JP4804329B2 - Positive photosensitive resin composition - Google Patents

Description

  The present invention relates to a positive-type photosensitive resin composition used as a surface protective film and an interlayer insulating film of a semiconductor device, a method for producing a heat-resistant cured relief pattern using the positive-type photosensitive resin composition, and The present invention relates to a semiconductor device having a cured relief pattern.

A polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like is used for a surface protective film and an interlayer insulating film of a semiconductor device. This polyimide resin is generally provided in the form of a photosensitive polyimide precursor composition. By applying, patterning with actinic rays, development, thermal imidization treatment, etc., a surface protective film and interlayer insulation are formed on a semiconductor device. A film or the like can be easily formed, and the process can be significantly shortened as compared with the conventional non-photosensitive polyimide precursor composition.
However, the 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. Solvent measures 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 obtained by mixing an alkaline aqueous solution-soluble hydroxypolyamide, such as a polybenzoxazole (hereinafter also referred to as PBO) precursor, with a photoactive component such as a photosensitive diazoquinone compound is used as a positive photosensitive resin. The method used as a composition has attracted attention in recent years (see, for example, Patent Document 1).
The development mechanism of this positive photosensitive resin is that the photosensitive diazoquinone compound in the unexposed area is insoluble in the alkaline aqueous solution, but the photosensitive diazoquinone compound undergoes a chemical change upon exposure to become an indenecarboxylic acid compound. It makes use of being soluble in an alkaline aqueous solution. By using the difference in dissolution rate with respect to the developer between the exposed portion and the unexposed portion, a relief pattern of only 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 thermoset film characteristics as a polyimide film, so the PBO precursor composition is a promising alternative to organic solvent-developed polyimide precursors. It is attracting attention as a material. However, the PBO precursor composition obtained by the methods disclosed so far still has many points to be improved.

  For example, in recent years, semiconductor devices that are inferior in heat resistance compared to conventional products have been developed, and a decrease in the thermosetting temperature as a surface protective film and an interlayer insulating film is required, and in particular, thermosetting at 300 ° C. or less is required. There are many things. However, the conventional PBO precursor composition needs to use a low molecular weight substance having a certain degree of solubility in the alkaline aqueous solution as the resin component of the composition in order to exhibit developability with respect to the alkaline aqueous solution. When the molecular weight is used, the physical properties (mechanical properties) after thermosetting may be lowered.

As a method for solving this problem, a technique for introducing a thermopolymerizable functional group into a terminal portion of a resin component has been proposed (see Patent Document 2). However, even if a thermopolymerizable functional group is introduced into the terminal portion, the physical properties after thermosetting are still insufficient, particularly in the region where the thermosetting temperature is 300 ° C. or lower. Moreover, the technique which improves the physical property after thermosetting by adding a crosslinking agent and bridge | crosslinking a polymer is proposed (refer patent document 3). However, due to the reactivity of the crosslinking agent, there are still many problems such as defects in the stability of the composition and the lithography performance.

JP 63-096162 A JP 05-197153 A JP 2000-039714 A

  The present invention relates to a novel positive photosensitive resin composition capable of obtaining a cured film having excellent mechanical properties even under low heat treatment temperature conditions without impairing positive lithography performance, 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.

As a result of intensive research to solve the above problems, the present inventor has obtained a positive photosensitive resin composition that can solve the above problems by combining an acrylate compound with a hydroxypolyamide having a specific structure. As a result, the inventors have found that the present invention can be obtained and have made the present invention.
That is, the present invention is (A) 100 parts by mass of hydroxypolyamide having a repeating unit represented by the following general formula (1) and having an end group having no thermopolymerizable functional group, (B) A positive photosensitive resin composition comprising 1 part by mass to 100 parts by mass of an acrylate compound and 1 to 100 parts by mass of (C) a photosensitive diazoquinone compound.

（式中、Ｘ₁は少なくとも６個以上の炭素原子を有する４価の芳香族基、Ｘ₂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、Ｙ₁およびＹ₂は少なくとも６個以上の炭素原子を有する２価の芳香族基、ｍは２〜１０００の整数、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。）

Wherein X ₁ is a tetravalent aromatic group having at least 6 carbon atoms, X ₂ is a divalent organic group having at least 2 carbon atoms, and Y ₁ and Y ₂ are at least 6 Divalent aromatic group having the above 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 X ₁ and Y (The order of arrangement of m dihydroxydiamide units including ₁ and n diamide units including X ₂ and Y ₂ is not limited.)

