Photosensitive resin composition, method for manufacturing patterned cured film, patterned cured film, and semiconductor element

Abstract

The present application relates to a photosensitive resin composition, a patterned cured film using the photosensitive resin composition, a method for producing a patterned cured film, and a semiconductor element, the photosensitive resin composition containing (A) an alkali-soluble resin having an imide bond and a phenolic hydroxyl group and (B) a compound that generates an acid by light.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition, a method for manufacturing a patterned curing film, the patterned curing film, and a semiconductor device. Background Technology

[0002] In recent years, with the increasing integration and miniaturization of semiconductor devices, there is a growing demand for surface protective layers and interlayer insulating layers that possess heat resistance, mechanical properties, and good adhesion to copper wiring. As a material for forming an insulating layer that simultaneously possesses these properties, photosensitive resin compositions containing alkali-soluble resins have been developed (see, for example, Patent Documents 1 to 4). These photosensitive resin compositions are coated onto a substrate and dried to form a resin film. The resin film is then exposed and developed to obtain a patterned resin film (a patterned resin film). Finally, by heating and curing the patterned resin film, a patterned cured film (a patterned cured film) can be formed, which can be used as both a surface protective layer and an interlayer insulating layer.

[0003] Previous technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2008-309885

[0006] Patent Document 2: Japanese Patent Application Publication No. 2007-57595

[0007] Patent Document 3: Japanese Patent Application Publication No. 2016-24306

[0008] Patent Document 4: International Publication No. 2010 / 073948 Summary of the Invention

[0009] The technical problem to be solved by the invention

[0010] The photosensitive resin composition used in the surface protective layer and interlayer insulation layer needs to have microprocessability for high-density wiring, low curing shrinkage for multilayering, and excellent mechanical strength to improve reliability.

[0011] The purpose of this invention is to provide a photosensitive resin composition capable of forming a patterned cured film with high resolution capable of microprocessing, low curing shrinkage, and excellent mechanical strength.

[0012] means for solving technical problems

[0013] One aspect of the present invention relates to a photosensitive resin composition comprising (A) an alkali-soluble resin having imide bonds and phenolic hydroxyl groups and (B) a compound that generates an acid upon exposure to light.

[0014] Another aspect of the present invention relates to a method for manufacturing a patterned resin film, comprising: a step of coating a portion or the entire surface of a substrate with the above-mentioned photosensitive resin composition and drying it to form a resin film; a step of exposing a portion or the entire surface of the resin film; a step of developing the exposed resin film with an alkaline aqueous solution to form a patterned resin film; and a step of heating the patterned resin film.

[0015] Another aspect of the invention relates to a patterned cured film having a pattern comprising a cured product of the aforementioned photosensitive resin composition. Another aspect of the invention also relates to a semiconductor device having the aforementioned patterned cured film as an interlayer insulating layer or a surface protective layer.

[0016] Invention Effects

[0017] According to the present invention, a photosensitive resin composition capable of forming a patterned curable film with high resolution, low curing shrinkage, and excellent mechanical strength that can be micro-processed is available. Furthermore, according to the present invention, a patterned curable film using the photosensitive resin composition, a method for manufacturing the same, a semiconductor element, and an electronic device are also available. Detailed Implementation

[0018] The embodiments of the present invention will now be described in detail. However, the present invention is not limited to the following embodiments. In this specification, "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid," and the same applies to other similar expressions such as (meth)acrylate. In this specification, "solid component" refers to the non-volatile component contained in the photosensitive resin composition after the removal of volatile substances such as water and solvents, and refers to the component that does not volatilize and remains after the resin composition is dried, and also includes components that are liquid, sugar-like, or waxy at room temperature of approximately 25°C.

[0019] In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the desired effect of the process is achieved. When viewed in a top view, the term "layer" includes not only the structure of a shape formed across the entire surface, but also the structure of a shape formed in a portion of the surface. The numerical range indicated by "~" represents the range in which the values ​​described before and after "~" are respectively the minimum and maximum values. Within the numerical ranges described in stages in this specification, the upper or lower limit of the numerical range for a certain stage can be replaced by the upper or lower limit of the numerical range for other stages. Within the numerical ranges described in this specification, the upper or lower limit of the numerical range can be replaced by the values ​​shown in the embodiments.

[0020] [Photosensitive Resin Composition]

[0021] The photosensitive resin composition of one embodiment contains (A) an alkali-soluble resin having an imide bond and a phenolic hydroxyl group (hereinafter, sometimes referred to as "component (A)") and (B) a compound that generates an acid upon exposure to light (hereinafter, sometimes referred to as "component (B)"). The photosensitive resin composition of this embodiment can be suitably used as a positive photosensitive resin composition. Hereinafter, the morphology of the positive photosensitive resin composition will be described in detail.

[0022] <(A) Component: Alkali-soluble resin>

[0023] In this specification, alkali-soluble resin refers to a resin that is soluble in an alkaline aqueous solution (developer). Furthermore, the alkaline aqueous solution is an alkaline solution such as tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution. A 2.38% by mass TMAH aqueous solution is typically used in development. For example, it can be confirmed that component (A) is soluble in the alkaline developer as follows.

[0024] A varnish obtained by dissolving resin in any solvent is spin-coated onto a substrate such as a silicon wafer to form a coating film with a thickness of approximately 5 μm. This coating film is then immersed at 20–25°C in any one of an aqueous solution of TMAH, an aqueous solution of a metal hydroxide, or an aqueous solution of an organic amine. As a result, when the coating film can be uniformly dissolved, it can be considered that the resin is soluble in an alkaline developer.

[0025] (A) The resin is composed of the following components: from the viewpoint of solubility in alkaline aqueous solution, high resolution, and low curing shrinkage, it has phenolic hydroxyl groups and from the viewpoint of mechanical strength, it has imide bonds.

[0026] (A) The phenolic hydroxyl group of the component may be derived from the structure of phenol, o-cresol, m-cresol or p-cresol. (A) The imide bond of the component may be bonded to an aromatic ring.

[0027] (A) The component can be a resin having a bisphenolimide backbone. The bisphenolimide backbone can be a structure based on the reaction of tetracarboxylic dianhydride with an aminophenol compound.

