JP2004302430A - Positive photosensitive resin composition, method for manufacturing pattern and electronic part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition having excellent sensitivity and resolution by using a solubility converting agent having an alkali-soluble group protected by a protecting group which can be eliminated under acid conditions, and further having appropriate solubility of the resin itself with an alkaline aqueous solution by using a polyoxazole precursor having the molecular end sealed with an organic group, and to provide a positive photosensitive resin composition having high adhesion property and heat resistance by compounding a compound which can induce the elimination reaction of the protecting group in the above solubility converting agent by irradiation of radiation. <P>SOLUTION: The composition contains: (A) a polyoxazole precursor having an organic group derived from a carboxylic acid residue in the molecular end; (B) a compound which generates an acid by irradiation of active rays; and (C) a compound having an organic group which is decomposed by an acid catalytic effect to convert into a hydrogen atom. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protection film and an interlayer insulating film of a semiconductor element. However, as semiconductor devices become more highly integrated and larger in recent years, there has been a demand for thinner and smaller sealing resin packages, and methods such as LOC (lead-on-chip) and surface mounting by solder reflow have been adopted. Therefore, characteristics suitable for being formed as a protective film on the outermost surface of a semiconductor circuit more than before, that is, a polyimide resin excellent in mechanical characteristics, heat resistance, etc. are required. .

  On the other hand, photosensitive polyimides having photosensitive characteristics imparted to the polyimide resin itself have been conventionally used because they have a feature that a pattern forming process can be simplified and a complicated manufacturing process can be shortened.

  Such a conventional photosensitive polyimide and a heat-resistant photoresist using the precursor thereof are well known. For example, in the case of a negative photosensitive resin, a polyimide obtained by a method of introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond (for example, see Patent Documents 1 to 4), a soluble resin having a photopolymerizable olefin. Polyimides (for example, see Patent Documents 5 to 10), self-sensitized polyimides having a benzophenone skeleton and having an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded (for example, see Patent Documents 11 and 12) and the like Is mentioned. Also, these uses are well known.

  However, the above-mentioned negative type photosensitive resin has a problem of resolution caused by the absorption wavelength of the photosensitive agent, and a problem of lowering the production yield depending on the application. Further, in the above-mentioned polyimide resin, since the structure of the polymer to be used is limited, the physical properties of the finally obtained coating are limited, and some of them are not suitable for multipurpose use.

  Further, the above-mentioned negative photosensitive resin requires an organic solvent such as N-methylpyrrolidone at the time of development. Since the amount of the developer used is several times the amount of the photosensitive polyimide precursor composition used, there is a problem that a large load is imposed on the environment when processing the waste developer. Further, since an organic solvent developing solution and a rinsing solution are often expensive and greatly affect device manufacturing costs, it is desired to use an inexpensive developing solution and a rinsing solution. Therefore, there is a demand for a photosensitive polyimide composition that can be easily processed with a waste developer and can be developed with an inexpensive aqueous developer (aqueous alkaline solution).

  Examples of the positive photosensitive resin that can be developed with an aqueous developer (aqueous alkaline solution) include a method of introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (see, for example, Non-Patent Document 1). A method of mixing a naphthoquinonediazide compound with a soluble hydroxylimide or polyoxazole precursor (for example, see Patent Documents 13 and 14) and a method of introducing naphthoquinonediazide into a soluble polyimide via an ester bond (for example, see Non-Patent Document 2) A composition containing a positive photosensitive resin or a polyimide precursor resin obtained by the above method and a naphthoquinonediazide-based photosensitive agent (for example, see Patent Document 15) is known.

  However, the positive photosensitive resin that can be developed with this aqueous developer (alkaline aqueous solution) also has low sensitivity and resolution due to the problem associated with the absorption wavelength of the photosensitive agent, similarly to the negative photosensitive resin. Further, since the structure of the polymer used is limited as described above, a problem similar to that of the negative photosensitive resin occurs.

  Carboxylic acids such as a material in which a diazonaphthoquinone compound is mixed with a polybenzoxazole precursor (for example, see Patent Document 16) and a material in which a phenol site is introduced into a polyamic acid via an ester bond (for example, see Patent Document 17) Materials having a phenolic hydroxyl group introduced in place of are also proposed, but these materials have insufficient developability. In addition, there is a problem that the film of the unexposed portion is reduced and the resin is separated from the base material. For the purpose of improving such developability and adhesion, materials mixed with a polyamic acid having a siloxane moiety in a polymer skeleton (for example, see Patent Documents 18 and 19) have been proposed. , The storage stability deteriorates. Therefore, for the purpose of improving storage stability and adhesion, a material in which an amine terminal group is sealed with a polymerizable group (for example, see Patent Documents 20 to 22) has also been proposed. However, these materials use a diazoquinone compound containing a large number of aromatic rings as an acid generator, so that the mechanical properties after thermosetting are significantly reduced and the sensitivity is low. hard.

  For the purpose of improving the problems of the diazoquinone compound, materials using various chemical amplification systems have been proposed. As a material to which this chemical amplification system is applied, for example, a chemically amplified polyimide (for example, see Patent Document 23), a chemically amplified polyimide, a polybenzoxazole precursor (for example, see Patent Documents 24 to 30), and the like. No. However, among these, those with high sensitivity have low molecular weights, so that deterioration in film properties is observed. On the other hand, those having excellent film properties have a high molecular weight, so that their solubility becomes insufficient and a decrease in sensitivity is observed. The positive photosensitive polyimide precursor composition or the positive photosensitive polybenzoxazole precursor composition is a positive photosensitive resin composition comprising a polyimide precursor or a polybenzoxazole precursor and a quinonediazide-based photosensitive agent. Higher sensitivity, but not enough contrast. Therefore, none of these materials can be said to be practically usable, and at present, there is no material sufficient for practical use.

