JP5571914B2 - Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device - Google Patents

Description

  The present invention relates to a photosensitive resin composition for alkali development that gives excellent resolution, a method for producing a highly heat-resistant cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern. .

  Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics and the like has been used as a surface protective film and an interlayer insulating film of a semiconductor element. This polyimide resin is usually formed by applying an imidization treatment after applying a non-photosensitive polyimide precursor or a photosensitive polyimide precursor composition. When this polyimide resin needs to be patterned, a photosensitive polyimide precursor composition is generally used. The reason is that, if a photosensitive polyimide precursor composition is used, after applying it, imagewise exposure is performed with actinic rays, and then a polyimide pattern is easily formed by processing such as development and thermal imidization. This is because the process can be greatly shortened as compared with the case where non-photosensitive polyimide is used.

  However, when patterning is performed using this photosensitive polyimide precursor composition, it is necessary to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developer in the development step. However, there are problems such as effects on the factory working environment and other processes, and countermeasures or technical developments for developing without using organic solvents are strongly demanded. In response to this, recently, various proposals have been made on heat-resistant photosensitive resin materials that can be developed with a dilute alkaline aqueous solution as in the case of photoresists (Patent Documents 1 and 2).

Japanese Examined Patent Publication No. 01-046862 JP 63-096162 A Japanese Patent Publication No. 03-002355 JP 2006-045423 A JP 2006-104371 A

Latest Polyimide Japan Polyimide Study Group NTS

  However, the method of using polyamic acid as a polyimide precursor and mixing it with a photoactive component such as naphthoquinone diazide (hereinafter also referred to as “NQD”) has been put into practical use despite being simple and inexpensive. It wasn't. The reason is that the required lithographic characteristics cannot be satisfied, and one of the typical drawbacks is that a residue is generated in the pattern.

  Conventionally, as a method for suppressing imidization of polyamic acid, a method of keeping the temperature low (Non-patent Document 1), a method of coexisting a metal compound (Patent Document 3), a method of adding a specific diazabicyclo derivative (the above-mentioned patent) Document 4) A method of adding a boron trifluoride derivative (Patent Document 5) is known.

  However, it is practically difficult to keep the temperature always low during the photosensitive process, and when a metal compound or a boron derivative coexists, the electrical properties of the cured film are lowered. In addition, the addition of a diazabicyclo derivative changes NQD, which is a photosensitive component, and significantly reduces the photosensitive characteristics.

  Therefore, the photosensitive resin composition for alkali development using polyamic acid is excellent in sensitivity even when alkali development is performed, and the film after thermal imidization can maintain the electrical characteristics expected of a polyimide resin film. Was not proposed.

  The present invention is a photosensitive resin composition for alkali development that is highly sensitive, has no pattern residue when alkali development is performed, and has excellent patterning characteristics, and high heat resistance using the photosensitive resin composition An object of the present invention is to provide a method for producing a cured relief pattern and a semiconductor device having the cured relief pattern.

  The present inventors relate to the cause of residue generation on the pattern when polyamic acid is used as a polyimide precursor, and when polyamic acid comes into contact with a basic substance such as tetramethylammonium hydroxide in an alkaline developer during development. It was considered that the polyamic acid is imidized, so that the solubility in a developing solution is lowered and insolubilized to be a residue. Furthermore, the present inventors have found that the generation of a residue during alkali development can be prevented by including a specific compound in the polyamic acid composition, and the present invention has been completed. That is, the present invention is as follows.

｛式中、Ｒ₁及びＲ₂はそれぞれ独立に水素原子又は炭素数１〜１０の有機基を表し、Ｒ₁及びＲ₂のうち少なくとも一方が炭素数６以上の有機基であり、Ｒ₃は炭素数１以上の有機基を表す。｝で表される化合物１〜１００質量部と、
（ｃ）感光剤１〜５０質量部と
を含む、アルカリ現像用の感光性樹脂組成物。 [1] (a) 100 parts by mass of polyamic acid;
(B) The following general formula (1):

{Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or an organic group having 1 to 10 carbon atoms, at least one of R ₁ and R ₂ is an organic group having 6 or more carbon atoms, R ₃ is An organic group having 1 or more carbon atoms is represented. } 1 to 100 parts by mass of a compound represented by:
(C) A photosensitive resin composition for alkali development, containing 1 to 50 parts by mass of a photosensitizer.

｛式（２）中、Ｒ₄及びＲ₅はそれぞれ独立に水素原子又は炭素数１〜１０の有機基を表し、そして、式（３）中、Ｒ₆は炭素数１〜１０の有機基を表す。｝で表される、上記［１］に記載の感光性樹脂組成物。 [2] In the compound (b), R ₃ is represented by the following general formula (2) or (3):

{In Formula (2), R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 10 carbon atoms; and, in Formula (3), R ₆ represents an organic group having 1 to 10 carbon atoms. Represent. } The photosensitive resin composition as described in [1] above.

[3] A step of applying the photosensitive resin composition according to [1] or [2] to a substrate,
Exposing the photosensitive resin composition with actinic radiation through a mask to form a cured portion of the photosensitive resin composition, or directly irradiating the photosensitive resin composition with light, an electron beam or an ion beam. Forming an irradiated portion of the photosensitive resin composition,
A method for producing a cured relief pattern, comprising: a step of forming a relief pattern by eluting and removing the exposed portion or the irradiated portion; and a step of heating the relief pattern to form a cured relief pattern.

  [4] A semiconductor device having a cured relief pattern obtained by the production method according to [3].

  According to the present invention, a photosensitive resin composition for alkali development that has high sensitivity, no residue is generated in the pattern when alkali development is performed, and has excellent patterning characteristics, and a high heat-resistant cured relief using the same. A pattern manufacturing method and a semiconductor device having the cured relief pattern can be provided.

