JP3455697B2 - Photosensitive resin composition, method for producing pattern, and electronic component - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-type photosensitive resin composition, a method for producing a pattern using this composition, and an electronic component. More specifically, the present invention relates to surface protection of an electronic component such as a semiconductor element by heat treatment. The present invention relates to a positive photosensitive resin composition which is a polyimide-based or polyoxazole-based heat-resistant polymer applicable as a film, an interlayer insulating film, etc., a method for producing a pattern using this composition, and an electronic component.

[0002]

2. Description of the Related Art Polyimide has excellent heat resistance and mechanical properties,
Further, it is widely used as a surface protective film and an interlayer insulating film of a semiconductor element because of its advantages such as easy film formation and flattened surface. When polyimide is used as a surface protective film and an interlayer insulating film, the step of forming through holes and the like is mainly performed by an etching process using a positive photoresist. However, there is a problem in that the process includes coating and peeling of the photoresist and is complicated. Therefore, heat-resistant materials having photosensitivity have been studied for the purpose of streamlining the work process.

Regarding the photosensitive polyimide composition obtained by this study, (1) a polyimide precursor composition having a photosensitive group introduced by an ester bond (Japanese Patent Publication No. 52-30207, etc.), (2) polyamic acid by actinic radiation A composition containing a compound containing a dimerizable or polymerizable carbon-carbon double bond and an amino group and an aromatic bisazide (Japanese Patent Publication No.
No. 36861) is known. When the photosensitive polyimide precursor composition is used, it is usually applied on a substrate in a solution state, dried, irradiated with an actinic ray through a mask, and developed to form a pattern.

However, the compositions of the above (1) and (2) require the use of an organic solvent for the developing solution. Since the amount of the developing solution used is several times as much as the amount of the photosensitive polyimide precursor composition used, there is a problem that a large load is placed on the environment when the waste developing solution is treated. For this reason, particularly in recent years, from the viewpoint of the environment, a photosensitive polyimide composition that can be developed with an aqueous developer that is easy to treat a waste developer has been desired. Also, (1)
Since the compositions of (2) and (2) are of a negative type, it is necessary to change the mask used in the exposure step when switching from an etching process using a positive type photoresist to a negative type photosensitive polyimide precursor. There is.

Then, as a positive type photosensitive polyimide precursor composition made to solve these problems, (3) o
A polyimide precursor in which a -nitrobenzyl group is introduced through an ester bond (JP-A-60-37550, etc.),
(4) Polyamic acid ester containing carboxyl group and o
-A composition containing a quinonediazide compound (Japanese Patent Laid-Open No. 4-16
No. 8441), and (5) a composition containing a polyamic acid ester containing a hydroxyl group and an o-quinonediazide compound ( special
( Kaihei 3-115461, etc.) and (6) a composition containing a polyamic acid ester and an o-quinonediazide compound (Japanese Patent Laid-Open No. 2-181149, etc.) are known. In recent years, polyoxazole has been reported as a heat-resistant polymer similar to polyimide, and (7) a positive photosensitive composition containing this polyoxazole precursor and an o-quinonediazide compound is also known (JP-A-6-60140). No.

By the way, the degree of integration of semiconductor elements has been improved year by year, and along with this, improvement in fine processing technology is desired. As one of the technologies that enables fine processing, there is a shortening of the exposure wavelength in the lithography process, and the exposure light source during pattern formation using a positive photoresist is
The conventional g-line (436 nm) to i-line (365 nm) are becoming mainstream. Therefore, it is required for the photosensitive polyimide precursor to be able to form a pattern by using the i-line as an exposure light source from the viewpoint of making the exposure apparatus common.

Further, as described above, the polyimide or polyoxazole used as the surface protective film of the semiconductor or the interlayer insulating film is usually used as the precursor composition. However, especially when stored in a solution state at room temperature, the color of the photosensitive resin composition is discolored, or the residual film after development in the evaluation under the same conditions is lowered after standing,
There is a problem that the target film thickness cannot be obtained. It is considered that this is because the photosensitizer o-quinonediazide is decomposed by the basic terminal of the polymer in the system, so that the effect of suppressing dissolution in the developer is reduced.

[0008]

The present invention overcomes the above-mentioned problems of the prior art. That is, the inventions according to claims 1 to 6 provide a photosensitive resin composition having excellent storage stability, stable photosensitive characteristics, and good heat resistance. In addition to the above problems, the inventions of claims 2 to 4 among these claims provide a photosensitive resin composition having higher sensitivity and excellent pattern shape.

According to the invention of claim 7, the use of the composition having excellent storage stability makes it possible to suppress fluctuations in the photosensitive characteristics, has high resolution, and produces a pattern having a good shape. It provides the law. Also,
The invention according to claim 8 provides a highly reliable electronic component by having a precise pattern with a good shape.

[0010]

The present invention relates to a photosensitive resin composition containing (A) an alkali aqueous solution-soluble polymer, (B) an o-quinonediazide compound, and (C) a compound exhibiting acidity. In the present invention, the component (A) is
The present invention relates to a photosensitive resin composition which is polyimide, its precursor, polyoxazole or its precursor.

