JP2003121998A - Photosensitive polymer composition, method for producing pattern and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative heat-resistant photosensitive polymer composition having high sensitivity and excellent in pattern shape and resolution because development time is shortened and a high residual film ratio of an exposed area can be maintained, to provide a method for producing a relief pattern having high resolution and a good shape by using the composition and to further provide a heat-resistant photosensitive polymer composition convertible to a polyimide-base heat-resistant polymer by heating and electronic parts using this composition. SOLUTION: The photosensitive polymer composition comprises (a) a polyimide precursor or a polyimide soluble in an aqueous alkali solution, (b) a compound which generates an acid under light, (c) a compound having one or more tertiary alcohols having a hydroxyl group on carbon bonding directly to an aromatic ring and (d) a compound having two or more alkoxymethyl groups and phenolic hydroxyl groups in one molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant photosensitive polymer composition and a method for producing a relief pattern using this composition, more specifically, a surface protective film for electronic parts such as semiconductor devices by heat treatment. The present invention relates to a heat-resistant photosensitive polymer composition that is a polyimide-based heat-resistant polymer applicable as an interlayer insulating film, etc., a method for producing a relief pattern using this composition, and an electronic component.

[0002]

2. Description of the Related Art Polyimide has been widely used as a surface protective film and an interlayer insulating film for semiconductor devices because it has excellent heat resistance and mechanical properties, is easy to form a film, and has a flat surface. .

When using polyimide as a surface protective film or 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, 1.
1. A polyimide precursor composition having a photosensitive group introduced by an ester bond (Japanese Patent Publication No. 52-30207, etc.); Carbon capable of dimerizing or polymerizing polyamic acid with actinic radiation
A composition containing a compound containing a carbon double bond and an amino group and an aromatic bisazide (Japanese Patent Publication No. 3-36861) is known.

When the photosensitive polyimide composition is used, it is usually applied on a substrate in a solution state, dried, irradiated with an actinic ray through a mask, and the exposed portion is removed with a developing solution to form a pattern.

The above compositions 1 and 2 are of a negative type utilizing a crosslinking reaction by radical active species generated by light irradiation,
Use an organic solvent for development. However, these cross-linked pattern forming materials require a large amount of irradiation for pattern formation, increase in molecular weight due to dark reaction due to the inclusion of a cross-linking agent, large change in viscosity of the composition during storage, low storage stability, etc. I have a problem. Further, in recent years, there has been an increasing demand for an aqueous developing solution from an organic solvent in view of environmental problems.

On the other hand, as the negative pattern forming material based on the polarity conversion reaction of the tertiary alcohol, not the crosslinking reaction, those described in JP-A-2-290917, JP-A-4-165359 and JP-A-7-104473 are known. Has been. These polarity conversion type pattern forming materials are characterized by higher sensitivity, higher resolution, and better dimensional accuracy and stability than cross-linking type pattern forming materials.
These are intended to be used as a photoresist for semiconductor fine processing, and are usually removed after etching a base film using the photoresist as a mask. However, there is no example of such a method of semi-permanently incorporating a polarity conversion type pattern forming material as a buffer coat film or an interlayer insulating film into a semiconductor element.

[0008]

The present invention overcomes the above-mentioned problems of the prior art.

That is, the inventions according to claims 1 to 7 provide a heat-resistant photosensitive polymer composition capable of shortening the developing time, maintaining a high residual film ratio, and being excellent in pattern shape and resolution. The invention of claim 8 provides a method for producing a relief pattern, which has a high resolution and can obtain a pattern of good shape by using the composition.

Further, the invention according to claim 9 provides a highly reliable electronic component by having a precise relief pattern having a good shape.

[0011]

The present invention provides (a) a polyimide precursor or polyimide soluble in an aqueous alkali solution,
(B) a compound that generates an acid by light, (c) a compound having at least one tertiary alcohol having a hydroxyl group on the carbon directly bonded to an aromatic ring, and (d) two or more alkoxys in the molecule The present invention relates to a photosensitive polymer composition containing a compound having a methyl group and a phenolic hydroxyl group.

