JP2001083704A - Photosensitive resin composition, its pattern forming method, semiconductor device using same and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali developable positive type photosensitive resin composition capable of forming a high resolution relief pattern by incorporating a resin soluble in an aqueous alkali solution, a material which generates an acid under light and a specified pyridinium salt. SOLUTION: The photosensitive resin composition contains a resin soluble in an aqueous alkali solution, a material which generates an acid under light and a pyridinium salt of formula I, wherein R1-R5 are each a monovalent organic group or H, at least, one of R1-R5 is the organic group, R6 is a monovalent organic group and X1- an anion. The resin may be a polyamide acid of formula II, where R7 is a tetravalent organic group selected from diphenyl ether, diphenylsulfone and diphenylhexafluoropropane and R8 is a divalent organic group selected from diphenylsulfone and 2,2'-dimethylphenyl. A cured body of the photosensitive resin composition is formed on the circuit forming face or the protective film forming face of a semiconductor device.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition having excellent heat resistance and a method of forming a pattern thereof, and a semiconductor device using the same and a method of manufacturing the same.

[0002]

2. Description of the Related Art Heat-resistant resins represented by polyimide are:
Since it is easier to form a film than an inorganic material, and has a low dielectric property and a high toughness, it is useful for a buffer coat film or the like of a semiconductor element. In the above-mentioned application to semiconductor elements and the like, it is necessary to form a pattern of a heat-resistant resin film.

[0003] Pattern formation using a non-photosensitive resin composition involves steps such as coating and stripping of a photoresist, which complicates the process and is disadvantageous in cost. In addition, the dimensional accuracy is reduced by transferring the relief pattern via the photoresist. Therefore, in order to simplify the process of fine processing and increase the precision, it is advantageous to form a pattern using a photosensitive resin composition that can be finely processed by direct light.

[0004] The photosensitization of polyimide is best studied among heat-resistant resins. In particular, there have already been many proposals for a method of forming a pattern using a negative photosensitive polyimide or a method of manufacturing a semiconductor element. . However, when forming a pattern using a negative-type material utilizing a crosslinking reaction or manufacturing a semiconductor element, there is a problem that the exposed portion swells with a developing solution, and it is difficult to perform high-resolution fine processing.

In some cases, a positive type material is required in the process, and it is desired to develop a method of forming a pattern using a positive type photosensitive polyimide or a method of manufacturing a semiconductor device. In particular, from the viewpoint of preventing environmental pollution and improving the working environment, a pattern forming method using a developing solution mainly using a chlorine-based solvent or an organic solvent or a pattern forming method using an alkaline water-based solvent instead of a semiconductor element manufacturing method as a developing solution. Development of a method and a method of manufacturing a semiconductor device is desired.

At present, semiconductor devices having a buffer coat film formed of the above-described non-photosensitive polyimide or negative-type photosensitive polyimide have been manufactured. However, in these semiconductor elements, there is a problem that a defect due to insufficient resolution of the buffer coat film easily occurs.

[0007] With the miniaturization and high integration of semiconductor devices, the demand for the resolution of the buffer coat film is further increasing, and the reliability of a buffer coat film made of a positive photosensitive polyimide, photosensitive polybenzoxazole or the like has been increasing. There is a demand for a semiconductor device having high performance.

As a positive photosensitive resin composition which can be developed with an alkaline aqueous solvent, there have been proposed a composition in which a photosensitive group is introduced into a polyimide precursor by a covalent bond, and a system in which a photosensitive substance is added. As the former, there is a photosensitive polyamide acid nitrobenzyl ester (Japanese Patent Publication No. 1-59571). Examples of the latter include a photosensitive heat-resistant material comprising a polyamic acid and an orthoquinonediazidesulfonic acid ester derivative (JP-A-4-168441 and JP-A-4-204738), and a photosensitive material comprising a polyamic acid and an orthoquinonediazidosulfonimide derivative. And heat-resistant materials (JP-A-6-258836).

However, orthoquinonediazide, which is widely used, is a photosensitive material mainly for novolak-type photoresists, and has almost no dissolution inhibiting effect on polyimide precursors, especially on polyamic acid. Therefore,
In the photosensitive resin composition using the polyimide precursor and orthoquinonediazide, both the dissolution inhibiting effect in the unexposed portion and the dissolution promoting effect in the exposed portion were small, and sufficient sensitivity, resolution, and aspect ratio could not be obtained.

[0010]

One of the problems in realizing an alkali-developable positive photosensitive resin is controlling the dissolution rate in an alkaline aqueous developer.

Polyamic acid among the polyimide precursors has a very high dissolution rate in an alkaline aqueous developer. Therefore, in order to sensitize polyamic acid, it is necessary to lower the dissolution rate by designing the structure of polyamic acid or adding an effective dissolution inhibitor.

As an attempt to reduce the dissolution rate of polyamic acid, a partially imidized polyamic acid (Japanese Patent Publication No.
No. 2426) and a photosensitive resin composition comprising a polyamic acid / polyamic acid ester copolymer (JP-A-4-204738). However, when the carboxyl group concentration is reduced by the above means, there is a problem that the film swells in an alkaline aqueous developer and is difficult to dissolve.

As dissolution inhibitors, dihydropyridine derivatives (JP-A-05-113668, JP-A-05-113668)
JP-A-281717) has been reported, but has a problem that the resolution is low.

On the other hand, in the case of a polyamic acid ester, a photosensitive resin composition comprising a polyamic acid ester having a carboxyl group in a diamine portion (JP-A-4-168441) is used in order to adjust the dissolution rate in an alkaline aqueous developer. Although reported, the resolution is still low. Therefore, formation of a high-resolution relief pattern or fabrication of a semiconductor element has not been realized by the process using the photosensitive resin composition.

In view of the above, an object of the present invention is to provide a novel photosensitive resin composition, a pattern forming method thereof, a semiconductor device using the same, and a method of manufacturing the same.

[0016]

The gist of the present invention to achieve the above object is as follows.

(1) a resin soluble in an aqueous alkali solution,
A substance that generates an acid by light, and a compound represented by the formula [1]:

[0018]

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[Wherein R _{1 to} R ₅ are a monovalent organic group or a hydrogen atom, at least one of which is a monovalent organic group, R
₆ is a monovalent organic group, and X ₁ ~ is an anion].

(2) The resin soluble in the alkaline aqueous solution is represented by the formula [2]

[0021]

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Wherein R ₇ is a tetravalent organic group selected from diphenyl ether, diphenylsulfone and diphenylhexafluoropropane; R ₈ is diphenylsulfone;
(2) Bivalent organic group selected from 2,2′-dimethylbiphenyl].

(3) The resin soluble in the alkaline aqueous solution is represented by the formula [3]

[0024]

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[Wherein R ₉ and R ₁₂ are tetravalent organic groups,
R ₁₁ and R ₁₄ are monovalent organic groups; R ₁₀ is a divalent organic group having a phenolic hydroxyl group and / or a carboxyl group;
R ₁₃ is a divalent organic group, and y representing the constitutional ratio of the repeating unit is from 40 to 100 mol%].

(4) The resin soluble in the alkaline aqueous solution is represented by the formula [4]

[0027]

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The photosensitive resin composition according to (1), which is a polybenzoxazole precursor represented by the formula: wherein R ₁₅ is a divalent organic group and R ₁₆ is a tetravalent organic group.

(5) The pyridinium salt is represented by the formula [5]

[0030]

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Wherein R ₁₇ and R ₁₈ are aryl groups and X ₂ to are anions. The substance which generates an acid by light is an orthoquinone diazide compound (2).
The photosensitive resin composition according to any one of (1) to (4).

(6) a resin soluble in an aqueous alkali solution,
Applying a photosensitive resin composition containing a substance that generates an acid by light and a pyridinium salt represented by the formula [1] onto a substrate, irradiating an electromagnetic wave through a photomask, A method for forming a pattern, comprising a step of developing the reactive resin composition with an alkaline aqueous developer.

(7) The resin soluble in the aqueous alkali solution contained in the photosensitive resin composition is represented by the formula [2] to [4].
The pattern forming method according to (6), which is represented by any one of the above.

(8) The pattern forming method according to (7), wherein the pyridinium salt contained in the photosensitive resin composition is represented by the formula [5], and the substance which generates an acid by light is an orthoquinonediazide compound. .

(9) a resin soluble in an aqueous alkali solution,
A substance that generates an acid by light and a cured product of a photosensitive resin composition containing a pyridinium salt represented by the formula [1] are formed on a circuit formation surface or a protective film formation surface of a semiconductor element. A semiconductor element characterized by the following.

(10) The resin soluble in the aqueous alkaline solution contained in the photosensitive resin composition is represented by the formula [2] to
The semiconductor device according to (9), which is represented by any of [4].

(11) The semiconductor device according to (10), wherein the pyridinium salt contained in the photosensitive resin composition is represented by the formula [5], and the substance that generates an acid by light is an orthoquinonediazide compound.

(12) A resin soluble in an aqueous alkali solution, a substance capable of generating an acid by light, and a compound represented by the above formula [1]
A photosensitive resin composition containing a pyridinium salt represented by
The method includes a step of applying to a circuit formation surface or a protection film formation surface of a semiconductor element, a step of irradiating an electromagnetic wave through a photomask, a step of developing with an alkaline aqueous developer, and a step of baking the formed pattern. Manufacturing method of semiconductor device.

(13) The resin soluble in the aqueous alkali solution contained in the photosensitive resin composition is represented by the formula [2] to
The method for producing a semiconductor device according to (12), which is represented by any of [4].