In the present invention, the component (A) has the general formula (I)

[Chemical 2] (In the formula, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group. Group, at least one of which is a monovalent organic group), is a photosensitive resin composition which is a polyamic acid ester having a repeating unit represented by the formula:

The present invention also relates to a photosensitive resin composition in which R ² in the general formula (I) is a divalent organic group having a phenolic hydroxyl group. The present invention also provides the above (C).
The component relates to a photosensitive resin composition, which is a compound showing an acidity with an acid dissociation constant (pKa) at 25 ° C. of 10 or less. The present invention also relates to the photosensitive resin composition, wherein the component (C) is an organic acid.

The present invention also provides a method for producing a pattern, which comprises the steps of coating and drying the above-mentioned photosensitive resin composition on a supporting substrate, exposing, exposing with an alkali developing solution, and heat treating. Regarding The present invention also relates to an electronic component having the pattern obtained by the above manufacturing method as a surface protective film or an interlayer insulating film.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) used in the present invention is a polymer which is soluble in an aqueous alkali solution and therefore generally has an acidic group. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfone group, and the like. The polymer used in the present invention preferably has a carboxyl group or a phenolic hydroxyl group. By having an acidic group, the polymer becomes soluble in an alkaline aqueous solution used as a developing solution. After the exposure, a pattern can be formed in the exposed area by changing the o-quinonediazide compound which is the component (b). The alkaline aqueous solution is an alkaline aqueous solution in which tetramethylammonium hydroxide, metal hydroxide, amine and the like are dissolved in water.

The type of the polymer as the component (A) includes polyimide precursors such as polyamic acid, polyamic acid ester, and polyamic acid amide, polyhydroxyamide as polyoxazole precursor, polyoxazole, other polyamides, polyimides, It is preferable because it has excellent film physical properties such as the heat resistance of the pattern in which a polymer having excellent heat resistance such as polybenzoxazole is formed. Among these,
A polyimide precursor, a polyimide, a polyoxazole precursor, and a polyoxazole, which become a resin film having excellent heat resistance by curing reaction after forming a pattern, are preferable. Among them, the polyamic acid ester having the repeating unit represented by the general formula (I) is preferable because it has excellent adhesion to the substrate.

In the above general formula (I), the tetravalent organic group represented by R ¹ is a tetracarboxylic acid, a dianhydride or a derivative thereof, which can react with a diamine to form a polyimide structure. It is a residue and is preferably a tetravalent aromatic group or an aliphatic group, preferably having 4 to 40 carbon atoms, and more preferably a tetravalent aromatic group having 4 to 40 carbon atoms. The aromatic group means a group containing an aromatic ring (benzene ring, naphthalene ring, etc.). As the tetravalent aromatic group, those having all tetravalent bonding sites on the aromatic ring are preferable. These binding sites are divided into two sets of two binding sites, and the two binding sites are preferably located at the ortho position or the peri position of the aromatic ring. The above-mentioned two sets may be present on the same aromatic ring or may be present on different aromatic rings bonded via various bonds.

The divalent organic group having a carboxyl group or a phenolic hydroxyl group represented by R ² in the general formula (I) means an amino group of a diamine compound capable of reacting with tetracarboxylic acid to form a polyimide structure. It is a residue removed, and an aromatic group or an aliphatic group is preferable, one having 2 to 40 carbon atoms is preferable, and an aromatic group having the above-mentioned number of carbon atoms is more preferable. Here, the aromatic group is preferably one in which the two bonding sites are directly present on the aromatic ring,
In this case, the two binding sites may be present on the same aromatic ring or different aromatic rings. Further, it is preferable to have 1 to 8 carboxyl groups or phenolic hydroxyl groups, and it is preferable that these also be directly bonded to the aromatic ring. Among these, those having a phenolic hydroxyl group are preferred because of high sensitivity. In the general formula (I), the monovalent organic group represented by R ³ and R ⁴ is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group and has 1 carbon atom.
Those of -20 are preferable.

The polyamic acid ester may have a repeating unit other than the repeating unit represented by the general formula (I). For example, the following general formula (II)

[Chemical 3] (In the formula, R ⁵ represents a tetravalent organic group, R ⁶ represents a divalent organic group having neither a carboxyl group nor a phenolic hydroxyl group, and R ⁷ and R ⁸ independently represent a hydrogen atom or a monovalent organic group. And a repeating unit represented by

4 represented by R ⁵ in the general formula (II)
As the valent organic group, the same groups as those described above for R ¹ can be mentioned. Further, in the general formula (II), the divalent organic group having no carboxyl group and a phenolic hydroxyl group represented by R ^6, that in the description of the R ² does not have any carboxyl group and a phenolic hydroxyl group Except for R ² , the same as those shown in the description of R ² can be mentioned. Further, in the general formula (II), the monovalent organic group represented by R ⁷ and R ⁸ is the same as R ³ above.
And those similar to those shown in the description of R ⁴ .