In the present invention, the component (a) is represented by the general formula (I)

[0013]

[Chemical 9]

(In the formula, R ¹ represents a tetravalent organic group, and R ²
Is a divalent organic group) and is a polyimide precursor having a repeating unit represented by the formula 1. The photosensitive polymer composition according to claim 1. Further, in the present invention, the component (a) is represented by the general formula (II)

[0015]

[Chemical 10]

(In the formula, R ¹ represents a tetravalent organic group, and R ³
Represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and R ⁴ each independently represents a monovalent organic group), and is a polyimide precursor having a repeating unit represented by the formula. And a photosensitive polymer composition. Further, in the present invention, the component (c) has the following general formula (II
I) to (VII)

[0017]

[Chemical 11]

[0018]

[Chemical 12]

[0019]

[Chemical 13]

[0020]

[Chemical 14]

(In the formula, R5 and R6 represent a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R7 to R10 are hydrogen,
Halogen, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, a hydroxy group, an atom selected from a phenyl group, or an atomic group). The present invention relates to a photosensitive polymer composition according to claims 1 to 3. Further, the present invention is
The component (d) has the following general formula (VII)

[0022]

[Chemical 15]

(In the formula, X represents a single bond or a divalent organic group, R represents an alkyl group or an alkenyl group, and R ¹¹
And R ¹² each independently represents an alkyl group or an alkenyl group, m and n are each independently 1 or 2, and p and q
Are each independently an integer of 0 to 3), The photosensitive polymer composition according to claim 1.

The present invention further includes a release process which comprises a step of coating and drying the above-mentioned photosensitive polymer composition on a supporting substrate, an exposing step, a developing step using an alkali developing solution, and a heat treating step. The present invention relates to a manufacturing method for a pattern. The present invention also relates to a relief pattern obtained by the above production method.
The present invention relates to an electronic component having a surface protective film or an interlayer insulating film.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Since the component (a) in the present invention needs to be soluble in an alkaline aqueous solution used as a developing solution, a polymer selected from a polyimide precursor or a polyimide soluble in an alkaline aqueous solution. Is. Therefore, the polymer preferably has an acidic group in the molecule. The type of polymer in the present invention is excellent in heat resistance, and exhibits excellent properties as an interlayer insulating film or a surface protective film of a semiconductor device or a multilayer wiring board. Therefore, polyimide, or polyamic acid, polyamic acid ester, or polyamic acid amide is used. And other polyimide precursors.

Since the component (a) has an acidic group, it is soluble in an alkaline aqueous solution used as a developer, but after exposure, the acid produced by photolysis of the component (b) is the component (C). Since the tertiary alcohol undergoes an intramolecular dehydration reaction and changes to an isopropenyl group, its solubility is significantly reduced. As a result, the dissolution rate of the exposed area decreases,
Since there is a difference in dissolution rate from the unexposed portion, a relief pattern can be formed. Further, by containing the component (d), the solubility of the unexposed portion is increased, the development time can be shortened, and a high residual film rate can be obtained.

The alkaline aqueous solution is an alkaline aqueous solution in which tetramethylammonium hydroxide, metal hydroxide, amine and the like are dissolved in water.
Examples of the acidic group in the component (a) include a carboxyl group, a phenolic hydroxyl group, and a sulfo group.
The polymer used in the present invention preferably has a carboxyl group or a phenolic hydroxyl group.

In the above general formulas (I) and (II), R
^The tetravalent organic group represented by ¹ reacts with a diamine,
A residue of a tetracarboxylic acid, a dianhydride thereof, or a derivative thereof which can form a structure of a polyimide precursor;
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 aromatic group means a group containing an aromatic ring (benzene ring, naphthalene ring, etc.). Four
As the valent aromatic group, those in which all of the four bonding sites are present on the aromatic ring are preferable. These binding sites are
It is preferably divided into two sets of two binding sites, and the two binding sites are located at the ortho position of the aromatic ring. The above-mentioned two sets may be present in the same aromatic ring, or may be present in different aromatic rings which are bonded via various bonds.

In the general formula (I), the divalent organic group represented by R ² is a diamine capable of reacting with tetracarboxylic acid, a dianhydride thereof or a derivative thereof to form a structure of a polyimide precursor. Is a residue excluding the amino group of
An aromatic group or an aliphatic group is preferable, and the number of carbon atoms is 2 to 4
0 is more preferable, and an aromatic group is further preferable.
Here, the aromatic group is preferably one in which the two binding sites are directly present on the aromatic ring, and in this case, the two binding sites are present in the same aromatic ring or different aromatic rings. You may. In the general formula (II), the divalent organic group having a carboxyl group or a phenolic hydroxyl group represented by R ³ is a structure of a polyimide precursor by reacting with tetracarboxylic acid, a dianhydride thereof or a derivative thereof. Which is a residue excluding an amino group of a diamine having a carboxyl group or a phenolic hydroxyl group, which is preferably an aromatic group or an aliphatic group, and which has 2 to 40 carbon atoms excluding the carboxyl group. More preferably, an aromatic group is even 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 also preferable that these are also directly bonded to the aromatic ring.