(14) The semiconductor device according to (13), wherein the pyridinium salt contained in the photosensitive resin composition is represented by the formula [5], and the substance generating an acid by light is an orthoquinonediazide compound. Manufacturing method.

[0041]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a pyridinium salt acts as a dissolution inhibitor for a resin soluble in an aqueous alkali solution. Since the orthoquinonediazide compound is mainly a photosensitive material for a novolak-based photoresist, it hardly exhibits a dissolution-inhibiting effect on alkali-soluble resins other than the novolak-based resin, particularly, a resin having a carboxyl group. Therefore, the sensitivity, resolution, and aspect ratio were insufficient.

The pyridinium salt used in the present invention exhibits a large dissolution inhibiting effect due to interaction with an alkali-soluble resin having a phenolic hydroxyl group, a carboxyl group and the like.
By giving an appropriate dissolution rate in an alkaline aqueous developer, a high resolution and a high aspect ratio of the photosensitive resin composition can be realized.

R _{1 to} R ₅ in the above formula [1] are monovalent organic groups or hydrogen atoms, and at least one of them is a monovalent organic group. Monovalent organic groups include methyl,
Ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl, benzyl, phenyl,
t-butylphenyl, naphthyl, methoxy, ethoxy,
Propoxy, butoxy, benzyloxy, phenoxy,
Examples include, but are not limited to, benzoyl, oxazolyl, pyridyl, pyridinium salts and the like.

When R _{1 to} R ₅ are all hydrogen atoms,
It shows no dissolution inhibiting effect on the resin soluble in the aqueous alkali solution, and the dissolution rates of the unexposed portion and the exposed portion are both too high,
It is difficult to form a pattern.

R ₆ in the above formula [1] is a monovalent organic group, and is methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl, benzyl, phenyl, pentafluorobenzyl, t- Examples include, but are not limited to, butylbenzyl, naphthylmethyl, biphenylmethyl, pyridyl, pyridinium salts and the like.

X ₁ ~ in the above formula [1] represents an anion,
Cl ~, Br ~, I ~ , CN ~, SCN ~, NO 3 ~, ClO 4
~, BF ₄ ~, PF ₆ ~, SbF ₆ ~, CF ₃ SO ₃ ~, p-TS
~ (Paratoluenesulfonic acid) and the like, but are not limited thereto.

In the case where the structure of the above formula [1] is the structure of the above formula [5], the effect of inhibiting the dissolution of the pyridinium salt in the resin soluble in the aqueous alkali solution is further enhanced, and the effect of the present invention is exerted more. You.

In the above formula [5], R ₁₇ and R ₁₈ are aryl groups, such as phenyl, t-butylphenyl, naphthyl, biphenyl and the like; X ₂ ~ is an anion;
l ~, Br ~, I ~ , CN ~, SCN ~, NO 3 ~, ClO 4 ~, B
Specific examples of the structure include F ₄ ~, PF ₆ ~, SbF ₆ ~, CF ₃ SO ₃ ~, p-TS ~, but are not limited thereto.

[0049] Among the pyridinium salt represented by the formula (1), compound the anion X ₁ ~ is a halide ion, typically a pyridine compound having as a substituent R ₁ to R _5, the R ₆ It can be obtained by performing an addition reaction with a halide in an organic solvent.

The pyridinium salt in which X ₁ -is other than a halide ion is formed by an ion exchange reaction between the halide salt of pyridinium having the same R ₁ -R ₅ and the desired sodium salt or silver salt of X _1-. can get. The pyridinium salt represented by the formula [5] is obtained in the same manner.

Examples of the acid generating substance by light include orthoquinone diazide compounds, alkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonic acid esters, nitrobenzylsulfonic acid esters, α-hydroxymethylbenzoinsulfonic acid esters, and N-hydroxy acids. Specific structures include imidosulfonic acid ester, α-sulfonyloxyketone, and disulfonyldiazomethane, but are not limited thereto.

The acid generator generated by light exerts an effect of accelerating the dissolution of the photosensitive resin composition in the exposed area by the generated acid.
Further, when the photoacid generator is an orthoquinonediazide compound, the effect of accelerating the dissolution of the exposed portion is further enhanced, and a high resolution and a high aspect ratio can be realized.

The orthoquinonediazide compound may be any compound having an orthoquinonediazide group in the molecule, and its structure is not particularly limited. Examples of the orthoquinonediazide group include a 1,2-naphthoquinone-2-diazide-4-sulfonyl group and a 1,2-naphthoquinone-2-diazide-5-sulfonyl group.

The above-mentioned orthoquinonediazide compound is usually obtained by a condensation reaction of orthoquinonediazidesulfonic acid chloride with a compound having a hydroxyl group or a compound having an amino group.

The resin soluble in an aqueous alkali solution has a functional group such as a hydroxyl group, a carboxyl group, a carbamoyl group, and a mercapto group. And the like. Polyamic acids, polyamic acid esters, and polybenzoxazole precursors are particularly preferred from the viewpoints of easy handling of the varnish, solubility in an alkaline aqueous solution, heat and mechanical properties of the cured film, and the like.

The high resolution and high aspect ratio of the photosensitive resin composition of the present invention are exhibited more highly with respect to the specific alkali-soluble resins represented by the formulas [2] to [4].

In the above formula [2] representing polyamic acid, R ₇ is diphenyl ether, diphenyl sulfone,
It is a tetravalent organic group selected from diphenylhexafluoropropane, and R ₈ is a divalent organic group selected from diphenylsulfone, 2,2′-dimethylbiphenyl.

The above polyamic acid can be easily obtained by polyaddition polymerization of an acid anhydride and a diamine.

Examples of the acid anhydride include 3,3 ′, 4,4′-diphenyloxytetracarboxylic dianhydride, 3,3 ′, 4,
4'-diphenylsulfonetetracarboxylic dianhydride,
Specific examples include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic dianhydride. On the other hand, examples of the diamine include 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, and 2,2′-dimethylbenzidine as specific structures.

The weight average molecular weight of the polyamic acid is not particularly limited, but the solubility in a solvent, the handleability as a photosensitive varnish, the solubility in a developing solution, the physical properties of a finally obtained film, etc. Considering 1,000 ~ 1,000
0.00 is preferred. If the weight average molecular weight is less than 1,000, the mechanical properties of the film deteriorate, and
If it is larger than 000, it is difficult to dissolve in a solvent, and the handleability as a varnish decreases. The weight average molecular weight is
It is measured by a gel permeation chromatograph method, and is determined by conversion using a standard polystyrene calibration curve.

The amount of the pyridinium salt to be added is not particularly limited, but is preferably 5 to 20 parts by weight based on 100 parts by weight of the polyamic acid in consideration of the dissolution inhibiting effect and the physical properties of the finally obtained film. Is preferred. If the addition amount is less than 5 parts by weight, the dissolution inhibiting effect is not sufficient, and the resolution and aspect ratio during exposure and development are reduced. On the other hand, if the addition amount is more than 20 parts by weight, the mechanical properties of the finally obtained film deteriorate.

On the other hand, in the above formula [3] showing the structure of the polyamic acid ester, R ₉ and R ₁₂ are tetravalent organic groups,
₁₁ , R ₁₄ are monovalent organic groups. R ₁₀ is a divalent organic group having a phenolic hydroxyl group and / or a carboxyl group, and R ₁₃ is a divalent organic group. Y representing the constitutional ratio of the repeating unit is 40 to 100 mol%.

The structures of R ₉ and R ₁₂ are not particularly limited, and they may be the same or different. Specific examples of the structure include benzene, biphenyl, benzophenone, diphenyl ether, diphenyl sulfone, and diphenylhexafluoropropane.
Diphenyl ether, diphenyl sulfone, and diphenylhexafluoropropane give polyamide acid esters having excellent transparency, and are particularly preferred.

The structures of R ₁₁ and R ₁₄ are not particularly limited, and they may be the same or different. Specific examples include an alkyl group having 1 to 10 carbon atoms.

The structure of R ₁₃ is not particularly limited, and specific structures include benzene, tetramethylbenzene, biphenyl, terphenyl, benzophenone, diphenyl ether, diphenyl sulfide, diphenyl sulfone, and diphenylhexafluoropropane. But tetramethylbenzene, diphenylsulfone,
Diphenylhexafluoropropane gives a polyamic acid ester with excellent transparency and is particularly preferred.

Specific structures of R ₁₀ include 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl ether, , 4 '
-Dihydroxydiphenyl sulfide, 3,3'-dihydroxybiphenyl, phenol, benzoic acid and the like, and 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) propane And benzoic acid give a polyamic acid ester having excellent transparency, and are particularly preferred.

A resin composition comprising a polyamic acid ester containing no phenolic hydroxyl group or carboxyl group has poor solubility in an alkaline aqueous solvent, peels off during development, and cannot form an image.

[0068] Also, the resin composition comprising a polyamic acid ester containing a phenolic hydroxyl group or carboxyl group, y is the content of the repeating unit having an R ₁₀ must be 40 to 100 mol%, y Is 4
When the amount is less than 0 mol%, the solubility in an alkaline aqueous solvent is poor, and swelling and peeling occur during development, so that an image cannot be formed. When y is 40 to 100 mol%, good solubility in an alkaline aqueous solvent is provided, and high-resolution and high-contrast image formation can be performed.

The above polyamic acid ester is usually obtained by preparing a tetracarboxylic diester from a tetracarboxylic dianhydride and an alcohol, chlorinating the carboxylic acid with a chlorinating agent such as thionyl chloride, and reacting it with a diamine. Can be

Examples of the acid anhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride. 3,3 ', 4,4'-diphenyloxytetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,4-
Specific examples include (dicarboxyphenyl) hexafluoropropanoic dianhydride.