｛式中、Ｒ₁及びＲ₂はそれぞれ独立に水素原子又は炭素数１〜１０の有機基を表し、Ｒ₁及びＲ₂のうち少なくとも一方が炭素数６以上の有機基であり、Ｒ₃は炭素数１以上の有機基を表す。｝で表される化合物（以下、単に「（ｂ）化合物」ともいう。）１〜１００質量部と、
（ｃ）感光剤１〜５０質量部と
を含む、アルカリ現像用の感光性樹脂組成物を提供する。本発明のアルカリ現像用の感光性樹脂組成物を構成する各成分について、以下具体的に説明する。なお本明細書で記載する一般式中、各符号で表される構造は、分子中に複数存在する場合特記がない限り互いに独立であり、すなわち互いに同一でも異なってもよい。 <Photosensitive resin composition>
The present invention comprises (a) 100 parts by mass of polyamic acid,
(B) The following general formula (1):

{Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or an organic group having 1 to 10 carbon atoms, at least one of R ₁ and R ₂ is an organic group having 6 or more carbon atoms, R ₃ is An organic group having 1 or more carbon atoms is represented. } (Hereinafter also simply referred to as “(b) compound”) 1 to 100 parts by mass,
(C) A photosensitive resin composition for alkali development comprising 1 to 50 parts by mass of a photosensitive agent is provided. Each component constituting the photosensitive resin composition for alkali development of the present invention will be specifically described below. In addition, in the general formula described in this specification, the structures represented by the respective symbols are independent of each other unless otherwise specified, that is, they may be the same or different from each other unless otherwise specified.

(A) Polyamic acid (a) Polyamic acid is usually dehydrated and closed when heated at 200 to 400 ° C. and converted to polyimide, so that the photosensitive resin composition of the present invention can be used for forming a polyimide resin pattern. In addition, (a) polyamic acid has the general formula (4):

{Wherein X represents a tetravalent organic group, Y represents a divalent organic group, a plurality of M each independently represents a hydrogen atom or a monovalent organic group, and two M in the formula At least one of them is a hydrogen atom, and n is an integer of 2 to 100. }, For example, part may be imidized, or part of the carboxylic acid-derived structure may be converted by an ester group, an amide group, or the like. It may be. N in the general formula (4) is 2 or more from the viewpoint of physical properties of the cured relief pattern, and is 100 or less from the viewpoint of resolution.

  (A) The polyamic acid is typically obtained by polycondensation of a tetracarboxylic dianhydride and a diamine. Tetracarboxylic dianhydride is represented by the following structure.

{Wherein X has the same meaning as defined in formula (4). }

  X is preferably a tetravalent organic group having 2 to 30 carbon atoms. When the number of carbon atoms of X is 2 or more (a) The solubility of polyamic acid in an organic solvent can be maintained, and when it is 30 or less, the heat resistance of the finally obtained polyimide may be impaired. Absent.

  Examples of the tetravalent organic group corresponding to X include an aromatic ring structure and an alicyclic structure, and specific examples include the following structures.

  The following is mentioned as a preferable example of the tetravalent organic group applicable to said X.

  Diamine is represented by the following structure.

{Wherein Y has the same meaning as defined in general formula (4). }

  Y is preferably a divalent organic group having 2 to 30 carbon atoms. When the number of carbon atoms of Y is 2 or more (a) The solubility of the polyamic acid in an organic solvent can be maintained, and when it is 30 or less, the heat resistance of the finally obtained polyimide may be impaired. Absent.

  Examples of the divalent organic group corresponding to Y include aromatic ring structures and alicyclic structures, and specific examples include the following compounds.

{Wherein, n ₁ represents an integer of 1 to 10, R ₇ represents an organic group having 1 to 5 carbon atoms, R ₈ represents a hydrogen atom or an organic group having 1 to 5 carbon atoms. }

The following is mentioned as a preferable example of the bivalent organic group applicable to said Y.

  Moreover, in order to improve the adhesiveness of a cured relief pattern and a base material, a silicon diamine can be selected as a diamine containing a Y structure, and examples thereof include bis (4-aminophenyl) dimethylsilane, bis ( 4-aminophenyl) tetramethylsiloxane bis (p-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4 -Aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane and the like.

  (A) The terminal group of the polyamic acid may be sealed with an organic group. (A) When the terminal of the polyamic acid is sealed, it is expected that the mechanical properties (particularly the elongation) of the coating film after heat curing and the cured relief pattern shape will be good. (A) In polycondensation to obtain a polyamic acid, when the tetracarboxylic acid component is used in excess of the diamine component, the blocking group reacts with a carboxylic acid anhydride such as an amino group or a hydroxyl group. It is preferable to use a compound having a functional group that can be used. Examples of the compound having a functional group capable of reacting with carboxylic anhydride include aniline, cyclohexylamine, norborneneamine, norbornaneamine, ethanolamine, propargylamine, iminodiacetonitrile, cyclohexanol and the like.

  Conversely, when the diamine component is used in excess of the tetracarboxylic acid component, the blocking group reacts with amino groups such as acid anhydrides, carboxylic acids, acid chlorides, isocyanate group-containing compounds. A compound having a functional group to be obtained is used. Examples of the compound having a functional group capable of reacting with an amino group include acetic anhydride, 4-norbornene-1,2-dicarboxylic anhydride, methyl-4-norbornene-1,2-dicarboxylic anhydride, 4-cyclo Hexenyl-1,2-dicarboxylic anhydride, phthalic anhydride, succinic anhydride, 2-buten-1-yl succinic anhydride, itaconic anhydride, cyclohexyl-1,2-dicarboxylic anhydride, 4- Methylcyclohexyl-1,2-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, norbornane-2,3-carboxylic anhydride, 1,8-naphthalene Dicarboxylic anhydride, di-t-butyl dicarbonate, benzoyl chloride, methane sulfonic acid chloride, p-toluene sulfonic acid chloride, phenyl isocyanate And the like.