In the general formula (II), the monovalent organic group represented by R ⁴ is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably one having 1 to 20 carbon atoms.

The polyimide precursor having the repeating units represented by the general formulas (I) and (II) may have repeating units other than the repeating units represented by the general formulas (I) and (II). . For example, the following general formula (VII)

[0032]

[Chemical 16]

(In the formula, R ⁵ represents a tetravalent organic group, and R ⁶
Has no carboxyl group or phenolic hydroxyl group 2
A valent organic group, and R ⁷ represents a monovalent organic group).

In the general formula (VII), the description of the tetravalent organic group represented by R ⁵ is as described above in the general formulas (I) and (II).
Is the same as the description of R ¹ of. In the general formula (VII), the description of the divalent organic group represented by R ⁶ is the same as the description of R ^{2 in} the general formula (I). Furthermore, in the general formula (VII), the monovalent organic group among the groups represented by R ⁷ is the same as the description of the general formula (II) R ⁴ .

The general formula (II) and the general formula (VI
In I), there are two groups represented by R ⁴ and R ⁷ in each repeating unit, which may be the same or different. Further, in a plurality of repeating units, R ¹ ,
The groups represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ may be the same or different.

The molecular weight of the polyimide precursor or polyimide of the component (a) in the present invention is preferably 3,000 to 200,000 in terms of weight average molecular weight, and 5,000.
More preferably, it is from 100,000. The molecular weight can be measured by a gel permeation chromatography method and converted using a standard polystyrene calibration curve to obtain a value. In the present invention, when the component (a) is a polyamic acid, it can be obtained, for example, by reacting a tetracarboxylic dianhydride and a diamine in an organic solvent. Also, (a)
When the component is a polyamic acid ester, for example, a tetracarboxylic acid diester dihalide (chloride, bromide, etc.), a diamine having a carboxyl group or a phenolic hydroxyl group, and further a diamine having no carboxyl group or a phenolic hydroxyl group, if necessary. Can be obtained by reacting with. In this case, the reaction is preferably carried out in an organic solvent in the presence of a dehalogenating agent. Also,
When the component (a) is a polyamic acid partial ester composed of the general formulas (I) and (VII), it can be obtained by reacting the above-mentioned tetracarboxylic dianhydride, tetracarboxylic diester dihalide and diamine. 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 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 dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride Anhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,2,
3,4-cyclopentanetetracarboxylic dianhydride,
1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2, 3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3 Aromatic tetracarboxylic dianhydrides such as 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride The thing is preferable and these can be used individually or in combination of 2 or more types.

In the polyamic acid ester, an alcohol compound is used as a raw material which becomes an ester site of its side chain. Examples of the alcohol compound include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Alkyl alcohol such as sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, phenol, benzyl. Alcohol and the like are preferable, and these can be used alone or in combination of two or more kinds. Diamine is used as a raw material of the polyamic acid. Examples thereof include 4,4′-diaminodiphenyl ether, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, benzicin, 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, 1,4-bis (4-aminophenoxy)
Aromatic diamine compounds such as benzene are preferable, and these can be used alone or in combination of two or more kinds. Further, in the case where the carboxyl group of the tetracarboxylic acid does not remain like the polyamic acid ester, the polyamic acid amide, and the polyimide, in order to make the polymer soluble in an alkaline aqueous solution, a carboxyl group, a phenolic hydroxyl group, etc. A diamine having an acidic group of is required, and as such a diamine, for example, 2,5-
Diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5
-Diaminobenzoic acid, 2,5-diaminoterephthalic acid,
Bis (4-amino-3-carboxyphenyl) methylene, bis (4-amino-3-carboxyphenyl) ether, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-5 , 5'-dicarboxy-2,2'-dimethylbiphenyl, 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3'-diamino-4,4'-dihydroxy Biphenyl, 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) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis ( Aromatic diamines such as 4-amino-3-hydroxyphenyl) hexafluoropropane are preferred,
These may be used alone or in combination of two or more.

