JP2011203294A - Negative photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition, forming a pattern having an excellent lithography performance and forward tapered sectional form.SOLUTION: The negative photosensitive resin composition contains: (a) 100 mass parts alkali water soluble resin; (b) 0.1-20 mass parts compound which generates acid by irradiation of active light; (c) 1-50 mass parts compound which can be crosslinked or polymerized by action of acid; and (d) 1-50 mass parts compound having at least one (meth)acryloyl group in a molecular structure.

Description

  The present invention relates to a negative photosensitive resin composition that can be used as a precursor of a heat resistant resin used as, for example, a surface protective film or an interlayer insulating film of a semiconductor device, and heat resistance using the negative photosensitive resin composition The present invention relates to a method for producing a cured relief pattern having a semiconductor device, a semiconductor device having the cured relief pattern, and a method for producing the same.

  Polymer materials such as photosensitive polyimide resins and photosensitive polybenzoxazole resins have been frequently used for applications such as surface protection films and interlayer insulating films of semiconductor elements. Conventional photosensitive polyimides were mainly developed using an organic solvent as the developer, but organic solvent waste liquids are usually incinerated, so from the viewpoint of environmental protection and waste liquid treatment costs, alkaline aqueous solutions There is an increasing demand for development. For example, a photosensitive resin composition that can be developed in a positive alkaline developer, in which an orthoquinonediazide compound is blended as a photosensitive agent with a polyimide resin having a phenolic hydroxyl group has been proposed (Patent Document 1). A positive photosensitive composition in which a dibenzonaphthoquinone compound is blended with a polybenzoxazole precursor has also been proposed (Patent Document 2). These photosensitive resin compositions use a diazoquinone compound containing a large number of aromatic rings as a photosensitizer, so the sensitivity is low, and it is necessary to increase the amount of photosensitizer used. Therefore, the mechanical properties after thermosetting are significantly reduced. There is a problem of making it. In addition, since these photosensitive resin compositions are positive, there is a problem that it is difficult to take a difference in solubility in a developing solution between an exposed area and an unexposed area, and the film thickness of the pattern area is large.

  Therefore, it contains (a) an alkali-soluble polymer having a phenolic hydroxyl group in the polymer skeleton, (b) a compound that generates an acid upon irradiation with actinic rays, and (c) a compound that can be crosslinked or polymerized by generating an acid. A negative photosensitive resin composition characterized by the above has been proposed as a composition excellent in sensitivity, resolution, and heat resistance, and capable of obtaining good cured film properties (Patent Document 3 and Patent Document 4).

Japanese Patent No. 2906737 JP-A-1-46862 Japanese Patent No. 3877767 Japanese Patent No. 3966590

  In recent years, multi-layer wiring technology by miniaturization, high integration and high speed of semiconductor elements is being adopted. In order to form the second-layer wiring, the cross-sectional shape of the relief pattern formed as the interlayer insulating film is preferably a forward tapered shape. In the case of the alkali chemical amplification negative composition as proposed in Patent Documents 3 and 4 above, in order to make the cross-sectional shape forward tapered, the amount of the compound generating an acid by irradiation with actinic rays is increased, and the crosslinking is performed by the generation of the acid. Alternatively, a technique such as increasing the amount of the compound that can be polymerized is effective. However, in these methods, the exposed portion is further cured, while the crosslinking reaction due to the heat of the unexposed portion is simultaneously promoted, resulting in lithographic problems such as an increase in development time and a decrease in resolution. In the literature currently reported, the example which can make a forward taper-shaped pattern shape and litho performance compatible is not found yet.

  The present invention relates to a negative photosensitive resin composition capable of forming a pattern having excellent lithographic performance and having a forward tapered cross-sectional shape suitable for multilayer wiring, and curing using the negative photosensitive resin composition It is an object of the present invention to provide a method for manufacturing a relief pattern, a semiconductor device having the cured relief pattern, and a method for manufacturing the semiconductor device.

  As a result of intensive studies to solve the above problems, the present inventors have found that a negative photosensitive resin composition that solves the above problems can be obtained by using a compound having a specific structure. The present invention has been made. That is, the present invention is as follows.

