and if it exceeds 100 minutes, the ring-closing compound formed tends to be deteriorated and the workability tends to be reduced.

The photosensitive resin composition of the present invention is characterized by containing the above-mentioned polymer compound, and can impart photosensitivity by various methods. For example, by introducing a carbon-carbon unsaturated bond group into a side chain (for example, a carboxyl group, a hydroxyl group, or the like) of a polymer compound by an ionic bond or a covalent bond, and giving a structure that is crosslinked by light to the polymer compound itself, it is exposed to light. A method of imparting photosensitivity, a method of imparting photosensitivity by mixing a reactive monomer having a carbon-carbon unsaturated double bond, and a method of mixing a photosensitizer such as a photoacid generator or a photobase generator. Method.

In the case of producing a negative photosensitive resin composition in the photosensitive resin composition of the present invention, it is preferable that a photopolymerization initiator is contained together with the polymer compound. Examples of the photopolymerization initiator include 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-hydroxycyclohexylphenylketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl, diphenyldisulfide, phenanth Lenquinone, 2-isopropylthioxanthone, riboflavin tetrabutyrate, 2,6-bis (p-diethylaminobenzal) -4-methyl-4-azacyclohexanone, N-ethyl-N- (p-chlorophenyl) glycine, N- Phenyldiethanolamine, 2- (o-ethoxycarbonyl) oxyimino-1,3-diphenylpropanedione, 1-phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one, 3,3
4,4, -tetra (t-butylperoxycarbonyl)
Benzophenone, 3,3, -carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl)
-Bis- [2,6-difluoro-3- (pyr-1-yl) phenyl] titanium and the like. These are used alone or in combination of two or more.

The amount of the photopolymerization initiator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the polymer compound. . If this amount is less than 0.01 parts by weight,
Light sensitivity tends to be inferior, and when it exceeds 30 parts by weight, mechanical properties of the film tend to be inferior.

In the case of a negative photosensitive resin composition, an addition polymerizable compound having a carbon-carbon unsaturated double bond may be contained. Examples of such an addition polymerizable compound include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, Trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,
4-butanediol dimethacrylate, 1,6-hexanediol methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,
3-acryloyloxy-2-hydroxypropane,
Examples include 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide and the like. These are used alone or in combination of two or more.

The addition polymerizable compound is preferably used in an amount of 1 to 200 parts by weight based on 100 parts by weight of the polymer compound. If the amount is less than 1 part by weight, the photosensitive characteristics including solubility in a developing solution tend to be poor, and
If it exceeds 00 parts by weight, the mechanical properties of the film tend to be poor.

The photosensitive resin composition of the present invention may contain an azide compound, if necessary. As azide compounds, for example,

Embedded image And the like. These are used alone or in combination of two or more.

The amount of the azide compound used is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the polymer compound. If this amount is less than 0.01 parts by weight,
Light sensitivity tends to be inferior, and when it exceeds 30 parts by weight, mechanical properties of the film tend to be inferior.

Further, the negative photosensitive resin composition may contain a radical polymerization inhibitor or a radical polymerization inhibitor 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, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-1-naphthylamine, N-phenyl-2- Examples include naphthylamine, cuperon, phenothiazine, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like. These are used alone or in combination of two or more.

The amount of the radical polymerization inhibitor or the radical polymerization inhibitor to be used is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the polymer compound.
More preferably, the amount is from 0.05 to 10 parts by weight. If the amount is less than 0.01 part by weight, the stability during storage tends to be poor, and if it exceeds 30 parts by weight, the photosensitivity and the mechanical properties of the film tend to be inferior.

On the other hand, when producing a positive photosensitive resin composition, it is preferable to use a compound which generates an acid by light together with a polymer compound. The compound that generates an acid by light is a photosensitizer, and has a function of generating an acid and increasing the solubility of a portion irradiated with light in a developing solution (aqueous alkaline solution). Examples of the type include o-quinonediazide compounds, allyldiazonium salts, diallyliodonium salts, triallylsulfonium salts, and the like. There is no particular limitation, but o-quinonediazide compounds are preferred because of their high sensitivity.

The o-quinonediazide compound is, for example, o
-It is obtained by subjecting a quinonediazidosulfonyl chloride to a condensation reaction with a hydroxy compound, an amino compound and the like in the presence of a dehydrochlorination catalyst. Examples of the o-quinonediazide sulfonyl chloride include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride,
Naphthoquinone-1,2-diazide-4-sulfonyl chloride and the like can be used.

