JP4925732B2 - Positive photosensitive resin composition - Google Patents

Description

  The present invention provides a positive photosensitive resin composition that is a precursor of a heat resistant resin used as a surface protective film and an interlayer insulating film of a semiconductor device, and has heat resistance using the positive photosensitive resin composition. The present invention relates to a method for manufacturing a cured relief pattern and a semiconductor device having the cured relief pattern.

  Polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like are widely used for surface protection films and interlayer insulating films of semiconductor devices. The polyimide resin is currently generally provided in the form of a photosensitive polyimide precursor composition. In the process of manufacturing a semiconductor device, the precursor composition is applied to a substrate such as a silicon wafer, patterned with actinic rays, developed, and subjected to a thermal imidization treatment to become a part of the semiconductor device. A surface protective film, an interlayer insulating film, or the like can be easily formed. Therefore, the manufacturing process of a semiconductor device using a photosensitive polyimide precursor composition is a manufacturing process using a conventional non-photosensitive polyimide precursor composition that needs to be patterned by a lithography method after forming a surface protective film or the like. Compared with the process, it has the feature that the process can be greatly shortened.

By the way, the conventional photosensitive polyimide precursor composition needs to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the development process. Measures to remove organic solvents have been demanded. In response to this, recently, various proposals have been made on heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution, as with photoresists.
Among them, a PBO precursor composition in which an alkaline aqueous solution-soluble hydroxypolyamide that becomes a heat-resistant resin after curing, for example, a polybenzoxazole (hereinafter also referred to as PBO) precursor, is mixed with a photoacid generator such as a photosensitive diazoquinone compound. In recent years, a method of using it as a positive photosensitive resin composition has attracted attention (see, for example, Patent Document 1).

The development mechanism of this positive photosensitive resin composition is such that the photosensitive diazoquinone compound and the PBO precursor in the unexposed area have a low dissolution rate in an alkaline aqueous solution, whereas the photosensitive diazoquinone compound is converted to indenecarboxylic by exposure. This is based on the fact that the dissolution rate in the alkaline aqueous solution of the exposed portion is increased by chemically changing to an acid compound. By utilizing the difference in the dissolution rate with respect to the developer between the exposed portion and the unexposed portion, a relief pattern composed of the unexposed portion can be created.
The PBO precursor composition described above can form a positive relief pattern by exposure and development with an alkaline aqueous solution. Further, heat generates an oxazole ring, and the cured PBO film has the same thermosetting film characteristics as a polyimide film. Therefore, the PBO precursor composition is a promising organic solvent development type polyimide precursor composition. Has attracted attention as an alternative material.

On the other hand, the transition of packaging methods for semiconductor devices using the PBO film material is also remarkable. Instead of the conventional LOC package that connects a lead frame to a semiconductor device with a gold wire, in recent years, there is a tendency to make the package into a multi-layer wiring from the viewpoint of improvement of integration degree and function and miniaturization of chip size. There has also been a technique in which rewiring is performed on the upper layer of the PBO film material and the PBO film material is laminated again. For this reason, this PBO film material is required to have good adhesion to a rewiring metal, particularly copper. As a conventional method for improving the adhesion to a substrate made of silicon, there is a method of adding a coupling agent such as an alkoxysilane compound to the composition. However, the coupling agent has a problem that sufficient adhesion to a copper substrate cannot be obtained (see, for example, Patent Document 2).
In addition, in the polyamic acid composition that is a polyimide precursor, it is known to add a copper ion reaction inhibitor such as benzotriazole or tetrazole for the purpose of rust prevention when contacting a copper metal (for example, patents). Reference 3).

Japanese Examined Patent Publication No. 63-096162 Japanese Patent No. 3449858 Japanese Patent Laid-Open No. 10-228107

  The present invention relates to a positive photosensitive resin composition capable of obtaining a cured film having excellent positive lithography performance such as sensitivity and resolution and excellent adhesion to a copper substrate, and a cured relief using the composition. It is an object of the present invention to provide a pattern manufacturing method and a semiconductor device having the cured relief pattern.

