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WO2018179330A1 - Composition de résine photosensible, procédé de fabrication de film durci à motifs, produit durci, film isolant intercalaire, couche de revêtement de couverture, film protecteur de surface et composant électronique - Google Patents

Composition de résine photosensible, procédé de fabrication de film durci à motifs, produit durci, film isolant intercalaire, couche de revêtement de couverture, film protecteur de surface et composant électronique Download PDF

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Publication number
WO2018179330A1
WO2018179330A1 PCT/JP2017/013589 JP2017013589W WO2018179330A1 WO 2018179330 A1 WO2018179330 A1 WO 2018179330A1 JP 2017013589 W JP2017013589 W JP 2017013589W WO 2018179330 A1 WO2018179330 A1 WO 2018179330A1
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WIPO (PCT)
Prior art keywords
photosensitive resin
film
formula
group
resin composition
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PCT/JP2017/013589
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English (en)
Japanese (ja)
Inventor
皓 朝田
篤太郎 吉澤
越晴 土屋
崇司 川守
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HD MicroSystems Ltd
Original Assignee
Hitachi Chemical DuPont Microsystems Ltd
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Priority to JP2019508103A priority Critical patent/JPWO2018179330A1/ja
Priority to PCT/JP2017/013589 priority patent/WO2018179330A1/fr
Priority to TW107111419A priority patent/TW201841992A/zh
Publication of WO2018179330A1 publication Critical patent/WO2018179330A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present invention relates to a photosensitive resin composition, a method for producing a patterned cured film, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.
  • the multi-die fanout wafer level package (Multi-die Fanout Wafer Level Packaging) is a package that is manufactured by encapsulating multiple dies in one package. Attracting attention because it can be expected to achieve lower cost and higher performance than conventional fan-out wafer level packages that are manufactured by sealing one die.
  • Patent Document 3 Furthermore, from the viewpoint of miniaturization and high integration of electronic equipment, there is a demand for higher resolution in the pattern cured film formed by heat curing a patterned resin film, but conventional materials are limited to higher resolution. (For example, Patent Document 3).
  • An object of the present invention is to provide a photosensitive resin composition that has a cured film exhibiting high adhesiveness to a copper substrate even when cured at 200 ° C. or less, and is excellent in resolution, and the photosensitive resin composition. It is to provide a method for producing a patterned cured film, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.
  • the present inventors have combined resolution and adhesive properties by combining a polyimide precursor with a radical polymerizable compound having an aliphatic cyclic structure and a compound having a specific structure. And the present invention has been completed.
  • the following photosensitive resin composition and the like are provided.
  • A a polyimide precursor;
  • B a radically polymerizable compound having an aliphatic cyclic structure;
  • C a compound represented by the following formula (1); Containing a photosensitive resin composition.
  • R 1 is an organic group represented by the following formula (2),
  • R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and
  • R 3 is an alkyl group having 1 to 3 carbon atoms.
  • R 4 is a monovalent organic group
  • X is an oxygen atom, a sulfur atom or a carbonyl group
  • s is an integer of 0 to 5
  • A is a tetravalent organic group represented by the following formula (4)
  • B is a divalent organic group containing at least one aromatic ring, and R 5 and R 6.
  • a cured film showing high adhesion to a copper substrate even when cured at 200 ° C. or lower is obtained, and the photosensitive resin composition having excellent resolution and the photosensitive resin composition are obtained.
  • the method for producing a cured pattern film, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component can be provided.
  • a or B may include either one of A and B, or may include both.
  • process is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included.
  • the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the content of each component in the photosensitive resin composition is such that when there are a plurality of substances corresponding to each component in the photosensitive resin composition, unless otherwise specified, Means the total amount of the plurality of substances present.
  • the exemplary materials may be used singly or in combination of two or more unless otherwise specified. “(Meth) acryl” means “methacryl” or “acryl”.
  • the photosensitive resin composition of the present invention includes (a) a polyimide precursor, (b) a radical polymerizable compound having an aliphatic cyclic structure, and (c) a compound represented by the following formula (1).