As the hydroxy compound, for example,
Hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane,
2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxy Benzophenone, 2,3,4,2 ', 3'-pentahydroxybenzophenone, 2,3,4,3', 4 ', 5'-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane , Bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,
Examples thereof include 10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane.

As the amino compound, for example, p-
Phenylenediamine, m-phenylenediamine, 4,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, o
-Aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino- 4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-
Hydroxyphenyl) sulfone, bis (3-amino-4)
-Hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like.

The o-quinonediazidosulfonyl chloride and the hydroxy compound or the amino compound are blended so that the total of the hydroxy group and the amino group is 0.5 to 1 equivalent per 1 mol of the o-quinonediazidosulfonyl chloride. Is preferred. The preferred ratio of the dehydrochlorination catalyst to o-quinonediazide sulfonyl chloride is 0.95 /
The range is from 1 to 1 / 0.95. The preferred reaction temperature is 0 to 40 ° C, and the preferred reaction time is 1 to 10 hours.

As the reaction solvent, for example, a solvent such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the catalyst for dehydrochlorination include sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like. The component that generates an acid by light is a polymer compound 10 in view of the film thickness and sensitivity after development.
It is preferably used in an amount of 5 to 100 parts by weight, more preferably 10 to 40 parts by weight, based on 0 parts by weight.

The photosensitive resin composition of the present invention can be obtained in a solution state by dissolving the polymer compound in a solvent and then dissolving other components. As the solvent,
For example, non-protons such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-butyrolactone, cyclohexanone, and cyclopentanone Soluble polar solvents are used alone or in combination of two or more.

The photosensitive resin composition of the present invention may further contain an organic silane compound, an aluminum chelate compound, a silicon-containing polyamic acid, etc. in order to enhance the adhesion of the cured film to the substrate. Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. Can be Examples of the aluminum chelate compound include aluminum tris (acetylacetonate) and aluminum acetylacetate diisopropylate.

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 an immersion method, a spray method, a screen printing method, a spin coating method or the like, and most of the solvent is removed. By heating and drying, a coating film having no tackiness can be obtained. Although there is no particular limitation on the thickness of this coating film, from the viewpoint of circuit characteristics and the like, it is 4 to 50 μm.
m, more preferably 6 to 40 μm, particularly preferably 10 to 40 μm, and most preferably 20 to 35 μm. Further, since the photosensitive resin composition of the present invention can form a film having a low residual stress, it is suitable for application to a large-diameter wafer such as a silicon wafer having a diameter of 12 inches or more. On this coating film, after exposure to a pattern by irradiating actinic rays or actinic rays through a mask on which a desired pattern is drawn, the unexposed portion or the exposed portion is developed and dissolved with an appropriate developing solution, By removing, a desired pattern can be obtained.

The photosensitive resin composition of the present invention is suitable for i-line exposure using an i-line stepper or the like.
A contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, a g-ray stepper, other ultraviolet rays, a visible light source, X-rays, and an electron beam can also be used.

As the developing solution, for example, a good solvent (N, N-dimethylformamide, N, N
N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), mixed solvents of the above good solvents and poor solvents (lower alcohols, ketones, water, aromatic hydrocarbons, etc.), and alkaline developers. When the polyimide precursor has alkali solubility, an alkaline solution can be used. As the alkaline aqueous solution, for example, an aqueous solution of 5% by weight or less such as sodium hydroxide, potassium hydroxide, sodium silicate, and tetramethylammonium hydroxide, preferably an aqueous solution of 1.5 to 3.0% by weight is used. However, a more preferred developer is a 1.5 to 3.0% by weight aqueous solution of tetramethylammonium hydroxide.
Further, a surfactant or the like can be added to the above-mentioned developer for use. Each of these is blended in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the developer.

After development, rinsing with water or a poor solvent, if necessary, and drying at about 100 ° C. are preferable to make the pattern stable. The resulting pattern can be made into a heat-resistant, low-stress relief pattern film by heating. The heating temperature at this time is 150
To 500 ° C, more preferably 200 to 400 ° C. If the heating temperature is less than 150 ° C., the mechanical properties and thermal properties of the obtained film tend to decrease, and if it exceeds 500 ° C., the mechanical properties and thermal properties of the film tend to decrease.