（式中、Ｘ₁ は少なくとも２個以上の炭素原子を有する４価の有機基であり、Ｘ₂ 、Ｙ₁ およびＹ₂ はそれぞれ独立に少なくとも２個以上の炭素原子を有する２価の有機基であり、ｍは２〜１０００の整数であり、ｎは０〜５００の整数であって、ｍ／（ｍ＋ｎ）＞０．５である。なお、Ｘ₁ およびＹ₁ を含むｍ個のジヒドロキシジアミド単位、並びにＸ₂ およびＹ₂ を含むｎ個のジアミド単位の配列順序は問わない。）
（Ｃ−７）４−カルボキシベンゾトリアゾール
（Ｃ−８）下式で表されるベンゾトリアゾール誘導体

（Ｃ−９）下式で表されるベンゾトリアゾール誘導体

（Ｃ−１０）下式で表されるベンゾトリアゾール誘導体

As a result of intensive studies to solve the above-mentioned problems, the present inventors have established a positive photosensitive resin that solves the above-mentioned problems by combining a hydroxy polyamide having a specific structure with a compound having a heterocyclic structure. The inventors have found that a composition can be obtained, and have made the present invention.
That is, the first of the present invention is (A) 100 parts by mass of a hydroxy polyamide having a repeating unit represented by the following general formula (1), (B) a photoacid generator 1 to 50 which is a compound having a naphthoquinonediazide structure. And at least one heterocyclic compound selected from the group consisting of parts by mass, (C) a compound having a tetrazole structure, a compound having an oxazole structure , and the following ( C-7) to (C-10), A positive photosensitive resin composition comprising 0.1 to 30 parts by mass of a heterocyclic ring-containing compound excluding mercaptobenzoxazole.

Wherein X ₁ is a tetravalent organic group having at least 2 or more carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having at least 2 carbon atoms. M is an integer of 2 to 1000, n is an integer of 0 to 500, and m / (m + n)> 0.5, where m dihydroxydiamides including X ₁ and Y ₁ The order of arrangement of the n diamide units including the units and X ₂ and Y ₂ is not limited.)
(C-7) 4-Carboxybenzotriazole (C-8) A benzotriazole derivative represented by the following formula

(C-9) A benzotriazole derivative represented by the following formula

(C-10) A benzotriazole derivative represented by the following formula

In the positive photosensitive resin composition of the present invention, the photoacid generator is preferably a compound having a naphthoquinonediazide structure. The heterocyclic ring-containing compound is preferably a compound having at least one heterocyclic structure selected from the group consisting of triazole, tetrazole, oxazole, thiazole, and imidazole.
The second aspect of the present invention is that (1) the positive photosensitive resin composition described above is formed on a substrate in the form of a layer or film, and (2) exposure with actinic radiation through a mask, A method for producing a cured relief pattern, which comprises directly irradiating an electron beam or an ion beam, (3) dissolving and removing an exposed portion or an irradiated portion, and (4) heat-treating the obtained relief pattern.
Furthermore, a third aspect of the present invention is a semiconductor device having the above-described cured relief pattern layer.

  ADVANTAGE OF THE INVENTION According to this invention, not only is it excellent in positive lithography performance such as sensitivity and resolution, but also a positive photosensitive resin composition having good adhesion to a copper substrate, and a cured relief using the positive photosensitive resin composition A pattern manufacturing method and a semiconductor device having the cured relief pattern are provided.

<Positive photosensitive resin composition>
Each component which comprises the positive photosensitive resin composition of this invention is demonstrated concretely below.
(A) Hydroxypolyamide Hydroxypolyamide, which is the base polymer of the positive photosensitive resin composition of the present invention, has a repeating unit represented by the following general formula (1) and has a structure of Y ₁ (COOH) _2. Essentially, m dihydroxydiamide units obtained by polycondensation of dicarboxylic acid and bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ are essential. Here, the two groups of amino group and hydroxy group of the bisaminophenol are each in the ortho position, and the hydroxy polyamide is heated to about 280 to 400 ° C. to close the ring, It changes to some polybenzoxazole. m is preferably in the range of 2 to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 20.

該ヒドロキシポリアミドには、必要に応じて、上記一般式（１）のジアミド単位ｎ個を縮合させてもよい。該ジアミド単位は、Ｘ₂ （ＮＨ₂ ）₂ の構造を有するジアミンおよびＹ₂ （ＣＯＯＨ）₂ の構造を有するジカルボン酸を重縮合させて得ることができる。ｎは０〜５００の範囲が好ましく、０〜１０の範囲がより好ましい。ヒドロキシポリアミド中における上記のジヒドロキシジアミド単位の割合が高いほど現像液として使用するアルカリ性水溶液への溶解性が向上するので、ｍ／（ｍ＋ｎ）の値は０．５以上であることが好ましく、０．７以上であることがより好ましく、０．８以上であることが最も好ましい。

If necessary, the hydroxypolyamide may be condensed with n diamide units of the above general formula (1). The diamide unit can be obtained by polycondensation of a diamine having a X ₂ (NH ₂ ) ₂ structure and a dicarboxylic acid having a Y ₂ (COOH) ₂ structure. n is preferably in the range of 0 to 500, and more preferably in the range of 0 to 10. The higher the proportion of the above-mentioned dihydroxydiamide units in the hydroxypolyamide, the better the solubility in an alkaline aqueous solution used as a developer. Therefore, the value of m / (m + n) is preferably 0.5 or more. It is more preferably 7 or more, and most preferably 0.8 or more.