In the component (A), the ratio of the repeating units of the general formulas (I) and (II) is 0, where m / (m + n) is the number of the former and n is the latter. 0.2-1 is preferable, and 0.4-1 is more preferable. If this value is less than 0.2, the solubility in an alkaline aqueous solution tends to be poor.

In the polyamic acid ester as the component (A), the total amount of repeating units in which the carboxyl groups of tetracarboxylic acid residues are completely esterified is preferably 50 to 100% with respect to the total number of repeating units. , 80
-100% is more preferable, and 90-100 is especially preferable. In addition, the repeating unit referred to here is one unit composed of one acid residue and one diamine residue.

The weight average molecular weight of the component (A) is preferably 3,000 to 200,000, and is preferably 5,0.
00-100,000 are more preferable. The molecular weight is measured by gel permeation chromatography-method,
The value can be obtained by converting using a standard polystyrene calibration curve. In the general formulas (I) and (II),
Groups represented by ^{R 3, R 4, R 7} , R 8 are two in the repeating unit, but they may be the same or different.
Further, in a plurality of repeating units, R ¹ , R ² ,
The groups represented by R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different.

In the present invention, the polyamic acid ester may be, for example, a tetracarboxylic acid diester dihalide (chloride, bromide, etc.), a diamine compound having a carboxyl group or a phenolic hydroxyl group, and optionally a carboxyl group or a phenolic hydroxyl group. It can be obtained by reacting with a diamine compound which does not have it.
In this case, the reaction is preferably carried out in an organic solvent in the presence of a dehalogenation catalyst.

The tetracarboxylic acid diester dihalide is preferably tetracarboxylic acid diester dichloride. The tetracarboxylic acid diester dichloride can be obtained by reacting a tetracarboxylic acid diester obtained by reacting a tetracarboxylic acid dianhydride with an alcohol compound with thionyl chloride.

As a raw material of the polyamic acid ester,
In addition, tetracarboxylic dianhydride is generally used as the other polyimide precursor or polyimide raw material. The tetracarboxylic dianhydride, for example,
Pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-
Biphenyltetracarboxylic dianhydride, 2,2 ', 3,
3'-biphenyltetracarboxylic dianhydride, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid Dianhydride, 1,2,5,6-
Naphthalenetetracarboxylic dianhydride, 2,3,6,7
-Naphthalene tetracarboxylic dianhydride, 1,4,5,
8-naphthalenetetracarboxylic dianhydride, 2,3
5,6-pyridinetetracarboxylic dianhydride, 3,4
9,10-Perylene tetracarboxylic dianhydride, 2,2
Aromatic tetracarboxylic dianhydrides such as -bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride are preferable, and these can be used alone or in combination of two or more.

In the above-mentioned polyamic acid ester, an alcohol compound is used as a raw material for the ester portion, and specific examples thereof include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and sec-. Butyl alcohol, tert-butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, isoamyl alcohol, 1-hexanol, 2
Alkyl alcohols such as hexanol and 3-hexanol, phenol, and benzyl alcohol are preferable, and these can be used alone or in combination of two or more kinds.

Further, diamine is used as a raw material of the polyamic acid ester and as a raw material of other polyimide precursors and polyimide. The diamine having a carboxyl group or a phenolic hydroxyl group is used for imparting an acidic group to the polymer when the carboxyl group of the tetracarboxylic acid does not remain like the polyamic acid ester, polyamic acid amide, or polyimide. . Examples of such compounds include 2,5-
Diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5
-Diaminobenzoic acid, 2,5-diaminoterephthalic acid,
Bis (4-amino-3-carboxyphenyl) methylene, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethyl Biphenyl, 1,3-diamino-
4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-
Dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-)
Aromatic diamine compounds such as hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, and bis (4-amino-3-carboxyphenyl) methane are preferable, and these are used alone or in combination with 2 Combinations of more than one type can be used.

The diamine having no carboxyl group or phenolic hydroxyl group is, for example, 4,4'-
Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether,
Aromatic diamine compounds such as 1,4-bis (4-aminophenoxy) benzene are preferable, and these are used alone or in 2
Combinations of more than one type can be used.

In addition, in order to improve heat resistance, 4,4'-diaminodiphenyl ether-3-sulfonamide and 3,4'-diaminodiphenyl ether-diamine are used as diamines.
4-sulfonamide, 3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3'-diaminodiphenyl ether-4-sulfonamide, 4,4'-diaminodiphenyl ether-3 -Carboxamide, 3,
Sulfonamide group or carboxamide such as 4'-diaminodiphenylether-4-carboxamide, 3,4'-diaminodiphenylether-3'-carboxamide, 3,3'-diaminodiphenylether-4-carboxamide The diamine compound having a group can be used alone or in combination of two or more, and when used in combination, it is preferably used in an amount of 15 mol% or less in the total amount of the diamine compound, and used in a range of 10 mol% or less. More preferably.