The present invention also includes (1) forming the above-mentioned positive photosensitive resin composition on a substrate in the form of a layer or a film, and (2) exposing with actinic radiation through a mask, A method for producing a cured relief pattern, which comprises directly irradiating an ion beam, (3) eluting or removing an exposed portion or an irradiated portion, and (4) heat-treating the obtained relief pattern.
Furthermore, the present invention is a semiconductor device having the above-described cured relief pattern.

  According to the present invention, a positive photosensitive resin composition having not only excellent positive lithography performance such as sensitivity and resolution but also good mechanical properties of a cured film after low-temperature heat treatment, and the positive photosensitive resin composition are provided. A method for producing a cured relief pattern used, and a semiconductor device having the cured relief pattern are provided.

<Positive photosensitive resin composition>
Each component constituting the positive photosensitive resin composition of the present invention will be specifically described 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, there are m hydroxydiamide units which can be obtained by polycondensation of dicarboxylic acid and bisaminophenol having the structure of X1 (NH ₂ ) ₂ (OH) ₂ . Here, the two amino groups and the hydroxy group of the bisaminophenol are each in the ortho position, and the hydroxypolyamide is closed by heating at about 250 to 400 ° C., and is a heat resistant resin. Changes to 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.

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. If the ratio of the diamide unit in the hydroxy polyamide is too high, the solubility in an alkaline aqueous solution used as a developer is lowered. Therefore, the value of m / (m + n) is preferably 0.5 or more, 0.7 More preferably, it is more 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, 1,3- And diamino-4,6-dihydroxybenzene. 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, 4,4 At least one 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, wherein the hydrogen atom of the aromatic nucleus of these aromatic diamines, such as' -diaminobenzanilide, etc. And compounds substituted by groups or atoms.

  Further, silicon diamine can be selected in order to enhance the adhesion to the substrate. Examples of this include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, and bis (4 -Aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) 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価の基を意味する。） 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.

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

Moreover, tetracarboxylic dianhydride can also be used as a dicarboxylic acid ring-opened with monoalcohol, monoamine or the like as Y ₁ or Y ₂ component. Examples of monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, and benzyl alcohol. Examples of monoamine include butylamine and aniline. The following etc. are mentioned as an example of tetracarboxylic acid.

（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価の基を意味する。）

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

Further, trimellitic acid chloride can be reacted with bisaminophenol to produce a tetracarboxylic dianhydride, which can be ring-opened in the same manner as described above and used as a dicarboxylic acid. Examples of the tetracarboxylic dianhydride obtained here include the following.

（式中、Ｘ₃は上述のビスアミノフェノールを表す。）

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

Furthermore, the carboxylic acid residue of the hydroxypolyamide produced by reacting tetracarboxylic dianhydride and bisaminophenol (which may contain a diamine) is esterified or amidated with a monoalcohol or monoamine. You can also
The above-mentioned polycondensation method of dicarboxylic acid and bisaminophenol is a method of using dicarboxylic acid and thionyl chloride to produce diacid chloride and then reacting with bisaminophenol, and dicarboxylic acid and bisaminophenol to dicyclohexyl. Examples thereof include a method of polycondensation with carbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

In the hydroxy polyamide having the repeating unit represented by the general formula (1), the terminal portion is an organic group having no thermopolymerizable functional group (hereinafter referred to as a sealing group). When an organic group having no thermopolymerizable functional group is used as the sealing group, the physical properties after thermosetting are superior compared to the case where an organic group having a thermopolymerizable functional group is used as the sealing group. Here, the thermally polymerizable functional group is, for example, a functional group containing an ethylenically unsaturated double bond such as a methacryl group, an acrylic group, or a norbornene group, or an acetylenic group such as an ethynyl group or a propargyl group. It shall mean a functional group containing a saturated triple bond.
In polycondensation of hydroxypolyamide, when the dicarboxylic acid component is used in excess compared to the sum of the bisaminophenol component and the diamine component, the terminal portion becomes a carboxyl group, so that the aliphatic saturated compound having an amino group, a hydroxyl group, etc. Alternatively, an aromatic compound is reacted to form a sealing group. Examples of the compound in this case include aniline, cyclohexylamine, norbornaneamine, ethanolamine, cyclohexanol and the like.

