JP4627030B2 - 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. This polyimide resin is currently often 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, this photosensitive polyimide precursor composition requires the use of an organic solvent such as N-methyl-2-pyrrolidone as a developer in the development process. Countermeasures are being sought. In response, recently, various heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution have been proposed in the same manner as photoresists.
Among them, an alkaline aqueous solution-soluble hydroxypolyamide, for example, polybenzoxazole (hereinafter also referred to as “PBO”) precursor, which becomes a heat-resistant resin after curing, is mixed with a photoacid generator such as a photosensitive diazoquinone compound. A method of using the composition as a positive photosensitive resin composition has attracted attention in recent years as disclosed in, 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 including 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. Furthermore, since an oxazole ring is generated by heat and the cured PBO film has the same thermosetting film characteristics as a polyimide film, the PBO precursor composition is a promising organic solvent development type polyimide precursor composition. It is attracting attention as an alternative material.
However, the PBO precursor composition has a problem that the sensitivity is lower than that of the photosensitive polyimide precursor composition, and there is a demand for a more sensitive composition.
Therefore, as a composition for improving sensitivity and resolution, a method of adding a compound having at least one ester bond in the molecule as a solvent has been proposed. Specifically, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether are proposed. Acetate, ethoxyethyl propionate, and 3-methylmethoxypropionate are disclosed in Patent Document 2.

JP 63-096162 A JP 2005-189458 A

  The present invention relates to a positive photosensitive resin composition excellent in positive lithography performance such as sensitivity and resolution, a method for producing a cured relief pattern using the composition, and a semiconductor device having the cured relief pattern. The purpose is to provide.

（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。） The present inventor has found that a positive-type photosensitive resin composition that solves the above-mentioned problems can be obtained by combining an electron-donating group-containing acetic acid benzyl ester compound with a hydroxy polyamide having a specific structure. It came to.
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) 1 to 50 parts by mass of a photoacid generator, and (C) an alkoxy group. A positive photosensitive resin composition comprising 0.01 to 70 parts by mass of an acetic acid benzyl ester compound having any substituent selected from the group consisting of an alkyl group and a cyano group.

(In the formula, X ₁ is a tetravalent organic group having at least 2 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 dihydroxys including X ₁ and Y ₁ (The order of arrangement of the diamide units and n diamide units including X ₂ and Y ₂ is not limited.)

（式中、Ｒ₁ は少なくとも１個以上の炭素原子を有するアルキル基、及び不飽和基である。）

また、本発明の第二は、（１）上記のポジ型感光性樹脂組成物を層またはフィルムの形で基板上に形成し、（２）マスクを介して化学線で露光するか、光線、電子線またはイオン線を直接照射し、（３）露光部または照射部を溶出または除去し、（４）得られたレリーフパターンを加熱処理する、ことを特徴とする硬化レリーフパターンの製造方法である。
さらに、本発明の第三は、上述の製造方法により得られる硬化レリーフパターン層を有してなる半導体装置である。 In the composition of the present invention, the photoacid generator is preferably a compound having a naphthoquinonediazide structure. The acetic acid benzyl ester compound is preferably a compound represented by the following general formula (2), and more preferably a compound represented by the following general formula (3).

(In the formula, R ₁ is an alkyl group having at least one carbon atom and an unsaturated group.)

In the second aspect of the present invention, (1) the positive photosensitive resin composition described above 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, which comprises direct irradiation with an electron beam or ion beam, (3) elution or removal of an exposed portion or irradiated portion, and (4) heat treatment of the obtained relief pattern. .
Furthermore, a third aspect of the present invention is a semiconductor device having a cured relief pattern layer obtained by the above-described manufacturing method.

  According to the present invention, a positive photosensitive resin composition excellent in positive lithography performance such as sensitivity and resolution, a method for producing a cured relief pattern using the positive photosensitive resin composition, and the cured relief pattern are provided. A semiconductor device is 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 m dihydroxydiamide units of the following general formula (1). The dihydroxydiamide unit has a structure obtained by polycondensation of a dicarboxylic acid having a Y ₁ (COOH) ₂ structure and a bisaminophenol having a X ₁ (NH ₂ ) ₂ (OH) ₂ structure. The two amino groups and hydroxy groups of the bisaminophenol are each in the ortho position, and the hydroxypolyamide is closed by heating to about 280 to 400 ° C. to form a polybenz which is a heat resistant resin. Change to oxazole. 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 30.