Examples of the diamine containing a phenolic hydroxyl group or a carboxyl group include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2,2-bis (3-amino-4-hydroxyphenyl). Propane, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfide, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2, Specific examples include 4-diaminophenol and 3,5-diaminobenzoic acid.

On the other hand, as the diamine containing no phenolic hydroxyl group or carboxyl group, 1,4-diaminobenzene, 1,4-diaminotetramethylbenzene,
4,4'-diaminobiphenyl, 4,4'-diaminoterphenyl, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone ,
Specific structures include 3,3′-diaminodiphenyl sulfone, 2,2-bis (4-aminophenyl) hexafluoropropane and the like.

The weight average molecular weight of the polyamic acid ester is not particularly limited. However, considering the solubility in a solvent, the handleability as a photosensitive varnish, the solubility in a developer, and the physical properties of the finally obtained film. , 1,000-1
00000 is preferred. Weight average molecular weight of 1,000
If it is smaller, the mechanical properties of the film deteriorate, and
If it is larger than 1,000,000, it becomes difficult to dissolve in a solvent.

The weight average molecular weight can be measured by gel permeation chromatography and converted by using a standard polystyrene calibration curve.

The amount of the pyridinium salt to be added is not particularly limited, but is preferably 0.2 to 8 parts by weight based on 100 parts by weight of the polyamic acid ester. If the addition amount is less than 0.2 parts by weight, the dissolution inhibiting effect is not sufficient, and the resolution and aspect ratio during exposure and development are reduced.
On the other hand, if the addition amount is more than 8 parts by weight, the solubility in the developer decreases.

In the above formula [4] representing the polybenzoxazole precursor, R ₁₅ is a divalent organic group,
R ₁₆ is a tetravalent organic group.

The structure of R ₁₅ is not particularly limited.
Benzene, biphenyl, benzophenone, diphenyl ether, diphenyl sulfide, diphenyl sulfone,
Specific examples of the structure include diphenylhexafluoropropane, and benzene, diphenylether, diphenylsulfone, and diphenylhexafluoropropane are particularly preferable in terms of varnish easiness, solubility in an alkaline aqueous solution, and transparency.

The structure of R ₁₆ is not particularly limited, and specific structures include biphenyl, benzophenone, diphenyl ether, diphenylsulfone, diphenylpropane, and diphenylhexafluoropropane. Diphenylsulfone, diphenylpropane, and diphenylhexafluoropropane are particularly preferred in terms of ease of preparation of the varnish, solubility in an aqueous alkali solution, and transparency.

The above polybenzoxazole precursor is
Usually, it is obtained by chlorinating a dicarboxylic acid with a chlorinating agent such as thionyl chloride and reacting it with dihydroxydiamine.

The dicarboxylic acids include terephthalic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4 '
-Benzophenone dicarboxylic acid, 4,4'-diphenyloxydicarboxylic acid, 4,4'-diphenyl sulfide dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid,
2,2-bis (4-carboxyphenyl) hexafluoropropane and the like are mentioned as specific structures.

On the other hand, as dihydroxydiamine,
3,3′-dihydroxy-4,4′-diaminobiphenyl,
3,3′-diamino-4,4′-dihydroxybenzophenone, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 2,2- Bis (3-amino-4-
Specific structures include hydroxyphenyl) propane and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

The weight-average molecular weight of the polybenzoxazole precursor is not particularly limited, but may be, for example, solubility in a solvent, handleability as a photosensitive varnish, solubility in a developing solution, and Considering physical properties,
000 to 1,000,000 is preferred. If the weight average molecular weight is less than 1,000, the mechanical properties of the film will be reduced. If it is more than 1,000,000, it will be difficult to dissolve in a solvent, and the handleability as a varnish will be reduced. The weight average molecular weight is determined by gel permeation chromatography and converted using a standard polystyrene calibration curve.

The amount of the pyridinium salt to be added is not particularly limited, but in consideration of the dissolution inhibiting effect and the physical properties of the finally obtained film, the polybenzoxazole precursor 10
It is preferable to add 0.2 to 10 parts by weight to 0 part by weight. If the amount is less than 0.2 parts by weight, the dissolution inhibiting effect is not sufficient, and the resolution and aspect ratio during exposure and development are reduced. On the other hand, when the amount is more than 10 parts by weight, the solubility in the developer decreases.

The photosensitive resin composition of the present invention can be easily prepared by mixing a soluble resin, a substance capable of generating an acid by light, and a pyridinium salt in the aqueous alkali solution synthesized by the above method.

If the polymer has the repeating units represented by the formulas [2], [3] and [4], a copolymer of polyamic acid / polyamic acid ester / polybenzoxazole precursor or The present invention can be directly applied to a blend of polyamic acid / polyamic acid ester / polybenzoxazole precursor.

Similarly, if it has the repeating units represented by the formulas [2], [3] and [4], the terminal of the polyamic acid, the polyamic acid ester and the polybenzoxazole precursor The present invention can be applied as it is regardless of (acid component, diamine component).

Needless to say, it can be used in combination with a triplet sensitizer, an adhesion improver composed of various silicon compounds, a surfactant and the like.

The photosensitive resin composition of the present invention can be coated on a substrate, irradiated with electromagnetic waves through a photomask, and developed with an alkaline aqueous developer to form a relief pattern.

Examples of the substrate include a glass substrate, a quartz substrate, a semiconductor, a metal, a metal oxide insulator, and silicon nitride.
Several hundred nm to several tens μm using a spinner or a coating machine
Can be formed.

Next, in the step of irradiating an electromagnetic wave, the photosensitive resin composition coated on the substrate is irradiated with a single wavelength of ultraviolet light, visible light, radiation, g-ray, i-ray, excimer laser or the like through a photomask. By irradiation with light or the like, a high-definition relief pattern can be formed. In order to suitably use the photosensitive resin composition of the present invention, i-ray irradiation is preferable.

In the developing step, a relief pattern is obtained by removing the exposed portion with a developing solution. The photosensitive resin composition is designed to be suitable for an alkaline aqueous developer, and includes sodium hydroxide, potassium hydroxide, sodium silicate,
Ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide and the like are used as a developer.

Similarly, the photosensitive resin composition of the present invention was applied to a circuit forming surface or a protective film forming surface of a semiconductor element, irradiated with an electromagnetic wave through a photomask, and developed with an alkaline aqueous developing solution. By curing (baking) the pattern, a semiconductor element having a buffer coat film can be manufactured.

A coating of the photosensitive resin composition on a silicon chip having a semiconductor circuit formed by a predetermined process on a silicon wafer such as a logic, a memory, a gate array or the like is formed by using a spinner or a coating machine. You. Thereafter, the relief pattern formed by irradiation with electromagnetic waves and development is preferably cured (fired) at 200 to 400 ° C.
By doing so, a semiconductor element having a heat-resistant resin layer having a relief pattern, such as polyimide or polybenzoxazole, can be manufactured.

A semiconductor device in which a cured product of the photosensitive resin composition of the present invention is formed on a circuit forming surface or a protective film forming surface of a semiconductor device is excellent in heat-resistant resin such as polyimide and polybenzoxazole. The high heat resistance, mechanical characteristics, and high-definition pattern reduce the rejection rate, and a highly reliable one can be obtained.

[0095]

The abbreviations of the compounds used in the examples and comparative examples are shown below.

Pyromellitic dianhydride: PMDA 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride: BTDA 3,3', 4,4'-diphenyloxytetracarboxylic dianhydride: ODPA 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride: DSDA 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride: 6FDA 4,4'-diphenyloxydicarboxylic Acid: DCPE Isophthalic acid: IPA 4,4'-diaminodiphenyl ether: DDE 4,4'-diaminodiphenyl sulfone: DDSO 2,2'-dimethylbenzidine: DMAP 1,4-diaminotetramethylbenzene: TMPDA 3,5-diamino Benzoic acid: DABA 2,2-bis (3-amino-4-hydroxyphenyl)
Hexafluoropropane: Bis-APAF 2,2-bis (3-amino-4-hydroxyphenyl)
Propane: Bis-APP bis (3-amino-4-hydroxyphenyl) sulfone: Bis-APS 1-benzyl-3- (4- (1,2-naphthoquinone-2)
-Diazido-5-sulfonyloxy) phenyl) urea:
BI-Q 4- (1,2-Naphthoquinone-2-diazide-4-sulfonamido)-(1,2-naphthoquinone-2-diazide-4-sulfonyloxy) benzene: pAPQ tri (4- (1,2- Naphthoquinone-2-diazide-5
-Sulfonyloxy) phenyl) methane: TM-300 tri (4- (1,2-naphthoquinone-2-diazide-4)
-Sulfonyloxy) phenyl) methane: TM-300
(4) Benzenesulfonic acid-o-nitrobenzyl ester: N
BPS [Synthesis example 1] After dissolving 8.5 g (40 mmol) of DMAP in 70 ml of 1-methyl-2-pyrrolidinone, 12.4 g (40 mmol) of ODPA was added.
Stirred at room temperature for 10 hours.

The reaction solution was dropped into 1 liter of water to obtain 18 g of a white polyamic acid (ODPA // DMAP) solid. 100 ml of tetrahydrofuran, N, N '
-100 ml of dimethylformamide, 1.2 g of phosphoric acid,
An eluate was prepared by mixing 1 g of lithium bromide, and the weight-average molecular weight was measured by gel permeation chromatography. The result was 28,000 in terms of standard polystyrene.

The polyamic acids used in the following Examples and Comparative Examples were all synthesized according to Synthesis Example 1. When the molecular weights of the acid dianhydride and the diamine were different from those of the present synthesis example, the synthesis was carried out in the same molar number as in the present synthesis example.