  (A) A general method can be used for the synthesis of the polyamic acid. As a typical example, a polymerization proceeds by mixing a tetracarboxylic dianhydride containing a structure of X and a diamine containing a structure of Y in a polymerization solvent, and stirring the solution as it is (a) polyamide An acid can be obtained. When the terminal is modified, a compound necessary for terminal modification may be added after the polymerization of the polyamic acid, or a compound necessary for terminal modification may be added to the reaction solution before or during the polymerization. During polymerization or after polymerization, the reaction solution may be heated as necessary to imidize part of the polyamic acid. By imidizing a part of the polyamic acid in advance, (a) the solubility of the polyamic acid in an alkali developer is adjusted, and the lithographic performance of the photosensitive resin composition is controlled. Stability can be improved. In addition, it is also preferable to adjust the alkali solubility of the polyamic acid or improve the stability by converting a part of the carboxylic acid portion of the polyamic acid to, for example, an ester group or an amide group. As a typical synthesis method in such a case, a method in which a tetracarboxylic dianhydride containing a structure of X is reacted with an alcohol or an amine and then condensed with a diamine containing a structure of Y using a condensing agent. It is done.

(A) When imidating a part of the polyamic acid or (a) converting a part of the carboxylic acid-derived part of the polyamic acid into an ester group, an amide group, etc., when all the carboxylic acids are not converted ( a) When the carboxylic acid number of the polyamic acid is 100%, (a) 30% or more of the carboxylic acid number is imidized, ester group, amide group, etc. from the viewpoint of solubility of the polyamic acid in an alkaline developer. It is preferable that the carboxylic acid remains as it is without being converted to. Further (a) From the viewpoint of solubility of the polyamic acid in an alkaline developer, the number of carboxylic acids remaining without being subjected to the imidization and conversion is more preferably 40% or more, and 50% or more. More preferably it is.

  (A) The reaction solution at the time of synthesizing the polyamic acid can be used as a raw material for the resin composition as it is, or precipitated in a poor solvent such as water, benzene, toluene, hexane, filtered and dried (a). You may manufacture the photosensitive resin composition from a polyamic acid as a raw material.

  (A) The polymerization solvent used in the synthesis of the polyamic acid is not particularly limited as long as the obtained (a) polyamic acid is soluble, but N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”). ), Γ-butyrolactone (hereinafter also referred to as “GBL”), N, N-dimethylacetamide (hereinafter also referred to as “DMAc”), dimethyl sulfoxide (hereinafter also referred to as “DMSO”), and the like. It is mentioned as a thing.

  The weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”) of (a) polyamic acid used in the present invention is preferably 3,000 to 100,000, and 5,000. More preferably, it is -50,000, Most preferably, it is 7,000-30,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of physical properties of the cured relief pattern, and is preferably 100,000 or less from the viewpoint of resolution. Tetrahydrofuran (hereinafter also referred to as “THF”) and NMP are recommended as developing solvents for GPC. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended to select standard monodisperse polystyrene from Showa Denko's organic solvent standard sample STANDARD SM-105.

｛式中、Ｒ₁及びＲ₂はそれぞれ独立に水素原子又は炭素数１〜１０の有機基を表し、Ｒ₁及びＲ₂のうち少なくとも一方が炭素数６以上の有機基であり、Ｒ₃は炭素数１以上の有機基を表す。｝で表される。本発明の感光性樹脂組成物が（ｂ）化合物を含むことにより、（ａ）ポリアミド酸の塗膜がアルカリ現像液と接触した時に、塗膜中に存在する（ｂ）化合物が塗膜全体のアルカリ現像液への溶解性を保つことができ、これにより残渣の発生を防ぐことができる。（ｂ）化合物の作用機構は明らかでないが、本発明の感光性樹脂組成物が基板に塗布されて塗膜となった状態で、（ｂ）化合物が、（ａ）ポリアミド酸のアミド結合やカルボキシル基と相互作用して（ａ）ポリアミド酸のイミド化を起きにくくしており、一度アルカリ現像液に溶解した（ａ）ポリアミド酸がイミド化により析出して再付着するという現象を防いでいると考えられる。 (B) Compound The (b) compound used in the present invention has the following general formula (1):

{Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or an organic group having 1 to 10 carbon atoms, at least one of R ₁ and R ₂ is an organic group having 6 or more carbon atoms, R ₃ is An organic group having 1 or more carbon atoms is represented. }. When the photosensitive resin composition of the present invention contains the compound (b), when the (a) polyamic acid coating film comes into contact with the alkaline developer, the (b) compound present in the coating film Solubility in an alkali developer can be maintained, thereby preventing generation of a residue. (B) Although the mechanism of action of the compound is not clear, in the state where the photosensitive resin composition of the present invention is applied to a substrate to form a coating film, (b) the compound is (a) an amide bond or carboxyl of polyamic acid. (A) it is difficult to cause imidation of the polyamic acid by interacting with the group, and (a) the polyamic acid once dissolved in the alkaline developer is prevented from being precipitated and reattached by imidation. Conceivable.

In the general formula (1), at least one of R ₁ and R ₂ is an organic group having 6 or more carbon atoms from the viewpoint of the effect of preventing the generation of residues. R ₁ and R ₂ are preferably groups having no hydroxyl group, carboxylic acid group and amino group, respectively, from the viewpoint of further preventing the generation of residues. And from the viewpoint of the further effect of preventing the generation of residues, R ₁ , R ₂ and R ₃ are preferably groups having no hydroxyl group, carboxylic acid group and amino group.

In the compound (b), R ₃ is represented by the following general formula (2) or (3):

{In Formula (2), R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 10 carbon atoms; and, in Formula (3), R ₆ represents an organic group having 1 to 10 carbon atoms. Represent. } Is preferably represented.