JP-A-49-11541 JP-A-50-40922 JP-A-54-145794 JP-A-56-38038, etc. JP-A-59-108031 JP-A-59-220730 JP-A-59-232122 JP-A-60-6729 JP-A-60-72925 JP-A-61-57620 JP-A-59-219330 JP-A-231533 JP-B-64-60630 U.S. Pat. No. 4,395,482 JP-A-52-13315 JP-A-1-46862 JP-A-10-307393 JP-A-4-31861 JP-A-4-46345 JP-A-5-197153 JP-A-9-183846 JP 2001-183835 A JP-A-3-763 JP-A-7-219228 JP-A-10-186664 JP-A-11-202489 JP-A-2000-56559 JP 2001-194791 A JP 2002-526793 A U.S. Pat. No. 6,143,467 J. Macromol. Sci. Chem. , A24, 10, 1407, 1987 Macromolecules, 23, 1990

  The present invention is excellent in sensitivity and resolution by using a solubility converter in which an alkali-soluble group is protected by a protecting group which can be removed under acid conditions. Further, by using a polyoxazole precursor having a molecular end sealed with an organic group, a positive photosensitive resin composition is provided, in which the resin itself has appropriate solubility in an aqueous alkaline solution. Further, the positive type photosensitive resin composition solves the above-mentioned problems of conventional photoresists by compounding a compound capable of inducing a elimination reaction of a protective group in the solubility converter by irradiation with radiation. In addition, the present invention provides a positive photosensitive resin composition having excellent adhesiveness and heat resistance.

  Further, the present invention provides a method for producing a pattern which can be developed with an aqueous alkali solution, has excellent sensitivity, resolution and heat resistance, and provides a pattern having a good shape, by using the composition. Further, the present invention provides a highly reliable electronic component (semiconductor device) by having a pattern having a good shape and characteristics.

（式中、Ｒ¹は二価の有機基、Ｒ²は四価の有機基、Ｒ³は一価の前記カルボン酸残基より誘導される有機基を示し、いずれも複数ある場合は同一でも異なっていてもよく、ｎは整数であり、繰り返し単位数を示す）で表されるポリオキサゾール前駆体であることを特徴とする上記［１］に記載のポジ型感光性樹脂組成物。
［３] 前記有機基Ｒ³が、アルキル基、アリール基、アセタールまたはケタールを構成する基、シリル基、シリルエーテル基、アルコキシカルボニル基、アルコキシアルキル基、アルキルシリル基からなる群より選ばれる少なくとも１種であることを特徴とする上記［２］に記載のポジ型感光性樹脂組成物。
［４] 前記（Ｃ）成分が、分子中に芳香環を有し、かつ−ＯＲ（但し、Ｒは酸の作用で分解し、水素原子に変換し得る一価の有機基を示す）で示される基、及び／又は−ＣＯＯＲ（但し、Ｒは酸の作用で分解し、水素原子に変換し得る一価の有機基を示す）で示される基を有する化合物であることを特徴とする上記［１］〜［３］のいずれか１つに記載のポジ型感光性樹脂組成物。
［５] 前記（Ｃ）成分が、下記一般式（２）

（式中、Ｘは有機基、Ｒは酸の作用で分解し、水素原子に変換し得る一価の有機基を示し、いずれも複数ある場合は同一でも異なっていてもよく、ａ、ｂはそれぞれ０以上の整数であり、ａ＋ｂは１以上の整数を示す）で表される化合物であることを特徴とする上記［１］〜［３］のいずれか１つに記載のポジ型感光性樹脂組成物。
［６] 前記（Ｃ）成分が、下記一般式（３）

（式中、Ｘ’は有機基、Ｒは酸の作用で分解し、水素原子に変換し得る一価の有機基を示し、いずれも複数ある場合は同一でも異なっていてもよく、ａ、ｂはそれぞれ０以上の整数を示す）で表される繰り返し単位を有する化合物であることを特徴とする上記［１］〜［３］のいずれか１つに記載のポジ型感光性樹脂組成物。
［７] 前記有機基Ｒが、アルキル基、アリール基、アセタールまたはケタールを構成する基、シリル基、シリルエーテル基、アルコキシカルボニル基、アルコキシアルキル基、アルキルシリル基からなる群より選ばれる少なくとも１種であることを特徴とする上記［５］または［６］に記載のポジ型感光性樹脂組成物。
［８] 上記［１］〜［７］のいずれか１つに記載のポジ型感光性樹脂組成物を支持基板上に塗布し、乾燥してポジ型感光性樹脂膜を得る工程と、前記ポジ型感光性樹脂膜を露光する工程と、前記露光後のポジ型感光性樹脂膜を加熱する工程と、前記加熱後のポジ型感光性樹脂膜をアルカリ水溶液を用いて現像する工程と、及び前記現像後のポジ型感光性樹脂膜を加熱処理する工程とを含むことを特徴とするパターンの形成方法。
［９] 上記［８］に記載の形成方法により得られるパターンの層を有してなる電子デバイスを有する電子部品であって、前記電子デバイス中に前記パターンの層が層間絶縁膜層及び／又は表面保護膜層として設けられたものであることを特徴とする電子部品。 That is, the present invention is as follows.
[1] (A) a polyoxazole precursor having an organic group derived from a carboxylic acid residue at its molecular terminal, (B) a compound capable of generating an acid upon irradiation with actinic rays, and (C) decomposition by acid catalysis And a compound having an organic group which can be converted to a hydrogen atom by the reaction.
[2] The component (A) is represented by the following general formula (1)

(Wherein, R ¹ represents a divalent organic group, R ² represents a tetravalent organic group, and R ³ represents an organic group derived from the monovalent carboxylic acid residue. The positive photosensitive resin composition according to the above [1], which is a polyoxazole precursor represented by the following formula (1):
[3] The organic group R ³ is at least one selected from the group consisting of an alkyl group, an aryl group, a group constituting an acetal or a ketal, a silyl group, a silyl ether group, an alkoxycarbonyl group, an alkoxyalkyl group, and an alkylsilyl group. The positive photosensitive resin composition according to the above [2], which is a seed.
[4] The component (C) has an aromatic ring in the molecule and is represented by -OR (where R represents a monovalent organic group which can be decomposed by the action of an acid and converted into a hydrogen atom). Wherein R is a compound having a group represented by -COOR (where R represents a monovalent organic group capable of being decomposed by the action of an acid and converted to a hydrogen atom). 1] The positive photosensitive resin composition according to any one of [3].
[5] The component (C) is represented by the following general formula (2)

(Wherein, X is an organic group, R is a monovalent organic group that can be decomposed by the action of an acid and converted into a hydrogen atom, and when there are two or more of them, they may be the same or different; The positive photosensitive resin according to any one of the above [1] to [3], wherein each of the positive photosensitive resin is a compound represented by the formula: Composition.
[6] The component (C) is represented by the following general formula (3)

(In the formula, X ′ is an organic group, R is a monovalent organic group that can be decomposed by the action of an acid and converted into a hydrogen atom, and when there are two or more of them, they may be the same or different; a, b Wherein each represents an integer of 0 or more), wherein the positive photosensitive resin composition according to any one of the above [1] to [3] is a compound having a repeating unit represented by the following formula:
[7] The organic group R is at least one selected from the group consisting of an alkyl group, an aryl group, a group constituting an acetal or a ketal, a silyl group, a silyl ether group, an alkoxycarbonyl group, an alkoxyalkyl group, and an alkylsilyl group. The positive photosensitive resin composition according to the above [5] or [6], wherein
[8] a step of applying the positive photosensitive resin composition according to any one of the above [1] to [7] on a support substrate and drying to obtain a positive photosensitive resin film; Exposing the positive photosensitive resin film, heating the positive photosensitive resin film after the exposure, developing the heated positive photosensitive resin film using an alkaline aqueous solution, and Subjecting the positive photosensitive resin film after development to a heat treatment.
[9] An electronic component having an electronic device having a pattern layer obtained by the formation method according to [8], wherein the pattern layer is an interlayer insulating film layer and / or an electronic device in the electronic device. An electronic component provided as a surface protective film layer.