The polyamic acid synthesized from the acid dianhydride A and the diamine B is referred to as polyamic acid (A // B).

[Synthesis Example 2] 3.1 g (10 mmol)
After adding 130 mmol of n-butyl alcohol to the ODPA and refluxing for 1 hour, excess n-butyl alcohol was distilled off to obtain a dibutyl ester of ODPA. 3g for this
(25 mmol) of thionyl chloride was added and refluxed for 1 hour. Excessive thionyl chloride was removed under reduced pressure to obtain ODPA dibutyl ester dicarboxylic chloride.

3.7 g (10 mmol) of Bis-AP
After dissolving AF in 10 ml of 1-methyl-2-pyrrolidinone, the above-mentioned solution of dibutyl ester dicarboxylic acid chloride in 10 ml of 1-methyl-2-pyrrolidinone was slowly added dropwise over 30 minutes while maintaining the temperature at 5 ° C. or lower. Stirring was continued for 1 hour.

Thereafter, the reaction solution was poured into 1 liter of water, and a white polyamic acid ester (ODPA (Bu) /
/ Bis-APAF) solids 5.8 g were obtained. The weight average molecular weight of the polyamic acid ester measured according to Synthesis Example 1 was 22,000 in terms of standard polystyrene.

The polyamic acid esters used in the following Examples and Comparative Examples were all synthesized according to Synthesis Example 2. When the molecular weights of the acid dianhydride and the diamine were different from those of the present synthesis example, the synthesis was carried out in the same molar number as in the present synthesis example. In the synthesis of a polyamic acid ester copolymer comprising a plurality of acid dianhydrides or diamines, the total molar amount of the acid dianhydride and the total molar amount of the diamine were made the same in this example.

The polyamic acid ester synthesized from the acid dianhydride A, the ester group C, and the diamine B is referred to as a polyamic acid ester (A (C) // B). Also, A
1, a copolymer comprising an acid dianhydride of A2 is prepared by using a polyamic acid ester (A1
(C) _x / A 2 (C) _y // B). Similarly, B1,
The copolymer composed of the diamine of B2 is prepared by using the polyamic acid ester (A (C) //
B1 _x / B2 _y ).

[Synthesis Example 3] 5.2 g (20 mmol)
Of DCPE in 1-methyl-2-pyrrolidinone (20
To this solution, 4.8 g (40 mmol) of thionyl chloride was added dropwise at room temperature to obtain an acid chloride of DCPE.

7.3 g (20 mmol) of Bis-AP
After dissolving AF in 20 ml of 1-methyl-2-pyrrolidinone, the above solution of dicarboxylic acid chloride in 1-methyl-2-pyrrolidinone was slowly added dropwise over 30 minutes while maintaining the temperature at 5 ° C. or lower, and the mixture was stirred for 1 hour. Continued. Thereafter, the reaction solution was poured into 1.5 liters of water, and a white polybenzoxazole precursor (DCPE // Bis-AP) was added.
AF) 10.5 g of a solid were obtained. The weight average molecular weight of the polybenzoxazole precursor measured according to Synthesis Example 1 was 26,000 in terms of standard polystyrene.

All the polybenzoxazole precursors used in the following Examples and Comparative Examples were synthesized according to Synthesis Example 3. When the molecular weights of dicarboxylic acid and dihydroxydiamine were different from those of the present synthesis example, the synthesis was carried out in the same molar number as in the present synthesis example.

The polybenzoxazole precursor synthesized from dicarboxylic acid A and dihydroxydiamine B is referred to as polybenzoxazole precursor (A // B).

Synthesis Example 4 A mixture of 6.4 mmol of 4-phenylpyridine and 6.4 mmol of benzyl bromide was dissolved in 6 ml of toluene and stirred at 45 ° C. for 8 hours. The precipitated solid was separated by filtration and washed with diethyl ether to obtain 1.7 g of white 1-benzyl-4-phenylpyridinium bromide solid (yield: 82%).

The halide salts of pyridinium used in the following Examples and Comparative Examples were synthesized according to Synthesis Example 4. When the molecular weight of the raw material was different from that of the present synthesis example, the synthesis was performed with the number of moles being the same as in the present synthesis example.

Synthesis Example 5 3 mmol of 1-benzyl-4-phenylpyridinium bromide was dissolved in 30 ml of a 20% aqueous methanol solution, and 4 mmol of sodium nitrate was added as a 3 ml aqueous solution. After stirring for 8 hours, the precipitated solid was separated by filtration and washed with water and diethyl ether to obtain 0.66 g (yield 71%) of white 1-benzyl-4-phenylpyridinium nitrate.

Most of the pyridinium salts having an anion other than the halide ion used in the following Examples and Comparative Examples were synthesized according to Synthesis Example 5. When the molecular weight of the raw material was different from that of the present synthesis example, the synthesis was performed with the number of moles being the same as in the present synthesis example.

Comparative Example 1 In this comparative example, preparation of a photosensitive resin composition containing no pyridinium salt and formation of a positive pattern were examined.

The polyamic acid (O) obtained in Synthesis Example 1
(DPA // DMAP: weight average molecular weight: 28,000)
Was dissolved in γ-butyrolactone so as to have a solid content of 23% by weight, and then BI-Q was added at 15 parts by weight based on the solid content to obtain a photosensitive resin composition.

The photosensitive resin composition was applied on a silicon wafer by a spin coating method, and dried at 110 ° C. for 3 minutes to prepare a film having a thickness of 9 μm. After irradiating 450 mJ / cm ^{2 with} light from a high-pressure mercury lamp through an i-line band-pass filter and a light-shielding mask, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to form a pattern.

Comparative Example 2 Preparation of a photosensitive resin composition containing no pyridinium salt and formation of a positive pattern were examined.

The polyamic acid ester (ODPA (Bu) // Bis-APAF: weight average molecular weight: 22,000) obtained in Synthesis Example 2 was dissolved in γ-butyrolactone so as to have a solid content of 30% by weight. Then, 15 parts by weight of pAPQ was added to the solid content to obtain a photosensitive resin composition.

This photosensitive resin composition was applied on a silicon wafer by spin coating, and then dried at 110 ° C. for 3 minutes to prepare a film having a thickness of 9 μm. After irradiating 350 mJ / cm ² with the light of a high-pressure mercury lamp through an i-line band-pass filter and a light-shielding mask, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to form a pattern.

[Comparative Example 3] Preparation of a photosensitive resin composition containing no pyridinium salt and formation of a positive pattern were examined.

A polybenzoxazole precursor (IPC // Bis-APS: weight average molecular weight: 19,000) synthesized according to Synthesis Example 3 was mixed with 1-methyl-2 so as to have a solid content of 25% by weight. -After dissolving in pyrrolidinone, 15 parts by weight of TM-300 was added to the solid content to obtain a photosensitive resin composition.

The photosensitive resin composition was applied on a silicon wafer by spin coating, and then dried at 120 ° C. for 3 minutes to prepare a film having a thickness of 9 μm. After irradiating 400 mJ / cm ² with the light of a high-pressure mercury lamp through an i-line band-pass filter and a light-shielding mask, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to form a pattern.

As shown in Table 1, in Comparative Examples 1 to 3, since the pyridinium salt represented by the above formula [1] was not added, the dissolution rates of the exposed portion and the unexposed portion were both too large, resulting in a difference in contrast. No pattern was formed.

[0123]

[Table 1]

[Comparative Examples 4 and 5] In this comparative example, the preparation of a photosensitive resin composition containing a pyridinium salt in which all of R _{1 to} R ₅ of the above formula [1] are hydrogen atoms and the formation of a positive pattern were examined. did.

According to Synthesis Example 1, polyamic acid (DS
DA // DDSO: weight average molecular weight: 30,500) and (6FDA // DDE: weight average molecular weight: 24,0)
00) was synthesized.

Further, a pyridinium salt was synthesized according to Synthesis Examples 4 and 5. In a γ-butyrolactone solution of a polyamic acid having a solid content of 23% by weight, a pyridinium salt and a photoacid generator were added in an amount of 18 parts by weight and 1 part by weight based on the solid content.
By adding 5 parts by weight, a photosensitive resin composition was obtained.

This photosensitive resin composition was applied on a silicon wafer by spin coating, and then dried at 110 ° C. for 3 minutes to prepare a film having a thickness of 9 μm. After irradiating 450 mJ / cm ^{2 with} light from a high-pressure mercury lamp through an i-line band-pass filter and a light-shielding mask, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to form a pattern. Further, the residual film ratio of the unexposed portion at the time of the just etch of the exposed portion was measured.

[Comparative Examples 6, 7] R ₁ to R _{1 of the} above formula [1]
Preparation of a photosensitive resin composition containing a pyridinium salt in which all of R ₅ are hydrogen atoms and formation of a positive pattern were studied.

.. [0129] conform to Synthesis Example 2, polyamic acid ester _{(ODPA (Bu) // DABA 0} 8 / DDSO 0 2:
Weight average molecular weight: 31,000) and (ODPA (B
u) // Bis-APAF: weight average molecular weight: 22.0
00) was synthesized.

A pyridinium salt was synthesized according to Synthesis Examples 4 and 5. A pyridinium salt and a photoacid generator were added to a solution of a polyamic acid ester having a solid content of 30% by weight in a γ-butyrolactone solution at 2 parts by weight and 15 parts by weight, respectively, based on the solid content to obtain a photosensitive resin composition.