  • R 1 is an organic group represented by the following formula (2)
  • R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 3 is an alkyl group having 1 to 3 carbon atoms.
  • R 4 is a monovalent organic group
  • X is an oxygen atom, a sulfur atom or a carbonyl group
  • s is an integer of 0 to 5
  • the photosensitive resin composition of the present invention exhibits high resolution by including the above components, it is possible to form a fine pattern and can be suitably used for further miniaturization of semiconductors expected in the future. .
  • high adhesion between the cured film and the substrate can be achieved, and in particular, by imparting hydrophobicity to the cured film, excellent adhesion can be exhibited even under high temperature and high humidity conditions. it can.
  • the photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.
  • each component used for the photosensitive resin composition will be described.
  • Each component may be simply referred to as (a) component, (b) component, and (c) component, respectively.
  • A is a tetravalent organic group represented by the following formula (4)
  • B is a divalent organic group containing at least one aromatic ring, and R 5 and R 6.
  • Y is an oxygen atom or a sulfur atom.
  • examples of the monovalent organic group represented by R 5 and R 6 include a monovalent organic group represented by the following formula (5) or an alkyl group having 1 to 4 carbon atoms. It is done.
  • R 7 to R 9 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m is an integer of 1 to 10)
  • R 7 and R 8 are preferably hydrogen atoms
  • R 9 is preferably an alkyl group having 1 to 3 carbon atoms (preferably a methyl group)
  • m is preferably an integer of 1 to 3 (Preferably 2).
  • examples of the divalent organic group containing at least one B aromatic ring include structures represented by the following formula (6).
  • R 10 to R 17 are each independently a hydrogen atom, a monovalent hydrocarbon group or a monovalent organic group having a halogen atom.
  • the monovalent hydrocarbon group in the formula (6) includes an alkyl group having 1 to 4 carbon atoms
  • the monovalent organic group having a halogen atom includes a haloalkyl group having 1 to 4 carbon atoms.
  • R 10 to R 17 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 10 and R 13 to R 17 are hydrogen atoms
  • R 11 and R 12 are 1 carbon atom. It may be an alkyl group of 4 to 4 (for example, a methyl group).
  • the polyimide precursor having the structural unit represented by the formula (3) uses, for example, a tetracarboxylic dianhydride represented by the following formula (7) and a diamino compound represented by the following formula (8) as raw materials. Can be manufactured. H 2 N—B—NH 2 (8) (In Formula (7), A is the same as A in Formula (3). In Formula (8), B is the same as B in Formula (3).)
  • the polyimide precursor (polyamic acid) comprises a tetracarboxylic dianhydride represented by the formula (7) and a diamino compound represented by the formula (8) in an organic solvent (for example, N— Methylpyrrolidone, ⁇ -butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide and the like).
  • an organic solvent for example, N— Methylpyrrolidone, ⁇ -butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide and the like.
  • an appropriate amount of alcohol represented by the following formula (9) or (10) is added, and the above-mentioned organic solvent is added.
  • R 5 and R 6 in the formula (3) is a monovalent organic group represented by the formula (5) or a carbon number of 1 to 4
  • the polyimide precursor which is the alkyl group of can be obtained.
  • R 18 is an alkyl group having 1 to 4 carbon atoms.
  • m and R 7 to R 9 are the same as R 7 to R 9 in Formula (5)). .
  • Examples of the alkyl group having 1 to 4 carbon atoms of R 18 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • the proportion of all R 5 and R 6 in which the monovalent organic group represented by the formula (5) is introduced by the above esterification is preferably 50 to 90 mol%, more preferably 70 to 90 mol%.
  • the esterification rate is calculated by NMR measurement.
  • the polyimide precursor having the structural unit represented by the formula (3) may have a structural unit other than the structural unit represented by the formula (3) in a part thereof. In this case, it is preferable that the ratio is less than 50 mol% in all the structural units.
  • the molecular weight of the component (a) polyimide precursor is not particularly limited, but is preferably 10,000 to 200,000 in terms of number average molecular weight.