  Conversely, if the sum of the bisaminophenol component and diamine component is used in excess compared to the dicarboxylic acid component, the terminal portion becomes an amino group, so that fatty acids having acid anhydrides, carboxylic acids, acid chlorides, isocyanate groups, etc. A group saturated compound or an aromatic compound is reacted to form a blocking group. Examples of compounds in this case include acetic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, norbornane-2, 3-carboxylic anhydride, phthalic anhydride, 1,8-naphthalenedicarboxylic anhydride, succinic anhydride, di-t-butyl dicarbonate, benzoyl chloride, methanesulfonic acid chloride, p-toluenesulfonic acid chloride, phenyl isocyanate Etc.

Preferred among the blocking groups are compounds selected from the group consisting of cyclohexylamine, cyclohexanol, 1,2-cyclohexanedicarboxylic anhydride, and 4-methylcyclohexane-1,2-dicarboxylic anhydride. Examples thereof include a sealing group having a structure in which a terminal portion of hydroxypolyamide is reacted. Among these, 1,2-cyclohexanedicarboxylic anhydride, or a sealing group having a structure in which 4-methylcyclohexane-1,2-dicarboxylic anhydride and a terminal portion of hydroxypolyamide are reacted is particularly preferable.

(B) Acrylate compound The acrylate compound used in the present invention refers to a compound selected from the group consisting of acrylic acid ester, methacrylic acid ester, acrylamide, and methacrylamide.
Specific examples of preferable ones include NK-ester series manufactured by Shin-Nakamura Chemical Co., Ltd .: M-20G, M-40G, M-90G, M-230G, CB-1, SA, S, AMP-10G, AMP-20G, AMP-60G, AM-90G, A-SA, LA, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, 701, BPE-100, BPE-200, BPE-500, BPE-1300, A-200, A-400, A-600, A-HD, A-NPG, APG-200, APG-400, APG-700, A-BPE-4, 701A, TMPT, A-TMPT, A-TMM-3, A-TMM-3L, and A-TMMT are mentioned.

  In addition, Kyoeisha Chemical Co., Ltd. light ester series: M, E, NB, IB, EH, ID, L, L-5, L-7, TD, L-8, S, MC, 130MA, 041MA, CH, THF, BZ, PO, IB-X, HO, HOP, HOA, HOP-A, HOB, A, HO-MS, HO-HH, HO-MPP, G, P-1M, P-2M, EG, 2EG, 4BG, 1.6HX, 1.9ND, TMP, G-101P, G-201P, BP-2EM, TB, IS, MTG, BO, CL, 3EG, 4EG, 9EG, 14EG, NP, M-3F, M- 4F, M-6F, FM-108, 1.3BG, and 1.10 DC.

In addition, Kyoeisha Chemical Co., Ltd. light acrylate series: IAA, LA, SA, BO-A, EC-A, MTG-A, 130A, DPM-A, PO-A, P-200A, NP-4EA, NP-8EA, THF-A, IB-XA, HOA, HOP-A, M-600A, HOA-MS, HOA-MPE, 3EG-A, 4EG-A, 9EG-A, 14EG-A, NP-A, 1.6HX-A, 1.9ND-A, DCP-A, BP-4EA, BP-4PA, TMP-A, TMP-6EO-3A, PE-3A, PE-4A, DPE-6A, BA-104, BA-134 and G-201P are mentioned.
Moreover, the epoxy ester series by Kyoeisha Chemical Co., Ltd .: M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M, and 3002A are mentioned.