In addition, in order to improve heat resistance, 4,4'-
Diaminodiphenyl ether-3-sulfonamide,
3,4'-diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-3 '
-Sulfonamide, 3,3'-diaminodiphenyl ether-4-sulfonamide, 4,4'-diaminodiphenyl ether-3-carboxamide, 3,4'-diaminodiphenyl ether-4-carboxamide, 3,4 '
-Diaminodiphenyl ether-3'-carboxamide, 3,3'-diaminodiphenyl ether-4-carboxamide diamine having a sulfonamide group or a carboxamide group can be used alone or in combination of two or more. It is preferably used in an amount of 15 mol% or less, more preferably 10 mol% or less, based on the total amount of the diamine compound. A method for synthesizing a polyamic acid is known, and it can be obtained by reacting a tetracarboxylic dianhydride and a diamine in an organic solvent.

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

A method for synthesizing a tetracarboxylic acid diester dichloride is known, and for example, it can be obtained by dropping thionyl chloride into a tetracarboxylic acid diester dissolved in an organic solvent to cause a reaction. The ratio (molar ratio) of tetracarboxylic acid diester to thionyl chloride is 1 / the latter.
The range of 1.1 to 1 / 2.5 is preferable, and 1 / 2.5
The range of 1.5 to 1 / 2.2 is more preferable. The reaction temperature is preferably -20 to 40 ° C, and the reaction time is 1 to 1
0 hours is preferred.

For the polyamic acid ester, for example, the above-mentioned diamine and a dehalogenating agent such as pyridine are dissolved in an organic solvent, and a tetracarboxylic acid diester dihalide dissolved in the organic solvent is added dropwise to react with it. It is obtained by pouring into a poor solvent, filtering the precipitate, and drying.
The ratio (molar ratio) of the total amount of diamine and the tetracarboxylic acid diester dihalide is 0.6 / 1 to 1 / the former / the latter.
The range of 0.6 is preferable, and the range of 0.7 / 1 to 1 / 0.7 is more preferable. The reaction temperature is preferably −20 to 40 ° C., and the reaction time is preferably 1 to 10 hours. The ratio of the dehalogenating agent and the tetracarboxylic acid diester dihalide is
The former / latter (molar ratio) is 0.95 / 1 to 1 / 0.95
Is preferable, and the range of 0.98 / 1 to 1 / 0.98 is more preferable.

In the synthesis of a polyamic acid ester, when a diamine compound having no acidic group such as a carboxyl group and a phenolic hydroxyl group is used in combination, the ratio of the diamine having an acidic group to the diamine having no acidic group is the same as the former 2
0 to 100 mol%, the latter 80 to 0 mol% and the total 100
Preferably, the former 40
˜100 mol%, the latter 60 to 0 mol% is more preferably used so that the total amount becomes 100 mol%. The former diamine is used to give the polyamic acid ester solubility in an aqueous alkaline solution.
If it is less than 0 mol%, the sensitivity tends to decrease and the developing time tends to be long.

As the component (b) used in the present invention for generating an acid by light, onium salts such as allyldiazonium salt, diallyliodonium salt, triallylsulfonium salt and naphthoylmethyltetramethylenesulfonium salt are used. be able to.

The counter anion of the onium salt is an alkylsulfonic acid such as trifluoromethanesulfonic acid, trifluoroacetic acid or methanesulfonic acid, an arylsulfonic acid such as toluenesulfonic acid, tetrafluoroboronic acid, hexafluoroantimonic acid or hexafluoroarsenic. Lewis acids such as acids are used.

The component (c) used in the present invention is a compound having at least one tertiary alcohol having a hydroxyl group on the carbon directly bonded to the aromatic ring. For example, 1,
3-bis (2-hydroxy-2-propyl) benzene,
1,3-bis (3-hydroxy-3-pentyl) benzene, 1,3-bis (2-hydroxy-2-propyl)-
5-methoxybenzene, 5-chloro-1,3-bis (2
-Hydroxy-2-propyl) benzene, 1,4-bis (2-hydroxy-2-propyl) benzene, 1,4-
Bis (3-hydroxy-3-pentyl) benzene, 1,
4-bis (2-hydroxy-2-propyl) -2,3
5,6-Tetramethylbenzene, 2-chloro-1,4-
Bis (2-hydroxy-2-propyl) benzene, 5-
Bromo-1,4-bis (2-hydroxy-2-propyl) benzene, 1,3,5-tris (2-hydroxy-)
2-propyl) benzene, 1,3,5-tris (3-hydroxy-3-pentyl) benzene, 1,5-bis (2
-Hydroxy-2-propyl) naphthalene, 1,4-bis (2-hydroxy-2-propyl) naphthalene 9,
10-bis (2-hydroxy-2-propyl) anthracene and the like can be mentioned.