In the synthesis of polyamic acid ester, a method for synthesizing a tetracarboxylic acid diester compound is known, and for example, the tetracarboxylic dianhydride and the alcohol compound are mixed in an organic solvent in the presence of a base. It can be obtained. The preferable ratio (molar ratio) of the carboxylic dianhydride and the alcohol compound is 1 / the latter.
The range is from 2 to 1/20, and a more preferable ratio is 1 /
The range is from 2.5 to 1/10, and the most preferable range is 1/2. The preferable reaction temperature is 10 to 60 ° C., and the preferable reaction time is 3 to 24 hours.

A method for synthesizing a tetracarboxylic acid diester dichloride is known and can be obtained, for example, by reacting a tetracarboxylic acid diester with thionyl chloride. A preferable ratio (molar ratio) of tetracarboxylic acid diester and thionyl chloride is 1 / 1.1-1.2.5 in the former / latter.
Is preferable, and the range of 1 / 1.5 to 1 / 2.2 is more preferable. The reaction temperature is preferably −20 to 40 ° C., and the reaction time is preferably 1 to 10 hours.

The polyamic acid ester is prepared, for example, by dissolving the above-mentioned diamine compound and a dehydrochlorination catalyst such as pyridine in an organic solvent, and dropping the tetracarboxylic acid diester dichloride dissolved in the organic solvent to cause a reaction. It can be obtained by charging in a solvent, filtering the precipitate, and drying. Examples of the organic solvent used in the reaction include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-butyrolactone and the like. These aprotic polar solvents are used alone or in combination of two or more. The ratio (molar ratio) of the total amount of the diamine compound and the tetracarboxylic acid diester dichloride is 0.6 / 1 to 1/0.
A range of 6 is preferred. The reaction temperature is preferably −20 to 40 ° C., and the reaction time is preferably 1 to 10 hours. The ratio of the dehydrochlorination catalyst to the tetracarboxylic acid diester dihalide is such that the former / latter (molar ratio) is in the range of 0.95 / 1 to 1 / 0.95.

When a diamine compound having neither a carboxyl group nor a phenolic hydroxyl group is used together in the synthesis of a polyamic acid ester, a diamine compound having a carboxyl group or a phenolic hydroxyl group and a diamine compound having no carboxyl group or a phenolic hydroxyl group are used. The ratio is preferably 20 to 100 mol% of the former and 80 to 0 mol% of the latter so that the whole is 100 mol%, and 40 to 100 mol% of the former and 60 to 0 mol% of the latter are 100 mol% in total. It is preferably used so as to be%. The former diamine compound is used to give the polyamic acid ester solubility in an aqueous alkaline solution, but if it is less than 20 mol%, the sensitivity tends to be low and the developing time tends to be long.

When the polymer having an acidic group soluble in an alkaline aqueous solution is a polyamic acid, since a carboxyl group as a residue of tetracarboxylic acid exists, a diamine compound having a carboxyl group or a phenolic hydroxyl group is used as the diamine. It does not have to be used. Polyamic acid can be obtained by directly reacting the tetracarboxylic dianhydride and diamine.

When the polymer having an acidic group soluble in an alkaline aqueous solution is polyamic acid amide or polyimide, a diamine compound having a carboxyl group or a phenolic hydroxyl group is generally used as a diamine. The usage ratio of the diamine compound having no phenolic hydroxyl group is the same as in the case of the synthesis of the polyamic acid ester.

The polyamic acid amide is a monoamine compound such as methylamine, ethylamine, n-propylamine, isopropylamine, n instead of the alcohol compound in the synthesis of the polyamic acid ester.
-Butylamine, sec-butylamine, tert-butylamine, isobutylamine, 1-pentylamine,
2-pentylamine, 3-pentylamine, isoamylamine, 1-hexylamine, 2-hexylamine, 3
-Primary amines such as hexylamine, secondary amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine and di-n-butylamine, alicyclic amines such as piperidine, piperazine and morpholine, aniline and benzylamine. It can be synthesized by using. Polyimide is obtained by dehydrating and ring-closing the above polyamic acid.

Examples of the polyoxazole precursor include hydroxypolyamides generally obtained by using dicarboxylic acid and dihydroxydiamine as raw materials. Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, 4,4-
Hexafluoroisopropylidenedibenzoic acid, 4,4-
Biphenyldicarboxylic benzoic acid, 4,4-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5
-Bromoisophthalic acid, 5-fluoroisophthalic acid, 5
-Aromatic dicarboxylic acids such as chloroisophthalic acid and 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
Aliphatic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid and succinic acid can be mentioned. These can be used alone or in combination of two or more. Of these, aromatic dicarboxylic acids are preferable in terms of heat resistance.

The hydroxydiamine is 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-hydroxy) Aromatic diamines such as phenyl) hexafluoropropane are preferred. It is preferable to use an aromatic diamine from the viewpoint of heat resistance, and polybenzoxazole can be obtained by using the aromatic diamine.

The component (B) used in the present invention, o-
The quinonediazide compound is a photosensitizer having a site that is converted to a carboxylic acid by light. This includes, for example, o-quinonediazide sulfonyl chlorides and hydroxy compounds,
A substance obtained by subjecting an amino compound or the like to a condensation reaction in the presence of a dehydrochlorination catalyst is used as the preferable substance. Examples of the o-quinonediazidesulfonyl chlorides 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.