[0028] From the viewpoint of further reducing curing shrinkage and further increasing mechanical strength, component (A) may have a structure of at least one of the compounds selected from the group consisting of the compound represented by formula (I), the compound represented by formula (II) and the compound represented by formula (III) as the bisphenolimide skeleton.

[0029]

[0030] In the formula, R 1 R 2 R 3 R4 R 5 and R 6 Each can be used independently to represent a hydrogen atom or a methyl group, R a and R b Each can be independently represented by an ether bond, a thioether bond, a carbonyl group, an alkylene group with 1 to 3 carbon atoms, or a single bond. Examples of alkylene groups with 1 to 3 carbon atoms include methylene, ethylene, ethylidene group, propylene, propylidene group, and isopropylene.

[0031] In the compounds represented by formula (I), formula (II) or formula (III), from the viewpoint of improving solubility, it is preferable that at least one of the hydroxyl groups represented by OH is bonded to the meta or ortho position of the imide group (imide bond).

[0032] From the viewpoint of achieving an excellent balance between solubility and mechanical strength, component (A) may contain a resin having structural units derived from compounds represented by formulas (1), (2), (3), (4), (5), or (6) below as the bisphenol imide backbone.

[0033]

[0034] R in equations (4) and (5) a The meaning of R in equation (II) a The meaning is the same, R in equation (6) b The meaning of R in equation (III) b The meanings are the same. From the perspective of improving solubility, R a Preferably, it is an ether bond or a carbonyl group, R b Isopropylidene is preferred.

[0035] (A) The component may also have structural units derived from cresol compounds such as o-cresol, m-cresol, and p-cresol, and may also have structural units derived from formaldehyde, bis(methoxymethyl)biphenyl, or dimethoxymethylbenzene.

[0036] (A) Component can be synthesized, for example, according to the usual synthesis method of phenolic varnish resin. (A) Component can be a reaction product of bisphenolimide compound and cresol compound, or a reaction product of bisphenolimide compound and cresol compound with formaldehyde, bis(methoxymethyl)biphenyl or dimethoxymethylbenzene. (A) Component can, for example, have the structure represented by the following formula.

[0037]

[0038] Considering the balance between solubility relative to alkaline aqueous solutions, photosensitivity, and the mechanical strength of the cured film, the weight-average molecular weight (Mw) of component (A) can be 1000–50000, 2000–45000, 3000–42000, 5000–40000, 10000–40000, or 15000–38000. Mw is a value obtained by measuring by gel permeation chromatography (GPC) and converting it using a standard polystyrene calibration curve.

[0039] <(B) Component: Compounds that generate acids through light>

[0040] The compound that generates acid upon light (by receiving light), as component (B), functions as a photosensitizer in the photosensitive resin composition. Component (B) increases the solubility of the light-received portion in an alkaline aqueous solution by generating acid upon receiving light irradiation. As component (B), compounds commonly referred to as photoacid-generating agents can be used. Examples of components (B) include, for instance, o-quinone diazides, aryl diazonium salts, diaryliodonium salts, and triarylsulfonium salts. Component (B) can be formed from only one of these compounds, or it can be configured to contain two or more. From the viewpoint of high sensitivity, component (B) can be an o-quinone diazide.

[0041] As an o-quinone diazide compound, for example, an o-quinone diazide compound obtained by condensing o-quinone diazidesulfonyl chloride with a hydroxyl compound and / or an amino compound in the presence of a dehydrochlorinating agent can be used.

[0042] Examples of ortho-quinone diazidesulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-6-sulfonyl chloride.

[0043] Examples of hydroxyl compounds include hydroquinone, resorcinol triazine, gallol, bisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone. Benzyl ketone, 2,3,4,2',3'-pentahydroxybenzophenone, 2,3,4,3',4',5'-hexahydroxybenzophenone, bis(2,3,4-trihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)propane, 4b,5,9b,10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindo[2,1-a]indene, tris(4-hydroxyphenyl)methane, and tris(4-hydroxyphenyl)ethane.

[0044] Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and bis(4-amino-3-hydroxyphenyl)hexafluoropropane.

[0045] Among these, from the viewpoint of the reactivity during the synthesis of ortho-quinone diazide compounds and the viewpoint of exposing the resin film within an appropriate absorption wavelength range, it can be a condensate of 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane with 1-naphthoquinone-2-diazido-5-sulfonyl chloride and a condensate of tris(4-hydroxyphenyl)methane or tris(4-hydroxyphenyl)ethane with 1-naphthoquinone-2-diazido-5-sulfonyl chloride.

[0046] Examples of dehydrochloric acid removers include sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, and pyridine.

[0047] Regarding the formulation of o-quinone diazidesulfonyl chloride with hydroxyl and / or amino compounds, it is preferred that the total molar number of hydroxyl and amino groups is 0.5 to 1 mole relative to 1 mole of o-quinone diazidesulfonyl chloride. The preferred formulation ratio of the dehydrochlorinating agent to o-quinone diazidesulfonyl chloride is in the range of 0.95 / 1 mole to 1 / 0.95 molar equivalent.

[0048] The preferred reaction temperature for the above reaction is 0–40°C, and the preferred reaction time is 1–10 hours. As a reaction solvent, for example, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, or N-methylpyrrolidone can be used.

[0049] From the perspective that the difference in dissolution rate between the exposed and unexposed parts increases and the sensitivity becomes better, the content of component (B) relative to 100 parts by mass of component (A) can be 1 to 50 parts by mass, 3 to 35 parts by mass, or 5 to 20 parts by mass.

[0050] <(C) Component: Thermal crosslinking agent>

[0051] The photosensitive resin composition of this embodiment may further contain a thermal crosslinking agent as component (D). Component (C) is a compound having a structure that reacts with component (A) to form a bridging structure when the patterned resin film is heated and cured. This prevents film embrittlement and melting. Examples of component (C) include compounds having phenolic hydroxyl groups, compounds having alkoxy groups, and compounds having epoxy groups.

[0052] The "compound having phenolic hydroxyl groups" described herein does not include component (A). As a thermal crosslinking agent, the compound having phenolic hydroxyl groups not only acts as a thermal crosslinking agent but also increases the dissolution rate of the exposed portion during development with an alkaline aqueous solution, thereby improving sensitivity. Considering the balance between solubility, photosensitivity, and mechanical strength relative to the alkaline aqueous solution, the Mw of such a compound having phenolic hydroxyl groups can be 3000 or less, 2000 or less, or 1500 or less.