This photosensitive resin composition was applied on a silicon wafer by spin coating, and then dried at 110 ° C. for 3 minutes to prepare a film having a thickness of 9 μm. After irradiating 350 mJ / cm ² with the light of a high-pressure mercury lamp through an i-line band-pass filter and a light-shielding mask, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to form a pattern.

Comparative Example 8 Preparation of a photosensitive resin composition containing a pyridinium salt in which all of R _{1 to} R _{5 in} the above formula [1] are hydrogen atoms and formation of a positive pattern were examined.

A polybenzoxazole precursor (IPC // Bis-APP: weight average molecular weight: 21,000) was synthesized according to Synthesis Example 3, and a pyridinium salt was synthesized according to Synthesis Examples 4 and 5. did.

In a 1-methyl-2-pyrrolidinone solution of a polybenzoxazole precursor having a solid content of 25% by weight,
The pyridinium salt and the photoacid generator were added in an amount of 3 parts by weight and 15 parts by weight, respectively, based on the solid content to obtain a photosensitive resin composition.

This photosensitive resin composition was applied on a silicon wafer by spin coating, and then dried at 120 ° C. for 3 minutes to prepare a film having a thickness of 9 μm. After irradiating 400 mJ / cm ² with the light of a high-pressure mercury lamp through an i-line band-pass filter and a light-shielding mask, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to form a pattern.

As shown in Table 1, in Comparative Examples 4 to 8, since R _{1 to} R _{5 of the} added pyridinium salt are all hydrogen atoms, there is no dissolution inhibiting effect, and the dissolution of exposed and unexposed parts The velocities were too high and there was no difference in contrast, and no pattern was formed.

Example 1 The preparation of a photosensitive resin composition containing a polyamic acid, a photoacid generator, and the pyridinium salt of the formula [1] and the formation of a positive pattern were examined.

Polyamide acid (6FDA // DDE: weight average molecular weight: 24,000) and 1-butyl-4-phenylpyridinium iodide which is a pyridinium salt of the above formula [1] were synthesized in Synthesis Example 1 and Synthesis Example 1, respectively. Synthesized according to Example 4.

Polyamic acid (6%) having a solid content of 23% by weight
FDA // DDE) in 1-butyrolactone solution with 1-butyl-4-phenylpyridinium iodide and TM-
300 to 18 parts by weight and 15 to solids
By weight, the photosensitive resin composition was obtained.

This photosensitive resin composition was applied onto a silicon wafer by spin coating, and then dried at 110 ° C. for 3 minutes to prepare a film having a thickness of 9 μm. After irradiating 450 mJ / cm ^{2 with} light from a high-pressure mercury lamp through an i-line band-pass filter and a light-shielding mask, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to form a pattern. Further, the residual film ratio of the unexposed portion at the time of the just etch of the exposed portion was measured.

As shown in Table 2, the effect of adding the pyridinium salt of the above formula [1] suppressed the dissolution rate in the developing solution, and it was impossible to form a 20 μm square in Comparative Example 1 where no pyridinium salt was added. Was formed. The residual film ratio of the unexposed portion was 41%.

[0142]

[Table 2]

[Examples 2 to 4] Preparation of a photosensitive resin composition containing a polyamic acid, a photoacid generator, and a pyridinium salt of the above formula [1] and formation of a positive pattern in the same manner as in Example 1. It was investigated.

After preparing a polyamic acid resin composition containing a pyridinium salt and a photoacid generator according to Example 1,
Coating, drying, exposure, and development were performed to try to form a pattern.

Further, the remaining film ratio of the unexposed portion at the time of the just etching of the exposed portion was measured. The polyamic acid (P
MDA // TMPDA), (BTDA // DDSO),
The weight average molecular weight of (6FDA // DDE) is 32,000, 30,000, 2
It was 4,000.

As shown in Examples 2 to 4 in Table 2, due to the effect of the addition of the pyridinium salt of the formula [1], 20 μm could not be formed in Comparative Example 1 where no pyridinium salt was added.
An m-square positive pattern was formed. The remaining film ratio of the unexposed portion was 37 to 43%.

[Examples 5 to 18] Preparation of a photosensitive resin composition containing a polyamic acid having a structure limited by the above formula [2], a photoacid generator, and a pyridinium salt of the above formula [1], and a positive mold The formation of the pattern was examined.

As the polyamic acid of the formula [2], (O
DPA // DMAP), (DSDA // DDSO),
(6FDA // DDSO) was synthesized according to Synthesis Example 1. The weight average molecular weights were 28,000, 30,500, and 26,000, respectively, in terms of standard polystyrene.
In addition, each pyridinium salt of the above formula [1] was synthesized in Synthesis Examples 4 and 5
Synthesized according to.

Next, in accordance with Example 1, a polyamic acid resin composition containing a pyridinium salt and a photoacid generator was prepared, applied, dried, exposed and developed to try to form a pattern. Further, the residual film ratio of the unexposed portion at the time of the just etch of the exposed portion was measured.

As shown in Examples 5 to 18 in Table 2, the effect of limiting the structure of polyamic acid to the above-mentioned formula [2] is as follows.
As compared with Examples 1 to 4 in which the structure of the polyamic acid was not limited, a positive pattern of 10 to 15 μm square was formed with higher definition. The remaining film ratio of the unexposed portion is 46 to 59%.
And 12 to 44% higher than the residual film ratio of 41% in Example 1 in which the structure of the polyamic acid is not limited.

[Examples 19 to 26] A photosensitive resin composition containing a polyamic acid and an orthoquinonediazide compound whose structure is limited by the above formula [2] and a pyridinium salt whose structure is limited by the above formula [5] Fabrication and formation of a positive pattern were studied.

The polyamic acid of the above formula [2] (ODPA /
/ DMAP), (DSDA // DDSO), (6FDA
// DDSO) was synthesized according to Synthesis Example 1. The weight average molecular weight was 28,0 in terms of standard polystyrene.
00, 30,500 and 26,000. Further, each pyridinium salt of the formula [5] was synthesized according to Synthesis Examples 4 and 5, and the photoacid generator was limited to an orthoquinonediazide compound.

According to Example 1, a polyamic acid resin composition containing a pyridinium salt and a photoacid generator was prepared, applied, dried, exposed to light, and developed to try to form a pattern. Further, the residual film ratio of the unexposed portion at the time of the just etch of the exposed portion was measured.

As shown in Table 3, the structures of the polyamic acid, the pyridinium salt, and the photoacid generator are not limited to the above formulas [2], [5] and the orthoquinonediazide compound, respectively. Examples 1-4,
Compared to Examples 5 to 18 in which only the structure of the polyamic acid was limited, a more precise 6-8 μm square positive pattern was formed. The remaining film ratio of the unexposed portion is 63 to 72%, which is 54 to 70% as compared with the remaining film ratio in Example 1 without these limitations.
It was improved by 76%, and also improved by 15 to 31% as compared with the residual film ratio in Example 5 in which only the structure of the polyamic acid was limited.

[0155]

[Table 3]

Comparative Examples 9 and 10 The preparation of a photosensitive resin composition containing a polyamic acid ester in which y in the formula [3] was 40 mol% or less and the formation of a positive pattern were examined.

Polyamic acid ester (DSDA (Me)
_{// DABA 0 3 / DDSO 0 7} :.. The weight average molecular weight: 1
9,500), (ODPA (Bu) // Bis-APA
_{. F 0 2 / TMPDA 0 8} :. Weight average molecular weight: 26,50
0) and the pyridinium salt of the formula [1] were synthesized according to Synthesis Example 2, and Synthesis Examples 4 and 5, respectively.

Next, in accordance with Comparative Example 6, a polyamic acid ester resin composition containing a pyridinium salt and a photoacid generator was prepared, applied, dried, exposed and developed to try to form a pattern.

As shown in Table 3, DABA and Bis
Since y representing the constitutional ratio of the repeating unit containing -APAF was 40 mol% or less, sufficient alkali solubility was not obtained, and the film swelled and peeled during development, and no pattern was formed.

Example 27 Preparation of a photosensitive resin composition containing a polyamic acid ester of the above formula [3], a photoacid generator, and a pyridinium salt of the above formula [1] and formation of a positive pattern were examined. .

Polyamic acid ester (ODPA (Bu)
_{// DABA 0 8 / DDSO 0 2} :.. The weight average molecular weight: 3
(1,000) and 1,4-dibenzylpyridinium nitrate were synthesized according to Synthesis Example 2 and Synthesis Examples 4 and 5, respectively.

[0162] solids content 30% by weight of the polyamic acid ester _{(ODPA (Bu) // DABA 0} . 8 / DDS
O _{0. 2)} of the γ- butyrolactone solution, 1,4 nitrate and pAPQ dibenzyl pyridinium, was obtained by adding 2 parts by weight and 15 parts by weight, respectively based on the solid content photosensitive resin composition.

The photosensitive resin composition was applied on a silicon wafer by a spin coating method, and dried at 110 ° C. for 3 minutes to prepare a film having a thickness of 9 μm. After irradiating 350 mJ / cm ² with the light of a high-pressure mercury lamp through an i-line band-pass filter and a light-shielding mask, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to form a pattern. Further, the residual film ratio of the unexposed portion at the time of the just etch of the exposed portion was measured.

As shown in Table 4, the effect of adding the pyridinium salt of the formula [1] suppressed the dissolution rate in the developing solution, and did not form 10 μm in Comparative Example 2 where no pyridinium salt was added. A positive pattern of corners was formed. The residual film ratio of the unexposed portion was 70%.

[0165]

[Table 4]

[Examples 28 to 37] In the same manner as in Example 27, a photosensitive resin composition containing a polyamic acid ester of the above formula [3], a photoacid generator and a pyridinium salt of the above formula [1] was prepared. Fabrication and formation of a positive pattern were studied.