The heating time at this time is 0.05 to 1
Preferably, it is 0 hours. This heating time is 0.0
If the time is less than 5 hours, the mechanical and thermal properties of the polyimide film tend to decrease, and if the time exceeds 10 hours, the mechanical and thermal properties of the polyimide film tend to decrease.

The photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, and specifically, surface protective films and interlayer insulating films of semiconductor devices and multilayer wiring boards. It can be used for forming an interlayer insulating film and the like. The electronic component of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

As an example of the electronic component of the present invention, an example of a semiconductor device manufacturing process will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate such as a Si substrate 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, and a first conductor layer is formed on the exposed circuit element. . A film 4 of a resin or the like as an interlayer insulating film is formed on the semiconductor substrate by a spin coating method or the like (step (a)).

Next, a photosensitive resin layer 5 of a chlorinated rubber type or a phenol novolak type is formed on the interlayer insulating film 4 by spin coating, and a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. Window 6A is provided as described above (step (b)). The interlayer insulating film 4 in the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride, and a window 6B is opened. Next, the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).

Further, using a known photolithography technique,
The conductor layer 7 is formed, and the electrical connection with the first conductor layer 3 is made completely (step (d)). When a multilayer wiring structure of three or more layers is formed, the above steps are repeated to form each layer.

Next, a surface protection film 8 is formed. In the example of this figure, the surface protective film is coated with the photosensitive resin composition by a spin coating method, dried, irradiated with light from a mask on which a pattern for forming a window 6C is formed on a predetermined portion, and then exposed to an alkaline aqueous solution. To form a pattern and heat to form a resin film of a relief pattern. This resin film protects the conductor layer from external stress, α rays, etc.
The obtained semiconductor device has excellent reliability. In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

[0073]

The present invention will be described below with reference to examples. Synthesis Example 1 Synthesis of 6,6′-dimethyl-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (MBDA) 4-methylphthalic anhydride (58.8 g, 0.363)
Mol), potassium bromate (66.7 g, 0.400 mol) and 250 ml of water were heated to 90 ° C., the heating bath was removed, and 250 ml of concentrated sulfuric acid was added under strong stirring.
Was slowly added dropwise. After completion of the dropwise addition, a heating bath was attached again, and the mixture was stirred at 90 to 100 ° C for 3 hours. The mixture was allowed to cool to room temperature, and the resulting solid was separated by filtration and washed with cold water. The filtrate was extracted three times with ether, and the combined organic layers were washed with water and then with a saturated saline solution, and dried over anhydrous sodium sulfate.
The solid obtained by concentrating this ether solution and the solid previously filtered off were combined, and water was removed by azeotropic distillation with toluene, whereby 5-bromo-4-methylphthalic acid was obtained as a crude product.

To the crude 5-bromo-4-methylphthalic acid was added 100 ml of thionyl chloride, and the mixture was refluxed under heating for 4 hours. After cooling to room temperature, 200 ml of methanol was added and the mixture was refluxed under heating for 5 hours. After cooling to room temperature, methanol was distilled off under reduced pressure, and the remaining oil was distilled to give 5-bromo-4.
-Methyl phthalate was obtained (boiling point 156-1
59 [deg.] C / 5mmHg, 54.3g, 52% (yield from 4-methylphthalic anhydride)).

Anhydrous nickel (II) chloride (0.84 g,
6.5 mmol), biviridyl (1.02 g, 6.
5 mmol), triphenylphosphine (11.0 g,
41.9 mmol), zinc dust (13.1 g, 0.2
00g atom) and dimethylformamide (DMF)
80 ml of the suspension was heated to 60 ° C. under a nitrogen atmosphere to confirm dark brown coloration, and then heated to 100 ° C., and methyl 5-bromo-4-methylphthalate (33.2 g, 0.1
16 mol) in DMF (20 ml) was added dropwise. After stirring at 100 ° C. for 8 hours, the mixture was cooled to room temperature and poured into ice water. The mixture was filtered through celite, extracted with ether, washed with water and dried over anhydrous sodium sulfate. An oil obtained by concentrating this ether solution was purified by silica gel column chromatography to obtain a tetraester (12.65 g, 30.6 mmol, yield 53%). Recrystallization from methanol gave a more pure product. When the reaction is performed on a larger scale, the crude product is solidified, and the solid is washed with ether or an ether mixed with a small amount of hexane to omit the purification operation by column chromatography. Can also.