  The positive photosensitive resin composition of the present invention is excellent in mechanical properties, sensitivity, resolution and heat resistance. Further, according to the pattern forming method of the present invention, by using the composition, a pattern having excellent mechanical properties, sensitivity, resolution and heat resistance and having a good shape can be obtained. Further, the electronic component (semiconductor device) of the present invention has high reliability because it has a pattern having a good shape and good characteristics.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.
First, the polyoxazole precursor will be described in detail. In the polyoxazole precursor, R ¹ in the structure represented by the general formula (1) is specifically benzene, naphthalene, perylene, biphenyl, diphenyl ether, diphenylsulfone, diphenylpropane, diphenylhexafluoropropane, benzophenone, or the like. A typical example is a divalent aromatic hydrocarbon residue having a skeleton of, or a divalent aliphatic hydrocarbon residue having a skeleton such as ethane, propane, hexane, butane, cyclobutane, cyclohexane, and adamantane. But not limited to these.

The number of carbon atoms of the organic group represented by R ¹ is preferably from 4 to 30. Preferred groups include phenyl, biphenyl, diphenyl ether, diphenylhexafluoropropane, cyclohexane, and adamantane. Incidentally, if necessary, two or more of the groups exemplified above as R ¹ may be contained in the molecule of the polyamide derivative.

R ² in the structure represented by the general formula (1) is specifically diphenyl, diphenyl ether, diphenylthioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenylsulfoxide, diphenylsulfone, biphenyl, benzene, etc. Typical examples include, but are not limited to, tetravalent aromatic hydrocarbon residues having a skeleton of The number of carbon atoms is preferably from 6 to 30. Preferred groups include diphenylhexafluoropropane, diphenylisopropane, diphenylether, diphenylsulfoxide, and biphenyl. Incidentally, if necessary, two or more of the groups exemplified above can be contained as R ² .

  The polyoxazole precursor used in the present invention can be produced by using a dicarboxylic acid represented by the following general formula (4) and a diamino compound represented by the following general formula (5) as a part of raw materials.

（式中、Ｒ¹は前記一般式（１）におけるＲ¹と同じ有機基を示す）

(Wherein, R ¹ represents the same organic group as R ¹ in the general formula (1))

（式中、Ｒ²は前記一般式（１）におけるＲ²と同じ有機基を示す）

(Wherein, R ² represents the same organic group as R ² in the general formula (1))

  Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4,4′-biphenyldicarboxylic acid, 4,4′-dicarboxydiphenyl ether, and 4,4 ′ -Dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, -Aromatic dicarboxylic acids such as -chloroisophthalic acid and 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, oxalic acid, and malonic acid And aliphatic dicarboxylic acids such as succinic acid. May be used alone or in combination of two or more of these. Of these, aromatic dicarboxylic acids are preferred from the viewpoint of heat resistance.

  Examples of the dihydroxyamine include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexa Fluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, 4,6-diaminoresorcinol , 4,5-diaminoresorcinol, bis (4-amino- - aromatic diamines such as carboxyphenyl) methane and the like as preferred. By using an aromatic diamine, a polybenzoxazole precursor having good heat resistance can be obtained.

  The preferred ratio (molar ratio) of the diamine compound and the dicarboxylic acid compound is in the range of 0.6 / 1 to 1/1 in the former / latter. In the polybenzoxazole synthesized by setting the content within this range, a carboxylic acid residue can be arranged at the molecular terminal, whereby an organic group can be introduced at the molecular terminal as described later. In this case, a preferable reaction temperature is -30 to 40 ° C, and a preferable reaction time is 5 minutes to 10 hours.

  The polyoxazole precursor can be obtained, for example, by the following method. The dicarboxylic acid represented by the general formula (4) is converted to N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylene After halogenation using a halogenating agent such as thionyl chloride in an organic solvent (aprotic polar solvent) such as sulfone or γ-butyrolactone, the diamino compound represented by the general formula (5) and pyridine or the like are used. The reaction is carried out in the same organic solvent as described above in the presence of a suitable catalyst. The organic solvents may be used alone or in combination of two or more.

The reaction solution having undergone the above-described reaction is poured into a poor solvent such as water, methanol, ethanol, propyl alcohol, and acetone, crystallized, filtered, and dried. The hydroxypolyamide thus obtained is again dissolved in the above-mentioned organic solvent, and a suitable esterifying agent is acted on under an acid or a basic catalyst, if necessary, whereby the terminal carboxylic acid group is reacted with the above-mentioned compound. An organic group represented by R ³ in the general formula (1) can be introduced.

  Examples of the esterifying agent include various alcohols, various vinyl ethers, alkyl halides, trimethylsilyl chloride, halogenated methyl alkyl ethers, and halogenated ethyl alkyl ethers. The reaction solution is poured into a poor solvent such as water, methanol, ethanol, propyl alcohol or acetone, crystallized, filtered and dried to obtain a polyoxazole having the structural unit represented by the general formula (1). A precursor can be obtained.

  In the present invention, the polybenzoxazole precursor is, for example, via a dicarboxylic acid derivative obtained by reacting 1-hydroxybenzotriazole with a dicarboxylic acid, as disclosed in JP-A-9-183846. Then, it can be obtained by reacting this with dihydroxyamine.

  Further, in the present invention, the polybenzoxazole precursor may be, for example, as described in Polymer Letter. , Vol. 2, pp655-659 (1964), it can be obtained by reacting dicarboxylic acid dihalide (chloride, bromide) with dihydroxydiamine. In this case, the reaction is preferably performed in an organic solvent in the presence of a dehalogenation catalyst. Dicarboxylic acid dichloride can be obtained by reacting dicarboxylic acid with thionyl chloride. At this time, it is effective to make the molar ratio of thionyl chloride to dicarboxylic acid smaller than the equivalent amount so that the carboxylic acid group ends.