[0053] As compounds containing alkoxy groups, conventionally known compounds can be used. From the viewpoint of imparting high reactivity and heat resistance, compounds containing alkoxy groups can have methoxy groups or more than four methoxy groups. Compounds containing alkoxy groups offer an excellent balance between the solubility-promoting effect of the exposed portion and the mechanical strength of the cured film, therefore, compounds selected from those represented by the following formulas can be used.

[0054]

[0055] As the compound having an epoxy group, conventionally known compounds can be used. Examples of compounds having an epoxy group include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenolic varnish type epoxy compounds, cresolic varnish type epoxy compounds, alicyclic epoxy compounds, glycidylamine type epoxy compounds, heterocyclic epoxy compounds, halogenated epoxy compounds, and polyalkylene glycol diglycidyl ether.

[0056] As component (C), in addition to the compounds mentioned above, for example, aromatic compounds having a hydroxymethyl group such as bis[3,4-bis(hydroxymethyl)phenyl] ether and 1,3,5-tris(1-hydroxy-1-methylethyl)benzene, compounds having a maleimide group such as bis(4-maleimidephenyl)methane and 2,2-bis[4-(4'-maleimidephenoxy)phenyl]propane, compounds having a norbornene skeleton, polyfunctional acrylate compounds, compounds having an oxocyclic butyl group, compounds having a vinyl group, or end-capped isocyanate compounds can also be used.

[0057] From the perspective of heat resistance of the cured film and warpage of the coated substrate, the content of component (C) relative to 100 parts by mass of component (A) can be 1 to 70 parts by mass, 2 to 50 parts by mass, or 3 to 40 parts by mass.

[0058] <(D) Component: Elastomer>

[0059] From the viewpoint of improving the flexibility of the patterned cured film, the resin composition of this embodiment may also contain an elastomer as component (D). Examples of components (D) include styrene-based elastomers, olefin-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic elastomers, and silicone elastomers. These elastomers can be used alone or in combination of two or more. Furthermore, the framework of the elastomer component can be incorporated into component (A).

[0060] Acrylic elastomers can have the structural unit represented by the following formula (8). By having the structural unit represented by the following formula (8), acrylic elastomers improve the compatibility between components (A) and (D), thus sufficiently suppressing the turbidity of the photosensitive resin composition, thereby reducing the haze value of the patterned cured film while further improving the mechanical strength.

[0061]

[0062] In equation (8), R 17 R represents a hydrogen atom or a methyl group. 18 Hydroxyalkyl groups with 2 to 20 carbon atoms.

[0063] As R 18 The hydroxyalkyl groups representing 2 to 20 carbon atoms include, for example, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, hydroxyundecyl, hydroxydodecyl (sometimes called hydroxylauryl), hydroxytridecyl, hydroxytetradecyl, hydroxypentadecanyl, hydroxyhexadecyl, hydroxyheptadecyl, hydroxyoctadecyl, hydroxynonadecanyl, and hydroxyicosyl. These groups can be linear or branched.

[0064] In equation (8), from the viewpoint of further improving the compatibility and mechanical strength with component (A), R 18 Preferably, it is a hydroxyalkyl group with 2 to 15 carbon atoms, more preferably a hydroxyalkyl group with 2 to 10 carbon atoms, and even more preferably a hydroxyalkyl group with 2 to 8 carbon atoms.

[0065] Monomers that serve as the structural unit represented by formula (8) include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyheptyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxynonyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxyundecyl (meth)acrylate, hydroxydodecyl (meth)acrylate (sometimes called lauryl (meth)acrylate), hydroxytridecyl (meth)acrylate, hydroxytetradecyl (meth)acrylate, hydroxypentadecanyl (meth)acrylate, hydroxyhexadecyl (meth)acrylate, hydroxyheptadecyl (meth)acrylate, hydroxyoctadecyl (meth)acrylate, hydroxynonadecanyl (meth)acrylate, and hydroxyeicosyl (meth)acrylate. These monomers may be used alone or in combination of two or more.

[0066] From the viewpoint of further improving compatibility with component (A) and the elongation at break of the cured film, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxyundecyl (meth) acrylate, or hydroxydodecyl (meth) acrylate are preferred.

[0067] Component (D) can be an acrylic elastomer formed solely of the structural units represented by formula (8), or an acrylic elastomer having structural units other than those represented by formula (8). In the case of an acrylic resin having structural units other than those represented by formula (8), the proportion of the structural units represented by formula (8) in the acrylic resin relative to the total amount of component (D) can be 0.1 to 30 mol%, 0.3 to 20 mol%, or 0.5 to 10 mol%.

[0068] Acrylic elastomers can also have the structural units represented by the following formula (9).

[0069]

[0070] In equation (9), R 19 R represents a hydrogen atom or a methyl group. 20 This indicates a monovalent organic group having a primary, secondary, or tertiary amino group. By giving component (D) the structural unit represented by formula (9), the solubility inhibition of the unexposed portion relative to the developer and its adhesion to the metal substrate can be further improved.

[0071] Examples of monomers that give an acrylic elastomer having the structural unit represented by formula (9) include, for example, aminoethyl (meth)acrylate, N-methylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N-ethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, N-methylaminopropyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate. Acrylates, N-ethylaminopropyl (meth)acrylates, N,N-diethylaminopropyl (meth)acrylates, piperidin-4-yl (meth)acrylates, 1-methylpiperidin-4-yl (meth)acrylates, 2,2,6,6-tetramethylpiperidin-4-yl (meth)acrylates, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth)acrylates, (piperidin-4-yl)meth(meth)acrylates, and 2-(piperidin-4-yl)ethyl(meth)acrylates. These monomers can be used alone or in combination of two or more.

[0072] Among these, from the viewpoint of further improving the adhesion of the patterned cured film to the substrate and its compatibility with component (A), in formula (9), R 20 Preferably, it is a monovalent organic group represented by the following formula (10).