Aronix series manufactured by Toa Gosei Co., Ltd .: M-101, M-102, M-110, M-111, M-113, M-117, M-120, M-208, M-210, M-211, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-305, M-309, M-310, M-315, M- 320, M-350, M-360, M-400, M-408, M-450, M-5300, M-5400, M-5600, and M-5700.
Moreover, Nippon Oil & Fat Co., Ltd. Blemmer series: BMA, IBMA, CHMA, EHMA-25, TBCHMA, LMA, SLMA, CMA, SMA, VMA, VMA-70, B-12, CHA, LA, SLA, CA, SA, VA, B-18A, g, GH, GH-LC, GS, GLM, GLM-R, GMR-H, GMR-R, GAM, GAM-R, G-FA-80, QA, E, PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, P, PP-1000, PP-500, PP-800, AP-150, AP-400, AP-550, AP-800, 50 PEP-300, 70 PEP-350B, AEP, 55 PET-400, 30 PET-800, 55 PET-800, AET, 30 PPT-800, 50 PPT- 00, 70PPT-800, APT, 10PPB-500B, 10APB-500B, PME-100, PME-200, PME-350, PME-400, PME-550, PME-1000, PME-4000, AME-400, AEE- 100, 50POEP-800B, 50AOEP-800B, PLE-200, ALE-200, ALE-800, PSE-200, PSE-400, PSE-1300, ASEP, PKEP, AKEP, ANE, ANE-1300, ANP-300, 43ANEP-500, 70ANEP-550, 75ANEP-600, AAE-300, PDE-50, PDE-100, PDE-150, PDE-200, PDE-400, PDE-600, PDE-1000, ADE-200, ADE- 4 0, PDP-400, ADP-200, ADP-400, PDT-650, ADT-250, PDET, 50ADET-1800, PDPT, 30ADPT-4000, 30PDC-800B, 80PDC-950B, 20PDC-1300B, 40PDC-1700B, 30ADC-800B, PDBE-200, PDBE-250, PDBE-450, PDBE-1300, ADBE-200, ADBE-250, ADBE-450, PDBP, ADBP, PDBEP, ADBEP, and 43PDBPE-800B.
Furthermore, Koshinsha make: DMAEA, DMAPAA, DMAA, ACMO, NIPAM, DEAA, etc. are mentioned.

Among these acrylate compounds, compounds having two or more thermopolymerizable functional groups are particularly preferable. These compounds may be used alone or in combination of two or more.
1-100 mass parts is preferable with respect to 100 mass parts of this hydroxy polyamide, and, as for the compounding quantity to the hydroxy polyamide of an acrylate type compound, 5-30 mass parts is more preferable. If the blending amount of the acrylate compound is less than 1 part by mass, sufficient elongation of the film after thermosetting cannot be obtained. Conversely, if it exceeds 100 parts by mass, the stability of the composition is deteriorated.

(C) Photosensitive diazoquinone compound The photosensitive diazoquinone compound used in the present invention is a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure. US Pat. No. 2,772,972, No.2 , 797,213, 3,669,658 and the like. As an example of a preferable thing, the following are mentioned, for example.

（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.)

Preferred naphthoquinonediazide sulfonic acid ester groups include the following.

Among these photosensitive diazoquinone compounds, the following are particularly preferable.

  1-100 mass parts is preferable with respect to 100 mass parts of this hydroxy polyamide, and, as for the compounding quantity to the hydroxy polyamide of a photosensitive diazoquinone compound, 10-30 mass parts is more preferable. If the blending amount of the photosensitive diazoquinone compound is less than 1 part by mass, the resin patterning property is poor. Conversely, if it exceeds 100 parts by mass, the tensile elongation of the cured film is remarkably lowered, and the development residue in the exposed part ( Scum) becomes extremely intense.

(D) Other additives For the positive photosensitive resin composition of the present invention, phenol compounds, dyes, surfactants, stabilizers that have been conventionally used as additives for photosensitive resin compositions, if necessary. It is also possible to add an adhesion aid or the like for improving the adhesion to the substrate.
More specifically, the additive includes a ballast agent 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.
The addition amount in the case of adding a phenol compound is preferably 0 to 50 parts by mass and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the hydroxy polyamide. When the addition amount exceeds 50 parts by mass, the heat resistance of the film after thermosetting is lowered.

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. When the addition amount exceeds 10 parts by mass, the heat resistance of the film after thermosetting is lowered.

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, for example, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxysilylethyl) pyridine, and 3-methacryloxypropyl. Trialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkyl Examples thereof include silane (also referred to as aminosilane), a reaction product of aminosilane and acid anhydride or acid dianhydride, and aminosilane having an amino group converted to a urethane group or a urea group.

In this case, methyl group, ethyl group, butyl group, etc. as the alkyl group, maleic anhydride, phthalic anhydride, etc. as the acid anhydride, pyromellitic dianhydride as the 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 a carbonylamino group. By adding an adhesion assistant, the adhesion of the coating film to the wafer can be improved.
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. When the addition amount exceeds 30 parts by mass, the heat resistance of the film after thermosetting is lowered.

In the present invention, these components are 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, a method for producing a cured relief pattern by applying the positive photosensitive resin composition of the present invention to a substrate 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, methods such as spray, paddle, dip, and ultrasonic can be used. Distilled water, deionized water, etc. can be used for the rinse liquid.