  The terminal group is preferably a monovalent organic group. In this respect, preferred organic groups include, for example, alkyl groups, aryl groups, groups constituting an acetal or ketal, silyl groups, silyl ether groups, alkoxycarbonyl groups, alkoxyalkyl groups, alkylsilyl groups, and the like. It is not limited to. Among them, an alkoxycarbonyl group having 2 to 10 carbon atoms and an alkoxyalkyl group are more preferable.

  Preferred examples of the esterifying agent for introducing these groups include tert-butyl chloride, trimethylsilyl chloride, chloromethyl ethyl ether, chloroethyl ethyl ether, chloromethyl propyl ether, and chloromethyl tert-butyl ether. It is also preferable to introduce a tetrahydropyranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, etc. by causing a vinyl ether compound to act under an acid catalyst.

  As described above, in the present invention, the component (A) is a polyoxazole precursor, but has an organic group whose molecular terminal is derived from a carboxylic acid residue. This allows the composition of the present invention to have an appropriate dissolution rate and exposure sensitivity during pattern formation. Further, film loss due to development is small, development can be performed in a short time, and fine processing can be performed. Such a polyoxazole precursor becomes a resin film having excellent heat resistance by causing a curing reaction after the formation of the relief pattern.

In the polyoxazole precursor having the structure represented by the general formula (1) used in the present invention, the substitution rate of the organic group represented by R ³ is 0.1% or more of the carboxylic acid in all polymer molecules, and % Is preferable in order to give a suitable dissolution rate and exposure sensitivity to the composition of the present invention, and more preferably 1% or more and 50% or less. If it is less than 0.1%, the film loss of the unexposed portion will be large, and if it is more than 80%, the developing time may be long. This substitution rate can be calculated from the integrated intensity ratio of the ¹ H-NMR spectrum. At this time, the amount of carboxylic acid is quantified based on the number of repeating units in all polymer molecules, and this number of repeating units can be calculated based on the charge ratio at the time of polymer synthesis.

  In the polyoxazole precursor having a structure represented by the general formula (1) used in the present invention, a part thereof has a repeating unit other than the repeating unit in the structure represented by the general formula (1). May be. In this case, the proportion is preferably 50% or less of all the repeating units.

  The molecular weight of the polyoxazole precursor of the component (A) is not particularly limited, but is generally preferably from 3,000 to 200,000, more preferably from 5,000 to 100,000, in average molecular weight. The degree of dispersion obtained by dividing the weight average molecular weight by the number average molecular weight is preferably from 1 to 4, more preferably from 1 to 3. The molecular weight can be measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

  The polyoxazole precursor having the structure represented by the general formula (1) is preferable because it has excellent transparency in the i-line region, solubility of the exposed portion in an alkali developing solution, and adhesion to a substrate.

  In the composition of the present invention, a compound capable of generating an acid by irradiation with actinic rays (hereinafter, referred to as an acid generator) is used as the component (B) together with the polyoxazole precursor used as the component (A). Examples of the actinic ray include a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, an i-ray stepper, a g-ray stepper, other ultraviolet rays, a visible light source, an X-ray, and an electron beam. . The component (B) is not particularly limited as long as the component (B) is irradiated with active actinic radiation to generate an acid by irradiating the component (B). The amount of the component (B) is preferably 0.01 to 50 parts by weight, and more preferably 0.01 to 50 parts by weight, based on 100 parts by weight of the component (A) in order to improve the sensitivity and resolution during exposure. The content is more preferably 20 parts by weight, and further preferably 0.5 to 20 parts by weight.

  The acid generator (B) used in the present invention exhibits an acidity upon irradiation with actinic rays such as ultraviolet rays, and has an organic group, which is a component (C), which can be decomposed by an acid catalyst and converted into a hydrogen atom. It has a conversion (specifically, elimination of the protecting group R) action of the compound (specifically, a solubility conversion agent). Examples of the compound of the component (B) include an onium salt, a halogen-containing compound, a quinonediazide compound, and a sulfonic acid ester compound.

  Examples of the onium salt include an iodonium salt, a sulfonium salt, a phosphonium salt, an ammonium salt, a diazonium salt and the like. Preferably, a diaryliodonium salt, a triarylsulfonium salt, and a trialkylsulfonium salt (the carbon number of the alkyl group is 1-8), diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, and aryldiazonium salts. As the counter anion of the onium salt, for example, tetrafluoroboric acid, hexafluoroantimonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid and the like are preferable.

  Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon-based compound and a haloalkyl group-containing heterocyclic compound, and preferably trichloromethyltriazine, bromoacetylbenzene, and the like.

  Examples of the quinonediazide compound include a diazobenzoquinone compound and a diazonaphthoquinone compound.

  Examples of the sulfonic acid ester compound include esters of an aromatic compound having a phenolic hydroxyl group with an alkylsulfonic acid or an aromatic sulfonic acid. As the aromatic compound having a phenolic hydroxyl group, for example, phenol, resorcinol, pyrogallol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene and the like can be mentioned. Examples of the alkylsulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butylsulfonic acid, and camphorsulfonic acid. Examples of the aromatic sulfonic acid include benzenesulfonic acid, naphthylsulfonic acid, aromatic tetracarboxylic acid ester, aromatic sulfonic acid ester, nitrobenzyl ester, oximesulfonic acid ester, aromatic N-oxyimidosulfonate, and aromatic sulfamide. , A haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, and naphthoquinonediazide-4-sulfonic acid ester.

  Such compounds can be used in combination of two or more, if necessary, or in combination with other sensitizers. Among them, aromatic oxime sulfonic acid esters and aromatic N-oxyimido sulfonates are preferred in terms of high sensitivity, and diaryliodonium salts and triarylsulfonium salts can be expected to have an appropriate dissolution inhibiting effect in unexposed areas. Is preferred.

  The component (C) used in the present invention has an organic group that can be decomposed by an acid catalyst and converted into a hydrogen atom. Accordingly, a dissolution inhibiting effect is expected in an unexposed portion, and a dissolution promoting effect is expected in an exposed portion, so that an appropriate contrast can be exhibited.

  The component (C) used in the present invention is not particularly limited in its structure. However, in a compound having a phenolic hydroxyl group or a carboxyl group, some or all of the hydrogen atoms of the phenolic hydroxyl group or the carboxyl group may be acidified. Compounds substituted with a decomposable group are preferred.