[0073]

[0074] In formula (10), Y represents an alkylene group with 1 to 5 carbon atoms, and R 21 R 22 R 23 R 25 and R 25 Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and e represents an integer from 0 to 10.

[0075] In equation (9), R is given as 20Monomers representing structural units with monovalent organic groups as indicated by formula (10) include, for example, piperidin-4-yl (meth)acrylate, 1-methylpiperidin-4-yl (meth)acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth)acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth)acrylate, (piperidin-4-yl)meth(meth)acrylate, and 2-(piperidin-4-yl)ethyl(meth)acrylate. Among these, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is commercially available as FA-711MM, and 2,2,6,6-tetramethylpiperidin-4-yl methacrylate is available as FA-712HM (both manufactured by Denko Materials Co., Ltd. (formerly Hitachi Chemical Co., Ltd.)), and is therefore preferred.

[0076] When component (D) has the structural unit represented by formula (10), from the viewpoint of compatibility with component (A) and solubility relative to the developer, the proportion of the structural unit represented by formula (9) relative to the total amount of component (D) is preferably 0.3 to 10 mol%, more preferably 0.4 to 6 mol%, and even more preferably 0.5 to 5 mol%.

[0077] Acrylic elastomers can also have the structural unit represented by the following formula (11). By giving acrylic elastomers the structural unit represented by formula (11), the thermal shock resistance of the cured film can be further improved.

[0078]

[0079] In equation (11), R 26 R represents a hydrogen atom or a methyl group. 27 It refers to alkyl groups with 4 to 20 carbon atoms.

[0080] As R 27 Alkyl groups representing 4 to 20 carbon atoms include, for example, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl (sometimes called lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl. These groups can be straight-chain or branched.

[0081] In formula (11), considering alkali solubility, thermal shock resistance, and compatibility with component (A), R 27 Preferably, it is an alkyl group having 4 to 16 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms, and even more preferably an alkyl group having 4 carbon atoms (n-butyl).

[0082] Examples of monomers represented by formula (11) include butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate (sometimes called lauryl methacrylate), tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecanyl methacrylate, octadecyl methacrylate, nonadecanyl methacrylate, and eicosyl methacrylate. These monomers can be used alone or in combination of two or more.

[0083] Among these, from the viewpoint of further increasing the elongation at break and further decreasing the elastic modulus, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, or dodecyl methacrylate (also known as lauryl methacrylate) are preferred.

[0084] When component (D) has the structural unit represented by formula (11), the proportion of the structural unit represented by formula (11) relative to the total amount of component (D) is preferably 50 to 93 mol%, more preferably 55 to 85 mol%, and even more preferably 60 to 80 mol%. By making the proportion of the structural unit represented by formula (11) above 50 to 93 mol%, the thermal shock resistance of the cured film can be further improved.

[0085] Acrylic elastomers may also have the structural unit represented by the following formula (12). By giving the acrylic elastomer the structural unit represented by formula (12), the alkali solubility of the exposed portion of the resin film can be further improved.

[0086]

[0087] In equation (12), R 28 It represents a hydrogen atom or a methyl group.

[0088] Examples of monomers that can be given the structural unit represented by formula (12) include acrylic acid and methacrylic acid.

[0089] When component (D) has the structural unit represented by formula (12), the proportion of the structural unit represented by formula (12) relative to the total amount of component (D) is preferably 5 to 35 mol%, more preferably 10 to 30 mol%, and even more preferably 15 to 25 mol%. By making the composition ratio of the structural unit represented by formula (12) 5 to 35 mol%, the compatibility with component (A) and the alkali solubility of the exposed part can be further improved.

[0090] Regarding acrylic elastomers, for example, they are obtained by mixing monomers containing structural units represented by the above formula (8) and monomers containing structural units represented by formulas (9), (11) or (12) as needed, stirring in solvents such as ethyl lactate, toluene, and isopropanol, and heating as needed.

[0091] The monomers used in the synthesis of acrylic elastomers may also contain monomers other than those that provide the structural units represented by formulas (8), (9), (11) and (12).

[0092] Examples of such monomers include N-(meth)acryloyloxyethyl hexahydrophthalimide, 1,4-cyclohexanediethanol mono(meth)acrylate, benzyl (meth)acrylate, 4-methylbenzyl (meth)acrylate, esters of vinyl alcohols such as acrylonitrile and vinyl-n-butyl ether, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, α-bromo(meth)acrylate, α-chloro(meth)acrylate, β-furanyl (meth)acrylate, β-styryl (meth)acrylate, maleic acid, maleic anhydride, monomethyl maleic acid, monoethyl maleic acid, monoisopropyl maleic acid and other maleic acid monoesters, fumaric acid, cinnamic acid, α-cyanocinonic acid, itaconic acid, crotonic acid and propynic acid. These monomers can be used alone or in combination of two or more.

[0093] The Mw of component (D) can be 2000–100000, 3000–60000, 5000–50000, or 10000–40000. A Mw value above 2000 improves the thermal shock resistance of the cured film, while a value below 100000 improves its compatibility and developability with component (A). Mw is a value obtained by gel permeation chromatography (GPC) and conversion using a standard polystyrene calibration curve.

[0094] From the perspective of balancing the alkali solubility of the exposed part, the alkali solubility inhibition of the unexposed part, the adhesion to the metal substrate, and the thermal shock resistance, the content of component (D) relative to 100 parts by mass of component (A) can be 1 to 50 parts by mass, 2 to 30 parts by mass, or 3 to 20 parts by mass.

[0095] <(E) Ingredients: Adhesive Additives>

[0096] The photosensitive resin composition of this embodiment may contain an adhesive aid as component (E). A photosensitive resin composition containing component (E) can provide a patterned cured film with good adhesion to a substrate. Component (E) may contain a nitrogen-containing aromatic compound represented by the following formula (7).

[0097]

[0098] In equation (7), R 51 R represents a hydrogen atom or a hydrocarbon group. 52 Represents a hydrogen atom, amino group, or phenyl group. A and B independently represent a nitrogen atom or a carbon atom and the hydrogen atom bonded to it (CH).

[0099] From the viewpoint of further improving the adhesion to the substrate, the nitrogen-containing aromatic compound represented by formula (7) can be the nitrogen-containing aromatic compound represented by formula (7a) below. R in formula (7a) 52 The meaning of R in equation (7) 52 The meanings are the same.