[1] (a) Alkaline aqueous solution-soluble resin: 100 parts by mass, (b) Compound that generates acid upon irradiation with actinic rays: 0.1 to 20 parts by mass, (c) Compound that can be crosslinked or polymerized by the action of acid A negative photosensitive resin composition comprising: 1 to 50 parts by mass, and (d) a compound having at least one (meth) acryloyl group in the molecular structure: 1 to 50 parts by mass.
[2] The compound (d) having at least one (meth) acryloyl group in the molecular structure is represented by the following general formula (1):
{Wherein, R ₁ and R ₂ are each independently hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms, and p and q are each independently , 0, 1 or 2, and p and q are not 2 at the same time. R ₃ and R ₄ are each independently an alkylene group having 1 to 4 carbon atoms, and when R ₃ and R ₄ are different from each other, — (R ₃ —O) — and — (R ₄ —O) )-May represent a block structure or a random structure. j and k are each independently 0 or a positive integer, and the sum of j and k is 1 to 40. R ₅ is hydrogen or a CH ₃ group. }
And the following general formula (2):
{In the formula, R ₆ and R ₇ are each independently an alkylene group having 1 to 4 carbon atoms, and when R ₆ and R ₇ are different from each other, — (R ₆ —O) — and — ( The repeating unit represented by R ₇ —O) — may constitute a block structure or a random structure. m and n are each independently 0 or a positive integer, and the sum of m and n is 1 to 40. R ₈ and R ₉ are each independently hydrogen or a CH ₃ group. }
The negative photosensitive resin composition according to the above [1], which is at least one compound selected from the group consisting of compounds represented by:
[3] The aqueous alkali-soluble resin (a) is soluble in at least one alkaline aqueous solution selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, polyamide, polyamic acid, polyamic acid ester, novolak resin, and epoxy resin. The negative photosensitive resin composition according to the above [1] or [2], which is a resin.
[4] The (a) aqueous alkali-soluble resin is represented by the following general formula (3):
{Wherein R ₁₀ is an organic group having an aromatic ring, and R ₁₁ is an aromatic group, an alicyclic group, or an aliphatic group having 2 to 10 carbon atoms. }
The negative photosensitive resin composition in any one of said [1]-[3] which is a polyamide which has a repeating unit represented by these.
[5] A photosensitive resin layer forming step of forming a photosensitive resin layer made of the negative photosensitive resin composition according to any one of [1] to [4] on a substrate,
An exposure step of exposing the photosensitive resin layer with actinic rays;
A heating step of heating the exposed photosensitive resin layer;
A method for producing a cured relief pattern, comprising: a developing step of developing the heated photosensitive resin layer to form a relief pattern; and a heating and curing step of heating the obtained relief pattern to form a cured relief pattern.
[6] A semiconductor device having a cured relief pattern formed by the method for producing a cured relief pattern according to [5] above on a silicon wafer substrate or a copper wafer substrate.
[7] A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured relief pattern according to [5] as part of the process.

  According to the present invention, a negative photosensitive resin composition having negative lithography performance in which the cross-sectional shape of the pattern is a forward taper, a method for producing a cured relief pattern using the negative photosensitive resin composition, and A semiconductor device having the cured relief pattern and a manufacturing method thereof can be provided.

1 is an SEM (scanning electron microscope) image showing the cross-sectional shape of the cured relief pattern formed in Examples 1 to 7 and Comparative Example 1. FIG.

<Negative photosensitive resin composition>
The negative photosensitive resin composition according to the present invention comprises (a) an aqueous alkali-soluble resin: 100 parts by mass, (b) a compound that generates an acid upon irradiation with active light: 0.1-20 parts by mass, (c) A compound that can be crosslinked or polymerized by the action of an acid: 1 to 50 parts by mass, and (d) a compound having at least one (meth) acryloyl group in the molecular structure: 1 to 50 parts by mass . Hereinafter, although the negative photosensitive resin composition which concerns on this invention is demonstrated concretely, this invention is not limited by the following specific examples.
Hereinafter, the components (a) to (d) of the negative photosensitive resin composition according to the present invention will be described in detail.

(A) Alkaline aqueous solution-soluble resin The (a) alkaline aqueous solution-soluble resin used in the present invention typically has at least one of a hydroxyl group, a carboxyl group, and a sulfonic acid group in at least one of the main chain and the side chain. Resin. Examples of the (a) aqueous alkali-soluble resin include at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, polyamide, polyamic acid, polyamic acid ester, novolac resin, and epoxy resin. It is done. Among these, polyamideimide, polyamide, polyamic acid, polyamic acid ester, and the like are preferable from the viewpoints of both heat resistance and the photosensitive characteristics of the photosensitive composition to be constituted. Of these, polyamide is particularly preferred.

  Polyamide includes a resin having a polybenzoxazole precursor structure, a resin having a polyamic acid structure, or a resin having a polyamic acid ester structure, wherein at least one of a main chain and a side chain has a hydroxyl group, a carboxyl group, and a sulfone. A resin having at least one of acid groups is preferred. Among these, from the viewpoint of heat resistance after the final heating, the following general formula (3):

{Wherein R ₁₀ is an organic group having an aromatic ring, and R ₁₁ is an aromatic group, an alicyclic group, or an aliphatic group having 2 to 10 carbon atoms. }
Polyamide having a repeating unit represented by A part of these resins may be ring-closed to have a polybenzoxazole structure.

The polyamide having the repeating unit represented by the general formula (3) includes, for example, a dicarboxylic acid having a structure of R ₁₁ (COOH) ₂ and a dihydroxydiamine having a structure of R ₁₀ (NH ₂ ) ₂ (OH) _2. It can be obtained by polycondensation. The manufacturing method will be described later.

R ₁₀ is preferably a group having an aromatic ring from the viewpoint of heat resistance and securing appropriate solubility in an aqueous alkali solution, and includes the following:

An aromatic group selected from is particularly preferred.

Preferred dihydroxydiamines having the structure of R ₁₀ (NH ₂ ) ₂ (OH) ₂ are, for example, 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4 '-Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino -4-hydroxyphenyl) methane, 2,2'-bis- (3-amino-4-hydroxyphenyl) propane, 2,2'-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2, 2′-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2 2′-bis- (4-amino-3-hydroxyphenyl) propane, 4,4′-diamino-3,3′-dihydroxybenzophenone, 3,3′-diamino-4,4′-dihydroxybenzophenone, 4,4 '-Diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4- Examples include dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene. These dihydroxydiamines can be used alone or in combination of two or more.