  As the compound having a phenolic hydroxyl group or a carboxyl group, a compound having 1 to 15 benzene rings and 1 to 20 phenolic hydroxyl groups or carboxyl groups in a molecule is preferable. Further, as these compounds, resinous compounds such as phenol novolak resin and polyvinyl phenol may be used. Further, a polyimide precursor or a polybenzoxazole precursor which is the component (A) may be used. That is, a polyamic acid ester having a phenolic hydroxyl group or a carboxyl group, a polyamic acid, or a polyhydroxyamide may be used. Some or all of the hydrogen atoms of the phenolic hydroxyl group or carboxyl group of these compounds are used after being substituted by an acid-decomposable group.

  The above is described in more detail as follows. That is, the component (C) used in the present invention preferably has a structure represented by the general formula (2) or (3) because of excellent sensitivity and resolution. In the general formula (2), a and b are each an integer of 0 or more, a + b is an integer of 1 or more, and preferably a + b is an integer of 10 or less. In the general formula (3), a and b are each an integer of 0 or more, and preferably, a + b is an integer of 10 or less.

  Preferred examples of the monovalent group that can be decomposed by an acid catalyst and converted into a hydrogen atom include those that form an acetal or ketal having the following structure.

（式中、Ｒ’、Ｒ”及びＲ'''は各々独立に炭素数５以下のアルキル基を示し、Ｘは炭素数３以上（好ましくは２０以下）の２価のアルキレン基（側鎖を有していてもよい）を示す）

(Wherein R ′, R ″ and R ′ ″ each independently represent an alkyl group having 5 or less carbon atoms, and X represents a divalent alkylene group having 3 or more carbon atoms (preferably 20 or less) May be included)

  Specific examples include a tetrahydropyranyl group, a tetrahydrofuranyl group, an alkyl-substituted tetrahydropyranyl group, an alkyl-substituted tetrahydrofuranyl group, an alkoxy-substituted tetrahydropyranyl group, and an alkoxy-substituted tetrahydrofuranyl group. However, the present invention is not limited to these. The most preferred group is a tetrahydropyranyl group. These are preferred in terms of sensitivity and resolution.

  Further, examples of the monovalent group that can be decomposed by the action of an acid and converted into a hydrogen atom include a monovalent alkoxyalkyl group, an alkylsilyl group, and an alkoxycarbonyl group. Although there is no particular limitation, the preferred number of carbon atoms is 2 to 8 for an alkoxyalkyl group, 1 to 20 for an alkylsilyl group, and 2 to 15 for an alkoxycarbonyl group.

  Specifically, methoxymethyl, ethoxymethyl, isopropoxymethyl, tert-butoxymethyl, ethoxyethyl, methylsilyl, ethylsilyl, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyl A butoxycarbonyl group is exemplified as a typical example, but is not limited thereto. Preferred groups are a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a methoxyethyl group, a t-butyldimethylsilyl group, and a t-butoxycarbonyl group. These are preferred in terms of sensitivity and resolution.

  Further, as for R in the substituent represented by -COOR, a monovalent alkyl group can be used. Although there is no particular limitation on these, the preferred number of carbon atoms is 1 to 10.

  Specific examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and amyl. Most preferred groups are ethyl, isopropyl and tert-butyl. These are preferred in terms of sensitivity and resolution.

  In the present invention, X or X ′ in the structure represented by the general formula (2) or (3) is specifically diphenyl, diphenyl ether, diphenylthioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane. An aromatic hydrocarbon residue having a skeleton such as diphenylsulfoxide, diphenylsulfone, benzene, naphthalene, and perylene, and an aliphatic hydrocarbon residue having a skeleton such as ethane, propane, butane, cyclobutane, cyclohexane, and adamantane, or One having the following structure:

（式中、Ｙ、Ｙ’は炭素数１〜２０の有機基を示す）

(Wherein, Y and Y ′ each represent an organic group having 1 to 20 carbon atoms)

（式中、Ｚ、Ｚ’はアルキル基あるいはアルキル置換または無置換のヘテロ原子を示す）

(Wherein, Z and Z ′ represent an alkyl group or an alkyl-substituted or unsubstituted heteroatom)

  These substituents can be easily introduced, for example, by reacting a compound having a phenolic hydroxyl group or a carboxyl group with a vinyl ether compound under an acid catalyst. Further, the compound can be easily introduced by reacting a chloride of a substituent to be introduced under an alkali catalyst such as an amine.

（式中、Ｙ、Ｙ’は炭素数１〜２０の有機基を示し、Ｒは前記同様、酸触媒作用で分解し、水素原子に変換し得る有機基を示す。いずれも同一分子に複数あるときは同じでも異なっていても良い。ｐは繰り返し単位を表す１以上の整数である）で表される化合物、又は繰り返し単位を有する化合物を挙げることができる。ポリマーの場合には分子量は重量平均分子量で１０００〜３００００のものが好ましい。 Preferred as the solubility converter (C) is the following general formula

(In the formula, Y and Y ′ each represent an organic group having 1 to 20 carbon atoms, and R represents an organic group that can be decomposed by an acid catalyst and converted into a hydrogen atom, as described above. And p may be the same or different. P is an integer of 1 or more representing a repeating unit), or a compound having a repeating unit. In the case of a polymer, the molecular weight is preferably 1,000 to 30,000 in terms of weight average molecular weight.

  When the component (C) is an oligomer or a polymer, the amount of the component (C) is preferably 1 to 500 parts by weight based on 100 parts by weight of the component (A) from the viewpoint of sensitivity and film quality after curing. More preferably, it is 10 to 300 parts by weight. In other cases, the amount is preferably 1 to 50 parts by weight, more preferably 1 to 25 parts by weight, per 100 parts by weight of the component (A).

  The solvent used in the present invention is not particularly limited as long as it is a solvent which can well dissolve and uniformly dissolve the components (A) to (C), and for example, N-methyl-2-pyrrolidone, N , N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-butyrolactone, cyclohexanone, cyclopentanone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate And aprotic polar solvents such as those described above. These may be used alone or in combination of two or more.

  The solvent used in the present invention is used in an amount of 50 to 500 parts by weight, preferably 80 to 400 parts by weight, per 100 parts by weight of the component (A) from the viewpoint of the coating film thickness.

  The positive photosensitive resin composition of the present invention can contain an organic silane compound, an aluminum chelate compound and the like in order to enhance the adhesion of the cured film to the substrate. Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, and n- Propylphenylsilanediol, isopropylphenylsilanediol, n-butylcyphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol , N-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol , Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol , N-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (Ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldi (Droxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropyldroxysilyl) benzene, 1,4-bis (dibutylhydroxy) Silyl) benzene and the like. Examples of the aluminum chelate compound include aluminum tris (acetylacetonate) and aluminum acetylacetate diisopropylate. When using these adhesion-imparting agents, it is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the component (A).