Examples of the hydroxy compound include:
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, tris (4-hydroxyphenyl) ethane and the like.

As the amino compound, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-
Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 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-quinonediazidesulfonyl chloride and the hydroxy compound and / or the amino compound are blended so that the total of the hydroxy group and the amino group is 0.5 to 1 equivalent to 1 mol of the o-quinonediazidesulfonyl chloride. It is preferable. A preferable ratio of the dehydrochlorination catalyst to o-quinonediazidesulfonyl chloride is 0.95 /
The range is from 1 to 1 / 0.95. The preferable reaction temperature is 0 to 40 ° C., and the preferable reaction time is 1 to 10 hours.

As the reaction solvent, for example, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone are used. Examples of the dehydrochlorination catalyst include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like. The component (B) is 5 parts with respect to 100 parts by weight of the component (A) from the viewpoint of the film thickness after development and sensitivity.
To 100 parts by weight, preferably 10 to 40 parts by weight.

In the present invention, the compound (C) exhibiting acidity can improve the storage stability of the photosensitive resin composition. The o-quinonediazide compound which is the component (B) contained in the composition of the present invention is generally easily decomposed due to the presence of a basic substance. In the composition of the present invention, a basic group may remain as the end of the polymer, and in this case,
By adding a compound showing acidity which is the component (C),
It is possible to prevent decomposition of the o-quinonediazide compound as the component (B) and stabilize the characteristics of the photosensitive resin composition. The addition of the component (C) does not deteriorate other excellent characteristics of the present invention.

As the compound showing an acidity which is the component (C), one having an acid dissociation constant (pKa) at 25 ° C. of 10 or less is preferable. Further, since the photosensitive resin composition of the present invention is mainly used as an electronic component, when an inorganic acid having a metal as a counter ion is used, the metal may adversely affect a circuit or the like, and therefore an organic acid is used. It is preferable.

Examples of such compounds include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, paproic acid,
Phenylacetic acid, lactic acid, oxalic acid, fumaric acid, phthalic acid,
Maleic acid, malonic acid, dichloroacetic acid, trichloroacetic acid, benzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, o-chloroacetic acid, m-chloroacetic acid, p-chloroacetic acid, fluoroacetic acid , Trifluoroacetic acid, phenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, p-phenolsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid,
Organic acids such as trifluoromethanesulfonic acid can be mentioned.

Of these, acetic acid is preferable because it does not remain in the film because it volatilizes after prebaking, it hardly affects the photolithographic property, and the workability is improved because it is easy to handle.

In the photosensitive resin composition of the present invention,
The blending amount of the component (C) is 0.01 to 20 with respect to 100 parts by weight of the component (A) from the viewpoints of sensitivity and an allowable range of developing time.
Parts by weight, preferably 0.01 to 10 parts by weight,
Further, 0.1 to 5 parts by weight is preferable.

The photosensitive resin composition of the present invention is obtained by dissolving the components (A), (B) and (C) in a solvent and is obtained in a solution state. Examples of the solvent include N-methyl-
2-pyrrolidone, N, N-dimethylformamide, N,
N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone,
An aprotic polar solvent such as γ-butyrolactone, cyclohexanone, cyclopentanone is used alone or in combination of two or more kinds.

In order to improve the coating property, a solvent such as diethyl ketone, diisobutyl ketone , methyl amyl ketone, ethyl lactate, propylene glycol monomethyl ether acetate or the like can be used in combination. The amount of the solvent is not particularly limited, but generally the amount of the solvent in the composition is 20 to 90.
It is adjusted so as to be wt%.

The photosensitive resin composition of the present invention can contain an organic silane compound, an aluminum chelate compound, a silicon-containing polyamic acid and the like as an adhesion aid. Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane. To be Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetyl acetate aluminum diisopropylate, and the like.

Examples of the silicon-containing polyamic acid include those represented by the general formula (III)

[Chemical 4] (In the formula, R⁹Represents a tetravalent organic group, R^TenIs divalent organic
Group, R¹¹Represents a monovalent organic group, and q is an integer of 1 or more.
Polyamide having repeating unit represented by
Mention may be made of acids.

In the polyamic acid having a siloxane structure having a repeating unit represented by the general formula (III), the tetravalent organic group represented by R ⁹ is the residue of tetracarboxylic dianhydride which is a raw material of polyimide. Base, 4
A valent aromatic group or aliphatic group, which has 4 carbon atoms
To 40 are more preferable, and a tetravalent aromatic group having 4 to 40 carbon atoms is further preferable. The tetravalent aromatic group is
It is preferable that all tetravalent binding sites are present in the aromatic ring. These binding sites are preferably divided into two sets of two binding sites, and the two binding sites are present at adjacent carbons of the aromatic ring (that is, at the ortho position). The two sets may be on the same aromatic ring. It may be present in different aromatic rings linked via various bonds.