R ₁₁ is preferably an aromatic group from the viewpoint of heat resistance. When R ₁₁ is an aliphatic group, the carbon number of R ₁₁ is 2 or more, more preferably 3 or more from the viewpoint of ensuring appropriate solubility in an aqueous alkali solution, and 10 or less from the viewpoint of heat resistance. More preferably, it is 8 or less. Particularly preferred examples of R ₁₁ include ethylene group, propylene group, butylene group, pentene group, hexene group and the like.

Examples of the dicarboxylic acid having the structure of R ₁₁ (COOH) ₂ include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4,4′-biphenyldicarboxylic acid, 4 , 4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5 -Aromatic dicarboxylic acids such as bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, Phosphoric acid, suberic acid, azelaic acid, alicyclic and dicarboxylic acids aliphatic such as sebacic acid. Alternatively, dicarboxylic acid dichloride compounds obtained by chlorinating these dicarboxylic acids or derivatives of these dicarboxylic acids (for example, dicarboxylic acid imidazolide) may be used. These can be used alone or in combination of two or more.

The polyamide having the repeating unit represented by the general formula (3) is, for example, a compound selected from a diamine containing the structure of R ₁₀ and a dicarboxylic acid, dicarboxylic acid dichloride or dicarboxylic acid derivative containing the structure of R _11. Can be obtained by reacting. Examples thereof include a method in which a dicarboxylic acid is converted into a diacid chloride using thionyl chloride and then a diamine is acted thereon, or a method in which a dicarboxylic acid and a diamine are polycondensed with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

  The polyamide having a repeating unit represented by the general formula (3) may be used after its end group is sealed with an organic group (hereinafter referred to as a sealing group). In the polycondensation described above, when the dicarboxylic acid component is used in an excess number of moles compared to the diamine component, it is preferable to use a compound having an amino group or a hydroxyl group as the sealing group as the sealing agent. Examples of such sealants include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, hydroxyethyl acrylate and the like.

  On the other hand, when the diamine component is used in an excess number of moles compared to the dicarboxylic acid component, an acid anhydride, carboxylic acid, acid chloride, a compound having an isocyanate group or the like as a sealing group, etc. should be used as a sealing agent. Is preferred. Examples of such sealants include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methyl Examples include cyclohexanedicarboxylic acid anhydride, cyclohexenedicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, and tosylic acid chloride.

  For example, in the present invention, the molecular weight of the polyamide used as the (a) aqueous alkali-soluble resin can be obtained by the reaction described above, and the weight average molecular weight is preferably 4,000 to 150,000, and preferably 6,000 to 100,000. More preferred. The weight average molecular weight is preferably 4000 or more from the viewpoint of ensuring the mechanical properties and heat resistance of the material formed using the negative photosensitive resin composition of the present invention, while the negative photosensitive resin composition has From the viewpoint of alkali solubility and development speed, 150,000 or less is preferable. In addition, the value of the weight average molecular weight described in the present specification is a value measured according to the method described in Examples described later.

(B) Compound that generates acid upon irradiation with actinic ray (b) The compound that generates acid upon irradiation with actinic ray used in the present invention can be any compound that generates acid upon irradiation with actinic ray, It has the effect | action which supplies an acid to the compound which can be bridge | crosslinked or polymerized by the effect | action of below-mentioned (c) acid, and advances the bridge | crosslinking or superposition | polymerization at the time of exposure of the negative photosensitive resin composition of this invention. (B) As a compound which generate | occur | produces an acid by irradiation of actinic light, a well-known various compound can be used as what is called a photo-acid generator, For example, the following compounds are mentioned.

i) Trichloromethyl-s-triazines Tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -Bis (4,6-trichloromethyl) -s-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4 6-trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl) ) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) Bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6 -Trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (3,4,5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4 , 6-Trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio-β Styryl) - bis (4,6-trichloromethyl) -s-triazine.

ii) Diaryliodonium diphenyliodonium tetrafluoroborate, diphenyliodonium tetrafluorophosphate, diphenyliodonium tetrafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenyl Phenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4- Me Toxiphenylphenyliodonium-p-toluenesulfonate, bis (4-ter-butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) iodonium Trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate, and the like.

iii) Triarylsulfonium salts Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfo NATO, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium tri Fluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyl Trifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate, and the like.

  Among these compounds, trichloromethyl-s-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -bis (4, 6-trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6- Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine and the like, and diaryl iodonium salts include diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfone. Nato, 4-methoxyphenylphenyliodonium trifluoromethane For example, sulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, and triarylsulfonium salts include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyl. Suitable examples include diphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate and the like.

  As the above-mentioned compounds, triarylsulfonium salts are preferable from the viewpoint of photosensitive performance. In addition to the above, the following compounds can be used.

(1) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like, and specific examples include 1,2-naphthoquinone diazide of phenols. A 4-sulfonic acid ester compound can be mentioned.

(2) Sulfone compounds Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphena. Examples include silsulfone and bis (phenacylsulfonyl) methane.