Tetraester (6.54 g, 15.8)
(Mmol) was heated to reflux with 90 ml of a 4 mol / l aqueous sodium hydroxide solution for 8 hours. After allowing to cool to room temperature and further adding 40 ml of concentrated hydrochloric acid under ice-cooling, a white solid was precipitated. This was filtered and dried under reduced pressure to obtain tetracarboxylic acid. When this solid was kept at 180 ° C. under reduced pressure (5 mmHg) for 6 hours, an acid anhydride was produced (4.78 g, 14.8 mmol, 94% by weight (yield from ester)).

The analytical data of the obtained acid anhydride is shown below. mp 235-236 ° C IR (KBr) 1849, 1784, 1323
1257, 887, 737 cm ^-1 . 1H NMR (DMSO-d ₆ ) d = 2.19 (6
H, s), 7.89 (2H, s), 8.17
(2H, s). _{13C NMR (DMSO-d 6)} d = 20.0
9, 125.41, 126.88, 129.11,
131.21, 145.30, 146.22,
162.74, 162.91. MS m / z 322.

Synthesis Examples 2 to 5 (PA-1 and PA-5
7) A diamine component and N-methyl-2-pyrrolidone shown in Table 1 were added to a 100 ml flask equipped with a stirrer and a thermometer, and dissolved by stirring at room temperature, and an acid component shown in Table 1 was added to this solution. After stirring for 30 hours, a viscous polyimide precursor solution was obtained. Further, this solution was heated at 70 ° C. for 5 hours, the viscosity was adjusted to 80 poise (solid content: 25% by weight), and the polyimide precursor solutions (PA-1 and PA-5) were prepared.
To 7). The amounts of the diamine component, acid component and N-methyl-2-pyrrolidone (NMP) are shown in Table 1.

Synthesis Example 6 (PA-2) (1) In a 200 ml four-necked flask, 0.03 mol of the acid anhydride, 1.92 g (0.06 mol) of methanol, and 4.75 g of pyridine (0 .06 mol), N, N '
-70 ml of dimethylacetamide (DMAc)
Stirring at 60 ° C. resulted in a clear solution in 2 hours. After the solution was stirred at room temperature for 7 hours, the flask was cooled with ice and 8.57 g (0.072 mol) of thionyl chloride was added dropwise over 10 minutes. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain a solution containing acid chloride.

(2) Synthesis of Polyimide Precursor Into another 200 ml four-necked flask were charged 0.03 mol of the diamine shown in Table 1, 5.06 g (0.064 mol) of pyridine, and 50 ml of DMAc, and the flask was cooled with ice. (10 ° C. or lower) The acid chloride solution obtained in the above (1) was slowly dropped over 1 hour while stirring. Thereafter, the mixture was stirred at room temperature for 1 hour, poured into 1 liter of water, and the precipitated polymer was collected by filtration, washed twice, and dried in vacuum. This polymer powder was dissolved in γ-butyrolactone (γ-BL), and the viscosity was adjusted to 80 poise to obtain a polyimide precursor solution (PA-2).

The viscosity was measured using an E-type viscometer (EHD type, manufactured by Toki Sangyo Co., Ltd.) at a temperature of 25 ° C. and a rotation speed of 2.5 rpm. An infrared absorption spectrum (JIR-100, manufactured by JEOL Ltd.) of the dried polyimide precursor solution (PA-1 to PA-7) was measured by the KBr method. However, in each case, absorption of C ＝ O of the amide group was observed at around 1600 cm ⁻¹ and absorption of NH at around 3300 cm ⁻¹ .

Synthesis Examples 7 to 8 (PA-3 and PA-4) (1) 0.03 mol of dicarboxylic acid, 4.75 g (0.06 mol) of pyridine and 70 ml of DMAc shown in Table 1 in a 200 ml four-necked flask And dissolve with stirring. The flask was cooled with ice and 8.57 g of thionyl chloride (0.07 g) was added.
72 mol) in 10 minutes. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain a solution containing acid chloride.

(2) Synthesis of Polybenzoxazole Precursor Into another 200 ml four-necked flask were charged 0.03 mol of the diamine shown in Table 1, 5.06 g (0.064 mol) of pyridine, and 50 ml of DMAc, and the flask was placed on ice. While stirring with cooling, the acid chloride solution obtained in the above (1) is mixed with 1
It was dripped slowly over time. Thereafter, the mixture was stirred at room temperature for 1 hour, poured into 1 liter of water, and the precipitated polymer was filtered, washed twice, and dried in vacuum. This polymer powder was dissolved in γ-butyrolactone (γ-BL),
The solution was adjusted to poise to obtain a polybenzoxazole precursor solution (PA-3 to 4).