In the above general formula (III), two R
^The portion sandwiched by ¹⁰ is the residue of the silicone diamine compound excluding the amino group, and this portion preferably has 6 to 40 carbon atoms as a whole. 2 represented by R ¹⁰
The valent organic group preferably has 1 to 10 carbon atoms, and examples thereof include an alkylene group having the above carbon number and a phenylene group. Two R10s may be the same or different. Good. As the monovalent organic group represented by R11, an organic group having 1 to 5 carbon atoms is preferable, and an alkyl group having the above carbon number or a phenyl group is preferable. When using an adhesion assistant, 0.1 to 20 parts by weight is preferable with respect to 100 parts by weight of component (A), and 1 to 10 parts by weight.
More preferably parts by weight.

The photosensitive resin composition of the present invention contains a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , Si).
O ₂ etc.), silicon nitride, etc. are applied onto a supporting substrate and dried to form a film of the positive photosensitive resin composition. After that, irradiation with actinic rays such as ultraviolet rays, visible rays, and radiations is performed through a mask, and then the exposed portion is removed with a developing solution to obtain a positive relief pattern.

Drying is usually performed using an oven or a hot plate. The drying conditions are appropriately determined depending on the components of the photosensitive resin composition, but when a hot plate is used, it is preferably 60 to 140 ° C. for 30 seconds to 10 minutes.
If the drying temperature is low, the solvent does not volatilize sufficiently and tends to contaminate the coating device, the exposure device and the like. Further, if the drying temperature is high, the o-quinonediazide compound in the film of the photosensitive resin composition tends to decompose during drying.

Preferred examples of the developing solution include alkaline aqueous solutions of sodium hydroxide, potassium hydroxide, sodium silicate, tetramethylammonium hydroxide and the like. The base concentration of these aqueous solutions is 0.1
It is preferably set to 10% by weight. Further, an alcohol or a surfactant may be added to the above developer for use. Each of these may be added 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.

Then, the relief pattern obtained is applied with 15
By heat treatment at 0 to 450 ° C., a pattern of heat-resistant polyimide or heat-resistant polybenzoxazole having an imide ring, an oxazole ring, or another cyclic group is formed. INDUSTRIAL APPLICABILITY The photosensitive resin composition of the present invention can be used for electronic parts such as a semiconductor device and a multilayer wiring board, and specifically, 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 electronic component of the present invention is
There is no particular limitation except that it has a surface protective film or an interlayer insulating film formed using the composition, and various structures can be adopted.

An example of the manufacturing process of the semiconductor device of the present invention 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 a predetermined portion of the circuit element, and a first conductor layer is formed on the exposed circuit element. . A film 4 of polyimide 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 chlorinated rubber-based or phenol novolac-based photosensitive resin layer 5 is formed on the interlayer insulating film 4 by a spin coating method, and a predetermined portion of the interlayer insulating film 4 is exposed by a known photo-etching technique. Thus, the window 6A is provided (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 to open the window 6B. Then, the photosensitive resin layer 5 is completely removed 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, by using a known photo-etching technique, the second
The conductor layer 7 is formed, and the electrical connection with the first conductor layer 3 is completed (step (d)). When forming a multi-layer wiring structure having three or more layers, each layer can be formed by repeating the above steps.

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

[0063]

EXAMPLES The present invention will be described in detail below with reference to examples. Example 1 In a 0.5 liter flask equipped with a stirrer, a thermometer, and a Dimroth condenser, 24.82 g (0.83 g) of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride was added.
08 mol), 11.86 g of n-butyl alcohol (0.
16 mol), pyridine 0.24 g (0.0024 mol)
135 g of N-methylpyrrolidone was charged and reacted at room temperature for 15 hours with stirring to obtain 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester. Then thionyl chloride 15.2 in a flask at 0 ° C.
3 g (0.128 mol) was added dropwise and reacted for 1 hour,
A solution (α) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride was obtained.

Next, in a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, 95 g of N-methylpyrrolidone was charged, and 5.78 g (0.038 mol) of 3,5-diaminobenzoic acid was added. After adding 5.21 g (0.026 mol) of 4,4′-diaminodiphenyl ether and dissolving with stirring, 12.66 g of pyridine was added,
While maintaining the temperature at 0 to 5 ° C., a solution (α) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride was added dropwise over 20 minutes, and then 1
Stirring was continued for hours. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester having a weight average molecular weight of 30,000.

Polyamic acid n-butyl ester 30.0
Compound 5.5 obtained by reacting 0 g, 2,3,4,4′-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/3.
0 g and acetic acid 1.5 g were added to N-methylpyrrolidone 48.00.
It was dissolved in g with stirring. This solution was pressure-filtered using a Teflon filter having 3 μm pores to obtain a photosensitive composition.