A polyamic acid ester having a phenolic hydroxyl group or a carboxyl group shown in Table 4 was prepared according to Synthesis Example 2, and each pyridinium salt of the above formula [1] was prepared according to Synthesis Examples 4 and 5. Was synthesized.

Next, in accordance with Example 27, a polyamic acid ester resin composition containing a pyridinium salt and a photoacid generator was prepared, subjected to coating, drying, exposure, and development to try to form a pattern. Further, the residual film ratio of the unexposed portion at the time of the just etch of the exposed portion was measured.

As shown in Table 4, due to the effect of including the pyridinium salt of the formula [1], a positive pattern of 10 to 15 μm square was formed which was not formed in Comparative Example 2 in which no pyridinium salt was added. The unexposed portion had a residual film ratio of 60 to 72%.

[Examples 38 to 44] Preparation and positive pattern of a photosensitive resin composition containing a polyamic acid ester of the above formula [3], an orthoquinonediazide compound, and a pyridinium salt whose structure is limited by the above formula [5] Formation was studied.

Based on Synthesis Example 2, polyamic acid esters having a phenolic hydroxyl group or a carboxyl group represented by the above formula [3] shown in Table 5 were synthesized. Further, each pyridinium salt of the above formula [5] was synthesized according to Synthesis Examples 4 and 5. The photoacid generator was limited to orthoquinonediazide compounds.

Next, in accordance with Example 27, a polyamic acid ester resin composition containing a pyridinium salt and a photoacid generator was prepared, applied, dried, exposed and developed to try to form a pattern. Further, the residual film ratio of the unexposed portion at the time of the just etch of the exposed portion was measured.

As shown in Table 5, due to the effect of limiting the structure of the pyridinium salt to the above formula [5] and limiting the structure of the photoacid generator to the orthoquinonediazide compound, Examples 27 to 37 without these limitations were used. 4 with higher definition compared to
A positive pattern of about 6 μm square was formed. The residual film ratio of the unexposed portion was 75 to 84%, which was 7 to 20% higher than the residual film ratio in Example 27 in which the structures of the pyridinium salt and the photoacid generator were not limited to the above.

[0174]

[Table 5]

Example 45 Preparation of a photosensitive resin composition containing a polybenzoxazole precursor of the formula [4], a photoacid generator, and a pyridinium salt of the formula [1] and formation of a positive pattern It was investigated.

Polybenzoxazole precursor (DCPE
// Bis-APAF: weight average molecular weight: 26,000
0) and 1-benzyl-3-phenyl-pyridinium nitrate were synthesized in Synthesis Example 3 and Synthesis Examples 4 and 5, respectively.
Synthesized according to.

Polybenzoxazole precursor (DCPE // Bis-APAF) having a solid content of 25% by weight
To the methyl-2-pyrrolidinone solution, 3 parts by weight and 15 parts by weight of 1-benzyl-3-phenyl-pyridinium nitrate and pAPQ, respectively, based on the solid content were added to obtain a photosensitive resin composition.

This photosensitive resin composition was applied on a silicon wafer by spin coating, and then dried at 120 ° C. for 3 minutes to prepare a film having a thickness of 9 μm. After irradiating 400 mJ / cm ² with the light of a high-pressure mercury lamp through an i-line band-pass filter and a light-shielding mask, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to form a pattern. Further, the residual film ratio of the unexposed portion at the time of the just etch of the exposed portion was measured.

As shown in Table 6, the effect of the addition of the pyridinium salt of the above formula [1] suppressed the dissolution rate in the developing solution, and did not form 10 μm in Comparative Example 3 where no pyridinium salt was added. A positive pattern of corners was formed. The residual film ratio of the unexposed portion was 69%.

[0180]

[Table 6]

Examples 46 to 47 In accordance with Example 45, a polybenzoxazole precursor of the above formula [4]
Preparation of a photosensitive resin composition containing a photoacid generator and the pyridinium salt of the formula [1] and formation of a positive pattern were examined.

As shown in Table 6, the effect of adding the pyridinium salt of the formula [1] suppressed the dissolution rate in the developing solution, and was not formed in Comparative Example 3 where no pyridinium salt was added. A positive pattern having a size of about 15 μm square was formed. The unexposed portion had a remaining film ratio of 67 to 72%.

[Examples 48-50] Preparation of a photosensitive resin composition containing a polybenzoxazole precursor of the above formula [4], an orthoquinonediazide compound, and a pyridinium salt whose structure is limited by the above formula [5] The formation of a positive pattern was studied.

According to Synthesis Example 3, a polybenzoxazole precursor of the above formula [4] shown in Table 7 was synthesized. Further, each of the pyridinium salts of the formula [5] was synthesized according to Synthesis Examples 4 and 5
Synthesized according to. The photoacid generator was limited to orthoquinonediazide compounds.

Next, in accordance with Example 45, a polybenzoxazole precursor resin composition containing a pyridinium salt and an orthoquinonediazide compound was prepared, applied, dried, exposed and developed to try to form a pattern. Further, the residual film ratio of the unexposed portion at the time of the just etch of the exposed portion was measured.

As shown in Table 7, due to the effect of limiting the structure of the pyridinium salt to the formula [5] and limiting the structure of the photoacid generator to the orthoquinonediazide compound, Examples 45 to 47, which are not limited to these examples, are used. 4 with higher definition compared to
A positive pattern of about 6 μm square was formed. The remaining film ratio of the unexposed portion was 78 to 82%, which was improved by 13 to 19% as compared with the remaining film ratio in Example 45 in which the structures of the pyridinium salt and the photoacid generator were not limited to the above.

[0187]

[Table 7]

Example 51 The effect of a developing solution on pattern formation using a photosensitive resin composition containing a polyamic acid, a photoacid generator and the pyridinium salt of the above formula [1] was examined.

After the photosensitive resin composition used in Example 3 was prepared, application, drying and exposure were performed according to Example 1. Next, the coating film made of the photosensitive resin composition was developed using pure water, ethanol, hexane, an aqueous solution of 2.38% tetramethylammonium hydroxide, and four kinds of developing solutions to try to form a pattern. Was.

The above photosensitive resin composition was not developed at all in the exposed and unexposed areas with pure water, ethanol or hexane, and no pattern was formed.

On the other hand, in the pattern formation step using the photosensitive resin composition, a 20 μm square positive electrode was developed after developing with an aqueous solution of 2.38% tetramethylammonium hydroxide by combining with development with an alkaline aqueous developer. A mold pattern was formed, and the remaining film ratio of the unexposed portion was 43%.

Example 52 A developing solution used in pattern formation using a photosensitive resin composition containing a polyamic acid, a photoacid generator, and a pyridinium salt of the above formula [1], the structure of which was limited by the above formula [2], was used. The effect was examined.

After the photosensitive resin composition used in Example 15 was prepared, pattern formation was attempted using four kinds of developing solutions in accordance with Example 51.

The above photosensitive resin composition was not developed at all in the exposed and unexposed areas with pure water, ethanol or hexane, and no pattern was formed.

On the other hand, in the pattern formation step using the photosensitive resin composition, a 10 μm square positive electrode was developed after developing with an aqueous solution of 2.38% tetramethylammonium hydroxide by combining the development with an alkaline aqueous developer. A mold pattern was formed, and the remaining film ratio of the unexposed portion was 59%. By limiting the structure of the polyamic acid in the photosensitive resin composition to the above formula [2], compared to Example 45 in which the structure is not limited, the alkali resin-based developer is more suitable, and the positive pattern has higher definition. And the residual film ratio is 3
7% improvement.

Example 53 Pattern formation using a photosensitive resin composition containing a polyamic acid and an orthoquinonediazide compound whose structure is limited by the formula [2] and a pyridinium salt whose structure is limited by the formula [5] The effect of the developing solution on was examined.

After the photosensitive resin composition used in Example 21 was prepared, pattern formation was attempted using four types of developing solutions in accordance with Example 51.

The above photosensitive resin composition was not developed at all in the exposed and unexposed areas with pure water, ethanol or hexane, and no pattern was formed.

On the other hand, in the pattern formation step using the photosensitive resin composition, a 6 μm square positive electrode was obtained after the development with an aqueous solution of 2.38% tetramethylammonium hydroxide by combining with the development with an alkaline aqueous developer. A mold pattern was formed, and the remaining film ratio of the unexposed portion was 72%.

The structure of the polyamic acid in the photosensitive resin composition is represented by the formula [2], the structure of the photoacid generator is represented by the orthoquinonediazide compound, and the structure of the pyridinium salt is represented by the formula [5]
As compared with Example 52 in which only the structure of the polyamic acid was limited, the alkaline water-based developer was more suitable, the positive pattern became higher definition, and the residual film ratio was further improved by 22%.

Example 54 The effect of a developing solution on pattern formation using a photosensitive resin composition containing a polyamic acid ester of the above formula [3], a photoacid generator and a pyridinium salt of the above formula [1] was studied. did.

After the photosensitive resin composition used in Example 31 was prepared, application, drying and exposure were performed according to Example 27. Next, the coating film made of the photosensitive resin composition was developed using pure water, ethanol, hexane, an aqueous solution of 2.38% tetramethylammonium hydroxide, and four kinds of developing solutions to try to form a pattern. Was.

The above photosensitive resin composition was not developed at all in the exposed and unexposed areas with pure water, ethanol or hexane, and no pattern was formed.

On the other hand, in the pattern forming step using the photosensitive resin composition, by combining with a development with an aqueous alkali developing solution, after developing with an aqueous solution of 2.38% tetramethylammonium hydroxide, a 15 μm square A positive pattern was formed, and the residual film ratio of the unexposed portion was 60%.