(B) Specific examples of the compound include
1) Amide compounds such as benzanilide, N, N-diphenylacetamide, 3 ′, 4′-dimethylacetanilide, N, N-diphenyl-4-methoxybenzamide, p-acetaniside, p-acetoluidine, N-methylacetanilide,
2) Urethane compounds such as methyl N-phenylcarbamate, ethyl N-phenylcarbamate, ethyl N, N-diphenylcarbamate, ethyl N- (2-methyl-5-nitrophenyl) carbamate, N-cyclohexylcarbamine Acid methyl, ethyl N-cyclohexylcarbamate, phenyl N-cyclohexylcarbamate, methyl N-hexylcarbamate, ethyl N-hexylcarbamate, phenyl N-hexylcarbamate,
3) Urea compounds such as 1,3-dicyclohexylurea, diphenylurea, 1-methyl-3-phenylurea, 1,1-dimethyl-3-phenylurea, 3- (4-chlorophenyl) -1,1-dimethyl Examples include urea, N, N′-dimethyl-N, N′-diphenylurea, and N, N′-diethyl-N, N′-diphenylurea.

  These (b) compounds can be used alone or in admixture of two or more. Moreover, the compounding quantity of (b) compound with respect to 100 mass parts of (a) polyamic acid is 1-100 mass parts, and if the said compounding quantity is 1 mass part or more, (a) The photosensitive resin composition containing polyamic acid The effect of suppressing the residue is developed when the film is alkali-developed, and if it is 100 parts by mass or less, deterioration of the tensile elongation of the film formed after heat curing can be prevented. As for the said compounding quantity, it is more preferable that it is 3-80 mass parts, and it is still more preferable that it is 5-50 mass parts.

(C) Photosensitizer It is essential that the photosensitive resin composition of the present invention contains (c) a photosensitizer. (C) By selecting the kind of photosensitive agent, the photosensitive resin composition of the present invention can be made positive or negative. When the photosensitive resin composition is made positive, it is necessary to select a photoacid generator as (c) a photosensitive agent. As the photoacid generator, a naphthoquinone diazide compound (hereinafter also referred to as “NQD compound”), an onium salt, a halogen-containing compound, and the like can be used. From the viewpoint of solvent solubility and storage stability, the NQD structure described later is used. A photoactive substance (hereinafter, also referred to as “PAC”) compound having a hydrogen atom is preferred.

  Examples of the onium salt include an iodonium salt, a sulfonium salt, a hosiphonium salt, a phosphonium salt, an ammonium salt, and a diazonium salt, and an onium selected from the group consisting of a diaryl iodonium salt, a triaryl sulfonium salt, and a trialkyl sulfonium salt. Salts are preferred.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and the like, and trichloromethyltriazine is preferable.

  Examples of the naphthoquinone diazide compound include compounds having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure, and examples thereof include US Pat. No. 2,772,972, US Pat. No. 2,797. No. 213, U.S. Pat. No. 3,669,658, and the like. The naphthoquinonediazide structure includes 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinonediazide-5-sulfonic acid ester of the polyhydroxy compound. At least one compound selected from the group consisting of:

  The NQD compound is obtained by subjecting a naphthoquinone diazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride according to a conventional method, and subjecting the obtained naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound. For example, a polyhydroxy compound and a predetermined amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone or tetrahydrofuran, The reaction can be carried out in the presence of a basic catalyst for esterification, and the resulting product can be obtained by washing with water and drying.

  Preferred NQD compounds are described below.

  NQD compounds of polyhydroxy compounds represented by the following general formula (5)

{Wherein R _{9 to} R ₁₈ are each independently at least one monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group. Each of A _{1 to} A ₃ independently represents a single bond, —O—, —S—, —SO—, —SO ₂ —, —CO—, —CO ₂ —, a cyclopentylidene group, or cyclohexylene. Den group, phenylene group, or the following chemical formula:

(In the formula, R ₁₉ and R ₂₀ each independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an allyl group, and a substituted allyl group.)

(Wherein R _{21 to} R ₂₄ each independently represents a hydrogen atom or an alkyl group, and n ₆ is an integer of 1 to 5)

(In the formula, R _{25 to} R ₂₈ each independently represents a hydrogen atom or an alkyl group.)
And n _{2 to} n ₅ are each independently an integer of 1 or 2. }

  Specific examples of the compound include NQD compounds of polyhydroxy compounds described in [Chemical Formula 18] to [Chemical Formula 32] of JP-A No. 2001-109149.

  Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

  NQD compound of polyhydroxy compound represented by the following general formula (6)

{Wherein A ₄ represents the following chemical formula:

で表される有機基から選択される少なくとも１つの４価の基を表し、Ｒ₂₉〜Ｒ₃₂は、それぞれ独立に１価の有機基を表し、ｎ₇は０又は１であり、ｎ₈〜ｎ₁₁はそれぞれ独立に０〜３の整数であり、そしてｎ₁₂〜ｎ₁₅はそれぞれ独立に０〜２の整数である。）

At least one tetravalent group selected from the organic groups represented by the formula: R _{29 to} R ₃₂ each independently represents a monovalent organic group, n ₇ is 0 or 1, and n ₈ to n ₁₁ are each independently an integer of 0 to 3, and n ₁₂ ~n ₁₅ is each independently an integer of 0-2. )

  Specific examples of the compound include those described in [Chemical Formula 23] to [Chemical Formula 28] of JP-A No. 2001-092138. Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

  NQD compounds of polyhydroxy compounds represented by the following general formula (7)

{Wherein R ₃₃ represents a monovalent organic group having one or more carbon atoms, R ₃₄ and R ₃₅ each independently represents a hydrogen atom or a monovalent organic group, and n ₁₆ represents 3 8 of an integer, and n ₁₇ is an integer of 1 to 5. }

  Specific preferred examples include those described in [Chemical Formula 24] and [Chemical Formula 25] of JP-A-2004-347902.

  Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

{Wherein n ₁₈ is an integer from 0 to 9. }

  NQD compounds of polyhydroxy compounds represented by the following general formula (8)

{In the formula, R ₃₆ represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and A ₅ represents the following chemical formula:

で表される基から選択される少なくとも１つの２価の基を表す。｝

Represents at least one divalent group selected from the group represented by: }

  Specific examples of the compound include those described in [Chemical Formula 22] to [Chemical Formula 28] of JP-A No. 2003-131368.

  Among them, the following general formula:

{In the formula, R ₃₇ and R ₃₈ each independently represent —CH ₂ —, —O— or —S—, and R ₃₉ and R ₄₀ each independently represent a hydrogen atom or a methyl group. }
An NQD product of a polyhydroxy compound represented by the formula is preferred because of its high sensitivity and low precipitation in a positive photosensitive resin composition.

  NQD compounds of polyhydroxy compounds represented by the following general formula (9)

{Wherein R _{41 to} R ₄₃ each independently represents the following general formula:

(Wherein R ₄₄ represents an alkyl group or a cycloalkyl group, and n ₂₂ is an integer of 0 to 2).
In the formula, n _{19 to} n ₂₁ are each independently an integer of 0 to 2. }

  Specific examples of the compound include NQD compounds of polyhydroxy compounds described in [Chemical Formula 17] to [Chemical Formula 22] of JP-A-2004-109849.

  Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

  NQD compounds of polyhydroxy compounds represented by the following general formula (10)

{In the formula, R ₄₅ represents a hydrogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. }

  Specific examples of the compound include those described in [Chemical Formula 18] to [Chemical Formula 22] of JP-A No. 2001-356475.

  Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

  NQD compounds of polyhydroxy compounds represented by the following general formula (11)

{Wherein R ₄₆ represents the following general formula:

(In the formula, R ₅₀ represents an alkyl group or a cycloalkyl group, and n ₂₆ is an integer of 0 to 2.)
R _{47 to} R ₄₉ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group, and n _{23 to} n ₂₅ each independently represents an integer of 0 to 2 It is. }

  Specific examples of the compound include NQD compounds of polyhydroxy compounds described in [Chemical 15] and [Chemical 16] of JP-A-2005-008626.

  Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

  NQD compounds of polyhydroxy compounds represented by the following general formula (12)

{Wherein R ₅₁ and R ₅₂ each independently represent a monovalent organic group, n ₂₇ and n ₂₈ each independently represent an integer of 0 to 2, and 2 ≦ n ₂₇ + n ₂₈ ≦ 4 And n ₂₉ and n ₃₀ are each independently an integer of 0 to 3. }

  Specific examples of the compound include NQD compounds of polyhydroxy compounds described in [Chemical Formula 11] to [Chemical Formula 16] of JP-A No. 2004-077999.

  Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

  Specifically, other structures are preferably as follows.

  As a naphthoquinone diazide sulfonyl group in the above-mentioned NQD compound, both a 5-naphthoquinone diazide sulfonyl group and a 4-naphthoquinone diazide sulfonyl group are preferable. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed.

  Further, a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be used, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. Can also be used as a mixture.

  In this invention, the compounding quantity of (c) photosensitizer with respect to 100 mass parts of (a) polyamic acid is 1-50 mass parts, and it is preferable that it is 5-30 mass parts. (C) When the blending amount of the photosensitive agent is 1 part by mass or more, the patterning property of the resin is good, and when it is 50 parts by mass or less, the tensile elongation rate of the cured film is good, and There is little development residue (scum).

(D) Other components The photosensitive resin composition of the present invention contains, if necessary, a dye, a surfactant, an adhesion aid for enhancing adhesion to the substrate, a dissolution accelerator, a crosslinking agent, and the like. It is possible to make it.

  Examples of the dye include methyl violet, crystal violet, and malachite green. As a compounding quantity of dye, 0.1-30 mass parts is preferable with respect to 100 mass parts of (a) polyamic acid.

  Examples of the surfactant include nonionic surfactants made of polyglycols such as polypropylene glycol and polyoxyethylene lauryl ether, or derivatives thereof, as well as Florard (registered trademark, trade name, manufactured by Sumitomo 3M). Fluorosurfactants such as Megafac (registered trademark, trade name, manufactured by Dainippon Ink & Chemicals), Lumiflon (registered trademark, trade name, manufactured by Asahi Glass Co., Ltd.), such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) ), DBE (trade name, manufactured by Chisso Corporation), granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and other organosiloxane surfactants.

  As a compounding quantity in the case of using surfactant, 0.01-10 mass parts is preferable with respect to 100 mass parts of (a) polyamic acid.

  Examples of the adhesion assistant include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various alkoxy silanes.

  Specific preferred examples of alkoxysilane include, for example, tetraalkoxysilane, bis (trialkoxysilyl) methane, bis (trialkoxysilyl) ethane, bis (trialkoxysilyl) ethylene, bis (trialkoxysilyl) hexane, bis (Trialkoxysilyl) octane, bis (trialkoxysilyl) octadiene, bis [3- (trialkoxysilyl) propyl] disulfide, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (Trialkoxysilylethyl) pyridine, 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxy Propyl dialkoxyalkyl silane, 3-aminopropyl trialkoxy silane and 3-aminopropyl dialkoxyalkyl silane and acid anhydride or acid dianhydride reactant, 3-aminopropyl trialkoxy silane or 3-aminopropyl dialkoxyalkyl The thing etc. which converted the amino group of silane into the urethane group or the urea group can be mentioned. Examples of the alkyl group in the above compound include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the acid anhydride include maleic acid anhydride and phthalic acid anhydride, and acid dianhydrides. Examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, and the urethane group includes t-butoxycarbonyl. An amino group etc. are mentioned, A phenylamino carbonylamino group etc. are mentioned as a urea group.