  Examples of the aluminum chelate compound include aluminum tris (acetylacetonate) and aluminum acetylacetate diisopropylate.

  Further, the positive photosensitive resin composition of the present invention may contain a phenol compound or the like suitable for adjusting the solubility in an alkali developing solution.

  As the phenol compound, a compound containing 2 to 8 phenolic hydroxyl groups in a molecule can be used. For example, bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl- (4-hydroxyphenyl) methane, 3,3′-methylenebis (2-hydroxy-5-methylbenzenemethanol), 2,2′-methylenebis (4-methylphenol), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ) Ethane, 2,2-bis (4-hydroxyphenyl) propane, tris (2-hydroxyphenyl) methane, tris (4-hydroxyphenyl) methane, bis (2-hydroxyphenyl)-(4-hydroxyphenyl) methane, Bis (4-hydroxyphenyl)-(2-hydroxyphenyl) methane, 1, 1,1-Tris (2-hydroxyphenyl) ethane, 1,1-bis (2-hydroxyphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (2 -Hydroxyphenyl) ethane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-] Methylethyldiphenyl] ethane, 1,1-bis (2-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) -phenylmethane, bis (2-hydroxyphenyl) -phenylmethane, 4,4 ′ -Dihydroxy-3,3'-dimethyl-biphenyl and the like.

  In the positive photosensitive resin composition of the present invention, if necessary, a crosslinking agent which can react with a carboxylic acid or a hydroxyl group in the polymer during curing may be added in order to improve the mechanical properties of the cured film. Examples of the crosslinking agent used in the present invention include, for example, compounds represented by the following general formula.

（式中、Ｍは炭素数１〜２０の有機基を示し、Ｒは水素原子あるいは硬化時の熱で分解し、水素原子に変換し得る有機基を示す。いずれも同一分子に複数あるときは同じでも異なっていても良い。ｎは２以上の整数である。）

(Wherein, M represents an organic group having 1 to 20 carbon atoms, R represents a hydrogen atom or an organic group which can be converted into a hydrogen atom by being decomposed by heat at the time of curing. They may be the same or different, and n is an integer of 2 or more.)

  When these crosslinking agents are used, the amount is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the component (A).

  Further, the positive photosensitive resin composition of the present invention is added with an appropriate surfactant or leveling agent in order to prevent applicability, for example, striation (unevenness in film thickness) or improve developability. can do.

  Examples of the surfactant or the leveling agent include polyoxyethylene uraryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octyl phenol ether. Commercial products include Megafax F171 and F173. , R-08 (trade name of Dainippon Ink and Chemicals, Inc.), Florado FC430, FC431 (trade name of Sumitomo 3M Limited), organosiloxane polymers KP341, KBM303, KBM403, KBM803 (trade names of Shin-Etsu Chemical Co., Ltd.) And the like.

  Further, the positive photosensitive resin composition of the present invention may optionally contain a storage stabilizer, a dissolution inhibitor, and the like.

The positive photosensitive resin composition of the present invention is applied to a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ or SiO ₂ ), silicon nitride, or the like, and dried to dry the positive photosensitive resin composition. It can be a film of a conductive resin composition. Thereafter, irradiation with active light such as ultraviolet light, visible light, or radiation (exposure) is performed through a mask, and then heat treatment is performed as necessary. Then, the exposed portion is removed with a developing solution to form a positive relief pattern. can get.

  In the method of forming a pattern using the positive photosensitive resin composition of the present invention, first, the composition is applied to a suitable support, for example, a silicon wafer, ceramic, or aluminum substrate. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, the coating film is dried. Drying is usually performed using an oven or a hot plate. The drying conditions are appropriately determined depending on the components of the positive photosensitive resin composition. When a hot plate is used, drying is preferably performed at 60 to 140 ° C. for 30 seconds to 10 minutes. If the drying temperature is low, the fine pattern tends to peel off during development. On the other hand, when the drying temperature is high, the dissolution rate of the exposed portion in the developing solution decreases, and the sensitivity tends to decrease. Thereafter, radiation and actinic radiation are applied to the desired pattern shape. As the actinic ray, for example, radiation such as X-rays, electron beams, ultraviolet rays, and visible rays, and actinic rays can be used, and those having a wavelength of 200 nm to 500 nm are preferable. Monochromatic light such as g-line and i-line can also be used.

  Next, when a hot plate is used in order to diffuse the acid generated in the surface layer of the irradiated part to the bottom, it is preferable to perform heat treatment at 50 to 150 ° C. for 30 seconds to 10 minutes. When the heating temperature is low, the compound having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction does not efficiently decompose, and the sensitivity tends to decrease. If the heating temperature is high, the dissolution rate of the exposed portion in the developer decreases, and the development time tends to be long. Next, a pattern can be obtained by developing and dissolving and removing the irradiated portion.

  As the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as ammonia, primary amines such as ethylamine, n-propylamine, diethylamine, di-n- Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and quaternary amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline. An aqueous alkali solution such as an ammonium salt and an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or a surfactant thereto can be suitably used. Preferably, a 5% by weight or less aqueous solution of sodium hydroxide, potassium hydroxide, sodium silicate, tetramethylammonium hydroxide, choline or the like, more preferably a 1.5 to 3.0% by weight aqueous solution is used. A more preferred developer is a 1.5 to 3.0% by weight aqueous solution of tetramethylammonium hydroxide.

  As a developing method, for example, a method such as spray, paddle, immersion, or ultrasonic wave can be used. Next, the pattern formed by development is rinsed. Distilled water can be used as the rinsing liquid. Next, heat treatment is performed to obtain a final pattern having high heat resistance. The heating temperature is generally 150-450 ° C. By performing the heat treatment at 150 to 450 ° C., a relief pattern of a heat-resistant polymer having an oxazole ring or another cyclic group is obtained. The positive photosensitive resin composition of the present invention is suitable as a resin composition for forming a heat-resistant polymer having a thickness of 4 μm or more.

  Further, an alcohol or a surfactant may be added to the developer for use. Each of these may be added in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the developer.