Example 55 Development in pattern formation using a photosensitive resin composition containing a polyamic acid ester of the above formula [3], an orthoquinone diazide compound, and a pyridinium salt whose structure is limited by the above formula [5] The effect of the liquid was studied.

After the photosensitive resin composition used in Example 43 was prepared, pattern formation using four types of developing solutions was attempted in accordance with Example 54.

The above photosensitive resin composition was not developed at all in exposed and unexposed areas with pure water, ethanol and hexane, and no pattern was formed.

On the other hand, in the pattern forming step using the above photosensitive resin composition, by combining with a development with an aqueous alkaline developer, after developing with an aqueous solution of 2.38% tetramethylammonium hydroxide, a 4 μm square A positive pattern was formed, and the residual film ratio of the unexposed portion was 77%.

By limiting the structure of the photoacid generator in the photosensitive resin composition to the orthoquinonediazide compound and the structure of the pyridinium salt to the formula [5], respectively, as compared with Example 54, which does not limit these. Thus, the positive pattern became more precise, and the residual film ratio was improved by 28%.

Example 56 Effect of a developer on pattern formation using a photosensitive resin composition containing a polybenzoxazole precursor of the above formula [4], a photoacid generator and a pyridinium salt of the above formula [1] It was investigated.

After the photosensitive resin composition used in Example 47 was prepared, application, drying and exposure were performed according to Example 45. Next, the coating film made of the photosensitive resin composition was developed using pure water, ethanol, hexane, an aqueous solution of 2.38% tetramethylammonium hydroxide, and four kinds of developing solutions to try to form a pattern. Was.

The above photosensitive resin composition was not developed at all in exposed and unexposed areas with pure water, ethanol and hexane, and no pattern was formed.

On the other hand, in the pattern formation step using the above photosensitive resin composition, by combining with a development with an aqueous alkaline solution, a development with an aqueous solution of 2.38% tetramethylammonium hydroxide was carried out. A positive pattern was formed, and the residual film ratio of the unexposed portion was 67%.

Example 57 A polybenzoxazole precursor of the above formula [4], an orthoquinonediazide compound,
Further, the effect of a developing solution on pattern formation using a photosensitive resin composition containing a pyridinium salt whose structure was limited by the formula [5] was examined.

After preparing the photosensitive resin composition used in Example 49, pattern formation was attempted using four kinds of developing solutions in accordance with Example 56.

The above photosensitive resin composition was not developed at all in the exposed and unexposed areas with pure water, ethanol or hexane, and no pattern was formed.

On the other hand, in the pattern forming step using the photosensitive resin composition, by combining with a development with an aqueous alkali developing solution, after developing with an aqueous solution of 2.38% tetramethylammonium hydroxide, a 4 μm square A positive pattern was formed, and the remaining film ratio of the unexposed portion was 82%.

By limiting the structure of the photoacid generator in the photosensitive resin composition to the orthoquinonediazide compound and the structure of the pyridinium salt to the above formula [5], respectively, as compared with Example 56 which does not limit these. In addition, the alkaline pattern-based developer became more suitable, the positive pattern became higher definition, and the residual film ratio was improved by 22%.

Comparative Example 11 FIG. 1 is a schematic cross-sectional view showing a process for manufacturing a semiconductor device having a buffer coat film using a conventional non-photosensitive resin composition.

After bonding pads 2 were formed on semiconductor element wiring layer 1 by sputtering aluminum, 1 μm
An m-thick SiN layer 3 was formed by sputtering. afterwards,
Coating, drying, exposure, development, etching,
The resist was peeled off, and a hole was formed in the SiN layer in the pad portion. Further, non-photosensitive polyamic acid (PMDA ///
DDSO) 5 was applied, dried and baked to form a polyimide layer 6.

By repeating the application, drying, exposure, development, etching, and resist stripping steps of the resist layer 4 again, a 4 μm thick buffer coat film made of polyimide 5 having holes for bonding wire connection and fuse use is formed. did.

In the method of manufacturing a buffer coat film using a non-photosensitive polyimide, it was necessary to separately form a pattern of the SiN layer and the polyimide layer, and thus required 14 steps.

As shown in Table 8, since the resolution in pattern formation was not sufficient, poor opening of small-sized fuse holes occurred, and the number thereof was 12 out of 20 semiconductor elements.

[0224]

[Table 8]

Example 58 FIG. 2 shows a process for manufacturing a semiconductor device having a buffer coat film using the photosensitive resin composition of the present invention.

A method of manufacturing a semiconductor device using a photosensitive resin composition containing a polyamic acid, a photoacid generator, and the pyridinium salt of the above formula [1], and the reliability of the manufactured semiconductor device were examined.

SiN Layer 3 Formed According to Comparative Example 11
The photosensitive resin composition of Example 3 was applied thereon by spin coating, and then dried at 110 ° C. for 3 minutes to form a resin layer 7 having a thickness of 16 μm.

Using light from a high-pressure mercury lamp, 800 mJ / cm through an i-line band-pass filter and a light-shielding mask.
After ^two irradiation, 2.38% tetramethylammonium hydroxide
Developed in aqueous solution. Furthermore, it is baked at 350 ° C. for 1 hour,
Dry etching was performed with a CF ₄ / O ₂ mixed gas to form a 4 μm-thick buffer coat film made of polyimide 6 having holes for bonding wire connection and fuse use.

By using the photosensitive resin composition, S
After forming the iN layer 3, a buffer coat film could be formed in six steps of coating, drying, exposure, development, baking, and etching, which was simplified by eight steps as compared with Comparative Example 11 using a non-photosensitive polyimide.

[0230] Next, when the defective opening of the fuse hole in the DRAM semiconductor device of the same standard as that of Comparative Example 11 was examined, it was found that the photosensitive material containing the polyamic acid, the photoacid generator, and the pyridinium salt of the above formula [1] was used. By using the resin composition, the frequency of defective products was reduced to 6 out of 20 semiconductor devices, and 50% or less as compared with Comparative Example 11, and a more reliable semiconductor device was obtained. Was done.

FIG. 3 is an external view of a semiconductor device for DRAM manufactured using the buffer coat film. Note that FIG. 3 shows only 20 pads, but actually 48 pads and wire connection holes surrounding the pads are provided.
Further, a hole for a fuse was formed. The size of the wire connection hole and the fuse hole is 10
They were 0 μm square and 15 μm square.

Table 8 also shows the required number of steps and the defective opening ratio for Examples 58 to 64.

Example 59 A polyamic acid, a photoacid generator whose structure was limited by the above formula [2], and a compound represented by the above formula [1]
A method of manufacturing a semiconductor device using a photosensitive resin composition containing a pyridinium salt of Example 1 and the reliability of the manufactured semiconductor device were studied.

Using the photosensitive resin composition of Example 16,
According to the same procedure as in Example 58, a 4 μm-thick buffer coat film was formed on the semiconductor element coated with the SiN layer 3.

By adopting the production method using the photosensitive resin composition, eight steps were simplified as compared with the step using the non-photosensitive polyimide.

Further, by limiting the structure of the polyamic acid in the photosensitive resin composition to the above formula [2], a buffer coat film can be formed by irradiating light of a high pressure mercury lamp at 650 mJ / cm ^2. 19% higher sensitivity than in Example 58 in which the structure was not limited.

Next, when the defective opening of the fuse hole in the DRAM semiconductor element of the same standard as that of Comparative Example 11 was examined, the frequency of defective products was 20 due to the effect of limiting the structure of polyamic acid in the photosensitive resin. Four of the semiconductor elements were reduced to 67% or less as compared with Example 58, and a more reliable semiconductor element was obtained.

Example 60 A method for producing and manufacturing a semiconductor device using a photosensitive resin composition containing a polyamic acid ester of the above formula [3], a photoacid generator, and a pyridinium salt of the above formula [1] was prepared. The reliability of the semiconductor device was studied.

Using the photosensitive resin composition of Example 34,
According to the same procedure as in Example 58, a 4 μm-thick buffer coat film was formed on the semiconductor element coated with the SiN layer 3.

By adopting the manufacturing method using the photosensitive resin composition, eight steps were simplified as compared with the step using the non-photosensitive polyimide. In order to form a buffer coat film made of 4 μm thick polyimide, 12 μm
m before development and irradiation with light from a high-pressure mercury lamp of 500 mJ / cm ² was required.

Next, when the defective opening of the fuse hole in the DRAM semiconductor device of the same standard as that of the comparative example 11 was examined, two defective semiconductor devices out of the 20 semiconductor devices and the non-photosensitive polyimide of the comparative example 11 were compared. As compared with the semiconductor device using, the semiconductor device was reduced to 17% or less, and a highly reliable semiconductor device was obtained.

Example 61 A method of manufacturing a semiconductor device using a polybenzoxazole precursor of the above formula [4], a photoacid generator, and a photosensitive resin composition containing a pyridinium salt of the above formula [1] and The reliability of the manufactured semiconductor device was examined.

Using the photosensitive resin composition of Example 46,
According to the same procedure as in Example 58, a 4 μm-thick buffer coat film was formed on the semiconductor element coated with the SiN layer 3.

By adopting a production method using a photosensitive resin composition, eight steps were simplified as compared with the step using a non-photosensitive polyimide. In order to form a buffer coat film made of polybenzoxazole having a thickness of 4 μm, a film thickness before development of 11 μm and irradiation with light from a high-pressure mercury lamp of 500 mJ / cm ² were necessary. The drying after the application of the photosensitive resin composition was performed at 120 ° C. for 3 minutes.