(3) Sulfonic acid compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred examples include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl p-toluene sulfonate, and the like.

(4) Sulfonimide compound As specific examples of the sulfonimide compound, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like can be mentioned.

(5) Oxime ester compound 2- [2- (4-Methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (trade name of Ciba Specialty Chemicals) “Irgacure PAG121”), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name “Irgacure PAG103”), [2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name “Irgacure PAG108”), α- (n -Octanesulfonyl Kishiimino) -4-methoxybenzyl cyanide (Ciba Specialty Chemicals tradename "CGI725"), and the like.

(6) Diazomethane compound Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.

  In particular, from the viewpoint of sensitivity, the above (5) oxime ester compound group is preferable.

  (B) The compounding quantity of the compound which generate | occur | produces an acid by irradiation of actinic light is 0.1-20 mass parts with respect to 100 mass parts of (a) alkaline aqueous solution resin, Preferably it is 0.5-15 masses. Parts, more preferably 1 to 15 parts by mass. When the blending amount is 0.1 parts by mass or more, the amount of acid generated by irradiation with actinic rays (for example, radiation) becomes sufficient, and sufficient sensitivity of the negative photosensitive resin composition can be obtained. If a compounding quantity is 20 mass parts or less, the mechanical physical property after hardening of a negative photosensitive resin composition will be favorable.

(C) Compound that can be crosslinked or polymerized by the action of acid (c) A compound that can be crosslinked or polymerized by the action of acid (hereinafter also referred to as (c) cross-linking agent) can be polymer-crosslinked or polymerized by the action of acid. It can be any compound. (C) The crosslinking agent heats the coating film of the photosensitive resin layer comprising the negative photosensitive resin composition of the present invention with the acid supplied from the compound (b) that generates acid upon irradiation with actinic rays. In curing, (c) the cross-linking agent can cross-link (a) the aqueous alkali-soluble resin, or (c) the cross-linking agent itself can form a cross-linking network. Thereby, the heat resistance of the material formed from the negative photosensitive resin composition can be strengthened.

  (C) As a crosslinking agent, the melamine resin, urea resin, etc. by which N-position was substituted by the methylol group and / or the alkoxymethyl group are mentioned as a preferable thing. Those having three or more methylol groups and C1-C20 alkoxymethyl groups in the molecule are preferred from the viewpoint of high crosslinking performance.

  More specifically, N-methylol melamine, melamine resin, benzoguanamine resin, glycoluril resin, urea resin, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, alkoxymethylated urea resin, etc. Can be mentioned.

  Furthermore, (c) as a crosslinking agent, for example, commercially available Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170 , 1174, UFR65, 300 (Mitsui Cytec Co., Ltd.), Nicarax MX-270, -280, -290, Nicarak MS-11, Nicarak MW-30, -100, -300, -390, -750 ( As mentioned above, Sanwa Chemical Co., Ltd.) can be preferably used in practice. These compounds can be used alone or in combination of two or more.

  (C) The compounding quantity of a crosslinking agent is 1-50 mass parts with respect to 100 mass parts of (a) alkaline aqueous solution soluble resin, Preferably it is 1-40 mass parts, More preferably, it is 3-30 mass parts. . If the blending amount is 1 part by mass or more, crosslinking proceeds sufficiently and the patterning property is improved. If the blending amount is 50 parts by mass or less, the mechanical properties after heat curing (curing) are maintained. Be drunk.

(D) Compound having at least one (meth) acryloyl group in the molecular structure (d) A compound having at least one (meth) acryloyl group in the molecular structure used in the present invention (hereinafter also referred to as component (d)). ) Can be any compound having at least one (meth) acryloyl group in the molecular structure, and at least one (meth) acryloyl group causes the (d) component in the exposed area to participate in the crosslinking reaction. And has the effect of increasing the difference in dissolution rate (also referred to as contrast) in the developer between the exposed portion and the unexposed portion. As a result, excellent litho performance is imparted to the negative photosensitive resin composition of the present invention, and a forward relief-shaped cured relief pattern can be formed. In the present specification, the (meth) acryloyl group includes a methacryloyl group and an acryloyl group.

  As the component (d), for example: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate 4-hydroxybutyl methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraeth Glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, Hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol Diacrylate, 1,4-butanediol dimethacrylate 1,6-hexanediol diacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide N-methylolacrylamide, dimethacryloyloxyurea, dipentaerythritol hexaacrylate, dipentaerythritol hexameta Examples include acrylate, isocyanuric acid EO-modified triacrylate, and isocyanuric acid EO-modified trimethacrylate. These can be used alone or in combination of two or more.

  Among these, from the viewpoint of maintaining a balance between the resolution and the forward tapered shape, the following general formula (1):

{Wherein, R ₁ and R ₂ are each independently hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms, and p and q are each independently , 0, 1 or 2, and p and q are not 2 at the same time. R ₃ and R ₄ are each independently an alkylene group having 1 to 4 carbon atoms, and when R ₃ and R ₄ are different from each other, — (R ₃ —O) — and — (R ₄ —O) )-May represent a block structure or a random structure. j and k are each independently 0 or a positive integer, and the sum of j and k is 1 to 40. R ₅ is hydrogen or a CH ₃ group. }
And the following general formula (2):

{In the formula, R ₆ and R ₇ are each independently an alkylene group having 1 to 4 carbon atoms, and when R ₆ and R ₇ are different from each other, — (R ₆ —O) — and — ( The repeating unit represented by R ₇ —O) — may constitute a block structure or a random structure. m and n are each independently 0 or a positive integer, and the sum of m and n is 1 to 40. R ₈ and R ₉ are each independently hydrogen or a CH ₃ group. }
It is preferable that it is at least 1 type of compound selected from the group which consists of a compound represented by these.