In the photosensitive polymer composition of the present invention,
The blending amount of the component (c) is preferably 1 to 40 parts by weight, and 5 to 100 parts by weight of the component (a), from the viewpoint of the developing time of the unexposed area and the allowable width of the residual film ratio of the exposed area. 20 parts by weight is more preferred. The component (d) used in the present invention is a compound having two or more alkoxymethyl groups and a phenolic hydroxyl group in the molecule. By using this component (d), the dissolution rate of the unexposed area at the time of development with an aqueous alkaline solution can be increased and the development time can be shortened, while the exposed area is dehydrated by the acid generated by the alkoxymethyl group. Condensation occurs and it becomes difficult to dissolve in a developing solution, so that a high residual film rate can be maintained. As the component (d), a compound having a molecular weight of 1,500 or less is generally preferable, since the dissolution promoting effect on the unexposed portion decreases as the molecular weight increases.

In the compound represented by the general formula (VII), the divalent group represented by X is an alkylene group such as a methylene group, an ethylene group or a propylene group, an arylene group such as a phenylene group, or a hydrocarbon thereof. Examples include groups in which some or all of the hydrogen atoms of the group have been replaced with halogen atoms such as fluorine atoms, sulfone groups, carbonyl groups, ether bonds, thioether bonds, amide bonds, etc., and the following general formula (VIII)

[0049]

[Chemical 17]

(In the formula, each X'is independently a single bond, an alkylene group (for example, having 1 to 10 carbon atoms), or some or all of the hydrogen atoms thereof are substituted with halogen atoms. A group, a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond or the like, and R ¹³ is a hydrogen atom, a hydroxy group, an alkyl group or a haloalkyl group, and there are a plurality of them. In this case, they may be the same or different from each other, and m is 1 to 10).

In the general formula (VII), the group represented by X is

[0052]

[Chemical 18]

(In the formula, two A's are each independently a hydrogen atom,
Or an alkyl group having 1 to 10 carbon atoms) is preferable because of its high effect.

Specific examples of the compound represented by the general formula (VII) include bis (2-hydroxy-3-methoxymethyl-5-methylphenyl) methane and bis (2-hydroxy-3-ethoxymethyl-5-). Methylphenyl) methane, bis (2-hydroxy-3-propoxymethyl-5)
-Methylphenyl) methane, bis (2-hydroxy-3)
-Butoxymethyl-5-methylphenyl) methane, bis [2-hydroxy-3- (1-propenyloxy) methyl-5-methylphenyl] methane, bis (2-hydroxy-3-methoxymethyl-5-methylphenyl) Ethane, bis (2-hydroxy-3-ethoxymethyl-5-
Methylphenyl) ethane, 3,3'-bis (methoxymethyl) -4,4'-dihydroxybiphenyl, 3,3 '
-Bis (ethoxymethyl) -4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3 ', 5
5'-tetrakis (methoxymethyl) biphenyl, 4,
4'-dihydroxy-3,3 ', 5,5'-tetrakis (ethoxymethyl) biphenyl, bis (4-hydroxy-3-methoxymethylphenyl) methane, bis (4-hydroxy-3-ethoxymethylphenyl) methane, Examples thereof include bis [4-hydroxy-3,5-bis (methoxymethyl) phenyl] methane and bis [4-hydroxy-3,5-bis (ethoxymethyl) phenyl] methane.

In the photosensitive polymer composition of the present invention,
The blending amount of the component (d) is 1 with respect to 100 parts by weight of the component (a) from the viewpoints of the developing time and the allowable width of the residual film ratio of the unexposed portion.
-30 parts by weight is preferable, and 5-20 parts by weight is more preferable.

The photosensitive polymer composition of the present invention can be obtained by dissolving the components (a), (b), (c) and (d) in a solvent.

As the solvent, for example, N-methyl-2-
Pyrrolidone, N, N-dimethylformamide, N, N-
Dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-
An aprotic polar solvent such as butyrolactone is preferable,
These may be used alone or in combination of two or more.