The hydroxy polyamide may have n diamide units of the above general formula (1) as necessary. The diamide unit has a structure obtained by polycondensing a diamine having a structure of X ₂ (NH ₂ ) ₂ and a dicarboxylic acid having a structure of Y ₂ (COOH) ₂ . 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.
The order of arrangement of m dihydroxydiamide units containing X ₁ and Y ₁ and n diamide units containing X ₂ and Y ₂ is not limited.
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.

（式中、Ｘ₃ 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、前述したＸ₁ で示される有機基として好ましいものからなる群から選択される少なくとも１つの有機基であることが好ましい。） Further, as a compound having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , two pairs of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other (hereinafter referred to as “PBO precursor structure in the molecule”). Can also be used. For example, a diamine represented by the following formula obtained by reacting bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ with two molecules of nitrobenzoic acid and reducing it can be mentioned.

(In the formula, X ₃ is a tetravalent organic group having at least 2 carbon atoms, and is at least one organic group selected from the group consisting of preferable organic groups represented by X ₁ described above. Is preferred.)

（式中、Ｙ₃ は少なくとも２個以上の炭素原子を有する２価の有機基であり、後述するＹ₁ で示される有機基として好ましいものからなる群から選択される少なくとも１つの有機基であることが好ましい。） As another method for obtaining a diamine having a PBO precursor structure in the molecule, the dicarboxylic acid dichloride having the structure of Y ₃ (COCl) ₂ is reacted with two molecules of nitroaminophenol and reduced. There is also a method for obtaining a diamine.

(In the formula, Y ₃ is a divalent organic group having at least 2 carbon atoms, and is at least one organic group selected from the group consisting of preferable organic groups represented by Y ₁ described later. Is preferred.)

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 Ruoropuropan, 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′-diaminodiphenyl Urea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-a Minophenoxy) 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'-diaminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-amino Phenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-amino) Phenyl) fluorene, 4,4'-di- (3-aminophenoxy) diphenylsulfone, and 4,4'-diamidine At least one group selected from the group consisting of chlorine atoms, fluorine atoms, bromine atoms, methyl groups, methoxy groups, cyano groups, and phenyl groups, such as nobenzanilide and the aromatic nucleus of these aromatic diamines. Or the compound substituted by the 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 ₂ (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 −、及び単結合からなる群から選択される２価の基を示し、Ｒは、それぞれ独立に、水素原子、アルキル基、不飽和基、及びハロゲン原子からなる群から選択される基を示し、ｋは０〜４の整数を示す。） Examples of the dicarboxylic acid having Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ structures include dicarboxylic acids in which Y ₁ and Y ₂ are each selected from the following aromatic groups or aliphatic groups.

Wherein A is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and a single bond. R represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an unsaturated group, and a halogen atom, and k represents an integer of 0 to 4. )

A derivative of 5-aminoisophthalic acid can also be used for a part or all of the dicarboxylic acid having the Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ structures. 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 Chloroformic acid methyl ester, chloroformic acid ethyl ester, chloroformic acid n-propyl ester, chloroformic acid isopropyl ester, chloroformic acid isobutyl ester, chloroformic acid 2-ethoxy ester, chloroformic acid-sec-butyl ester, Benzyl chloroformate, 2-ethylhexyl chloroformate, allyl ester chloroformate, phenyl ester chloroformate, 2,2,2-trichloroethyl ester chloroformate, chloroformate -2-butoxyethyl ester, chloroformate-p-nitrobenzyl ester, chloroformate-p-methoxybenzyl ester, chloroformate isobornylbenzyl ester, chloroformate-p-biphenylisopropylbenzyl ester,

2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, S-t-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, trimethylchlorosilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoro Acetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, isocyanate , N-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, and cis-1,2-cyclohexanedicarboxylic anhydride, and glutaric anhydride. .

（式中、Ｂは、−ＣＨ₂ −、−Ｏ−、−Ｓ−、−ＳＯ₂ −、−ＣＯ−、−ＮＨＣＯ−、及び−Ｃ（ＣＦ₃ ）₂ −からなる群から選択される２価の基を意味する。）
または別法として、テトラカルボン酸二無水物とビスアミノフェノールもしくはジアミンを反応させて、生成するカルボン酸残基を、モノアルコールまたはモノアミンにより、エステル化またはアミド化することもできる。 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. Examples of the tetracarboxylic dianhydride include compounds represented by the following chemical formula.

Wherein B is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —. Means a valent group.)
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.

（式中、Ｘ₄ はＸ₁ （ＯＨ）₂ （ＮＨ−）₂ で表される２価の有機基を表す。） Also, trimellitic acid chloride is reacted with bisaminophenol to produce tetracarboxylic dianhydride, and ring-opened in the same manner as the above tetracarboxylic dianhydride and used as dicarboxylic acid You can also. Examples of the tetracarboxylic dianhydride obtained here include the following.