In the general formula (1), R ₁ and R ₂ are each not hydrogen, a hydroxyl group, from the viewpoint of not having a functional group that reacts with the component (c) by heat and ensuring appropriate solubility in an aqueous alkali solution. An alkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms, preferably hydrogen, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms. More preferably hydrogen, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. The number of carbon atoms of R ₃ and R ₄ is 1 to 4, preferably 2 to 4, and more preferably 2 to 3 from the viewpoint of ensuring solubility in an appropriate aqueous alkali solution. The total of j and k is 1 or more from the viewpoint of the resolution of the photosensitive composition, and 40 or less from the viewpoint of the heat resistance of the cured relief pattern, preferably 2 to 30, more preferably 3 to 30. R ₅ is hydrogen or a CH ₃ group from the viewpoint of high reactivity of the acryloyl group.

In the said General formula (2), carbon number of R < ₆ > and R < ₇ > is 1-4 from a viewpoint of ensuring the solubility in a suitable alkaline aqueous solution, Preferably it is 2-3. The total of m and n is 1 or more from the viewpoint of the resolution of the photosensitive composition and 40 or less from the viewpoint of the heat resistance of the cured relief pattern, preferably 2 to 30, and more preferably 3 to 30. R ₈ and R ₉ are hydrogen or CH ₃ group from the viewpoint that the reactivity of the acryloyl group is high.

  Among these, from the viewpoint of resolution and alkali dissolution rate, particularly preferably used as component (d) is mono- or diacrylate and methacrylate of ethylene glycol or polyethylene glycol, mono- or diacrylate of propylene glycol or polypropylene glycol, and Mono- or diacrylates and methacrylates of methacrylates, block copolymers of polyethylene glycol and polypropylene glycol. These can be used alone or in combination of two or more.

  In addition, the (meth) acryloyl group number density present in the negative photosensitive resin composition of the present invention is preferably 0.7 or less from the viewpoint of ensuring the forward tapered shape of the cross-sectional shape and the litho performance. More preferably, it is less than 0.5, More preferably, it is 0.45 or less. On the other hand, the (meth) acryloyl radical number density is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.05 or more, from the viewpoint of ensuring the cross-sectional shape forward taper.

  Here, the (meth) acryloyl group number density present in the negative photosensitive resin composition is defined as follows.

  The compounding quantity of the said (d) component in a negative photosensitive resin composition is 1-50 mass parts with respect to 100 mass parts of said (a) alkali aqueous solution soluble resin, More preferably, it is 5-40 mass parts. More preferably, it is 5-30 mass parts. If the blending amount is 1 part by mass or more, the cross-sectional shape can be ensured in a forward tapered shape, and if it is 50 parts by mass or less, high resolution can be secured.

(E) Sensitizer The negative photosensitive resin composition of the present invention can be blended with a sensitizer for improving photosensitivity, if necessary.

  Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylaminobenzylidene) cyclohexanone. 2,6-bis (4′-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) chalcone, 4,4′-bis (diethylamino) chalcone, 2- (4′-dimethylaminocinnamylidene) indanone, 2- (4′-dimethylaminobenzylidene) indanone, 2- (p-4′-dimethylaminobiphenyl) benzo Thiazole, 1,3-bis (4-dimethylaminobenzyl) Den) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethyl Aminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, N, N-bis (2-hydroxyethyl) aniline, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, 4-diethylaminobenzoic acid Amyl, benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, 1- ( tert-butyl) -5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2 -(P-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like.

  Among these, benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, and 1- (tert-butyl) -5-mercapto-1,2,3,4-tetrazole, coumarins having substituents at the 3-position and / or 7-position, flavones, dibenzalacetones, diben Formulating one or more sensitizers selected from the group consisting of zarcyclohexanes, chalcones, xanthones, thioxanthones, porphyrins, phthalocyanines, acridines, and anthracenes having a substituent at the 9-position. Is preferred. In use, it may be used alone or as a mixture of two or more.

  The blending amount in the case of blending the sensitizer is preferably 0.1 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (a) alkaline aqueous solution-soluble resin. .

(F) Polymerization inhibitor In the negative photosensitive resin composition of the present invention, a polymerization inhibitor is used to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition solution during storage, if necessary. Can be blended.

  Examples of such polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid. 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N- Ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt ,Screw 4-hydroxy-3,5-di-tert- butyl) phenyl methane, or the like can be used.

  When the polymerization inhibitor is blended, the blending amount is preferably 0.001 to 5 parts by mass, and 0.01 to 1 part by mass with respect to 100 parts by mass of the (a) alkaline aqueous solution-soluble resin. More preferred.