[0100]

[0101] Examples of components (E) include 1H-tetrazole, 5-aminotetrazole, 5-phenyltetrazole, and 5-methyltetrazole. Among these, from the viewpoint of providing better adhesion to the substrate, component (E) may include 1H-tetrazole or 5-aminotetrazole.

[0102] From the viewpoint of providing good adhesion and sensitivity to the substrate, the amount of component (E) relative to 100 parts by mass of component (A) can be 0.01 to 20 parts by mass, 0.015 to 10 parts by mass, or 0.02 to 7 parts by mass.

[0103] <Other Ingredients>

[0104] In addition to components (A) to (E) mentioned above, the photosensitive resin composition of this embodiment may also contain solvents, compounds that generate acid by heating, solubility promoters, solubility inhibitors, coupling agents, and surfactants or leveling agents.

[0105] (solvent)

[0106] The photosensitive resin composition of this embodiment exhibits the following effect: by containing a solvent, it is easily coated onto a substrate, thereby enabling the formation of a coating film of uniform thickness. Examples of solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, diphenylethylene acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methylpentyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether. One solvent can be used alone, or two or more can be used in combination. From the viewpoint of solubility and coating film uniformity, ethyl lactate or γ-butyrolactone is preferred.

[0107] (Compounds that produce acids upon heating)

[0108] By using a compound that generates acid upon heating, acid is produced when the patterned resin film is heated, promoting the reaction between components (A) and (C), i.e., a thermal crosslinking reaction, thereby improving the heat resistance of the patterned cured film. Furthermore, the compound that generates acid upon heating also generates acid upon light irradiation, thus increasing the solubility of the exposed portion in the alkaline aqueous solution. Therefore, the difference in solubility between the non-exposed and exposed portions relative to the alkaline aqueous solution further increases, further improving resolution.

[0109] Compounds that generate acids by heating are preferably compounds that generate acids by heating to 50–250°C. Examples of compounds that generate acids by heating include onium salts and salt groups formed by strong acids and imide sulfonates. The content of compounds that generate acids by heating relative to 100 parts by mass of component (A) can be 0.1–30 parts by mass, 0.2–20 parts by mass, or 0.5–10 parts by mass.

[0110] (Solubility accelerator)

[0111] By formulating a dissolution accelerator into the above-described positive photosensitive resin composition, the dissolution rate of the exposed portion during development with an alkaline aqueous solution can be increased, thereby improving sensitivity and resolution. Conventionally known dissolution accelerators can be used as dissolution accelerators. Examples of dissolution accelerators include compounds having carboxyl, sulfonyl, or sulfonamide groups. The content of the dissolution accelerator can be determined by the dissolution rate relative to the alkaline aqueous solution; for example, it can be set to 0.01 to 30 parts by mass relative to 100 parts by mass of component (A).

[0112] (Dissolution Inhibitor)

[0113] Dissolution inhibitors are compounds that inhibit the solubility of component (A) in an alkaline aqueous solution and are used to control residual film thickness, development time, and contrast. Examples of dissolution inhibitors include diphenyliodonitrate, bis(p-tert-butylphenyl)iodonitrate, diphenyliodobromide, diphenyliodochloride, and diphenyliodomonium iodide. From the viewpoint of the permissible range of sensitivity and development time, the concentration of dissolution inhibitor relative to 100 parts by weight of component (A) can be 0.01–20 parts by weight, 0.01–15 parts by weight, or 0.05–10 parts by weight.

[0114] (Coupled agent)

[0115] By formulating a coupling agent into a photosensitive resin composition, the adhesion between the formed patterned cured film and the substrate can be further improved. Examples of coupling agents include organosilane compounds and aluminum chelates. Examples of organosilane compounds include KBM-403, KBM-803, and KBM-903 (manufactured by Shin-Etsu Chemical Co., LTD., product names). The content of the coupling agent used relative to 100 parts by weight of component (A) can be 0.1 to 20 parts by weight or 0.5 to 10 parts by weight.

[0116] (surfactant or leveling agent)

[0117] By formulating a photosensitive resin composition with surfactants or leveling agents, coatability can be further improved. Specifically, for example, by including surfactants or leveling agents, streaks (uneven film thickness) can be further prevented, and developability can be further improved. Examples of such surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, and polyoxyethylene octylphenol ether. Commercially available products include MEGAFAC F-171, F-565, and RS-78 (manufactured by DIC CORPORATION, product names).

[0118] When using surfactants or leveling agents, the content relative to 100 parts by weight of component (A) can be 0.001 to 5 parts by weight or 0.01 to 3 parts by weight.

[0119] The photosensitive resin composition of this embodiment can be developed using an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH).

[0120] [Patterned Curing Film and its Manufacturing Method]

[0121] One embodiment of the pattern-cured film has a pattern comprising a cured product of the aforementioned photosensitive resin composition. The pattern-cured film is obtained by heating the aforementioned photosensitive resin composition. Hereinafter, a method for manufacturing the pattern-cured film will be described.

[0122] The method for manufacturing the patterned resin film according to this embodiment includes: a step of coating a portion or the entire surface of a substrate with the above-described photosensitive resin composition and drying it to form a resin film (coating / drying (film formation) step); a step of exposing a portion or the entire surface of the resin film (exposure step); a step of developing the exposed resin film with an alkaline aqueous solution to form a patterned resin film (development step); and a step of heating the patterned resin film (heat treatment step). Each step will be described below.

[0123] (Coating / Drying (Film Forming) Process)

[0124] First, the photosensitive resin composition of this embodiment is coated onto a substrate and dried to form a resin film. In this step, the photosensitive resin composition of this embodiment is spin-coated onto a substrate such as a glass substrate, semiconductor, metal oxide insulator (e.g., TiO2, SiO2), or silicon nitride using a spin coater or the like to form a coating film. The thickness of the coating film is not particularly limited, but can be 0.1 to 40 μm. The substrate with the coating film is dried using a hot plate, oven, or the like. The drying temperature and drying time are not particularly limited, but can be 80 to 140°C for 1 to 7 minutes. Thus, a resin film is formed on the substrate. The thickness of the resin film is not particularly limited, but can be 0.1 to 40 μm.