(In the formula, X ₄ represents a divalent organic group represented by X ₁ (OH) ₂ (NH—) ₂ ).

As a method of polycondensation of the dicarboxylic acid and bisaminophenol (diamine) to synthesize hydroxypolyamide, the dicarboxylic acid is converted to diacid chloride using thionyl chloride, and then bisaminophenol (diamine) acts. Or a method of polycondensation of dicarboxylic acid and bisaminophenol (diamine) with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.
In the hydroxypolyamide having a repeating unit represented by the general formula (1), it is also preferable to use the terminal group after sealing the end group 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.

（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。） 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 And U.S. 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.

(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、１〜５０質量部が好ましく、５〜３０質量部がより好ましい。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、５０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さ（スカム）が少ない。 Preferred naphthoquinone diazide sulfonic acid ester groups include the following groups.

1-50 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, 5-30 mass parts is more preferable. If the blending amount of the photosensitive diazoquinone compound is 1 part by mass or more, the patterning property of the resin is good, and if it is 50 parts by mass or less, the tensile elongation of the cured film is good and the development residue (scum) in the exposed part is high. Few.

(C) Acetic acid benzyl ester compound The acetic acid benzyl ester compound used in the present invention is preferably an acetic acid benzyl ester having any substituent selected from the group consisting of an alkoxy group, an alkyl group, and a cyano group. Specifically, acetic acid (4-methoxy) benzyl ester, acetic acid (4-ethoxy) benzyl ester, acetic acid (2-ethoxy) benzyl ester, acetic acid (3-cyano) benzyl ester, acetic acid (4-methyl) benzyl ester, Examples include acetic acid (3-methyl) benzyl ester, acetic acid (4-methyl) benzyl ester, and cyanoacetic acid benzyl. These acetic acid benzyl ester compounds may be used alone or in combination of two or more.
The blending amount of the above-mentioned acetic acid benzyl ester compound with respect to hydroxypolyamide is preferably 0.01 to 70 parts by mass, more preferably 0.1 to 50 parts by mass, and 1 to 30 parts by mass with respect to 100 parts by mass of the hydroxypolyamide. Particularly preferred. When the compounding amount of the acetic acid benzyl ester compound is 0.01 parts by mass or more, the development residue in the exposed part decreases, and when it is 70 parts by mass or less, the tensile elongation of the film after curing 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 about the additive, the phenol compound is a ballast agent used in the photosensitive diazoquinone compound, and a linear phenol compound such as paracumylphenol, bisphenols, resorcinol, or MtrisPC, MtetraPC. (Honshu Chemical Industry Co., Ltd .: trade name), non-linear phenolic compounds such as TrisP-HAP, TrisP-PHBA, TrisP-PA (Honshu Chemical Industry Co., Ltd .; trade name), 2 to 2 hydrogen atoms of the phenyl group of diphenylmethane Examples include compounds in which 5 are substituted with hydroxyl groups, and compounds in which 1 to 5 hydrogen atoms of the phenyl group of 2,2-diphenylpropane are substituted with hydroxyl groups. 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 above-mentioned photosensitive diazoquinone compound which is a phenol compound by which a part of phenolic hydrogen atom was 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. If 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, organic siloxane surfactants such as KP341 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name; manufactured by Chisso Corporation), or granol (trade name; manufactured by Kyoeisha Chemical Co., Ltd.) can be used. 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.
Specific preferred examples of the silane coupling agent include 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxy. Reaction of alkylsilane, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane with acid anhydride or acid dianhydride, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane The thing which converted the amino group into the urethane group and the urea group is mentioned. In this case, the alkyl group includes a methyl group, an ethyl group, a butyl group, the acid anhydride includes maleic anhydride, phthalic anhydride, the acid dianhydride includes pyromellitic dianhydride, 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, etc., urethane group is t-butoxycarbonylamino group, urea group is phenylaminocarbonylamino Groups and the like.
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 solvents 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”). ), Dimethylimidazolinone, tetramethylurea, dimethyl sulfoxide, diethylene glycol dimethyl ether (hereinafter also referred to as “DMDG”), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol Monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol Seteto, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, may be used alone 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 and the like. Specific preferred examples include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate and the like.
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. Apply. 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 is 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.