Next, when the defective opening of the fuse hole in the DRAM semiconductor element of the same standard as that of the comparative example 11 was examined, three out of the twenty semiconductor elements and the non-photosensitive polyimide of the comparative example 11 were defective. As compared with a semiconductor device using, the semiconductor device was reduced to 25% or less, and a highly reliable semiconductor device was obtained.

Example 62 A semiconductor device using a photosensitive resin composition containing a polyamic acid and an orthoquinonediazide compound whose structure is limited by the above formula [2], and a pyridinium salt whose structure is limited by the above formula [5] And the reliability of the manufactured semiconductor device were examined.

Using the photosensitive resin composition of Example 19,
According to the same procedure as in Example 58, a 4 μm-thick buffer coat film was formed on the semiconductor element coated with the SiN layer 3.

By adopting the manufacturing method using the photosensitive resin composition, eight steps were simplified as compared with the steps using the non-photosensitive polyimide.

The structure of the polyamic acid in the photosensitive resin composition is represented by the formula [2], the structure of the photoacid generator is represented by the orthoquinonediazide compound, and the pyridinium salt is represented by the formula [5]
, The light of the high-pressure mercury lamp is reduced to 50
By irradiating 0 mJ / cm ^2, a buffer coat film could be formed, and the sensitivity was further increased by 23% as compared with Example 59 in which only the structure of polyamic acid was limited.

Next, when the defective opening of the fuse hole in the DRAM semiconductor device of the same standard as in Comparative Example 11 was examined, the effect of limiting the structure of the polyamic acid, the photoacid generator and the pyridinium salt in the photosensitive resin was examined. As a result, no defective product was confirmed, and a highly reliable semiconductor device was obtained.

Example 63 A polyamic acid ester of the above formula [3], an orthoquinonediazide compound, and
The manufacturing method of a semiconductor device using a photosensitive resin composition containing a pyridinium salt whose structure was limited by the formula [5] and the reliability of the manufactured semiconductor device were examined.

Using the photosensitive resin composition of Example 39,
According to the same procedure as in Example 60, a 4 μm thick buffer coat film was formed on the semiconductor element coated with the SiN layer 3.

By adopting the manufacturing method using the photosensitive resin composition, eight steps were simplified as compared with the step using the non-photosensitive polyimide.

Further, by limiting the structure of the photoacid generator in the photosensitive resin composition to the orthoquinonediazide compound and the pyridinium salt to the above formula [5], the light of a high pressure mercury lamp is irradiated at 400 mJ / cm ^2. As a result, a buffer coat film was formed, and the sensitivity was increased by 20% as compared with Example 60 in which these structures were not limited.

Next, when the defective opening of the fuse hole in the DRAM semiconductor element of the same standard as that of Comparative Example 11 was examined, it was found that the structure of the photoacid generator and the pyridinium salt in the photosensitive resin was limited. No good products are confirmed at all,
A very reliable semiconductor device was obtained.

Example 64 A polybenzoxazole precursor of the above formula [4], an orthoquinonediazide compound,
In addition, a method of manufacturing a semiconductor device using a photosensitive resin composition containing a pyridinium salt whose structure was limited by the above formula [5] and the reliability of the manufactured semiconductor device were examined.

Using the photosensitive resin composition of Example 49,
A 4 μm thick buffer coat film was formed on the semiconductor element coated with the SiN layer 3 according to the same procedure as in Example 61.

By adopting the manufacturing method using the photosensitive resin composition, eight steps were simplified as compared with the step using the non-photosensitive polyimide.

[0259] Furthermore, the o-quinonediazide compound structure of the photoacid generator in the photosensitive resin composition, by irradiation 400 mJ / cm ² light of a high pressure mercury lamp by the limited respectively by the formula pyridinium salt (5) As a result, a buffer coat film was formed, and the sensitivity was increased by 20% as compared with Example 61 in which these structures were not limited.

Next, when the defective opening of the fuse hole in the DRAM semiconductor element of the same standard as that of Comparative Example 11 was examined, it was found that the structure of the photoacid generator and the pyridinium salt in the photosensitive resin was limited. No good products are confirmed at all,
A very reliable semiconductor device was obtained.

[0261]

According to the positive photosensitive resin composition of the present invention which can be developed with an alkaline aqueous solvent, a high-resolution relief pattern can be formed due to the dissolution inhibiting effect of the pyridinium salt.

In the method of manufacturing a semiconductor device using the positive photosensitive resin composition of the present invention, the steps can be greatly simplified.
A highly reliable one with few opening defects was obtained.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a process for manufacturing a semiconductor device having a buffer coat film using a conventional non-photosensitive resin composition.

FIG. 2 is a schematic cross-sectional view showing a manufacturing process of a semiconductor device having a buffer coat film using the photosensitive resin composition of the present invention.

FIG. 3 shows D prepared using the photosensitive resin composition of the present invention.
It is an external view of the semiconductor element for RAM.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Semiconductor element, 2 ... Al bonding pad, 3 ... S
iN, 4 ... photoresist, 5 ... non-photosensitive resin composition,
6 ... polyimide, 7 ... photosensitive resin composition.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takao Miwa 7-1-1, Omikacho, Hitachi City, Ibaraki Prefecture Within Hitachi Research Laboratory, Hitachi, Ltd. (72) Inventor Takumi Ueno 7-1, Omikamachi, Hitachi City, Ibaraki Prefecture No. 1 Hitachi, Ltd. Hitachi Research Laboratory (72) Inventor Yoshiaki Okabe 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture F Hitachi Term Hitachi Research Laboratory F-term (reference) 2H025 AA02 AA04 AA10 AB16 AC01 AC04 AC08 AD03 BE00 BE01 BG00 CB25 CB26 CB41 CB43 CB45 CB52 DA20 EA04 FA17 FA28

Claims (14)

[Claims] 1. A resin soluble in an aqueous alkali solution, a substance capable of generating an acid by light, and a compound represented by the formula [1]: Wherein R _{1 to} R ₅ are a monovalent organic group or a hydrogen atom, at least one of which is a monovalent organic group, R ₆ is a monovalent organic group, and X ₁ to is an anion. A photosensitive resin composition comprising a pyridinium salt represented by the formula: 2. The resin soluble in the alkaline aqueous solution,
Formula [2] [Wherein R ₇ is selected from diphenyl ether, diphenyl sulfone, and diphenylhexafluoropropane.
And R ₈ is a divalent organic group selected from diphenylsulfone and 2,2′-dimethylbiphenyl.] The photosensitive resin composition according to claim 1. 3. The resin soluble in the alkaline aqueous solution,
Formula [3] [Wherein, R ₉ and R ₁₂ are tetravalent organic groups, R ₁₁ and R ₁₄ are monovalent organic groups, R ₁₀ is a divalent organic group having a phenolic hydroxyl group and / or a carboxyl group, and R ₁₃ is The photosensitive resin composition according to claim 1, wherein y representing the constitutional ratio of the divalent organic group and the repeating unit is from 40 to 100 mol%]. 4. The resin soluble in the alkaline aqueous solution,
Formula [4] 2. A polybenzoxazole precursor represented by the formula: wherein R ₁₅ is a divalent organic group and R ₁₆ is a tetravalent organic group.
3. The photosensitive resin composition according to item 1. 5. The pyridinium salt of the formula [5] Wherein R ₁₇ and R ₁₈ are aryl groups and X ₂ to are anions. The substance capable of generating an acid by light is an orthoquinonediazide compound. 3. The photosensitive resin composition according to item 1. 6. A step of applying a resin soluble in an aqueous alkali solution, a substance generating an acid by light, and a photosensitive resin composition containing a pyridinium salt represented by the formula [1] onto a substrate, A pattern forming method comprising: irradiating an electromagnetic wave through a mask; and developing the photosensitive resin composition with an alkaline aqueous developer. 7. The pattern forming method according to claim 6, wherein the resin soluble in an aqueous alkaline solution contained in the photosensitive resin composition is represented by any one of the formulas [2] to [4]. 8. The pattern forming method according to claim 7, wherein the pyridinium salt contained in the photosensitive resin composition is represented by the formula [5], and the substance that generates an acid by light is an orthoquinonediazide compound. 9. A cured product of a resin soluble in an aqueous alkali solution, a substance capable of generating an acid by light, and a photosensitive resin composition containing a pyridinium salt represented by the formula [1] is used for forming a circuit of a semiconductor element. A semiconductor element formed on a surface or a surface on which a protective film is formed. 10. The semiconductor device according to claim 9, wherein the resin soluble in an aqueous alkali solution contained in the photosensitive resin composition is represented by any one of the formulas [2] to [4]. 11. The semiconductor device according to claim 10, wherein the pyridinium salt contained in the photosensitive resin composition is represented by the formula [5], and the substance that generates an acid by light is an orthoquinonediazide compound. 12. A method according to claim 1, wherein a resin soluble in an aqueous alkaline solution, a substance capable of generating an acid by light, and a photosensitive resin composition containing a pyridinium salt represented by the formula [1] are used for protecting a circuit forming surface of a semiconductor element or protecting the same. A method for producing a semiconductor device, comprising: a step of applying to a film formation surface, a step of irradiating an electromagnetic wave through a photomask, a step of developing with an alkaline aqueous developer, and a step of baking the formed pattern. 13. The method according to claim 12, wherein the resin soluble in the aqueous alkali solution contained in the photosensitive resin composition is represented by any one of the formulas [2] to [4]. 14. The method for producing a semiconductor device according to claim 13, wherein the pyridinium salt contained in the photosensitive resin composition is represented by the formula [5], and the substance that generates an acid by light is an orthoquinonediazide compound. .