Examples of the bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 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- ( -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-dihydroxybenzene, and 1,3 -Diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used alone or in combination.

Of these bisaminophenols having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , X ₁ is preferably an aromatic group selected from the following.

Examples of the diamine having the structure of X ₂ (NH ₂ ) ₂ include aromatic diamine and silicon diamine.
Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, Imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4,4′-diamino Phenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4 '-Diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-amino) Phenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, and 4, 4′-diaminobenzanilide and the like, and the hydrogen atom of the aromatic nucleus of these aromatic diamines is at least selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group A compound substituted by a kind of group or atom is mentioned.

Moreover, in order to improve adhesiveness with a base material, silicon diamine can be selected as a part or all of the diamine having the structure of X ₁ (NH ₂ ) ₂ , and examples thereof include bis (4-amino Phenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyl) Dimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, and the like.

〔式中、Ａは、−ＣＨ₂ −、−Ｏ−、−Ｓ−、−ＳＯ₂ −、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ₃ ）₂ −からなる群から選択される２価の基である。〕 Examples of the dicarboxylic acid having Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ structures include the case where Y ₁ and Y ₂ are aromatic groups selected from the following.

[In the formula, A is a divalent group selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —. It is the basis of. ]

Moreover, it is also preferable that a part of the dicarboxylic acid having the Y ₁ (COOH) ₂ and / or Y ₂ (COOH) ₂ structure is a derivative of 5-aminoisophthalic acid. The hydroxypolyamide of the present invention containing the derivative as a part of dicarboxylic acid becomes a copolymer composed of polyamide and polybenzoxazole crosslinked with a 5-aminoisophthalic acid moiety by heat treatment, and is used in the manufacturing process of a semiconductor device. TMAH solution (96 g of dimethyl sulfoxide, 4 g of tetramethylammonium hydroxide pentahydrate) and stripping solution (manufactured by Dynaloy; Uresolve SG: 80% methoxyethanol, 15% N-methylpyrrolidone, 5% potassium hydroxide) Chemical resistance against chemicals such as is improved.

  Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivative include 5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3, 6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1 -Cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, allyl succinic anhydride , Isocyanate ethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 3-cyclohexene-1-carboxylic acid chloride, 2-furancarboxylic acid chloride, crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propiolic acid chloride, tetrolic acid chloride, thiophene 2-acetyl chloride, p -Styrenesulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, chloroformate methyl ester, chloroformate ethyl ester, chloroformate n-propyl ester, chloroformate isopropyl ester, chloroformate isobutyl ester, 2-ethoxy chloroformate Ester, chloroformate-sec-butyl ester, chloroformate benzyl ester, chloroformate 2-ethylhexyl ester, chloroformate allyl ester, chloroformate phenyl ester, chloroformate 2,2,2-trichloroethyl ester, chloroformate-2-butoxyethyl ester, chloroformate-p-nitrobenzyl ester, chloroformate-p-methoxybenzyl ester, chloroformate isobornylbenzyl ester, chloro Chloroformic acid esters such as formic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di -T-butyl-dicarbonate, N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosila , Hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) Urea, phenyl isocyanate, n-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, and cis-1,2-cyclohexanedicarboxylic anhydride, glutaric anhydride , Etc.

〔式中、Ｂは、−ＣＨ₂ −、−Ｏ−、−Ｓ−、−ＳＯ₂ −、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ₃ ）₂ −からなる群から選択される２価の基である。〕 Furthermore, as a dicarboxylic acid having a Y ₁ (COOH) _{2 or} Y ₂ (COOH) ₂ structure, a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol or a monoamine can be used. Examples of monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, and benzyl alcohol. Examples of monoamine include butylamine and aniline. The following are mentioned as an example of tetracarboxylic acid.

[Wherein, B is a divalent group selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —. It is the basis of. ]

（式中、Ｘ₃ は上述のビスアミノフェノールを表す。） Alternatively, tetracarboxylic dianhydride can be reacted with bisaminophenol or diamine, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.
Alternatively, trimellitic acid chloride can be reacted with bisaminophenol to produce a tetracarboxylic dianhydride, which can be used as a dicarboxylic acid by ring opening in the same manner as the above tetracarboxylic anhydride. it can. Examples of the tetracarboxylic dianhydride obtained here include the following.