  • the number average molecular weight is measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
  • the component (b) is a radically polymerizable compound, and preferably has at least one group having a polymerizable unsaturated double bond that can be polymerized by a photopolymerization initiator (for example, a (meth) acryl group).
  • the number of groups having the polymerizable unsaturated double bond is preferably 2 or more, and more preferably 3 or less. Within this range, when the crosslinked structure is formed, the crosslinking density is moderate, good photosensitivity can be obtained, and pattern swelling after development can be suppressed.
  • aliphatic cyclic structure examples include tricyclodecane, adamantane, cyclohexane, norbornene, and the component (b) is preferably a compound having at least one structure selected from these.
  • R 19 to R 22 are each independently an aliphatic group having 1 to 4 carbon atoms or a monovalent organic group represented by the following formula (15).
  • a is an integer of 1 to 6 (preferably an integer of 1 to 3)
  • b is an integer of 1 to 12 (preferably an integer of 1 to 3)
  • c is an integer of 1 to 16 (preferably 1 to 3).
  • d is an integer of 1 to 16 (preferably an integer of 1 to 3, more preferably 2).
  • Each compound represented by the formulas (11) to (14) has at least one (preferably two or three) monovalent organic group represented by the formula (15).
  • R 19 to R 22 can be bonded to all possible substitution positions in the compounds represented by formulas (11) to (14).
  • R 29 to R 31 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (preferably a methyl group), and l is an integer of 0 to 10 (preferably 0 or 1).)
  • the photosensitive resin composition of the present invention may contain a radical polymerizable compound other than the radical polymerizable compound having an aliphatic cyclic structure.
  • a radical polymerizable compound other than the radical polymerizable compound having an aliphatic cyclic structure.
  • the compound for example, tetraethylene glycol dimethacrylate can be used.
  • the addition amount of the component (b) in the photosensitive resin composition is usually 1 to 50 parts by weight, preferably 5 to 50 parts by weight, more preferably 5 to 100 parts by weight of the component (a). To 30 parts by mass. If the amount is 1 to 50 parts by mass, the crosslinking density at the time of photopolymerization becomes appropriate, so that pattern swelling after development can be suppressed and a practical relief pattern can be obtained. In addition, the hydrophobicity of the cured film can be effectively improved. Furthermore, the influence on the unexposed area due to the scattered light from the substrate surface during exposure can be reduced, and the occurrence of post-development residues in the unexposed area can be suppressed.
  • the compound represented by the formula (1) used as the component (c) usually generates a radical by light and has high sensitivity to i-line which is a light source used for patterning.
  • R 1 is an organic group represented by the following formula (2)
  • R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 3 is an alkyl group having 1 to 3 carbon atoms.
  • R 4 is a monovalent organic group
  • X is an oxygen atom, a sulfur atom or a carbonyl group
  • s is an integer of 0 to 5
  • R 2 is preferably an alkyl group having 1 to 10 carbon atoms (preferably 1 to 8), more preferably a methyl group or a hexyl group.
  • R 3 is preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms, more preferably a methyl group or a phenyl group.
  • X is preferably a sulfur atom.
  • R 4 is preferably a hydroxyalkoxy group having 1 to 4 carbon atoms. s is preferably 0 or 1.
  • the formula (2) may be a group represented by the following formula (2 ′).
  • the photosensitive resin composition of the present invention may contain a compound that generates radicals by light other than the compound represented by the above formula (1).
  • examples of such compounds include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2′-diethoxyacetophenone, 2- Acetophenone derivatives such as hydroxy-2-methylpropiophenone and 1-hydroxycyclohexyl phenyl ketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethyl ketal, benzyl- ⁇ -methoxy Benzyl derivatives such as ethyl acetal, benzoin derivatives such as benzoin and benzoin methyl
  • the addition amount of the component (c) in the photosensitive resin composition is usually 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (a). More preferably, it is 0.1 to 5 parts by mass.
  • the amount is from 0.1 to 20 parts by mass, the amount of exposure light absorbed near the surface of the coating film becomes moderate, and the exposure light reaches the substrate sufficiently. Therefore, photocrosslinking can be performed uniformly in the film thickness direction, and a good relief pattern can be obtained.