Further, 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 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 heat-resistant photosensitive polymer composition of the present invention comprises
Further, if necessary, an organic silane compound, an aluminum chelate compound or the like can be contained as an adhesion aid.

Examples of the organic silane compound include γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ
Examples thereof include glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and ureapropyltriethoxysilane.

As the aluminum chelate compound, for example,
Examples include tris (acetylacetonate) aluminum, acetyl acetate aluminum diisopropylate, and the like.

Although the amount of the adhesion aid is not particularly limited,
The amount is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the component (a).

The heat-resistant photosensitive polymer composition of the present invention can be formed into a polyimide relief pattern through the steps of coating and drying on a supporting substrate, exposing, developing and heating. .

In the step of coating and drying on a supporting substrate, a glass substrate, a semiconductor, a metal oxide insulator (for example, Ti
O ₂ , SiO _2, etc.), on a support substrate such as silicon nitride,
This heat-resistant photosensitive polymer composition is spin-coated using a spinner or the like, and then dried using a hot plate, oven or the like.

Next, in the exposure step, the photosensitive polymer composition formed into a film on the supporting substrate is irradiated with actinic rays such as ultraviolet rays, visible rays and radiation through a mask.

In the developing step, a relief pattern is obtained by removing the exposed portion with a developing solution. Preferred examples of the developer include alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is preferably 0.1 to 10% by weight.

Further, an alcohol or a surfactant may be added to the above developing solution for use. Each of these is preferably 0.01 with respect to 100 parts by weight of the developer.
The amount can be added in the range of 10 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

Next, in the heat treatment step, the relief pattern obtained is subjected to heat treatment at preferably 150 to 450 ° C. to form a relief pattern of a heat-resistant polyimide having an imide ring or other cyclic group.

[0069]

EXAMPLES The present invention will be described below with reference to examples. Example 1 20.0 g of 4,4′-diaminodiphenyl ether was placed in a flask equipped with a stirrer and a thermometer and dissolved in 150 g of N-methyl-2-pyrrolidone. To this, 21.0 g of pyromellitic dianhydride was added at once together with 30 g of N-methyl-2-pyrrolidone, and the mixture was reacted at 50 ° C. for 3 hours.

2.1 g of diphenyliodonium triflate and 1,3,5-tris (2) were added to the obtained polymer solution.
-Hydroxy-2-propyl) benzene (4.1 g) and bis (2-hydroxy-3-methoxymethyl-5-methylphenyl) methane (2.1 g) were added and dissolved with stirring, and the solution was Teflon (registered trademark) having 3 μm pores. It pressure-filtered using the filter and the photosensitive polymer composition was obtained.

The photosensitive polymer composition thus obtained was spin-coated on a silicon wafer using a spinner, and dried by heating on a hot plate at 105 ° C. for 2 minutes to give 10.5 μm.
A coating film of An i-line stepper (manufactured by Hitachi, Ltd.) was used as an exposure device for this coating film, and a reticle was used.
The exposure was performed at 50 to 500 mJ / cm ² . Then, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide was used as a developing solution for paddle development for 55 seconds, and washed with pure water to obtain a relief pattern. By pattern observation,
The proper exposure amount was determined to be 200 mJ / cm ² . The residual film rate in the exposed area was 87%. When the obtained relief pattern was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere,
A polyimide film pattern was obtained. Example 2 20.0 g of 4,4′-diaminodiphenyl ether was placed in a flask equipped with a stirrer and a thermometer and dissolved in 150 g of N-methyl-2-pyrrolidone. Here 3,
3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 31.0 g was added to N-methyl-2-pyrrolidone 30
It was added together with g and reacted at 50 ° C. for 3 hours.

2.1 g of diphenyliodonium triflate and 1,3,5-tris (2) were added to the obtained polymer solution.
-Hydroxy-2-propyl) benzene (4.1 g) and bis (2-hydroxy-3-methoxymethyl-5-methylphenyl) methane (5.1 g) were added and dissolved with stirring, and this solution was filtered using a Teflon filter with 3 μm pores. A photosensitive polymer composition was obtained by pressure filtration.