(In the formula, X ₃ represents the above-mentioned bisaminophenol.)

As the polycondensation method of dicarboxylic acid and bisaminophenol, dicarboxylic acid is converted to diacid chloride using thionyl chloride and then bisaminophenol is allowed to act, or dicarboxylic acid and bisaminophenol are converted to dicyclohexylcarbodiimide. And the like. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.
In the hydroxypolyamide having the repeating unit represented by the general formula (1), it is also preferable to use the end group sealed with an organic group (hereinafter referred to as a sealing group). In the polycondensation of hydroxypolyamide, when the dicarboxylic acid component is used in an excess number of moles compared to the sum of the bisaminophenol component and the diamine component, an amino group or a compound having a hydroxyl group is used as the sealing group. Is preferred. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate.

  Conversely, when the sum of the bisaminophenol component and the diamine component is used in an excessive number of moles compared to the dicarboxylic acid component, the sealing group has an acid anhydride, carboxylic acid, acid chloride, isocyanate group, etc. It is preferable to use a compound. Examples of such compounds include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methyl cyclohexane dicarboxylic anhydride Products, cyclohexene dicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, and tosyl chloride.

(B) Photoacid generator As the photoacid generator contained in the positive photosensitive resin composition of the present invention, a photosensitive diazoquinone compound, an onium salt, a halogen-containing compound, and the like can be used. Compounds are preferred.
Examples of the onium salt include iodonium salts, sulfonium salts, fosiphonium salts, phosphonium salts, ammonium salts, and diazonium salts. An onium selected from the group consisting of diaryl iodonium salts, triaryl sulfonium salts, and trialkyl sulfonium salts. Salts are preferred.
Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferable.
The photosensitive diazoquinone compound is a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure. US Pat. No. 2,772,972, US Pat. No. 2,797,213 It is a known substance according to the specification and US Pat. No. 3,669,658. A compound having a naphthoquinone diazide structure is preferable, and examples thereof include the following compounds having a naphthoquinone diazide structure.

（式中、Ｑは、水素原子またはナフトキノンジアジドスルホン酸エステル基であり、すべてのＱが同時に水素原子であることはない。）

(In the formula, Q is a hydrogen atom or a naphthoquinone diazide sulfonate group, and all Qs are not hydrogen atoms at the same time.)

光酸発生剤のヒドロキシポリアミドに対する配合量は、該ヒドロキシポリアミド１００質量部に対し、１〜１００質量部が好ましく、１０〜３０質量部がより好ましい。光酸発生剤（感光性ジアゾキノン化合物）の配合量が１質量部以上だと樹脂のパターニング性が良好であり、１００質量部以下だと硬化後の膜の引張り伸び率が良好、かつ露光部の現像残渣（スカム）が少ない。 Preferred naphthoquinonediazide sulfonic acid ester groups include the following.

1-100 mass parts is preferable with respect to 100 mass parts of this hydroxy polyamide, and, as for the compounding quantity with respect to hydroxy polyamide of a photo-acid generator, 10-30 mass parts is more preferable. When the blending amount of the photoacid generator (photosensitive diazoquinone compound) is 1 part by mass or more, the patterning property of the resin is good, and when it is 100 parts by mass or less, the tensile elongation of the cured film is good and Less development residue (scum).

(C) Heterocycle-containing compound The heterocycle-containing compound used in the present invention is a ring structure in which at least one carbon atom of a 5-membered ring or 6-membered ring compound is substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. Refers to a compound having
Specifically, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 1,3-dimethyl-5-pyrazolone, 3,5-dimethylpyrazole, 5,5-dimethylhydantoin, 3-methyl-5-pyrazolone, 3 -Methyl-1-phenyl-5-pyrazolone, 2-methylimidazole, 1,10-phenanthroline, phenothiazine, phenoxazine, phenoxatin, mercaptobenzothiazole, mercaptobenzoxazole, methylthiobenzothiazole, dibenzothiazyl disulfide, methylthiobenzimidazole, Examples include benzimidazole, phenyl mercaptothiazoline, mercaptophenyl tetrazole, and mercaptomethyl tetrazole. Moreover, the following are mentioned as an example of benzotriazole.