Example 1 and Comparative Examples 1 to 3 Each of the polyimide precursors (PA-
1 and PA-5 to 7 g) solution, 2,6-
0.027 g of bis (4'-azidobenzal) -4-carboxycyclohexanone (CA), 0.027 g of 4,4'-bis (diethylamino) benzophenone (EAB)
And 0.054 g of 1-phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one (PDO)
Dimethylaminopropyl methacrylate (MDA) equivalent to the carboxyl group of the polyimide precursor.
P) was added, and the mixture was stirred and mixed to obtain Example 1 and Comparative Examples 1 to 3.
To obtain a uniform photosensitive resin composition solution.

[0085]

Embedded image

Examples 2 to 4 30 g of the polyimide precursor or polybenzoxazole precursor obtained in Synthesis Examples 6 to 8 was added to N-methylpyrrolidone 5
After stirring and dissolving in 4 g, 0.9 g of 3-isocyanatopropyltriethoxysilane was added, and the mixture was further stirred for 12 hours. 7.5 g of a compound obtained by reacting -sulfonyl chloride with the former / the latter at a molar ratio of 1/3 was dissolved to obtain a positive photosensitive resin composition solution used in Examples 2 to 4.

The obtained photosensitive resin composition solution was filtered through a filter, and each solution was spin-coated on a silicon wafer. Next, using a hot plate, the coating was heated at 100 ° C. for 150 seconds to form a 23 μm coating film, and then subjected to pattern masking and exposure with an i-line stepper. In Example 1 and Comparative Examples 1 to 3, this was further heated at 100 ° C. for 60 seconds, and N-methyl-2-pyrrolidone / water (75/25
(Weight ratio)), and a paddle development was performed to obtain a pattern.
By heating at 350 ° C. for 60 minutes for 0 minute, a polyimide relief pattern was obtained.

In Examples 2 to 4, after exposure, paddle development was performed using an aqueous solution of tetramethylammonium hydroxide.
A pattern was obtained at 100 ° C. for 30 minutes at 200 ° C.
For 30 minutes and at 400 ° C. for 60 minutes to obtain a polyimide or polybenzoxazole relief pattern. The relief patterns of Examples 1 to 4 had a good trapezoidal pattern shape reflecting that the pattern shape immediately after development was rectangular and had good resolution.
The relief patterns of Comparative Examples 1 to 3 had an undesirable inverted trapezoidal pattern shape reflecting that the pattern shape immediately after development was an inverted trapezoidal shape and the resolution was poor.

Each of the polyimide precursors and polybenzoxazole precursors (PA-1 to PA-1) obtained in Synthesis Examples 1 to 7
The transmittance of -7), the residual stress on the silicon wafer, and the resolution of the relief pattern were evaluated by the following methods. The evaluation results are shown in Table 2. The transmittance was determined using the obtained polyimide precursor and polybenzoxazole precursor (P
A-1 to PA-7) were spin-coated with a resin solution,
The coating film (20 μm) obtained by drying at 2 ° C. for 2 minutes and further at 105 ° C. for 2 minutes was measured with a spectrophotometer. Residual stress is obtained by forming a polyimide film or polybenzoxazole film on a 5-inch wafer and using a Tencor stress measuring device (F
LX-2320). The resolution was evaluated as the minimum size of a developable through hole using a through hole test pattern.

[0090]

[Table 1]

<Abbreviations> ODPA: oxydiphthalic dianhydride, s-BPDA: biphenyltetracarboxylic dianhydride, DDE: diaminodiphenyl ether, DMAP: 2,2′-dimethyl-4,4′-diaminobiphenyl, PPD: p-phenylenediamine

[0092]

[Table 2]

[0093]

The polymer compound of the present invention achieves both good i-line transmittance and low thermal expansion, and is useful as a material for a surface protective film or an interlayer insulating film of a semiconductor device having a low residual stress. . Further, the polymer compound of the present invention exhibits the above-mentioned effects and can form a resin film having good heat resistance.