[0125] (Exposure process)

[0126] Next, in the exposure process, active light such as ultraviolet light, visible light, and radiation is irradiated onto the resin film formed on the substrate via a mask. In the photosensitive resin composition of this embodiment, component (A) has high transparency relative to g, h, and i rays, so any one or all of g, h, and i rays can be used for irradiation.

[0127] (Developing process)

[0128] In the developing process, the exposed portion of the resin film after the exposure process is removed by using a developing solution, thereby patterning the resin film and obtaining a patterned resin film. As the developing solution, alkaline aqueous solutions such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (TMAH) are preferred. The concentration of salt groups in these aqueous solutions can be 0.1 to 10% by mass. Alcohols or surfactants can also be added to the above developing solutions. These can be prepared in the range of 0.01 to 10 parts by mass or 0.1 to 5 parts by mass relative to 100 parts by mass of the developing solution, respectively. When developing with the developing solution, the developing solution is applied to the resin film by methods such as spray development, mist development, immersion development, or agitation development, and placed at 18 to 40°C for 30 to 360 seconds. After placement, the patterned resin film is cleaned by washing with water and then rotary drying.

[0129] (Heat treatment process)

[0130] Next, in the heat treatment process, a patterned resin film can be formed by heat-treating the patterned resin film. From the viewpoint of fully preventing heat-induced damage to the semiconductor device, the heating temperature in the heat treatment process can be below 300°C, below 270°C, or below 250°C.

[0131] Regarding the heat treatment, ovens such as quartz tube furnaces, hot plates, rapid annealing furnaces, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces can be used. Furthermore, either atmospheric or inert atmospheres such as nitrogen can be selected, but nitrogen is preferred as it prevents oxidation of the pattern. The aforementioned heating temperature range is lower than conventional heating temperatures, thus minimizing damage to the support substrate and semiconductor device. Therefore, by using the pattern curing film manufacturing method of this embodiment, electronic devices can be manufactured with high yield. Furthermore, it contributes to energy saving in the process. Moreover, according to the positive photosensitive resin composition of this embodiment, the volume shrinkage (curing shrinkage) observed in the heat treatment process of photosensitive polyimide, etc., is small, thus preventing a decrease in dimensional accuracy.

[0132] The heat treatment time in the heat treatment process only needs to be sufficient to cure the positive photosensitive resin composition, but considering the balance with work efficiency, it is preferable to be about 5 hours or less.

[0133] Regarding heat treatment, in addition to the oven mentioned above, a microwave curing apparatus or a frequency conversion microwave curing apparatus can also be used. By using these apparatuses, the temperature of the substrate and semiconductor device can be maintained at the desired temperature (e.g., below 200°C) while only the resin film is effectively heated (see J. Photopolym. Sci. Technol., 18, 327-332 (2005)).

[0134] The patterned curable film of this embodiment can be used as an interlayer insulating layer or a surface protective layer for semiconductor devices. Semiconductor devices having an interlayer insulating layer or a surface protective layer formed from the curable film of the above-described photosensitive resin composition, and electronic devices including such semiconductor devices, can be manufactured. Semiconductor devices can be, for example, memory devices, packages, etc., having multilayer wiring structures, rewiring structures, etc. Examples of electronic devices include mobile phones, smartphones, tablet terminals, personal computers, and hard drive arms. By using the patterned curable film formed from the photosensitive resin composition of this embodiment, semiconductor devices and electronic devices with excellent reliability can be provided.

[0135] Example

[0136] The present invention will now be described in detail with reference to embodiments, but the present invention is not limited thereto.

[0137] The materials used in the embodiments and comparative examples will be shown below.

[0138] ((A) ingredient)

[0139] To synthesize component (A), a bisimide phenol compound having the structure (a1) to (a5), a cresol compound having the structure (b1) to (b2), 1,4-bis(methoxymethyl)benzene, 4,4-bis(methoxymethyl)biphenyl and 37% by mass of formaldehyde were prepared.

[0140] Alkali-soluble resins with the structural units (molar ratios) and Mw shown in Table 1 were synthesized. (c1) is the structure introduced by 1,4-bis(methoxymethyl)benzene, (c2) is the structure introduced by 4,4-bis(methoxymethyl)biphenyl, and (c3) is the structure introduced by formaldehyde.

[0141] A1: N,N'-bis(3-hydroxyphenyl)-pyromellitic tetramide, o-cresol, 1,4-bis(methoxymethyl)benzene, 37% by mass formaldehyde, γ-butyrolactone, and p-toluenesulfonic acid were added to a 1L three-necked flask equipped with a Dean-Stark apparatus. The reaction was carried out at 180°C with stirring for 6 hours while methanol, a reaction byproduct, was being removed in liquid form. The mixture was then cooled to 40°C. The cooled reaction solution was added dropwise to 1L of deionized water, and the precipitated resin was filtered out. The filtered resin was vacuum dried at 80°C for 12 hours to obtain the alkali-soluble resin of (A1).

[0142] A2~A8: The types and amounts of compounds were changed to form the structural units shown in Table 1. Otherwise, the same operation as (A1) was performed to obtain alkali-soluble resins of (A2)~(A8).

[0143] The Mw of component (A) was measured by gel permeation chromatography (GPC) and derived using a calibration curve for standard polystyrene. The calibration curve was approximated using a cubic equation of a universal calibration curve based on JIS K 7252-2 (2016) using five sample sets of standard polystyrene (PStQuick MP-H, PStQuick B [manufactured by TOSOH CORPORATION, product name]). The conditions for GPC are shown below.