(G) Silane coupling agent A silane coupling agent can be mix | blended with the negative photosensitive resin composition of this invention as needed. Specific preferred examples of the silane coupling agent include N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxysilylethyl) pyridine, and 3-methacryloxypropyltrialkoxy. Silane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxyalkylsilane, 3-aminopropyl dialkoxyalkylsilane, or Examples include acid anhydrides or acid dianhydride reactants, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane amino groups converted to urethane groups or urea groups, etc. Door can be. In this case, as the alkyl group, methyl group, ethyl group, butyl group, etc., maleic anhydride, phthalic anhydride, etc. as acid anhydride, pyromellitic dianhydride as acid dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, etc., t-butoxycarbonylamino group as a urethane group, phenylamino as a urea group Examples thereof include, but are not limited to, a carbonylamino group.

  When the silane coupling agent is blended, the blending amount is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the (a) alkaline aqueous solution-soluble resin. preferable.

  In addition to the above, various additives such as a scattered light absorber and a coating film smoothness-imparting agent can be appropriately blended in the negative photosensitive resin composition of the present invention.

Solvent A negative photosensitive resin composition solution can be prepared by arbitrarily adding a solvent to the negative photosensitive resin composition according to the present invention. The negative photosensitive resin composition solution is preferable because the viscosity can be adjusted according to the type and amount of the solvent. Suitable solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclopentanone Cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, etc. These may be used alone or in combination of two or more. Among these, N-methyl-2-pyrrolidone and γ-butyrolactone are particularly preferable.

  These solvents can be appropriately added to the negative photosensitive resin composition according to the present invention depending on the desired coating film thickness and viscosity, but (a) the solvent is used with respect to 100 parts by mass of the aqueous alkali-soluble resin. It is preferable to use in the range of 10 to 1000 parts by mass.

  For the purpose of improving coating properties, the above solvents and propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1, A mixed solvent obtained by mixing a solvent such as 3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, or methyl-3-methoxypropionate can also be used. A preferable addition amount of the above mixed solvent for the purpose of improving applicability is 10 to 900 parts by mass with respect to 100 parts by mass of the (a) alkaline aqueous solution-soluble resin.

  On the other hand, for the purpose of further improving the storage stability of the negative photosensitive resin composition over time, the following alcohols can be used in combination.

  Examples of the alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, benzyl alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, propylene glycol mono (n-propyl) ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono (n-propyl) ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, Such as monoalcohols, ethylene glycol, propylene glycol, etc. It can be mentioned Lumpur class. Among these, benzyl alcohol and ethylene glycol monophenyl ether are particularly preferable.

  The content of these alcohols in the solvent is preferably 50% by mass or less because the solubility of the polymer is good.

<Method for producing cured relief pattern>
The present invention includes a photosensitive resin layer forming step of forming on the substrate a photosensitive resin layer comprising the negative photosensitive resin composition of the present invention described above, an exposure step of exposing the photosensitive resin layer with actinic rays, A heating step for heating the exposed photosensitive resin layer, a developing step for developing the heated photosensitive resin layer to form a relief pattern, and a heating for heating the resulting relief pattern to form a cured relief pattern A method for producing a cured relief pattern including a curing step is also provided. Hereinafter, the manufacturing method of the hardening relief pattern which concerns on this invention is demonstrated concretely.

[Photosensitive resin layer forming step]
First, in this step, a photosensitive resin layer made of the negative photosensitive resin composition according to the present invention is used, for example, on a substrate such as a silicon wafer, a copper wafer, a ceramic substrate, or an aluminum substrate. It is applied by spin coating or by a coater such as a die coater or roll coater. As needed, this is dried at 50-140 degreeC using an oven or a hotplate, and a solvent is removed.

[Exposure process]
Second, in this step, the photosensitive resin layer formed as described above is exposed with actinic rays. Specifically, exposure with actinic radiation is performed through a mask using a contact aligner or a stepper, or light rays, electron beams, or ion beams are directly irradiated.

[Heating process]
Third, in this step, the photosensitive resin layer exposed as described above is subjected to heat treatment (that is, post-exposure baking (PEB)). This PEB treatment is a treatment for sensitizing the sensitivity of the photosensitive resin composition, and is necessary for obtaining the effects in the method for producing a cured relief pattern according to the present invention. The PEB temperature is preferably 80 to 160 ° C., more preferably 90 to 150 ° C. in consideration of sensitivity, the pattern shape to be obtained, and the like.

[Development process]
Fourth, in this step, the photosensitive resin layer formed on the substrate, which has been heat-treated as described above, is developed with an alkaline aqueous solution having an appropriate concentration. By the development process, a fine resin pattern can be transferred onto the substrate to form a relief pattern. A desired relief pattern is obtained by dissolving and removing an unexposed portion or an unirradiated portion of the photosensitive resin layer with a developing solution and subsequently rinsing with a rinsing solution. As a developing method, methods such as spray, paddle, dip, and ultrasonic can be used. As the rinsing liquid, distilled water, deionized water, or the like can be used.

  The developer used for developing the photosensitive resin layer formed by the negative photosensitive resin composition according to the present invention is (a) a solution that dissolves and removes the alkaline aqueous solution-soluble resin. It is a dissolved alkaline aqueous solution. The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.