  • the photosensitive resin composition of the present invention has, for example, 70 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, 99 mass% or more, 99.5 mass% or more, or 99.9 mass% or more. However, it may be the components (a) to (c) and the solvent described later, and optionally other components.
  • the photosensitive resin composition of the present invention may consist essentially of the components (a) to (c) and the solvent described below, and optionally other components. In this case, inevitable impurities may be included. Further, the photosensitive resin composition of the present invention may comprise only the components (a) to (c), the solvent described later, and optionally other components.
  • the photosensitive resin composition of the present invention comprises, as necessary, (1) a solvent, (2) a coupling agent, (3) a surfactant or a leveling agent, 4) A rust inhibitor, (5) a polymerization inhibitor, and (6) a compound that generates radicals upon heating may be contained.
  • a solvent for a solvent that is a solvent that is a solvent that is a solvent that is a solvent that is a solvent that is a solvent that has been heated.
  • the solvent is preferably a polar solvent from the viewpoint of dissolving the polyimide precursor as component (a).
  • polar solvents include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, N, N-dimethylformamide, dimityl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, ⁇ -butyrolactone, ⁇ - Examples include valerolactone, ⁇ -valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolidinone.
  • the coupling agent reacts with the polyimide precursor as the component (a) to crosslink in the step of heat-treating after applying, exposing and developing the photosensitive resin composition, or the coupling agent itself is polymerized. .
  • substrate can be improved more.
  • a silane coupling agent having a urea bond (—NH—CO—NH—) in the molecule, adhesion to the substrate can be further enhanced even when curing is performed at a low temperature of 200 ° C. or lower. it can.
  • a compound represented by the following formula (20) is more preferable because it exhibits excellent adhesion when cured at a low temperature.
  • R 32 and R 33 are each independently an alkyl group having 1 to 5 carbon atoms.
  • K is an integer of 1 to 10
  • j is an integer of 1 to 3.
  • Specific examples of the compound represented by the formula (20) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. , 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, and the like, preferably 3-ureidopropyltriethoxysilane.
  • silane coupling agent having a hydroxy group or a glycidyl group is used in combination with the above-mentioned silane coupling agent having a urea bond, there is an effect of improving the adhesion of the cured film to the substrate during low temperature curing.
  • silane coupling agent having a hydroxy group or a glycidyl group examples include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert- Butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propyl group
  • R 34 is a monovalent organic group having a hydroxy group or a glycidyl group
  • R 35 and R 36 are each independently an alkyl group having 1 to 5 carbon atoms. (It is an integer from 1 to 10, and h is an integer from 0 to 2.)
  • silane coupling agents having a hydroxy group or a glycidyl group the compound represented by the formula (21) is more preferable from the viewpoint of further improving the adhesion to the substrate.
  • silane coupling agents include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyl.
  • Triethoxysilane 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycid Xylethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybuty Triethoxysilane, and the like.
  • the silane coupling agent having a hydroxy group or glycidyl group is preferably a silane coupling agent having a group containing a nitrogen atom, specifically an amino group or an amide bond, together with the hydroxy group or glycidyl group.
  • Examples of the silane coupling agent having an amino group include bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, and bis (2-glycidoxy And methyl) -3-aminopropyltriethoxysilane and bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane.
  • silane coupling agent having an amide bond examples include silane coupling agents having an amide bond such as a compound represented by the following formula.
  • Z is a hydroxy group or a glycidyl group
  • e and f are each independently an integer of 1 to 3
  • R 37 is a methyl group, an ethyl group or a propyl group.
  • the content of the silane coupling agent is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, and more preferably 0.3 to 10 parts by weight with respect to 100 parts by weight of component (a). More preferably, it is part by mass.
  • surfactant or leveling agent By adding a surfactant or a leveling agent to the photosensitive resin composition, coatability (for example, suppression of striation (film thickness unevenness)) and developability can be improved.
  • the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.