[0144] (GPC conditions)

[0145] Detector: L-2490RI (Manufactured by Hitachi High-Tech Corporation)

[0146] Chromatographic column: Gelpack GL-R440+R450+R400M (manufactured by Hitachi High-Tech Corporation)

[0147] Eluent: Tetrahydrofuran (THF)

[0148] Temperature measured: 40℃

[0149] Flow rate: 2.05 mL / min

[0150] Concentration: 5 mg / mL

[0151] [Table 1]

[0152]

[0153] ((A') ingredient)

[0154] A'1: Cresol Phenolic Varnish Resin (Cresol / Formaldehyde Phenolic Varnish Resin, m-cresol / p-cresol (molar ratio) = 60 / 40, Mw = 12000, Manufactured by ASAHI YUKIZAI CORPORATION, Product Name "EP4020G")

[0155] A'2: To a 500 mL four-necked flask equipped with a thermometer, stirrer, and calcium chloride tube, 0.02 mol of ether diamine 4000 (manufactured by BASF), 0.08 mol of 1,12-diaminododecane, and 150 g of N-methyl-2-pyrrolidone were added, and the mixture was stirred at 60 °C to obtain a homogeneous diamine solution. 0.1 mol of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride was added dropwise to the diamine solution, and the mixture was reacted at 60 °C for 1 hour. Then, the mixture was heated to 170 °C while purging nitrogen gas into the reaction solution, and water was removed by azeotropic reaction with a portion of the solvent, thus obtaining solution A'2 as a polyimide resin solution.

[0156] ((B) component)

[0157] B1: 1,1-Naphthoquinone-2-diazido-5-sulfonate of 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane (esterification rate approximately 90%, manufactured by DAITO CHEMIX Co., Ltd., product name "PA28")

[0158] ((C) component)

[0159] C1: 4,4'-[1-[4-[1-[4-hydroxy-3,5-bis(methoxymethyl)phenyl]-1-methylethyl]phenyl]ethylidene]bis[2,6-bis(methoxymethyl)phenol] (manufactured by Honshu Chemical Industry Co., Ltd., product name "HMOM-TPPA")

[0160] C2: 3-functional epoxy isocyanurate (manufactured by Nissan Chemical Corporation, product name "TEPIC-VL")

[0161] ((D) component)

[0162] D1: 55g of ethyl lactate was weighed into a 100mL three-necked flask equipped with a stirrer, nitrogen inlet tube, and thermometer. Additionally, the following polymerizable monomers were also weighed: 34.7g of n-butyl acrylate (BA), 2.2g of lauryl acrylate (LA), 3.9g of acrylic acid (AA), 2.6g of hydroxybutyl acrylate (HBA), and 1,2,2,6,6-pentamethylpiperidin-4-ylmethacrylic acid (product name: FA-711MM, Denko Materials). 1.7 g of azobisisobutyronitrile (AIBN) and 0.29 g of azobisisobutyronitrile (AIBN) were mixed. Dissolved oxygen was removed by flowing nitrogen gas at a flow rate of 400 mL / min for 30 minutes while stirring at approximately 160 rpm at room temperature. Afterwards, the nitrogen flow was stopped, the flask was sealed, and the temperature was raised to 65°C in a constant temperature water bath over approximately 25 minutes. The polymerization reaction was carried out at 65°C for 10 hours to obtain D1 as an acrylic resin. The polymerization rate was 99%. The weight-average molecular weight of D1 was approximately 22,000. The molar ratios of the polymerizable monomers in D1 are as follows.

[0163] BA / LA / AA / HBA / FA711MM=69 / 2 / 20 / 5 / 4(mol%)

[0164] (E) component)

[0165] E1: 5-Aminotetrazole (manufactured by TOYOBO CO.,LTD., product name "HAT")

[0166] (Examples 1 to 9)

[0167] The photosensitive resin composition was prepared by mixing the amounts of components (A), (B), and (C) shown in Table 2, along with ethyl lactate as a solvent, and then pressurizing and filtering the mixture using a polytetrafluoroethylene filter with 0.2 μm pores.

[0168] (Comparative Examples 1 to 3)

[0169] The photosensitive resin composition was prepared in the same manner as in the examples, except that the amounts of components (A'), (B), and (C) shown in Table 3 were used.

[0170] [Evaluation of Photosensitive Resin Compositions]

[0171] (Appearance)

[0172] Visually inspect the appearance of the photosensitive resin composition. If it is transparent, it is classified as "A"; if it is slightly cloudy, it is classified as "B"; and if it is severely cloudy, it is classified as "C". If the cloudiness of the photosensitive resin composition is "A" or "B", then the alignment marks marked on the substrate during the manufacture of a semiconductor device having a patterned cured film formed using the photosensitive resin composition can be identified.

[0173] (Pattern opening)

[0174] A photosensitive resin composition was spin-coated onto a silicon substrate and heated at 120°C for 3 minutes to form a coating with a thickness of 7–9 μm. Next, reduction projection exposure was performed using an i-ray stepper (manufactured by Canon Inc., product name "FPA-3000iW") and i-rays (365 nm) through a mask with a square aperture pattern ranging from 1 μm × 1 μm to 100 μm × 100 μm. The exposure dose was 800 mJ / cm². 2 After exposure, the film was developed using a 2.38% TMAH aqueous solution and rinsed with water to obtain a patterned resin film. The aperture properties of the 100 μm × 100 μm square hole pattern were evaluated against the following criteria.

[0175] A: The pattern has opened, but there is no pattern peeling or undissolved opening.

[0176] B: The pattern has an opening, but it is possible to confirm that the pattern has peeled off or that it has not been dissolved in the opening.

[0177] C: Unable to form the pattern itself.

[0178] (Resolution)

[0179] The patterned resin film was heat-treated for 2 hours at 230°C (heating time 1 hour) under nitrogen atmosphere using an inert gas oven (manufactured by Koyo Thermo Systems Co., Ltd., product name "INH-9CD-S"), and the resolution of the cured film was evaluated. The minimum size of the opening in a square hole pattern ranging from 1μm × 1μm to 100μm × 100μm was defined as the index of microprocessability. The smaller the pattern size, the better the resolution of the microprocessing.

[0180] (Curing shrinkage)

[0181] Regarding the curing shrinkage rate, it is calculated based on the thickness of the patterned resin film before curing and the thickness of the patterned cured film after curing, using the following formula.