  Examples of inorganic alkali compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, Examples include lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia.

  Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, di- Examples thereof include n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, and triethanolamine.

  Further, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor, or the like can be added to the alkaline aqueous solution.

  After development, a desired relief pattern can be obtained by washing with a rinsing solution, which can be used as a negative image of a heat-resistant material precursor.

[Heat curing process]
Fifth, in this step, the relief pattern obtained as described above is heat-cured at a high temperature (for example, about 160 to 400 ° C.) so that the relief pattern is heat-resistant and chemical-resistant. Can be converted into a cured relief pattern formed of a heat-resistant material that is a cured product having excellent properties and mechanical properties.

<Semiconductor Device and Manufacturing Method of Semiconductor Device>
The present invention also provides a semiconductor device having a cured relief pattern formed on a silicon wafer substrate or a copper wafer substrate by the above-described method for producing a cured relief pattern of the present invention. In a semiconductor device, a cured relief pattern is formed on a silicon wafer substrate or a copper wafer substrate as, for example, a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip chip device protective film, or a protective film for a device having a bump structure. Can be formed.

  The present invention also provides a method for manufacturing a semiconductor device, which includes the above-described method for manufacturing a cured relief pattern according to the present invention as part of the process. A semiconductor device can be manufactured by combining each process of the manufacturing method of a hardening relief pattern mentioned above and the other process in the manufacturing method of a well-known semiconductor device.

  The negative photosensitive resin composition according to the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, liquid crystal alignment films and the like.

  Hereinafter, the present invention will be described more specifically, but the present invention is not limited to these specific examples.

In the synthesis examples, the weight average molecular weight (Mw) of the obtained polyamide is a gel permeation chromatography method (hereinafter also referred to as “GPC”) (converted to standard polystyrene (ShodexSTANDARDSM-105 manufactured by Showa Denko KK)). Measured with The analysis conditions for GPC are described below.
Column: Trade name Shodex 805M / 806M in series manufactured by Showa Denko KK Separation liquid: dimethylformamide 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name ShodexRI-930

<Synthesis of polyamide>
[Synthesis Example 1]
2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter also referred to as “6FAP”) was placed in a 2 L separable flask equipped with a stirrer, a thermometer sensor, and a nitrogen gas inlet tube. 109.9 g (0.30 mol), 43.5 g (0.55 mol) of pyridine, and 400 g of N-methyl-2-pyrrolidone were charged and dissolved while stirring while purging nitrogen gas at a flow rate of about 100 ml / min. After 6 FAP is completely dissolved, the solution is cooled to 0 ° C. or lower, and 4,4′-dicarboxydiphenyl ether chloride (hereinafter referred to as “DEDC”) dissolved in 240 g NMP so that the reaction solution temperature does not exceed 5 ° C. 79.7 g (0.27 mol) solution was added dropwise. After completion of dropping, the temperature was returned to room temperature and stirring was continued for 4 hours. Thereafter, 16.4 g (0.1 mol) of 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as “NA”) and 10 g of pyridine were added, and the mixture was stirred at 50 ° C. for 24 hours. Continued. The obtained reaction solution was dropped into ion-exchanged water while stirring to precipitate the polymer, and the precipitated polymer was filtered, and washed with ion-exchanged water until the pH value of the filtrate became 7. Thereafter, the polymer was vacuum-dried at 50 ° C. for 48 hours to obtain polyamide (P-1). The weight average molecular weight of this polyamide was 15,800.

[Synthesis Example 2]
The synthesis was performed except that the amount of DEDC used was 73.8 g (0.25 mol), and that the reaction solution was dropped directly into ion-exchanged water without adding NA for terminal reaction, followed by post-treatment. Performed as in Example 1. The obtained polyamide (P-2) had a weight average molecular weight of 12,700.

<Preparation of negative photosensitive resin composition>
[Examples 1 to 7, Comparative Example 1]
As shown in Table 1 below, (a) 100% by mass of the polyamide (P-1) or (P-2) obtained in the above synthesis example as an aqueous alkaline solution-soluble resin (component (a)), (b) activity 2- [2- (4-methylphenylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methyl) is a compound that generates an acid upon irradiation with light (component (b)). Phenyl) acetonitrile (manufactured by Ciba Japan, Irgacure PAG121), 5 parts by mass, (c) methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd., trade name) as a compound (component (c)) that can be crosslinked or polymerized by the action of acid Nicarac, product number MX-390, monomer 96 mass% or more, blending amount is shown in Table 1), (d) compound having at least one (meth) acryloyl group in the molecular structure ( d) Compounds D-1 to D-6 (Examples 1 to 7, blending amounts shown in Table 1) having the following structures as components) and 3- (triethoxysilyl) -N- (t-butoxy After dissolving 2 parts by mass of carbonyl) propylamine in 120 parts by mass of γ-butyrolactone, it was filtered through a 0.2 μm Teflon (registered trademark) filter to obtain a varnish which is a negative photosensitive resin composition solution.

  The (meth) acryloyl group number density in the negative photosensitive resin composition was calculated according to the following formula. The results are shown in Table 1.

  The chemical formula of the component (d) in Table 1 is shown below.