  As a compounding quantity in the case of using an adhesion assistant, 0.1-30 mass parts is preferable with respect to 100 mass parts of (a) polyamic acid.

  The compounding quantity of said compound can be 0-10 mass parts with respect to 100 mass parts of (a) polyamic acid, It is more preferable that it is 0.1-10 mass parts, 0.1-6 mass Part is more preferable, and 1 to 4 parts by mass is particularly preferable. When the blending amount is 0.1 part by mass or more, there is no development residue in the exposed part, and the adhesion between the film formed using the photosensitive resin composition and the substrate (particularly the silicon substrate) is good, When it is 10 parts by mass or less, the temporal stability in the adhesion is good.

  As the dissolution accelerator, a compound having a hydroxyl group or a carboxyl group is preferable. Examples of the compound having a hydroxyl group include the ballast agent used in the above-mentioned naphthoquinone diazide compound, paracumylphenol, bisphenols, resorcinol, and linear phenol compounds such as MtrisPC and MtetraPC, TrisP-HAP, TrisP -Non-linear phenolic compounds such as PHBA and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2 to 5 phenol substitutes of diphenylmethane, 1 to 5 phenol substitutes of 3,3-diphenylpropane, One-to-two reactant of 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane and 5-norbornene-2,3-dicarboxylic anhydride, bis- (3-amino-4-hydroxy Phenyl) sulfone and 1,2-cyclohexyldicarboxylic anhydride 1: 2 reaction product of, N- hydroxysuccinimide, N- hydroxy phthalimide, and the like N- hydroxy 5-norbornene-2,3-dicarboxylic acid imide.

  Examples of the compound having a carboxyl group include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2. -(1-Naphthyl) propionic acid, mandelic acid, atrolactic acid, acetylmandelic acid, α-methoxyphenylacetic acid, 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxy Examples thereof include mandelic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid and the like.

  As a compounding quantity in the case of using a solubility promoter, 0.1-30 mass parts is preferable with respect to 100 mass parts of (a) polyamic acid.

  Examples of the crosslinking agent include 1,1,2,2-tetra (p-hydroxyphenyl) ethane, tetraglycidyl ether, glycerol triglycidyl ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxy Epoxy compounds such as propoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone chromium (III) salt, acetylacetone magnesium (II) salt, acetylacetone nickel ( II) salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium (III) salt, Metal chelating agents such as trifluoroacetylacetone magnesium (II) salt and trifluoroacetylacetone nickel (II) salt, Nicalak MW-30MH, MW-100LH (trade name, manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, Cymel 303 (trade name) Melamine resin-based cross-linking agent such as Nikalac BL-60 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Cymel 1123, My Coat 102, My Coat 105 (trade name, manufactured by Mitsui Cytec) Urea resin resins such as benzoguanamine-based cross-linking agents, Nicalac MX-270, MX-280, MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), trimethylolpropane trimethacrylate, triallyl 1,3,5-benzenetricarboxylate , Triallyl trimellitic acid, pyromellitic acid Unsaturated bond-containing compounds such as raaryl ester, pentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) Can be mentioned.

  As a compounding quantity in the case of using a crosslinking agent, 0.1-30 mass parts is preferable with respect to 100 mass parts of (a) polyamic acid.

  The photosensitive resin composition of the present invention may be used as a photosensitive resin composition solution by dissolving the above-described components in a solvent to form a varnish. Examples of the solvent include NMP, GBL, DMAc, DMSO, diethylene glycol dimethyl ether, 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, methyl-3-methoxypropionate, etc. can be used alone or in combination. . Of these solvents, non-amide solvents are preferable from the viewpoint of little influence on photoresists, and specific more preferable examples include GBL, DMSO, cyclopentanone, cyclohexanone, isophorone and the like.

  As an addition amount in the case of adding a solvent to the photosensitive resin composition, 50-1000 mass parts is preferable with respect to 100 mass parts of (a) polyamic acid, and 100-900 mass parts is more preferable.

<Method for Manufacturing Cured Relief Pattern and Semiconductor Device>
The present invention also provides a method for producing a cured relief pattern using the above-described photosensitive resin composition of the present invention, and a semiconductor device having the cured relief pattern.

  In the present invention, the above-described photosensitive resin composition of the present invention is applied to a substrate, and the photosensitive resin composition is exposed to actinic radiation through a mask to form a cured portion of the photosensitive resin composition. Or a step of directly irradiating the photosensitive resin composition with a light beam, an electron beam or an ion beam to form an irradiated portion of the photosensitive resin composition, a relief by eluting and removing the exposed portion or the irradiated portion. There is also provided a method for producing a cured relief pattern comprising a step of forming a pattern, and a step of heating the relief pattern to form a cured relief pattern. Hereinafter, examples of preferred embodiments of the production method will be described.

  First, the photosensitive resin composition of the present invention is typically in the form of a photosensitive resin composition solution, for example, spin coating using a spinner on a substrate such as a silicon wafer, a ceramic substrate, an aluminum substrate, or a roll coater. The substrate with a resin composition film is obtained by coating with the above. This is dried at 50 to 140 ° C. using an oven, a hot plate or the like, and the solvent in the photosensitive resin composition solution is removed.

  Next, the photosensitive resin composition on the substrate is exposed to actinic radiation through a mask using a contact aligner, a stepper, or the like, or directly irradiated with a light beam, an electron beam or an ion beam. Thereby, an exposure part or an irradiation part is formed in a part of the photosensitive resin composition.

  Next, the above-mentioned exposed part or irradiated part is eluted and removed with an alkaline developer, and preferably, a desired relief pattern is obtained by rinsing with a rinsing liquid. As a developing method, methods such as spray, paddle, dip, and ultrasonic can be used. As the rinsing liquid, distilled water, deionized water, or the like can be used.