[0182] Curing shrinkage rate (%) = [1 - (film thickness of patterned cured film / film thickness of patterned resin film)] × 100

[0183] (Elongation at break, tensile strength)

[0184] A photosensitive resin composition was spin-coated onto a silicon substrate and heated at 120°C for 4 minutes to form a coating with a thickness of approximately 8–9 μm. Subsequently, a proximity exposure machine (manufactured by Canon Inc., product name "PLA-600FA") was used, and the film was exposed at 1000 mJ / cm² across the entire wavelength range using a mask. 2 The coating was exposed. After exposure, it was developed using a 2.38% aqueous solution of TMAH to obtain a resist pattern with a width of 10 mm. Subsequently, the resist pattern was heat-treated (cured) for 2 hours at 230°C (heating for 1 hour) under nitrogen atmosphere in an inert gas oven (INH-9CD-S) to obtain a cured film with a thickness of approximately 7 μm.

[0185] The cured film was peeled off from a silicon substrate, and the elongation at break of the peeled cured film was measured using an Autograph AGS-H100N manufactured by Shimadzu Corporation. The sample width was 10 mm and the film thickness was approximately 10 μm, with a clamping distance of 20 mm. The stretching speed was 5 mm / min, and the measurement temperature was set to approximately room temperature (20°C–25°C). The average of the top three measurements from five test pieces obtained under the same conditions was taken as the elongation at break and tensile strength.

[0186] [Table 2]

[0187]

[0188] [Table 3]

[0189]

[0190] The resin compositions of the examples containing component (A) can form cured films with good pattern opening properties and high resolution, low curing shrinkage, and high tensile strength. On the other hand, the resin compositions of Comparative Examples 2 to 3, which contain (A'2) as an imide resin, cannot form pattern openings. Furthermore, the resin composition of Comparative Example 1, which contains (A'1) as a phenolic resin, exhibits partial pattern peeling, and compared to the resin compositions of the examples, the cured film has greater curing shrinkage and poorer tensile strength.

[0191] (Examples 10-11)

[0192] The photosensitive resin compositions were prepared in the same manner as in Examples 1 to 9, except that the amounts of components (A) to (D) shown in Table 4 were used.

[0193] (Examples 12-13)

[0194] The photosensitive resin composition was prepared in the same manner as in Examples 1 to 9, except that the amounts of components (A) to (C) and (E) shown in Table 4 were used.

[0195] (Seamless fit)

[0196] A photosensitive resin composition was spin-coated onto a copper substrate (a substrate formed by sputtering TiN onto a silicon substrate, followed by sputtering copper onto the TiN), and heated at 120°C for 3 minutes to form a coating with a thickness of 10–11 μm. Subsequently, a curing process (heat treatment) was performed for 2 hours at 230°C (heating for 1 hour) under nitrogen atmosphere in an inert gas oven (INH-9CD-S) to obtain a cured film with a thickness of approximately 10 μm. The cured film was subjected to the cross-cutting test shown below, and its adhesion to the copper substrate was evaluated.

[0197] Using a cutting tool, draw 11 parallel lines at 1mm intervals in both the longitudinal and transverse directions on the center of the cured film surface on the copper substrate, creating a checkerboard pattern of scratches to achieve a 1cm spacing. 2 One hundred squares were formed, and the condition of the scratches was evaluated. Regarding the scratches, the cutting edge of the dicing tool was held at a certain angle of 35–45 degrees relative to the photosensitive film, penetrating the cured film to reach the copper substrate. Each scratch was created at a constant speed of 0.5 seconds. The more squares that adhered neatly to the copper substrate, the better the adhesion. The evaluation criteria are based on the results evaluated in four stages: A, B, C, and D.

[0198] A: There was no peeling at the intersection of the scratches and on each cell of the square, and the area of ​​the defect is less than 1% of the total area of ​​the square.

[0199] B: There is slight peeling at the intersection of the scratches, but no peeling on each cell of the square. The area of ​​the defect is less than 5% of the total area of ​​the square.

[0200] C: There is peeling on both sides and at the intersection of the scratch, and the area of ​​the defect is 5 to 50% of the total square area.

[0201] D: The width of the peel caused by the scratch is large, and the area of ​​the defect is greater than 50% of the total square area.

[0202] [Table 4]

[0203]

[0204] The photosensitive resin compositions of Examples 10 and 11 further improve the strength and elongation at break of the cured film by also containing component (D). The photosensitive resin compositions of Examples 12 and 13 further improve the good adhesion to the Cu substrate by also containing component (E).

Claims

1. A photosensitive resin composition comprising (A) an alkali-soluble resin having imide bonds and phenolic hydroxyl groups and (B) a compound that generates an acid upon exposure to light. The alkali-soluble resin is a resin having a structure derived from at least one of the compounds selected from the group consisting of compounds represented by formula (I), formula (II), and formula (III), and a structural unit derived from bis(methoxymethyl)biphenyl or dimethoxymethylbenzene. In the formula, R 1 R 2 R 3 R 4 R 5 and R 6 Each can be used independently to represent a hydrogen atom or a methyl group, R a and R b Each can be independently represented as an ether bond, a thioether bond, a carbonyl group, an alkylene group with 1 to 3 carbon atoms, or a single bond.

2. The photosensitive resin composition according to claim 1, wherein, The alkali-soluble resin has structural units derived from compounds represented by formula (1), (2), (3), (4), (5), or (6) below. In the formula, R a and R b Each can be independently represented as an ether bond, a thioether bond, a carbonyl group, an alkylene group with 1 to 3 carbon atoms, or a single bond.

3. The photosensitive resin composition according to claim 1, wherein, The compound that generates acid through light is an o-quinone diazide compound.

4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (C) a compound that undergoes a cross-linking reaction by heat.

5. The photosensitive resin composition according to claim 4, wherein, The compound that undergoes a cross-linking reaction through heat is a compound having alkoxy or epoxy groups.

6. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (D) an elastomer.

7. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (E) an adhesive aid.

8. The photosensitive resin composition according to claim 7, wherein, The adhesive additive is a nitrogen-containing aromatic compound.

9. A method for manufacturing a patterned curable film, comprising: The process of coating a portion or the entire surface of a substrate with the photosensitive resin composition of any one of claims 1 to 8 and drying it to form a resin film; The process of exposing a portion or the entire surface of the resin film; The process of developing an exposed resin film with an alkaline aqueous solution to form a patterned resin film; and The process of heating the patterned resin film.

10. A patterned cured film having a pattern comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 8.

11. A semiconductor device comprising the patterned cured film of claim 10 as an interlayer insulating layer or a surface protective layer.

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