The photosensitive polymer composition thus obtained was spin-coated on a silicon wafer using a spinner and dried by heating on a hot plate at 110 ° C. for 2 minutes to obtain 10.2 μm.
A coating film of An i-line stepper (manufactured by Hitachi, Ltd.) was used as an exposure device for this coating film, and a reticle was used.
The exposure was performed at 50 to 500 mJ / cm ² . Then, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide was used as a developing solution to perform paddle development for 50 seconds, followed by washing with pure water to obtain a relief pattern. By pattern observation,
The appropriate exposure amount was determined to be 150 mJ / cm ² . The residual film ratio in the exposed area was 89%. When the obtained relief pattern was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere,
A polyimide film pattern was obtained. Example 3 In a 0.3-liter flask equipped with a stirrer and a thermometer, 17.37 g (0.056 mol) of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, n
-Butyl alcohol 8.30 g (0.112 mol), triethylamine 0.28 g (0.0028 mol), N-
47.7 g of methylpyrrolidone (NMP) was charged, and the mixture was stirred and reacted at room temperature for 8 hours to obtain an NMP solution (α) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester. .

Then, in a 0.3-liter flask equipped with a stirrer and a thermometer, 5.2 parts of pyromellitic dianhydride were placed.
3 g (0.024 mol), methyl alcohol 1.54 g
(0.048 mol), triethylamine 0.12 g
(0.0012 mol) and 12.6 g of NMP were charged and reacted at room temperature for 4 hours with stirring to obtain an NMP solution (β) of pyromellitic acid dimethyl ester.

Next, an NMP solution (β) of dimethyl pyromellitic ester was added to NM of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester.
P solution (α) and after cooling the flask to 0 ° C.,
17.13 g (0.144 mol) of thionyl chloride was added dropwise and reacted for 1 hour to mix 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride and pyromellitic acid dimethyl ester dichloride. A solution (γ) was obtained.

Next, 105 g of N-methylpyrrolidone was placed in a 0.5 liter flask equipped with a stirrer and a thermometer.
, Bis (3-amino-4-hydroxyphenyl)
After 26.37 g (0.072 mol) of hexafluoropropane was added and dissolved by stirring, 22.78 g of pyridine was added.
(0.288 mol) was added, and the solution of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride and pyromellitic acid dimethyl ester dichloride were added while maintaining the temperature at 0 to 5 ° C. After the mixed solution (γ) was added dropwise over 20 minutes, the temperature was raised to 30 ° C and 1
Continue stirring for hours. The solution was poured into 3 l of water, the precipitate was collected and washed, and then dried under reduced pressure to obtain a polyamic acid ester (δ).

Polyamic acid ester (δ) 15.00
g, 0.5 g of diphenyliodonium triflate,
1,3,5-tris (2-hydroxy-2-propyl)
N-containing 3.0 g of benzene and 1.5 g of bis (2-hydroxy-3-methoxymethyl-5-methylphenyl) methane.
70.0 g of methylpyrrolidone was added and dissolved by stirring, and this solution was pressure-filtered using a Teflon filter having 3 μm pores to obtain a photosensitive polymer composition.

The photosensitive polymer composition thus obtained was spin-coated on a silicon wafer using a spinner and dried by heating on a hot plate at 110 ° C. for 2 minutes to give 10.8 μm.
A coating film of An i-line stepper (manufactured by Hitachi, Ltd.) was used as an exposure device for this coating film, and a reticle was used.
The exposure was performed at 50 to 500 mJ / cm ² . Then, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide was used as a developing solution to perform paddle development for 60 seconds, followed by washing with pure water to obtain a relief pattern. By pattern observation,
The appropriate exposure amount was determined to be 150 mJ / cm ² . The residual film ratio in the unexposed area was 92%. When the obtained relief pattern was heat-treated in a nitrogen atmosphere at 350 ° C. for 1 hour, a polyimide film pattern was obtained. Comparative Example 1 2.1 g of diphenyliodonium triflate and 1,3,5-tris (2-) were added to the polymer solution obtained in Example 1.
Hydroxy-2-propyl) benzene (4.1 g) was added and dissolved by stirring, and this solution was pressure-filtered using a Teflon filter having 3 μm pores to obtain a photosensitive polymer composition.