  The alkali developer is an alkaline aqueous solution in which (a) polyamic acid is dissolved and removed, and an alkali compound is dissolved. 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, a cured relief pattern having a polyimide structure can be formed by heat-treating the obtained relief pattern.

  An oven furnace, hot plate, vertical furnace, belt conveyor furnace, pressure oven, etc. can be used as a heating device for the heat treatment, and heating by hot air, infrared rays, electromagnetic induction, etc. is recommended as the heating method. Is done. As heating temperature, 150-450 degreeC is preferable and 200-400 degreeC is more preferable. The heating time is preferably 15 minutes to 8 hours, more preferably 1 hour to 4 hours. The atmosphere is preferably in an inert gas such as nitrogen or argon.

  The present invention also provides a semiconductor device having a cured relief pattern obtained by the manufacturing method of the present invention described above. The semiconductor device of the present invention uses the above-described cured relief pattern as a protective film for 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. It can manufacture by combining with a manufacturing method.

  The cured relief pattern produced by the above-described method for producing a cured relief pattern of the present invention is used not only for semiconductor applications, but also for interlayer insulation of multilayer circuits, cover coats of flexible copper-clad plates, solder resist films, liquid crystal alignment films, etc. Also useful.

  The present invention will be described more specifically based on reference examples, examples and comparative examples.

<Synthesis of polyamic acid>
[Reference Example 1]
Mixing and stirring 58.5 g (0.2 mol) of 3,3 ′-(m-phenylenedioxy) dianiline and 141.3 g of GBL in a separable flask with a capacity of 2 liters at room temperature (25 ° C.) in a dry nitrogen stream. The diamine was dissolved. This was cooled with a dry ice-Solmix AP-1 (manufactured by Nippon Alcohol Sales Co., Ltd.) bath, and 6.6 g (0.04 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was separately dissolved in 25.0 g of GBL. What was made to drop was dripped from the dropping funnel. The time required for the dropwise addition was 25 minutes, and the maximum reaction solution temperature was 0 ° C.

  After completion of the dropwise addition, the mixture was stirred for 18 hours while returning to room temperature, and then the reaction solution was analyzed by GPC to confirm that 5-norbornene-2,3-dicarboxylic acid anhydride did not remain.

  Next, this was cooled with a dry ice-Solmix AP-1 bath, and 55.8 g (0.18 mol) of 4,4'-oxydiphthalic dianhydride was charged as powder. The reaction solution temperature at this time was 3.2 ° C. at maximum. Stirring was continued for 2 hours while returning the reaction solution to room temperature to obtain polyamic acid (P-1).

  Thus, the weight average molecular weight by GPC of the polyamic acid (P-1) synthesize | combined was 25300 in polystyrene conversion.

[Reference Example 2]
In a 2 liter separable flask, 204.6 g (0.7 mol) of 3,3 ′-(m-phenylenedioxy) dianiline and 201.1 g of GBL were mixed and stirred at room temperature (25 ° C.) in a dry nitrogen stream. The diamine was dissolved. This was cooled with a dry ice-Solmix AP-1 bath, and a solution obtained by dissolving 76.6 g (0.47 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 200.0 g of GBL separately was added to a dropping funnel. More dripped. The time required for the dropwise addition was 50 minutes, and the maximum reaction solution temperature was 1 ° C.

After completion of the dropwise addition, the mixture was stirred for 18 hours while returning to room temperature, and then the reaction solution was analyzed by GPC to confirm that 5-norbornene-2,3-dicarboxylic acid anhydride did not remain.
Next, this was cooled with a dry ice-Solmix AP-1 bath, and 144.8 g (0.47 mol) of 4,4′-oxydiphthalic dianhydride was charged as a powder. The reaction solution temperature at this time was 2.9 ° C. at the maximum. The reaction solution was stirred for 2 hours while returning to room temperature and then heated at 70 ° C. for 2 hours, and then 35.5 g of GBL was added to obtain a polyamic acid (P-2) in which a part of the polyamic acid was imidized.
Thus, the weight average molecular weight by GPC of the polyamic acid (P-2) synthesize | combined was 8100 in polystyrene conversion.

[Reference Example 3]
It was synthesized in the same manner as in Reference Example 2 except that 140.2 g (0.7 mol) of 3,4'-diaminodiphenyl ether was used instead of 3,3 ′-(m-phenylenedioxy) dianiline, and was measured by GPC in terms of polystyrene. A polyamic acid (P-3) having a weight average molecular weight of 9000 was obtained.

<Preparation of photosensitive resin composition and its evaluation>
[Examples 1-8], [Comparative Examples 1-5]
250 parts by mass of the polyamic acid (P-1 to P-3) solution obtained in each of the above reference examples (100 parts by mass of the polyamic acid in the above), (c) as a photosensitizer (B) Compound (A-1 to A-4), Compound (A-5) of 15 parts by mass of diazoquinone compound and the amount shown in Table 1 (the amount in Table 1 is part by mass with respect to 100 parts by mass of polyamic acid) , A-6), NMP or DMAc) is dissolved in 50 parts by mass of GBL, and then filtered through a 1.0 μm filter to prepare a photosensitive resin composition. The patterning characteristics and the amount of change in imidization rate due to development Evaluated. The diazoquinone compound has the following structure:

｛式中、Ｑは、水素原子又は下記基：

を表し、Ｑの総数のうち８３％が下記基：

である｝を有し、上記（ｂ）化合物Ａ−１〜Ａ−４、及び化合物Ａ−５，Ａ−６は、それぞれ下記構造：

{Wherein Q is a hydrogen atom or the following group:

83% of the total number of Q is the following group:

And (b) the compounds A-1 to A-4 and the compounds A-5 and A-6 have the following structures:

を有する。なお、（ｂ）化合物Ａ−１〜Ａ−４は一般式（１）で表される構造を有し、化合物Ａ−５，Ａ−６、ＮＭＰ及びＤＭＡｃの構造は一般式（１）で表される構造と異なるが、表１では便宜上（ｂ）化合物の欄に示している。評価結果を表１に示す。

Have (B) Compounds A-1 to A-4 have the structure represented by the general formula (1), and the structures of the compounds A-5, A-6, NMP and DMAc are represented by the general formula (1). Although different from the structure shown, in Table 1, it is shown in the column of (b) compound for convenience. The evaluation results are shown in Table 1.