（式中、Ｒ₁ 、Ｒ₂ はそれぞれ一価の有機基であり、それぞれ下記の式で表されるが、これらに限定されるものではない。）

(In the formula, each of R ₁ and R ₂ is a monovalent organic group and is represented by the following formula, but is not limited thereto.)

Among the heterocyclic ring-containing compounds, compounds having at least one heterocyclic structure selected from the group consisting of triazole, tetrazole, oxazole, thiazole, and imidazole are preferable, and 5-mercapto-1-phenyltetrazole, 1, 2, A compound selected from the group consisting of 3-benzotriazole, benzothiazole, benzoxazole, benzimidazole, and 2-mercaptobenzoxazole is more preferable.
These heterocycle-containing compounds may be used alone or in combination of two or more.
0.1-30 mass parts is preferable with respect to 100 mass parts of this hydroxy polyamide, and, as for the compounding quantity with respect to hydroxy polyamide of a heterocyclic containing compound, 0.5-10 mass parts is more preferable. When the compounding amount of the heterocyclic ring-containing compound is 1 part by mass or more, the adhesiveness of the film after thermosetting to the copper substrate is good, and when it is 30 parts by mass or less, the stability of the composition is good.

(D) Other additives For the positive photosensitive resin composition of the present invention, phenol compounds, dyes, surfactants, and stabilizers known as additives for the positive photosensitive resin composition are optionally added. It is also possible to add an agent and / or an adhesion aid for enhancing the adhesion to the silicon wafer.
More specifically, the phenol compound includes ballast agents used in the photosensitive diazoquinone compound, paracumylphenol, bisaminophenol, resorcinol, and the like. By adding the phenol compound, the adhesion of the relief pattern during development can be improved and the generation of residues can be suppressed. In addition, a ballast agent means the phenol compound currently used as a raw material for the photosensitive diazoquinone compound which is a phenol compound by which some phenolic hydrogen atoms were naphthoquinone diazide sulfonate esterified.
When adding a phenol compound, 0-50 mass parts is preferable with respect to 100 mass parts of hydroxy polyamide, and 1-30 mass parts is preferable. When the addition amount is within 50 parts by mass, the heat resistance of the film after thermosetting is good.

Examples of the surfactant include polypropylene glycol, polyglycols such as polyoxyethylene lauryl ether, and nonionic surfactants made of derivatives thereof. Further, fluorine-based surfactants such as Fluorard (trade name, manufactured by Sumitomo 3M), MegaFac (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), or Sulflon (trade name, manufactured by Asahi Glass Co., Ltd.) can be used. Furthermore, organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corp.), or granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) can be mentioned. By adding the surfactant, it is possible to make it more difficult for the coating film to be repelled at the wafer edge during coating.
When the surfactant is added, the addition amount is preferably 0 to 10 parts by mass and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the hydroxy polyamide. If the addition amount is within 10 parts by mass, the heat resistance of the film after thermosetting is good.
Examples of the adhesion aid include various silane coupling agents such as alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy polymer, and epoxy silane.
The addition amount in the case of adding an adhesion assistant is preferably 0 to 30 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the hydroxy polyamide. If the addition amount is within 30 parts by mass, the heat resistance of the film after thermosetting is good.

In the present invention, these components are preferably dissolved in a solvent to form a varnish and used as a positive photosensitive resin composition. Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone (hereinafter also referred to as GBL), cyclopentanone, cyclohexanone, isophorone, N, N-dimethylacetamide (hereinafter also referred to as DMAc), and the like. Dimethyl sulfoxide, diethylene glycol dimethyl ether (hereinafter also referred to as DMDG), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 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, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate , It can be used individually or as a mixture of methyl 3-methoxy propionate or the like. Of these solvents, non-amide solvents are preferred because they have little influence on the photoresist. Specific preferred examples include γ-butyrolactone, cyclopentanone, cyclohexanone and isophorone.
The addition amount of the solvent is preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the hydroxy polyamide. The addition amount of the solvent is preferably set to a viscosity suitable for the coating apparatus and the coating thickness within the above range, because the production of the cured relief pattern can be facilitated.

<Curing relief pattern and method for manufacturing semiconductor device>
Next, the manufacturing method of the cured relief pattern of the present invention will be specifically described below.
First, the positive photosensitive resin composition of the present invention is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spinner or a coater such as a die coater or a roll coater. To do. This is dried at 50 to 140 ° C. using an oven or a hot plate to remove the solvent.
Second, exposure with actinic radiation is performed through a mask using a contact aligner or a stepper, or light, electron beam, or ion beam is directly irradiated.
Third, the exposed portion or the irradiated portion is dissolved and removed with a developing solution, followed by rinsing with a rinsing solution to obtain a desired relief pattern. As a developing method, a spray, paddle, dip, or ultrasonic method can be used. As the rinsing liquid, distilled water, deionized water or the like can be used.