The photosensitive composition immediately after being obtained was spin-coated on a silicon wafer using a spinner and dried by heating on a hot plate at 110 ° C. for 3 minutes to give a film of the photosensitive resin composition having a thickness of 7.8 μm. Got An i-line reduction projection exposure apparatus (LD-5010i manufactured by Hitachi, Ltd.) was used to coat the photosensitive polyimide precursor coating film with a mask of 100 to 5 through a mask.
An exposure of 00 mJ / cm ² was performed. Next, paddle development was performed for 60 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution as a developing solution and washed with pure water to obtain a relay pattern. The film thickness after development was 6.5 μm, and the residual film rate was 83%. As a result of pattern observation, the appropriate exposure amount was determined to be 350 mJ / cm ^2, and a pattern having a good shape was obtained with this exposure amount. Next, this relay pattern is heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere,
A polyimide film pattern having a thickness of 4.0 μm was obtained. Further, the same photosensitive resin composition that was left at room temperature for 1 week was evaluated in the same manner as above. Film thickness after heating and drying is 7.8μ
m, film thickness after development is 6.5 μm, suitable exposure amount is 350 m
It was J / cm ² , which was the same as the photosensitive characteristics of the above-mentioned photosensitive resin composition which was not left at room temperature.

Example 2 In a 0.5 liter flask equipped with a stirrer, a thermometer, and a Dimroth condenser, 28.66 g (0. 0,3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride) was added.
08 mol), 11.86 g of n-butyl alcohol (0.
16 mol), pyridine 0.24 g (0.0024 mol), N- methylpyrrolidone were charged 135 g, by stirring for 15 hours at room temperature the reaction, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic di n -Butyl ester was obtained. Then thionyl chloride 1 at 0 ° C. in a flask
5.23 g (0.128 mol) was added dropwise and reacted for 1 hour to obtain a solution (β) of 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid di-n-butyl ester dichloride.
Got

Then, in a 0.5 liter flask equipped with a stirrer, a thermometer, and a Dimroth condenser, 95 g of N-methylpyrrolidone was charged, and 23.44 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was charged.
(0.064 mol) was added, and the mixture was stirred and dissolved. Then, 12.66 g of pyridine was added and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid din was added while keeping the temperature at 0 to 5 ° C. -Butyl ester dichloride solution (β)
Was added dropwise over 1 hour, and stirring was continued for 1 hour. 4 solutions
The mixture was poured into liter of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester having a weight average molecular weight of 25,000.

Polyamic acid n-butyl ester 30.0
0 g, 4.00 g of a compound obtained by reacting tris (4-hydroxyphenyl) methane with naphthoquinone-1,2-diazide-5-sulfonyl chloride in a molar ratio of 1/3, and 1.0 g of acetic acid with N-methylpyrrolidone 48. It was dissolved in 100 g with stirring. This solution was pressure-filtered using a Teflon filter having 3 μm pores to obtain a photosensitive composition. The photosensitive composition immediately after being obtained was spin-coated on a silicon wafer using a spinner, and dried by heating on a hot plate at 100 ° C. for 3 minutes to form a film of a positive photosensitive resin composition of 8.4 μm. Obtained. The photosensitive polyimide precursor coating film was exposed to 100 to 500 mJ / cm ² through a mask using an i-line reduction projection exposure apparatus (LD-5010i manufactured by Hitachi, Ltd.). Next, paddle development was performed for 80 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution as a developing solution and washed with pure water to obtain a relay pattern. The film thickness after development was 6.8 μm, and the residual film rate was 81%. Moreover, as a result of pattern observation, the appropriate exposure amount is 450 mJ / c.
It was determined to be m ^2, and a pattern having a good shape was obtained with this exposure amount. Then, this pattern is placed in a nitrogen atmosphere at 350 ° C.
And heat-treated for 1 hour to obtain a polyimide film pattern having a thickness of 4.2 μm. Further, the same photosensitive resin composition that was left at room temperature for 1 week was evaluated in the same manner as above. The film thickness after heating and drying is 8.4 μm, the film thickness after development is 6.7 μm, and the appropriate exposure amount is 450 mJ / cm ^2, which is the same as the photosensitive characteristics of the above-mentioned photosensitive resin composition not left at room temperature. Met.

[0070]

[0071]

Comparative Example 1 Polyamic acid n-butyl ester 30.
A compound obtained by reacting 00g, 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/3.
50 g was dissolved in 48.00 g of N-methylpyrrolidone with stirring. This solution was pressure-filtered using a Teflon filter having 3 μm pores to obtain a photosensitive composition. The photosensitive composition immediately after obtained was spin-coated on a silicon wafer using a spinner and dried by heating on a hot plate at 110 ° C. for 3 minutes to obtain a film of the photosensitive resin composition having a thickness of 8.0 μm. . The photosensitive polyimide precursor coating film was exposed to 100 to 500 mJ / cm ² through a mask using an i-line reduction projection exposure apparatus (LD-5010i manufactured by Hitachi, Ltd.).
Next, paddle development was performed for 60 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution as a developing solution and washed with pure water to obtain a relay pattern. The film thickness after development was 6.6 μm, and the residual film rate was 83%. As a result of pattern observation, the appropriate exposure amount was determined to be 350 mJ / cm ^2, and a pattern having a good shape was obtained with this exposure amount. Then, this pattern is subjected to 1 at 350 ° C. under a nitrogen atmosphere
After heat treatment for an hour, a polyimide film pattern having a thickness of 4.0 μm was obtained. Further, the same photosensitive resin composition that was left at room temperature for 1 week was evaluated in the same manner as above. The film thickness after heating and drying was 8.0 μm, the film thickness after development was 5.0 μm, and the residual film ratio was 63%, which was lower than the above-mentioned photosensitive resin composition which was not left at room temperature. Oops. The color of the photosensitive composition which had been left at room temperature for one week was slightly discolored.