  In the positive photosensitive resin composition of the present invention, after the active actinic ray irradiation and the heat treatment after the actinic ray irradiation, the exposed portion has increased solubility in an aqueous alkali solution due to a change in the component (C), and has an unexposed portion. Since the dissolving speed of the compound is different, a relief pattern can be formed. Further, active actinic radiation irradiation and the acid generated by the actinic radiation irradiation attack the acid-decomposable group at the terminal of the polyoxazole precursor as the component (A), and the carboxylic acid group, which is an alkali-soluble group, reacts with the resin terminal. And supports increasing the dissolution rate difference between the unexposed portion and the exposed portion in the developing solution. Due to such structural changes of the components (A) and (C), the solubility in an alkali developing solution is greatly changed, the film loss due to development is small, development can be performed in a short time, and fine processing can be performed. . Such a polyoxazole precursor becomes a resin film having excellent heat resistance by performing a curing reaction after forming the relief pattern.

  The photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices and multilayer wiring boards, and specifically, a surface protective film and an interlayer insulating film of a semiconductor device, and an interlayer insulating film of a multilayer wiring board. And the like. The semiconductor device of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

  An example of the semiconductor device manufacturing process of the present invention will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. A series of steps from the first step to the fifth step is shown from top to bottom. In FIG. 1, a semiconductor substrate 1 such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer 3 is formed on the exposed circuit element. Is formed. An interlayer insulating film layer 4 is formed on the semiconductor substrate by a spin coating method or the like (first step).

  Next, a photosensitive resin layer 5 of a chlorinated rubber type, a phenol novolak type or the like is formed on the interlayer insulating film layer 4 by a spin coating method, and a predetermined portion of the interlayer insulating film layer 4 is exposed by a known photolithography technique. Window 6A is provided as described above (second step). The interlayer insulating film layer 4 of the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride, and a window 6B is opened. Next, the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (third step).

  Further, the second conductor layer 7 is formed by using a known photolithography technique (photolithography), and the electrical connection with the first conductor layer 3 is completely performed (fourth step). When a multilayer wiring structure of three or more layers is formed, the above steps are repeated to form each layer.

  Next, a surface protective film layer 8 is formed. In the example of this figure, the surface protective film layer is coated with the photosensitive resin composition by a spin coating method, dried, and irradiated with light from a mask on which a pattern for forming the window 6C is drawn on a predetermined portion. A pattern is formed by developing with an aqueous alkali solution, and heated to form a surface protective film (fifth step). The surface protective film protects the conductor layer from external stress, α-rays, and the like, and the semiconductor device obtained from this resin film has excellent reliability. In the above example, the interlayer insulating film layer can be formed using the photosensitive resin composition of the present invention.

  Hereinafter, the present invention will be described in more detail with reference to Examples. Note that the present invention is not limited to the following examples.

Synthesis Example 1 (Synthesis of polybenzoxazole precursor)
In a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyletherdicarboxylic acid and 90 g of N-methylpyrrolidone were charged, and the flask was cooled to 5 ° C. .64 g was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenylethertetracarboxylic acid chloride. Next, 87.5 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer and a thermometer, and 18.30 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added, followed by stirring. After dissolution, 8.53 g of pyridine was added, and while keeping the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyletherdicarboxylic acid chloride was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. The solution was poured into 3 liters of water, the precipitate was collected, washed three times with pure water, and dried under reduced pressure to obtain polyhydroxyamide (hereinafter referred to as polymer I). The polymer I had a weight average molecular weight of 14580 and a polydispersity of 1.6 as determined by standard polystyrene conversion. Next, 20 g of the polymer I and 100 g of N-methylpyrrolidone were charged into a 0.5-liter flask equipped with a stirrer and a thermometer, and dissolved by stirring. After dropwise addition of 0.4 g of methyl ethyl ether and further 0.4 g of triethylamine, stirring was continued for 30 minutes. This solution was poured into 2 liters of water, and the precipitate was collected, washed with pure water three times, and dried under reduced pressure to obtain a polyhydroxyamide having an ethoxymethyl group introduced into its terminal (hereinafter referred to as polymer II). ).

Synthesis Example 2
In a 0.5-liter flask equipped with a stirrer and a thermometer, 20 g of Polymer I and 100 g of N-methylpyrrolidone were charged and dissolved by stirring. Then, while maintaining the temperature at 0 to 5 ° C, 3,4- After 0.4 g of dihydro-2H-pyran was added dropwise, and 0.1 g of 12N hydrochloric acid was further added dropwise, stirring was continued for 30 minutes. The solution was poured into 2 liters of water, the precipitate was collected, washed three times with pure water, and dried under reduced pressure to obtain a polyhydroxyamide in which a tetrahydropyranyl group was selectively introduced into a terminal carboxyl group (hereinafter, referred to as a polyhydroxyamide). , Polymer III).

Synthesis Example 3
In a 0.5 liter flask equipped with a stirrer and a thermometer, Marcalinker M (trade name, manufactured by Maruzen Chemical Industry Co., Ltd., having a weight average molecular weight of 5,000 as determined by polystyrene conversion and a polydispersity of 2.5) was used. After stirring and dissolving 20 g of ethyl acetate and 200 g of ethyl acetate, 50 g of 3,4-dihydro-2H-pyran was added, then 0.3 g of 12N hydrochloric acid was added, and stirring was continued at room temperature for 70 hours. Thereafter, the reaction solution was transferred to a separating funnel, neutralized with 150 g of a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, and the organic layer was washed several times with 150 g of pure water. After taking out the organic layer and concentrating the organic layer by an evaporator, the concentrated organic layer is poured into n-hexane, and the precipitated resinous material is recovered, dried under reduced pressure, and the phenolic hydroxyl group is protected with a tetrahydropyranyl group. Polyvinyl phenol was obtained (hereinafter referred to as dissolution inhibitor I). The protection ratio of the tetrahydropyranyl group to the phenolic hydroxyl group of the dissolution inhibitor I was measured by ¹ H-NMR and found to be 95%.

Evaluation of photosensitive characteristics (Examples 1 to 18)
With respect to 100 parts by weight of the polybenzoxazole precursor, the component (B), the component (C) and, if necessary, the sensitizer were blended in the predetermined amounts shown in Table 1, and dissolved in γ-butyrolactone. . The chemical formulas of the components (B) (DIAS, DPI, MPI), the components (C) (C1 to C9), and the sensitizer (DMEA) in the composition of Table 1 are as shown in [Formula 11]. .

  The solution was spin-coated on a silicon wafer to form a coating film having a dry film thickness of 3 to 10 μm, and then exposed to i-line (365 nm) using an ultra-high pressure mercury lamp through an interference filter. After exposure, the film is heated at 120 ° C. for 3 minutes, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide until the silicon wafer on the exposed portion is exposed, and then rinsed with water to obtain a minimum exposure amount required for pattern formation. The resolution was determined. The results are shown in Table 2.