The developer used for developing the film formed from the positive photosensitive resin composition of the present invention is for dissolving and removing the alkali-soluble polymer and needs to be an alkaline aqueous solution in which an alkali compound is dissolved. is there. The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.
Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. , 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, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine, etc. are mentioned.

Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, and a resin dissolution inhibitor can be added to the alkaline aqueous solution. .
Finally, the obtained relief pattern can be heat-treated to form a heat-resistant cured relief pattern made of a resin having a polybenzoxazole structure.
The semiconductor device of the present invention uses the cured relief pattern of the present invention as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, or a protective film for a device having a bump structure. It can manufacture by combining with the manufacturing method of an apparatus.
The positive photosensitive resin composition of 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, or liquid crystal alignment films.

Hereinafter, the present invention will be described more specifically based on reference examples and examples. However, the present invention is not limited to these examples.
<Synthesis of hydroxy polyamide>
[Reference Example 1]
In a 2 liter separable flask, 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 75.9 g (0.96 mol) of pyridine, and 692 g of DMAc were added. The mixture was stirred and dissolved at room temperature (25 ° C.). A solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 88 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.
After completion of the dropwise addition, the mixture was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to confirm that characteristic absorption of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared.

Next, this was cooled to 8 ° C. with a water bath, and a solution obtained by dissolving 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 398 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of the dropwise addition, the reaction solution was dropped into 12 liters of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated and then vacuum-dried. 1) was obtained. The weight average molecular weight of the thus synthesized hydroxypolyamide by GPC was 14,000 in terms of polystyrene. The analysis conditions for GPC are described below.
Column: manufactured by Showa Denko KK, trade name: Shodex 805/804/803 in series Separation: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko, Trade name: Shodex RI SE-61

[Reference Example 2]
In a 1-liter three-necked flask, 18.1 g (0.10 mol) of 5-aminoisophthalic acid was dissolved in 200 g of N-methyl-2-pyrrolidone and 15.8 g (0.20 mol) of pyridine, and dissolved in 36 g of γ-butyrolactone. 11.9 g (0.11 mol) of ethyl chloroformate was added dropwise, and the mixture was stirred at room temperature for 2 hours. This was ice-cooled to 0 ° C., and 35.7 g of thionyl chloride (0.30 mol) dissolved in 105 g of γ-butyrolactone was added dropwise so as not to exceed 10 ° C. over 30 minutes. After stirring for 1 hour while cooling with ice so as not to exceed 10 ° C., the temperature was returned to room temperature, and unreacted thionyl chloride and by-product sulfurous acid gas were distilled off using a vacuum pump. This solution is designated as reaction solution 1.
Next, 90 g of γ-butyrolactone was dissolved in 29.5 g (0.10 mol) of 4,4′-oxybisbenzoic acid dichloride in a 0.5 liter Erlenmeyer flask. This solution is designated as reaction solution 2.

In a 2-liter separable flask, 80.6 g (0.22 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 283 g of dried N-methyl-2-pyrrolidone, and pyridine 31 After adding .6 g (0.40 mol), the mixture was cooled to 0 ° C., the reaction solution 1 and the reaction solution 2 were transferred to separate dropping funnels, and the reaction solution 1 and the reaction solution 2 were added dropwise simultaneously. After completion of dropping, the temperature was returned to room temperature and stirred for 2 hours. The reaction solution was transferred to a 10 liter beaker, and 5 liters of distilled water was added to the reaction solution to precipitate the produced polymer. The supernatant solution was removed, and 1.5 liters of tetrahydrofuran was added to redissolve. Further, 5 liters of distilled water was added to precipitate the produced polymer. The supernatant solution was removed, and 1.5 liters of tetrahydrofuran was added to redissolve. After performing this operation once again, the solution was dropped into 10 liters of distilled water through a column filled with anion exchange resin and cation exchange resin substituted with tetrahydrofuran, and the precipitate was collected by filtration at 40 ° C. Hydroxy polyamide (P-2) was obtained by vacuum drying for 48 hours. The weight average molecular weight in terms of polystyrene of P-2 measured by GPC was 12000 (Mw). The analysis conditions for GPC are described below.
Column: manufactured by Showa Denko KK, trade name: Shodex 805/804/803 in series Separation: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko, trade name: Shodex RI SE-61