The developer used for developing the photosensitive resin film formed with the positive photosensitive resin composition of the present invention is an alkaline aqueous solution in which an alkali-soluble polymer is dissolved and removed, and an alkali compound is dissolved. is required. 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, ammonia and the like.

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 and the like.
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, a resin dissolution inhibitor, or the like 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 having a polybenzoxazole structure.
The cured relief pattern created by the above-described manufacturing method is used to manufacture a known semiconductor device as 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. A semiconductor device can be manufactured by combining with the method. It is also useful as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like.

The present invention will be described based on reference examples and examples.
<Synthesis of hydroxy polyamide>
[Reference Example 1]
In a 3 L separable flask, 173.1 g (0.473 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 605.7 g of N, N-dimethylacetamide (DMAc) 71.2 g (0.9 mol) of pyridine was mixed and stirred at room temperature (25 ° C.) to obtain a uniform solution. A solution prepared by dissolving 132.80 g (0.45 mol) of 4,4′-diphenyl ether dicarbonyl chloride in 531.2 g of diethylene glycol dimethyl ether (DMDG) was added dropwise thereto from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for the dropping was 60 minutes, and the temperature of the reaction solution was 30 ° C. at the maximum.

3 hours after the completion of dropping, 6.9 g (0.045 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was left to stir at room temperature for 15 hours, and 99% of all amine end groups of the polymer chain were carboxylated. Sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). Thereafter, the reaction solution was dropped into 20 l of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water, dehydrated and then vacuum dried, and measured by gel permeation chromatography (GPC). Hydroxypolyamide P-1 having a weight average molecular weight of 30000 (polystyrene conversion) was obtained.
In addition, when further purification of the polymer is necessary, it can be carried out by the following method. That is, after redissolving the polymer obtained above in DMDG, this was treated with a cation exchange resin and an anion exchange resin, and the solution obtained thereby was poured into ion exchange water, and then the precipitated polymer was removed. A purified polymer can be obtained by filtration, washing with water, and vacuum drying.

[Reference Example 2]
In a separable flask having a volume of 5 l, 428.5 g (1.170 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 1499.8 g of N, N-dimethylacetamide (DMAc) , 178.0 g (2.25 mol) of pyridine were mixed and stirred at room temperature (25 ° C.) to obtain a uniform solution.
A solution prepared by dissolving 15.1 g (0.09 mol) of 4-methylcyclohexyl-1,2-dicarboxylic acid anhydride in 76 g of γ-butyrolactone (GBL) was added dropwise thereto. The time required for the dropping was 15 minutes, and the temperature of the reaction solution was 30 ° C. at the maximum.
After completion of the dropwise addition, the mixture was left stirring at room temperature for 15 hours, and it was confirmed that 4-methylcyclohexyl-1,2-dicarboxylic anhydride added by HPLC was consumed.

  Next, this was cooled to 0 ° C. with an ice bath, and separately, 265.6 g (0.9 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride and 45.7 g (0.225 mol) of isophthalic acid dichloride in GBL1373.7 g. Was dissolved from a dropping funnel. The time required for the dropping was 600 minutes, and the maximum reaction solution temperature was 12 ° C. 3 hours after the completion of dropping, the above reaction solution was dropped into 24 liters of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, washed with water, dehydrated appropriately, and then vacuum dried to obtain hydroxypolyamide P-2. It was. The weight average molecular weight of the thus synthesized hydroxypolyamide by GPC was 50000 in terms of polystyrene.

[Reference Example 3]
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 imidization of the product indicates that there are characteristic absorptions of imide groups at 1394 cm −1 and 1774 cm −1 in the IR spectrum, and there is no characteristic absorption of amide groups near 1540 cm −1 and 1650 cm −1, and an 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 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 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).

[Reference Example 4]
Resorcinol (102.4 g, 0.92 mol) and hexanal (92.0 g, 0.92 mol) were dissolved in ethanol (920 ml) in a two-necked three-neck flask. 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 previously synthesized in a separable flask having a volume of 2 l and 134.3 g (0.5 mol, naphtho) of 1,2-naphthoquinonediazide-4-sulfonyl chloride were synthesized. Quinonediazide sulfonic acid esterification rate 62.5% 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 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 the desired photosensitive diazoquinone compound (Q-2).