<Evaluation of photosensitive performance>
Photosensitive performance was evaluated as follows. The negative photosensitive resin composition solutions obtained in the above examples and comparative examples are spin-coated on a 6-inch silicon wafer substrate and then baked on a hot plate at 95 ° C. for 3 minutes to form a film having a thickness of about 14 μm. Obtained as a photosensitive resin layer. This film was exposed by changing the exposure amount stepwise through a reticle using an i-line stepper exposure machine (Nikon Corporation, NSR2005i8A). The exposed wafer was baked (PEB) after exposure for 3 minutes at 100 ° C., and a 2.38 mass% TMAH aqueous solution (AZ300MIF manufactured by Clariant Japan) was used, and the just development time (MDT, that is, the unexposed portion was Development was carried out with a development time of 110% of the time required for complete dissolution and removal (seconds), followed by rinsing with deionized water to obtain a relief pattern. The obtained relief pattern is observed under a microscope. The exposure amount of the portion where about 85% of the film thickness in the exposed region is maintained is the sensitivity (mJ / cm ² ), and the square relief pattern of the unexposed portion is completely The minimum via size dissolved and removed was defined as the resolution (μm). The results are shown in Table 2.

<Evaluation of cross-sectional shape>
The negative relief pattern obtained through the litho process was cured by heating in a nitrogen atmosphere at 320 ° C. for 1 hour. A cross-sectional shape of a line / space of 10 μm was observed with an SEM (scanning electron microscope). 1 is an SEM (scanning electron microscope) image showing the cross-sectional shape of the cured relief pattern formed in Examples 1 to 7 and Comparative Example 1. FIG.

  As can be seen from Table 2 and FIG. 1, in Examples 1 to 7, by blending the component (d) according to the present invention, the cross-sectional shape of the cured relief pattern becomes a forward tapered shape, and high-resolution photosensitive performance is achieved. Indicated. On the other hand, in Comparative Example 1, since the component (d) according to the present invention was not blended in the photosensitive composition, the cross-sectional shape was reverse tapered (overhanged), and the resolution was 30 μm. It was low.

  The negative photosensitive resin composition according to the present invention includes a surface protective film for a semiconductor device, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, a protective film for a device having a bump structure, and a multilayer circuit. It can be suitably used as an interlayer insulating film, a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film, and the like.

Claims (7)

  (A) Alkaline aqueous solution-soluble resin: 100 parts by mass, (b) Compound that generates an acid upon irradiation with actinic rays: 0.1 to 20 parts by mass, (c) Compound that can be crosslinked or polymerized by the action of an acid: 1 to 1 A negative photosensitive resin composition comprising 50 parts by mass and (d) a compound having at least one (meth) acryloyl group in the molecular structure: 1 to 50 parts by mass. The compound (d) having at least one (meth) acryloyl group in the molecular structure is represented by the following general formula (1):
{Wherein, R ₁ and R ₂ are each independently hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms, and p and q are each independently , 0, 1 or 2, and p and q are not 2 at the same time. R ₃ and R ₄ are each independently an alkylene group having 1 to 4 carbon atoms, and when R ₃ and R ₄ are different from each other, — (R ₃ —O) — and — (R ₄ —O) )-May represent a block structure or a random structure. j and k are each independently 0 or a positive integer, and the sum of j and k is 1 to 40. R ₅ is hydrogen or a CH ₃ group. }
And the following general formula (2):
{In the formula, R ₆ and R ₇ are each independently an alkylene group having 1 to 4 carbon atoms, and when R ₆ and R ₇ are different from each other, — (R ₆ —O) — and — ( The repeating unit represented by R ₇ —O) — may constitute a block structure or a random structure. m and n are each independently 0 or a positive integer, and the sum of m and n is 1 to 40. R ₈ and R ₉ are each independently hydrogen or a CH ₃ group. }
The negative photosensitive resin composition of Claim 1 which is at least 1 type of compound selected from the group which consists of a compound represented by these.   The (a) alkaline aqueous solution-soluble resin is at least one alkaline aqueous solution-soluble resin selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, polyamide, polyamic acid, polyamic acid ester, novolac resin, and epoxy resin. The negative photosensitive resin composition of Claim 1 or 2. The (a) alkaline aqueous solution-soluble resin has the following general formula (3):
{Wherein R ₁₀ is an organic group having an aromatic ring, and R ₁₁ is an aromatic group, an alicyclic group, or an aliphatic group having 2 to 10 carbon atoms. }
The negative photosensitive resin composition of any one of Claims 1-3 which is a polyamide which has a repeating unit represented by these. The photosensitive resin layer formation process which forms the photosensitive resin layer which consists of a negative photosensitive resin composition of any one of Claims 1-4 on a board | substrate,
An exposure step of exposing the photosensitive resin layer with actinic rays;
A heating step of heating the exposed photosensitive resin layer;
A method for producing a cured relief pattern, comprising: a developing step of developing the heated photosensitive resin layer to form a relief pattern; and a heating and curing step of heating the obtained relief pattern to form a cured relief pattern.   A semiconductor device having a cured relief pattern formed on a silicon wafer substrate or a copper wafer substrate by the method for producing a cured relief pattern according to claim 5.   The manufacturing method of the semiconductor device which contains the manufacturing method of the hardening relief pattern of Claim 5 as a part of process.