The present invention will be described more specifically based on reference examples and examples.
<Synthesis of hydroxy polyamide>
[Reference Example 1]
In a 2 L 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 at room temperature. (25 ° C.) The mixture was stirred and dissolved. 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 prepared by dissolving 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 398 g of DMDG was added dropwise from the 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. The polymer was recovered, appropriately washed with water and dehydrated, and then vacuum-dried. ) 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: Showa Denko Co., Ltd. Trade name: Shodex 805/804/803 in series Separation: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI SE-61

[Reference Example 2]
In a 1 l 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 (0.6 mol) of pyridine. Into this, 98.5 g (0.6 mol) of 5-norbornene-2,3-dicarboxylic 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%. The reaction solution was added dropwise to 1 liter of ion-exchanged water with stirring, and the precipitate was separated by filtration. To this, 500 ml of THF was added and dissolved by stirring. This homogeneous solution was dissolved in cation exchange resin: Amberlyst 15 (manufactured by Organo). ) The remaining pyridine was removed through a glass column packed with 100 g. Next, this solution was dropped into 3 l of ion-exchanged water under high-speed stirring to precipitate a product, which was filtered off and then vacuum-dried.
The product is imidized, it is not characteristic absorption of amide groups in the vicinity of 1540 cm ^-1 and 1650 cm ^-1 appear characteristic absorption of an imide group 1394Cm ^-1 and 1774 cm ^-1 in the IR spectrum is present, and NMR spectrum This 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 an additional 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. . The filtrate obtained at this time was added dropwise to 5 l of a 0.5% by weight 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 l 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).

<Preparation of positive photosensitive resin composition>
[Examples 1-4, Comparative Examples 1-3]
With respect to 100 parts by mass of the hydroxypolyamide (P-1) obtained in Reference Example 1, the photosensitive diazoquinone compound (Q-1) obtained in Reference Example 2 and the following C-1 to C- 5 parts of the acetic acid benzyl ester compound was dissolved in 170 parts by weight of GBL, and then filtered through a 0.2 μm filter. Type photosensitive resin composition was prepared.
(C-1) Acetic acid (4-methoxy) benzyl ester (C-2) Acetic acid (3-cyano) benzyl ester (C-3) Acetic acid (4-methyl) benzyl ester (C-4) Acetic acid benzyl ester (C- 5) Acetic acid (4-nitro) benzyl ester

<Evaluation of positive photosensitive resin composition>
(1) Evaluation of patterning characteristics The positive type photosensitive resin compositions of the above examples and comparative examples were spin-coated on a 5-inch silicon wafer with a spin coater (Daishin Screen Manufacturing Co., Ltd .: Dspin 636), and 120 on a hot plate. Pre-baking was performed at 180 ° C. for 180 seconds to form a coating film having a thickness of 11.5 μm. The film thickness was measured with a film thickness measuring device (Dainippon Screen Mfg. Co., Ltd .: Lambda Ace).
This coating film was exposed through a reticle with a test pattern by using a stepper (Nikon Corporation: NSR2005i8A) having an exposure wavelength of i-line (365 nm) while changing the exposure stepwise. Using an alkaline developer (manufactured by Clariant Japan Co., Ltd .: AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution), the development time was adjusted so that the film thickness after development was 9.8 μm under the condition of 23 ° C. After adjusting and developing, rinsing with pure water was performed to form a positive relief pattern. Table 2 shows the sensitivity, resolution, and peeling state of the positive photosensitive resin composition.
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.
[Peeling]
Whether there is peeling of the 10 μm pattern at the above exposure amount.

  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 (6)

(A) It consists of 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, (C) an alkoxy group, an alkyl group, and a cyano group. A positive photosensitive resin composition comprising 0.01 to 70 parts by mass of an acetic acid benzyl ester compound having any substituent selected from the group.

(In the formula, X ₁ is a tetravalent organic group having at least 2 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 dihydroxys including X ₁ and Y ₁ (The order of arrangement of the diamide units and n diamide units including X ₂ and Y ₂ is not limited.)   2. The positive photosensitive resin composition according to claim 1, wherein the photoacid generator is a compound having a naphthoquinone diazide structure. 3. The positive photosensitive resin composition according to claim 1, wherein the alkoxy group-containing acetic acid benzyl ester compound is a compound having a structure represented by the following general formula (2).

(In the formula, R ₁ is an alkyl group having at least one carbon atom and an unsaturated group.) The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the alkoxy group-containing acetic acid benzyl ester compound is a compound having a structure represented by the following chemical formula (3).

  (1) The positive photosensitive resin composition according to any one of claims 1 to 4 is formed on a substrate in the form of a layer or a film, and (2) is exposed with actinic radiation through a mask, A method for producing a cured relief pattern, which comprises directly irradiating a light beam, an electron beam or an ion beam, (3) eluting or removing an exposed portion or an irradiated portion, and (4) heat-treating the obtained relief pattern. .   A semiconductor device comprising a cured relief pattern layer obtained by the production method according to claim 5.