  • the content of the surfactant or leveling agent is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and more preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of component (a). Is more preferable.
  • rust inhibitor By adding a rust inhibitor, corrosion and discoloration of copper and copper alloy can be suppressed and prevented.
  • the rust inhibitor include triazole derivatives and tetrazole derivatives.
  • the content is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and 0.5 to 3 parts by weight with respect to 100 parts by weight of component (a). Is more preferable.
  • polymerization inhibitor By including a polymerization inhibitor (radical polymerization inhibitor, radical polymerization inhibitor), good storage stability can be ensured.
  • the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2- Examples thereof include naphthylamine, cuperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like.
  • the content of the polymerization inhibitor is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of component (a) from the viewpoint of the storage stability of the photosensitive resin composition and the heat resistance of the resulting cured film. 0.01 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is still more preferable.
  • the compound that generates radicals by heating include organic peroxides.
  • the organic peroxide include ketone peroxide such as methyl ethyl ketone peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexyl).
  • the content of the compound that generates radicals upon heating is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of component (a). Further preferred.
  • the above-described photosensitive resin composition of the present invention is coated on a substrate and dried to form a photosensitive resin film, the photosensitive resin film is subjected to pattern exposure, and the pattern-exposed resin film is organically treated.
  • the pattern cured film can be produced by a production method including a step of developing with a solvent to form a pattern resin film and a step of heat-treating the pattern resin film. Hereinafter, each step will be described.
  • Examples of the material for the substrate include glass, semiconductors, metal oxide insulators such as TiO 2 and SiO 2 , silicon nitride, copper, and copper alloys. Although there is no restriction
  • Drying can be performed using a hot plate, an oven, or the like.
  • the heating temperature is preferably 90 to 150 ° C., and more preferably 90 to 120 ° C. from the viewpoint of ensuring dissolution contrast.
  • the heating time is preferably 30 seconds to 5 minutes. Thereby, the photosensitive resin film which formed the photosensitive resin composition of this invention in the film form can be obtained.
  • the film thickness of the photosensitive resin film is preferably 5 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, and further preferably 5 to 30 ⁇ m.
  • a predetermined pattern can be exposed through a mask.
  • the actinic rays to be irradiated include ultraviolet rays including i rays, visible rays, radiations, and the like, and i rays are preferable.
  • a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine, or the like can be used as the exposure apparatus.
  • a patterned resin film By performing development processing on the obtained resin film, a patterned resin film (pattern resin film) can be obtained.
  • a negative photosensitive resin composition when used, an unexposed portion is removed with a developer.
  • the developer include an organic solvent, and a good solvent can be used alone, or a good solvent and a poor solvent can be appropriately mixed and used.
  • Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, ⁇ -acetyl-gammabutyrolactone, cyclopenta Non, cyclohexanone, etc. are used as poor solvents, such as toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether and water.
  • PMEA propylene glycol monomethyl ether acetate
  • the development time varies depending on the type of component (a) used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and from the viewpoint of productivity, 20 seconds to 5 minutes. More preferably, it is minutes.
  • a surfactant may be added to the developer.
  • the addition amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developer.
  • the pattern resin film is obtained by washing with a rinse solution to remove the developer.
  • a rinse solution distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or the like can be used alone or in an appropriate mixture, or in a stepwise combination.
  • a patterned cured film can be obtained by heat-treating the pattern resin film. Since the component (a) is a polyimide precursor, a dehydration ring-closing reaction is caused by the heat treatment step, and a corresponding polyimide can be obtained.
  • the photosensitive resin composition contains the compound that generates radicals by heating (6) described above, the functional group of the component (b) or the component (a) and A crosslinked structure can be formed by forming a crosslinked structure between the components (b).
  • the heating temperature is preferably 250 ° C. or lower, more preferably 120 to 250 ° C., and further preferably 160 to 200 ° C. By being within the above range, damage to the substrate and the device can be suppressed, the device can be produced with a high yield, and energy saving of the process can be realized.
  • the heating time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. By being within the above range, the crosslinking reaction or dehydration ring-closing reaction can sufficiently proceed.