[Reference Example 3]
In a 1-liter separable flask, 109.9 g (0.3 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 330 g of tetrahydrofuran (THF), 47.5 g of pyridine (0.6 mol) ), And 98.5 g (0.6 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added in powder form at room temperature. After stirring for 3 days at room temperature, the reaction was confirmed by HPLC. As a result, no starting material was detected and the product was detected as a single peak with a purity of 99%. This reaction solution was dropped as it was into 1 liter of ion-exchanged water with stirring, and the precipitate was filtered off, and then 500 ml of THF was added and dissolved by stirring. This homogeneous solution was dissolved in a cation exchange resin: Amberlyst 15 (organo) Residual pyridine was removed through a glass column packed with 100 g. Next, this solution was dropped into 3 liters of ion-exchanged water under high-speed stirring to precipitate a product, which was filtered off and then vacuum-dried.
The product is imidized, appear characteristic absorption of an imide group 1394Cm ^-1 and 1774 cm ^-1 in the IR spectrum, the absence of a characteristic absorption of amide groups in the vicinity of 1540 cm ^-1 and 1650 cm ^-1, and NMR The spectrum was confirmed by the absence of amide and carboxylic acid proton peaks.

Next, 65.9 g (0.1 mol) of the product, 53.7 g (0.2 mol) of 1,2-naphthoquinonediazide-4-sulfonyl chloride and 560 g of acetone were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 21.2 g (0.21 mol) of triethylamine with 106.2 g of acetone was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.
After completion of the dropwise addition, the mixture was allowed to stir at 20 ° C. for another 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. The reaction solution was then cooled in an ice water bath, and the precipitated solid was filtered off with suction. . The filtrate obtained at this time was added dropwise to 5 liters of a 0.5 wt% aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was again dispersed in 5 liters of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like product obtained was vacuum-dried at 40 ° C. for 24 hours to obtain a photosensitive diazoquinone compound (Q-1).

[Reference Example 4]
102.4 g (0.92 mol) of resorcinol and 92.0 g (0.92 mol) of hexanal were dissolved in 920 ml of ethanol. This was cooled to 0 ° C. and 148 ml of 12N hydrochloric acid was added dropwise and stirred. The mixture was then stirred at 70 ° C. for 10 hours under a nitrogen atmosphere. After reaching room temperature, the precipitate was removed by filtration. The solid obtained by washing the filtrate with water at 80 ° C. and drying was recrystallized with a mixed solvent of methanol, hexane and acetone. Thereafter, vacuum drying was performed to obtain a resorcin cyclic tetramer with a yield of 50%.
Next, 76.9 g (0.1 mol) of the resorcin cyclic tetramer obtained earlier, 134.3 g (0.5 mol, naphthoquinone diazide sulfonic acid esterification rate of 1,2-naphthoquinonediazide-4-sulfonyl chloride 62 0.55 equivalent) and 1057 g of tetrahydrofuran were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 53.1 g (0.525 mol) of triethylamine with 266 g of tetrahydrofuran was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath. After completion of the dropwise addition, the mixture was left to stir at 20 ° C. for another 30 minutes, and then 6.8 g of a 36 wt% hydrochloric acid aqueous solution was added at once. The reaction solution was then cooled in an ice water bath, and the precipitated solid was filtered off with suction. .
The filtrate obtained at this time was added dropwise to 10 liters of a 0.5 wt% aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was again dispersed in 5 liters of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like product obtained was vacuum-dried at 40 ° C. for 24 hours to obtain the desired photosensitive diazoquinone compound (Q-2).

<Preparation of positive photosensitive resin composition>
[Examples 1 , 3 , 6, Reference Examples 2, 4, 5, 7, 8, 14, Examples 9 to 13 , Comparative Example 1]
100 parts by mass of hydroxypolyamide (P-1 or P-2) obtained in Reference Example 1 or 2 above, photosensitive diazoquinone compound (Q-1 or Q-2) obtained in Reference Example 3 or 4 above 20 parts by mass and the following C-1 to C-10 heterocycle-containing compounds (Examples 1 , 3 , 6, Reference Examples 2, 4, 5, 7, 8, 14, Examples 9 to 13 ) or C After dissolving 3 parts by mass of a silane compound having a structure of -11 (Comparative Example 1) in 170 parts by mass of GBL, it was filtered through a 0.2 μm filter, and Examples 1 , 3 , and 6 described in Table 1 were used. The positive photosensitive resin compositions of Examples 2, 4, 5 , 7 , 8, 14, Examples 9 to 13 and Comparative Example 1 were prepared.
(C-1) 5-mercapto-1-phenyltetrazole (C-2) 1,2,3-benzotriazole (C-3) benzothiazole (C-4) benzoxazole (C-5) benzimidazole (C- 6) 2-mercaptobenzoxazole (C-7) 4-carboxybenzotriazole