The photosensitive resin composition of the present invention has both good i-line transmittance and low thermal expansion, and is useful as a material for a surface protective film or an interlayer insulating film of a semiconductor device having a low residual stress. is there. Further, according to the method for producing a relief pattern of the present invention, a pattern with good resolution can be formed by i-line exposure, and a resin film with low residual stress can be provided. Furthermore, the electronic component of the present invention has a low residual stress surface protective film or interlayer insulating film, and is excellent in reliability.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1: Semiconductor substrate, 2: Protective film, 3: 1st conductor layer,
4: interlayer insulating film layer 5: photosensitive resin layer, 6A, 6B, 6C: window, 7: second
Conductive layer, 8: Surface protective film layer.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G03F 7/022 G03F 7/022 7/027 514 7/027 514 7/028 7/028 7/038 504 7/038 504 7/40 501 7/40 501 H01L 21/027 H01L 21/312 B 21/312 D 21/30 502R F term (reference) 2H025 AA00 AA01 AA10 AA13 AA20 AB17 AC01 AD01 AD03 BC13 BC69 BC70 BC86 BE00 BE01 CB25 CB26 CB45 FA17 FA29 2H096 AA27 BA06 BA09 EA02 GA08 HA01 4J043 PA02 PA19 QB15 QB23 QB26 QB31 QB34 RA06 SA71 SB01 TA03 TA42 TA45 TA47 TB01 UA022 UA032 UA042 UA121 UA 122 UB131 UB1 UA1 UA1 UA2 UA1 UA1 UB322 UB352 UB401 UB402 VA011 VA012 VA021 VA022 VA031 VA032 VA041 VA042 VA051 VA052 VA061 VA062 VA081 VA082 VA101 XA04 XA13 YA13 YA23 ZA35 ZA52 ZB22 5F058 AA10 AC02 AC07 AD01 AF04 AG01 AH03

Claims (13)

[Claims] 1. A compound of the general formula (1) (Wherein, Z is a single bond, -O-, -CO-, -Si (CH
_{3) 2 -, - Si (} OCH 3) 2 -, - C (CH 3) 2
_{-, - C (CF 3)} 2 -, - C (CH 3) (CF 3)
—, —C (OCH ₃ ) ₂ —, —C (OCF ₃ ) ₂ — and —C (OCH ₃ ) (OCF ₃ ) —, wherein R and R ′ are each independently monovalent Which can be added or condensed to each other by light or heat to form a ring together with the Z)). 2. The polymer compound according to claim 1, wherein R and R ′ are both OH. 3. The polymer compound represented by the general formula (2): (Wherein, X is a tetravalent organic group, Y is a divalent organic group, R ¹ and R ² are each independently OH or a monovalent organic group, and at least one of X and Y is The polymer compound according to claim 1, which is a polyimide precursor having a repeating unit represented by the following general formula (1): 4. A polymer compound represented by the general formula (3): (Wherein X ′ is a divalent organic group, Y ′ is a tetravalent organic group, R ³ and R ⁴ are each independently a hydrogen atom or a monovalent organic group, and X ′ and Y 'Is a polybenzoxazole precursor having a repeating unit represented by the following general formula (1): 5. A photosensitive resin composition comprising the polymer compound according to claim 1, 2, 3 or 4. 6. The polymer compound is a polyimide precursor according to claim 3 or a polybenzoxazole precursor according to claim 4, and has a carbon-carbon unsaturated double bond in its structure. The photosensitive resin composition according to claim 5, which has negative photosensitive characteristics. 7. The photosensitive resin composition according to claim 6, further comprising a photopolymerization initiator. 8. The polymer of claim 3, wherein the polymer compound is a polyimide precursor according to claim 3 or a polybenzoxazole precursor according to claim 4, further comprising a compound capable of generating an acid by light. 6. A photosensitive material having the following photosensitive characteristics:
The photosensitive resin composition as described in the above. 9. The photosensitive resin composition according to claim 8, wherein the compound generating an acid by light is an o-quinonediazide compound. 10. A method for producing a relief pattern, comprising the steps of applying the photosensitive resin composition according to claim 5 on a support substrate, drying, exposing, developing, and heating. Law. 11. The method for producing a relief pattern according to claim 10, wherein the exposing step is performed using i-line as an exposure light source. 12. The method according to claim 10, wherein the supporting substrate is a silicon wafer having a diameter of 12 inches or more. 13. An electronic component having a relief pattern layer obtained by the production method according to claim 10.