(1) Evaluation of patterning characteristics The photosensitive resin composition obtained above was spin-coated on a 6-inch silicon wafer with a spin coater (clean track Mark-8) manufactured by Tokyo Electron Co., Ltd., and 120 ° C. and 180 ° C. on a hot plate. Pre-baking for 2 seconds was performed to form a coating film having a thickness of 10 μm. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg.

  This coating film is irradiated with i-line 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 stepwise. The film was exposed.

  The exposed coating film was contacted with the alkaline developer solution at 23 ° C. using an alkali developer (AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution) manufactured by AZ Electronic Materials. Development was performed under the condition of a liquid time of 40 seconds to form a positive pattern. Table 1 shows the sensitivity of the photosensitive resin composition and the evaluation results of the development residue.

  The sensitivity and development residue of the 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 (that is, 40 seconds).

[Development residue]
The relief pattern after development was observed with an optical microscope, and when no residue was observed in the exposed area at an exposure amount equal to or higher than the above sensitivity, it was marked as ◯.

(2) Imidation rate Three coating films were prepared for each photosensitive resin composition by applying and pre-baking in the same manner as the patterning property evaluation. One of them was used as the coating film (A) before development. Another sheet was developed in the same manner as the patterning property evaluation under the condition that the alkaline developer was in contact with the coating film for a period of 40 seconds to obtain a developed coating film (B). Further, one sheet at a time was heated in a vertical curing furnace VF200B manufactured by Koyo Thermo Systems Co., Ltd. under a nitrogen stream at 350 ° C. for 2 hours to obtain a cured coating film (C). The IR spectrum of each coating film at Centaurus (Thermospectra-Tech USA Inc.) was measured by ATR method, aromatic absorption intensity and 1500 cm ^-1 contraction vibration of C-N bonds of the imide group 1380 cm ^-1 The absorption strength of the stretching vibration of the ring was measured. The imidation ratio before and after development of each photosensitive resin composition was calculated by the following formula. Further, a value obtained by subtracting the imidization rate before development from the imidization rate after development was calculated as a change amount before and after development.

Pre-development imidization ratio = {(A ₁₃₈₀ ) / (A ₁₅₀₀ )} / {(C ₁₃₈₀ ) / (C ₁₅₀₀ )}
Post-development imidization ratio = {(B ₁₃₈₀ ) / (B ₁₅₀₀ )} / {(C ₁₃₈₀ ) / (C ₁₅₀₀ )}
A _1380: absorption intensity at 1380 cm ^-1 of the coating film (A) A _1500: absorption intensity at 1500 cm ^-1 of the coating film (A) B _1380: absorption intensity at 1380 cm ^-1 of the coating film (B) B _1500: coating (B) 1500 cm ^-1 absorption strength C ₁₃₈₀ : coating film (C) ₁₃₈₀ cm ^-1 absorption strength C ₁₅₀₀ : coating film (C) 1500 cm ^-1 absorption strength

  From the results shown in Table 1, it can be seen that by using the photosensitive resin composition of the present invention, no residue is generated in the pattern when alkali development is performed, and the change in the imidization ratio before and after development is small. On the other hand, in the compositions of Comparative Examples 1 to 5 using a compound that does not contain the compound (b) or a compound similar in structure to the compound (b), a residue is generated in the pattern by alkali development, before and after the development. It became clear that the change of the imidation ratio of was large.

  The photosensitive resin composition of this invention can be used suitably for formation of surface protection films, such as a semiconductor element, an interlayer insulation film.

Claims (3)

(A) 100 parts by mass of polyamic acid;
(B) benzanilide, N, N-diphenylacetamide, 3 ′, 4′-dimethylacetanilide, N, N-diphenyl-4-methoxybenzamide, p-acetoanisidide, p-acetotoluidine, N-methylacetanilide, N-phenylcarbamine Acid methyl, ethyl N-phenylcarbamate, ethyl N, N-diphenylcarbamate, ethyl N- (2-methyl-5-nitrophenyl) carbamate, methyl N-cyclohexylcarbamate, ethyl N-cyclohexylcarbamate, N -Phenyl cyclohexyl carbamate, methyl N-hexyl carbamate, ethyl N-hexyl carbamate, phenyl N-hexyl carbamate, 1,3-dicyclohexyl urea, 1-methyl-3-phenyl urea, 1,1-dimethyl-3 -Feni The group consisting of urea, 3- (4-chlorophenyl) -1,1-dimethylurea, N, N′-dimethyl-N, N′-diphenylurea, and N, N′-diethyl-N, N′-diphenylurea 1 to 100 parts by mass of one or more compounds selected from
(C) A photosensitive resin composition for alkali development, containing 1 to 50 parts by mass of a photosensitizer. Applying the photosensitive resin composition according to claim 1 to a substrate;
Exposing the photosensitive resin composition with actinic radiation through a mask to form a cured portion of the photosensitive resin composition, or directly irradiating the photosensitive resin composition with light, an electron beam or an ion beam. Forming an irradiated portion of the photosensitive resin composition,
A method for producing a cured relief pattern, comprising: a step of forming a relief pattern by eluting and removing the exposed portion or the irradiated portion; and a step of heating the relief pattern to form a cured relief pattern. A semiconductor device comprising a cured relief pattern obtained by the manufacturing method according to claim 2 .