(C-8) A benzotriazole derivative represented by the following formula

(C-9) A benzotriazole derivative represented by the following formula

(C-10) A benzotriazole derivative represented by the following formula

(C-11) Silane compound represented by the following formula

<Evaluation of positive photosensitive resin composition>
(1) Evaluation of patterning characteristics The positive photosensitive resin compositions of the above examples and comparative examples were spin-coated on a 5-inch silicon wafer by a spin coater (Dspin 636, manufactured by Dainippon Screen Mfg. Co., Ltd.) and hot plate Pre-baking was performed at 130 ° C. for 180 seconds to form a coating film having a thickness of 8.0 μm. The film thickness was measured with a film thickness measuring device (Lambda Ace, manufactured by Dainippon Screen Mfg. Co., Ltd.).
The coating film was exposed with a stepper (Nikon Corporation, NSR2005i8A) having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern while changing the exposure stepwise. Using an alkali developer (manufactured by Clariant Japan, AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution), the development time was adjusted so that the film thickness after development was 6.6 μm under the condition of 23 ° C. After adjusting and developing, rinsing with pure water was performed to form a positive relief pattern. The sensitivity and resolution of the positive photosensitive resin composition are shown in Table 2.
The sensitivity and resolution of the positive photosensitive resin composition were evaluated as follows.
[Sensitivity (mJ / cm ² )]
The minimum exposure amount that can completely dissolve and remove the exposed portion of the coating film during the development time.
[Resolution (μm)]
Minimum resolution pattern size at the above exposure.

(2) Adhesive evaluation to copper substrate 5 inches in which a copper thin film was previously formed by sputtering the positive type photosensitive resin compositions of the above examples and comparative examples with a spin coater (Dainippon Screen Mfg. Co., Ltd .; Dspin 636). A silicon wafer was spin-coated and prebaked at 120 ° C. for 180 seconds with a hot plate to form a coating film having a thickness of 11.0 μm. In a vertical curing furnace (manufactured by Koyo Lindberg), curing (heat curing treatment) was performed at 350 ° C. for 1 hour in a nitrogen atmosphere to obtain a polybenzoxazole (PBO) film as a heat-resistant coating. This is cut into 100 squares of 1 mm square, and cellophane tape is attached and peeled off, and the number of grids with the film remaining on the copper substrate is evaluated.
The evaluation results are shown in Table 2. The composition of the present invention exhibited a sufficient value not only for sensitivity resolution but also for adhesion on a copper substrate.

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

Claims (4)

(A) 100 parts by mass of a hydroxypolyamide having a repeating unit represented by the following general formula (1), (B) 1 to 50 parts by mass of a photoacid generator that is a compound having a naphthoquinonediazide structure, and (C) a tetrazole structure. A compound having an oxazole structure , and at least one heterocyclic compound selected from the group consisting of the following ( C-7) to (C-10), except for 2-mercaptobenzoxazole. A positive photosensitive resin composition comprising 0.1 to 30 parts by mass of a compound.

Wherein X ₁ is a tetravalent organic group having at least 2 or more carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having at least 2 carbon atoms. M is an integer of 2 to 1000, n is an integer of 0 to 500, and m / (m + n)> 0.5, where m dihydroxydiamides including X ₁ and Y ₁ The order of arrangement of the n diamide units including the units and X ₂ and Y ₂ is not limited.)
(C-7) 4-Carboxybenzotriazole (C-8) A benzotriazole derivative represented by the following formula

(C-9) A benzotriazole derivative represented by the following formula

(C-10) A benzotriazole derivative represented by the following formula

2. The positive photosensitive resin composition according to claim 1, wherein the heterocyclic ring-containing compound is at least one heterocyclic compound selected from the group consisting of a compound having a tetrazole structure and a compound having an oxazole structure. object.   (1) The positive photosensitive resin composition according to any one of claims 1 and 2 is formed on a substrate in the form of a layer or a film, and (2) exposure with actinic radiation through a mask, A method for producing a cured relief pattern, comprising directly irradiating a light beam, an electron beam or an ion beam, (3) dissolving and removing an exposed portion or an irradiated portion, and (4) heat-treating the obtained relief pattern.   The semiconductor device which has a hardening relief pattern layer obtained by the manufacturing method of Claim 3.