  As shown in Table 2, the residual film ratio after development was as high as 86% or more, and the dissolution rate difference between the unexposed portion and the exposed portion was large enough to form a pattern.

(Examples 19 to 20)
Polymers II and III as component (A), 9,10-dimethoxyanthracene-2-phenyliodonium sulfonate (hereinafter referred to as acid generator I) as component (B), dissolution inhibitor I as component (C), solvent Γ-butyrolactone, and these were combined and blended in a flask, and stirred and dissolved at room temperature to obtain a uniform solution state. Thereafter, this solution was subjected to pressure filtration using a 3 μm-pore Teflon (R) filter to obtain a positive photosensitive resin composition. For the components (A) to (C) and the solvent (γ-butyrolactone), four combinations were blended to prepare a positive photosensitive resin composition. Table 3 shows their composition.

The obtained positive photosensitive composition was spin-coated on a silicon wafer using a spinner and dried by heating at 90 ° C. for 2 minutes on a hot plate to obtain a 10 μm film of the positive photosensitive resin composition. . In order to evaluate the photosensitive characteristics, this coating film was exposed to 100 to 1100 mJ / cm ² through a reticle using an i-line reduction projection exposure apparatus (PFA3000iw manufactured by Canon). Next, after heating and drying at 120 ° C. for 2 minutes on a hot plate, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide is used as a developing solution, paddle developing is performed for 100 seconds, and the pattern is washed with pure water to form a relief pattern. Obtained. The residual film after development was measured to calculate the residual film ratio, and the proper exposure amount and minimum opening size were measured by pattern observation using a metallographic microscope. Table 4 shows the photosensitive characteristics of the positive photosensitive resin compositions of Examples 19 to 20.

  As shown in Table 4, the residual film ratios after development were all as high as 88% or more. In each case, a high-sensitivity and high-resolution relief pattern was formed.

Comparative Example 1
In the same manner as in Example 1, except that the polymer I having no terminal group was used instead of the polymer II, the photosensitive characteristics were evaluated in the same manner. As a result, the residual film ratio after development was 60%, the exposure amount was 660 mJ / cm ² , the minimum processing size was 15 μm, and the resolution was reduced due to the swelling of the unexposed portion, and a desired pattern could not be formed.

Comparative Example 2
In the same manner as in Example 1 except that isophthalic acid having no protective group introduced therein was used as the component (C), the photosensitive characteristics were evaluated in the same manner. As a result, the dissolution rate difference between the unexposed portion and the exposed portion was insufficient, and a pattern having a residual film ratio of 60% after development and a resolution of 30 μm could not be obtained at an exposure amount of 1 J / cm ² .

Comparative Example 3
The photosensitive characteristics were evaluated in the same manner as in Example 1 except that the component (B) was not added. As a result, no pattern could be obtained at all.

Comparative Example 4
The photosensitive characteristics were evaluated in the same manner as in Example 1 except that the component (C) was not added. As a result, the dissolution rate difference between the unexposed area and the exposed area was insufficient, and the residual film ratio after development was 74% at an exposure amount of 860 mJ / cm ² and the resolution was 20 μm.

  As described above, the positive photosensitive resin composition of the present invention is useful as a material for forming a surface protective film, an interlayer insulating film, and the like of a semiconductor element, and is particularly suitable as a material for forming a surface protective film.

It is a manufacturing process figure of the electronic component (semiconductor device) of a multilayer wiring structure.

Explanation of reference numerals

Reference Signs List 1 semiconductor substrate 2 protective film 3 first conductive layer 4 interlayer insulating film layer 5 photosensitive resin layer 6A, 6B, 6C window 7 second conductive layer 8 surface protective film layer

Claims (9)

  (A) a polyoxazole precursor having an organic group derived from a carboxylic acid residue at its molecular terminal, (B) a compound that generates an acid upon irradiation with actinic rays, and (C) hydrogen that is decomposed by acid catalysis to produce hydrogen. A positive photosensitive resin composition comprising a compound having an organic group that can be converted into an atom. The component (A) is represented by the following general formula (1)

(Wherein, R ¹ represents a divalent organic group, R ² represents a tetravalent organic group, and R ³ represents an organic group derived from the monovalent carboxylic acid residue. The positive photosensitive resin composition according to claim 1, wherein n is an integer, and n is an integer, and represents the number of repeating units. The organic group R ³ is at least one selected from the group consisting of an alkyl group, an aryl group, a group constituting an acetal or a ketal, a silyl group, a silyl ether group, an alkoxycarbonyl group, an alkoxyalkyl group, and an alkylsilyl group. The positive photosensitive resin composition according to claim 2, characterized in that:   A group in which the component (C) has an aromatic ring in the molecule and is represented by -OR (where R represents a monovalent organic group which can be decomposed by the action of an acid and converted into a hydrogen atom); And / or -COOR (wherein R is a monovalent organic group which is decomposed by the action of an acid and can be converted to a hydrogen atom). The positive photosensitive resin composition according to any one of the above. The component (C) is represented by the following general formula (2)

(Wherein, X is an organic group, R is a monovalent organic group that can be decomposed by the action of an acid and converted into a hydrogen atom, and when there are two or more of them, they may be the same or different; The positive photosensitive resin composition according to any one of claims 1 to 3, wherein each of the compounds is an integer of 0 or more, and a + b represents an integer of 1 or more. The component (C) is represented by the following general formula (3)

(In the formula, X ′ is an organic group, R is a monovalent organic group that can be decomposed by the action of an acid and converted into a hydrogen atom, and when there are two or more of them, they may be the same or different; a, b The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the compound has a repeating unit represented by the following formula:   The organic group R is at least one selected from the group consisting of an alkyl group, an aryl group, an acetal or a ketal, a silyl group, a silyl ether group, an alkoxycarbonyl group, an alkoxyalkyl group, and an alkylsilyl group. The positive photosensitive resin composition according to claim 5 or 6, wherein   A step of applying the positive photosensitive resin composition according to any one of claims 1 to 7 on a support substrate and drying to obtain a positive photosensitive resin film, Exposing, heating the exposed positive-type photosensitive resin film, developing the heated positive-type photosensitive resin film using an alkaline aqueous solution, and developing the positive-type photosensitive resin film. A step of subjecting the conductive resin film to a heat treatment.   An electronic component having an electronic device having a pattern layer obtained by the forming method according to claim 8, wherein the pattern layer is an interlayer insulating film layer and / or a surface protection film layer in the electronic device. An electronic component, characterized by being provided as:

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