The photosensitive polymer composition thus obtained was spin-coated on a silicon wafer using a spinner and dried by heating on a hot plate at 105 ° C. for 2 minutes to give a thickness of 10.0 μm.
A coating film of An i-line stepper (manufactured by Hitachi, Ltd.) was used as an exposure device for this coating film, and a reticle was used.
The exposure was performed at 50 to 500 mJ / cm ² . Then, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide was used as a developing solution to perform puddle development for 80 seconds, followed by washing with pure water to obtain a relief pattern. By pattern observation,
The proper exposure amount was determined to be 200 mJ / cm ² . The residual film rate in the exposed area was 78%. When the obtained relief pattern was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere,
A polyimide film pattern was obtained. Comparative Example 2 15.00 g of the polyamic acid obtained in Example 3, 0.5 g of diphenyliodonium triflate, 1,3,5-
Tris (2-hydroxy-2-propyl) benzene 3.
00.0 g of N-methylpyrrolidone was added and dissolved by stirring, and this solution was pressure filtered using a Teflon filter having 3 μm pores to obtain a photosensitive polymer composition.

The photosensitive polymer composition thus obtained was spin-coated on a silicon wafer using a spinner and dried by heating on a hot plate at 110 ° C. for 2 minutes to obtain 10.2 μm.
A coating film of An i-line stepper (manufactured by Hitachi, Ltd.) was used as an exposure device for this coating film, and a reticle was used.
The exposure was performed at 50 to 500 mJ / cm ² . Then, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide was used as a developing solution to perform paddle development for 100 seconds and washing with pure water to obtain a relief pattern. The appropriate exposure amount was determined to be 150 mJ / cm ² by pattern observation. The residual film ratio in the unexposed area was 82%. When the obtained relief pattern was heat-treated in a nitrogen atmosphere at 350 ° C. for 1 hour, a polyimide film pattern was obtained.

[0081]

EFFECT OF THE INVENTION The photosensitive polymer composition of the present invention has a high exposure sensitivity to i-line, can shorten the development time and maintain a high residual film rate, has a good resolution and a good pattern shape, and has a high heat resistance. It has excellent properties.

Further, according to the method for producing a relief pattern of the present invention, by using the above-mentioned photosensitive polymer composition having high sensitivity, high resolution and good pattern shape can be obtained, and the semiconductor device can be easily obtained. It is possible to form a surface protection film such as the above, an interlayer insulating film, and the like.

The electronic component of the present invention exhibits excellent characteristics as a surface protective film, an interlayer insulating film and the like.

Claims (9)

[Claims] 1. At least one of (a) a polyimide precursor or polyimide soluble in an alkaline aqueous solution, (b) a compound which generates an acid by light, and (c) a tertiary alcohol having a hydroxyl group on the carbon directly bonded to an aromatic ring. A photosensitive polymer composition comprising one or more compounds and (d) a compound having two or more alkoxymethyl groups and phenolic hydroxyl groups in the molecule. 2. The component (a) is represented by the general formula (I): The photosensitive polymer composition according to claim 1, which is a polyimide precursor having a repeating unit represented by the formula (wherein R ¹ represents a tetravalent organic group and R ² represents a divalent organic group). . 3. The component (a) has the general formula (II): (Wherein, R ¹ represents a tetravalent organic group, R ³ represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and R ⁴ independently represents a monovalent organic group) A polyimide precursor having a repeating unit of
2. The photosensitive polymer composition as described in 2 above. 4. The component (c) is represented by the following general formula (III):
(VII) embedded image [Chemical 4] [Chemical 5] [Chemical 6] (In the formula, R5 and R6 represent a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R7 to R10 represent hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or an unsubstituted alkyl group, 1 to 1 carbon atom.
4 represents an atom or atomic group selected from a substituted or unsubstituted alkoxy group, a hydroxy group, and a phenyl group)
The photosensitive polymer composition according to claim 1, which is a compound represented by: 5. The component (d) has the following general formula (VII): (In the formula, X represents a single bond or a divalent organic group, R represents an alkyl group or an alkenyl group, R ⁴ and R ⁵ each independently represent an alkyl group or an alkenyl group, and m and n are respectively Are independently 1 or 2, and p and q are independently 0 to
The photosensitive polymer composition according to claim 1 or 2, which is a compound represented by the formula (3). 6. The group represented by X in the compound represented by formula (VII) is: (In the formula, two A's each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). 7. The photosensitive polymer composition according to claim 5, wherein the compound represented by the general formula (VII) is bis (2-hydroxy-3-methoxymethyl-5-methylphenyl) methane. 8. A process of coating and drying the photosensitive polymer composition according to claim 1 on a supporting substrate, an exposing process, a developing process using an alkali developing solution, and a heat treatment. A method for producing a relief pattern including steps. 9. An electronic component having a relief pattern obtained by the manufacturing method according to claim 8 as a surface protective film or an interlayer insulating film.