<Preparation of positive photosensitive resin composition>
100 parts by mass of the hydroxy polyamide (P-1 or P-2) obtained in Reference Examples 1 and 2 above, and the photosensitive diazoquinone compound (Q-1 or Q-2) obtained in Reference Examples 3 and 4 above. 20 parts by mass, an acrylate compound having a structure of the following formula C-1, C-2, C-3, C-4, or C-5, or an epoxy compound having a structure of C-6 (also referred to as a crosslinking agent) .) After dissolving 10 parts by mass in 170 parts by mass of GBL, the positive type photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 and 2 described in Table 1 were filtered through a 0.2 μm filter. Prepared.

(C-1) NK ester 4G

(C-2) NK ester 9G

（Ｃ−４）ブレンマーＰＤＴ−６５０

（Ｃ−５）ブレンマーＰＤＢＥ−４５０

(C-3) Aronix M315

(C-4) Blemmer PDT-650

(C-5) Blemmer PDBE-450

(C-6) Epolite 3002 (manufactured by Kyoeisha Chemical Co., Ltd.)

<Evaluation of positive photosensitive resin composition>
(1) Evaluation of patterning characteristics The positive photosensitive resin composition is spin-coated on a 5-inch silicon wafer with a spin coater (Dspin 636) manufactured by Dainippon Screen Mfg. Co., Ltd., and pre-baked at 130 ° C. for 180 seconds on a hot plate. A film having a film thickness of 10.0 μm was formed. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg.
This coating film was exposed through a reticle with a test pattern using a Nikon stepper (NSR2005i8A) having an exposure wavelength of i-line (365 nm) while changing the exposure amount stepwise. Using an alkali developer (AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution) manufactured by AZ Electronic Materials, the development time was adjusted so that the film thickness after development was 8 μm at 23 ° C. Then, it was developed and rinsed with pure water 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) Evaluation of mechanical properties The positive photosensitive resin composition was spin-coated on a 5-inch silicon wafer on which an aluminum film was previously formed by sputtering with a spin coater (Dspin 636) manufactured by Dainippon Screen Mfg. Co., Ltd. Prebaking was performed at 120 ° C. for 180 seconds to form a coating film having a thickness of 11.0 μm. This coating film was exposed with PLA-501F manufactured by Canon Inc. using a photomask having a 10 mm strip pattern. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute, and then rinsed with pure water for 30 seconds. In a vertical curing furnace (manufactured by Koyo Lindberg), curing (heat curing treatment) was performed at 300 ° C. for 1 hour in a nitrogen atmosphere to obtain a polybenzoxazole (PBO) film as a heat resistant coating. This film was immersed in a 3% hydrofluoric acid aqueous solution, the strip-shaped film was peeled off, thoroughly washed with pure water, and dried to obtain a strip-shaped test sample. This test sample was pulled with Tensilon (weight = 2 kgf, pulling speed = 40 mm / min), and the elongation at break was measured and evaluated in mechanical properties as shown in Table 2.

(3) Stability evaluation The rate of change in viscosity after standing at room temperature for 1 week was measured and shown in Table 2. If the rate of change in viscosity was within 5%, the stability was considered good.
From Table 2, by using the positive photosensitive resin composition of the present invention, not only can a relief pattern with good stability, high sensitivity and high resolution be formed, but also at 300 ° C. for 1 hour. It was found that a cured film having good mechanical properties can be obtained under the curing conditions described above. On the other hand, it turned out that the composition of Comparative Examples 1-2 which does not contain the acrylate type compound which satisfy | fills the requirements of this invention has the bad stability of a composition, or a favorable mechanical characteristic is not acquired.

  The positive photosensitive resin composition of 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 an interlayer of a multilayer circuit. 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 an repeating unit represented by the following general formula (1), and a terminal part having no thermopolymerizable functional group, (B) acrylate-based compounds 1 to 100 A positive photosensitive resin composition containing 1 part by mass of (C) a photosensitive diazoquinone compound.

Wherein X ₁ is a tetravalent aromatic group having at least 6 carbon atoms, X ₂ is a divalent organic group having at least 2 carbon atoms, and Y ₁ and Y ₂ are at least 6 Divalent aromatic group having the above 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 X ₁ and Y (The order of arrangement of m dihydroxydiamide units including ₁ 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 terminal portion of the hydroxypolyamide (A) is an organic group having a cyclohexyl group.   (1) The positive photosensitive resin composition according to claim 1 or 2 is formed on a substrate in the form of a layer or a film, and (2) exposed with actinic radiation through a mask, or a light beam, an electron beam or A method for producing a cured relief pattern, comprising directly irradiating 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 having a cured relief pattern obtained by the manufacturing method according to claim 3.