Comparative Example 2 Polyamic acid n-butyl ester 30.
00 g, 4.00 g of a compound obtained by reacting tris (4-hydroxyphenyl) methane with naphthoquinone-1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/3, and 1.0 g of acetic acid with N-methylpyrrolidone 48. It was dissolved in 100 g with stirring. This solution was pressure-filtered using a Teflon filter having 3 μm pores to obtain a photosensitive composition.

The photosensitive composition immediately after being obtained was spin-coated on a silicon wafer using a spinner and dried by heating on a hot plate at 100 ° C. for 3 minutes to give a positive photosensitive resin composition of 8.2 μm. A film of An i-line reduction projection exposure apparatus (LD-5010i, manufactured by Hitachi, Ltd.) was used to coat this photosensitive polyimide precursor coating film through a mask.
The exposure was performed at 0 to 500 mJ / cm ² . Then 2.3
Paddle development was performed for 80 seconds using an 8 wt% tetramethylammonium hydroxide aqueous solution as a developing solution, and washed with pure water to obtain a relay pattern. The film thickness after development was 6.6 μm, and the residual film rate was 80%. As a result of pattern observation, the appropriate exposure amount was determined to be 450 mJ / cm ^2, and a pattern having a good shape was obtained with this exposure amount. Then, this pattern is heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere,
A polyimide film pattern having a thickness of 4.0 μm was obtained.

The same photosensitive resin composition that had been allowed to stand for 1 week at room temperature was evaluated in the same manner as above. The film thickness after heating and drying was 8.0 μm, the film thickness after development was 4.8 μm, and the residual film ratio was 60%, resulting in deterioration of the photosensitivity as compared with the above-mentioned photosensitive resin composition not left at room temperature. Oops. The color of the photosensitive composition which had been left at room temperature for one week was slightly discolored.

As can be seen from the above-mentioned Examples and Comparative Examples, in the Examples of the present invention, no deterioration of the photosensitive resin composition and no change in the photosensitive characteristics were observed even when left at room temperature, showing good stability. It was On the other hand, in Comparative Example, when left at room temperature for 1 week, deterioration of the photosensitive resin composition due to decomposition of the photosensitizer and deterioration of photosensitivity were observed.

[0077]

The photosensitive resin composition according to the present invention is excellent in storage stability, exhibits stable photosensitivity over a long period of time, and has good heat resistance. In addition to the above problems, the photosensitive resin composition according to claims 2 to 4,
Further, the sensitivity is high and the pattern shape is excellent.

According to the method for producing a pattern according to claim 7, the use of the composition having excellent storage stability makes it possible to suppress the fluctuation of the photosensitive characteristics and obtain a good shape with high resolution. Is. The electronic component according to claim 8 provides a highly reliable electronic component by having a precise pattern with a good shape.

[Brief description of drawings]

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

[Explanation of symbols]

1 ... Semiconductor substrate, 2 ... Protective film, 3 ... First conductor layer,
4 ... Interlayer insulating film layer 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window, 7 ... Second
Conductor layer, 8 ... Surface protective film layer.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Takanori Ansai Inventor Takanori Ansai 4-13-1, Higashimachi, Hitachi, Ibaraki Prefecture Hitachi Chemical DuPont Micro Systems Co., Ltd. Yamazaki Development Center (72) Inventor Nagatoshi Fujieda, 4 Higashimachi, Hitachi, Ibaraki Chome 13-1 Hitachi Chemical DuPont Micro Systems Co., Ltd. Yamazaki Development Center (56) Reference JP-A-3-115461 (JP, A) JP-A-4-284455 (JP, A) JP-A-4-168441 (JP, A) JP-A-9-319082 (JP, A) JP-A-5-34914 (JP, A) JP-A-2-213847 (JP, A) JP-A-52-40125 (JP, A) Table 5-7500932 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (6)

(57) [Claims] 1. An (A) aqueous alkali solution-soluble polymer,
A photosensitive resin composition comprising (B) an o-quinonediazide compound and (C) acetic acid . 2. The photosensitive resin composition according to claim 1, wherein the component (A) is polyimide, a precursor thereof, polyoxazole or a precursor thereof. 3. The component (A) has the general formula (I): (In the formula, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group. The photosensitive resin composition according to claim 2, which is a polyamic acid ester having a repeating unit represented by a group, at least one of which is a monovalent organic group. 4. The photosensitive resin composition according to claim 3, wherein R ² in the general formula (I) is a divalent organic group having a phenolic hydroxyl group. 5. A step of applying the photosensitive resin composition according to any one of claims 1 to 4 on a supporting substrate and drying it, exposing it, developing it with an alkali developing solution, and heating it. A method of manufacturing a pattern including. 6. An electronic component having a pattern obtained by the manufacturing method according to claim 5 as a surface protective film or an interlayer insulating film.