  • the atmosphere for the heat treatment may be in the air or in an inert atmosphere such as nitrogen. From the viewpoint of preventing the pattern resin film from being oxidized, a nitrogen atmosphere is preferable.
  • Examples of the apparatus used in the heat treatment step include a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.
  • [Cured product] It can be set as hardened
  • the cured product of the present invention may be the above-described pattern cured film or a cured film having no pattern.
  • the pattern cured film or the cured product can be used as an interlayer insulating film, a cover coat layer, or a surface protective film.
  • Electronic components such as highly reliable semiconductor devices, multilayer wiring boards, and various electronic devices can be manufactured using the interlayer insulating film, the cover coat layer, the surface protective film, and the like.
  • FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.
  • a semiconductor substrate 1 such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer 3 is formed on the exposed circuit element. Is formed. Thereafter, an interlayer insulating film 4 is formed on the semiconductor substrate 1 by spin coating or the like.
  • a photosensitive resin film 5 such as a chlorinated rubber system or a phenol novolac system is formed on the interlayer insulating film 4 by a spin coating method, and a window is formed so that a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique.
  • 6A is provided.
  • the interlayer insulating film 4 from which the window 6A is exposed is selectively etched by dry etching means using a gas such as oxygen or carbon tetrafluoride to open the window 6B.
  • the photosensitive resin film 5 is removed using an etching solution that corrodes only the photosensitive resin film 5 without corroding the first conductor layer 3 exposed from the window 6B.
  • the second conductor layer 7 is formed by using a known photolithography technique, and electrical connection with the first conductor layer 3 is performed.
  • each layer can be formed by repeating the above steps.
  • the surface protective film 8 is formed.
  • the photosensitive resin composition of the present invention is applied and dried by a spin coat method, irradiated with light from a mask on which a pattern for forming a window 6 ⁇ / b> C is formed in a predetermined portion, and then with an organic solvent. Development is performed to form a pattern, and heating is performed to form the surface protective film 8.
  • the surface protective film 8 protects the conductor layer from external stress, ⁇ rays and the like, and the obtained semiconductor device is excellent in reliability.
  • the interlayer insulating film 4 can also be formed using the photosensitive resin composition of the present invention.
  • Synthesis example 1 [Component (a): Synthesis of polyimide precursor a1] 7.07 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2′-dimethylbiphenyl-4,4′-diamine (DMAP) were added to N-methyl- The product was dissolved in 30 g of 2-pyrrolidone (NMP) and stirred at 30 ° C. for 4 hours and then overnight at room temperature to obtain polyamic acid. Thereto was added 9.45 g of trifluoroacetic anhydride under water cooling, followed by stirring at 45 ° C.
  • NMP 2-pyrrolidone
  • the reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain the target polyimide precursor (polyamic acid derivative) a1.
  • required by GPC method standard polystyrene conversion of the polyimide precursor a1 was 35,000.
  • the esterification rate by HEMA computed by NMR measurement was 80 mol% (the remaining 20 mol% is a carboxy group).
  • the measurement conditions for NMR measurement are as follows. Measuring equipment: “AV400M” manufactured by Bruker Biospin Magnetic field strength: 400MHz Reference material: Tetramethylsilane (TMS) Solvent: Dimethyl sulfoxide (DMSO)
  • Examples 1 to 6 and Comparative Examples 1 to 2 [Preparation of photosensitive resin composition] Photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were prepared with the components and blending amounts shown in Table 1.
  • the photosensitive resin composition is a negative type.
  • the compounding quantity of Table 1 is a mass part of each component with respect to 100 mass parts of (a) component. Each component used is as follows.
  • ⁇ (B) component radically polymerizable compound having an aliphatic cyclic structure>
  • B1 Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “A-DCP”, a compound represented by the following formula)
  • B2 1,3-diacrylate adamantane (Mitsubishi Gas Chemical Co., Ltd., trade name “ADDA”, a compound represented by the following formula)
  • B′1 Tetraethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “TEGDMA”, a compound represented by the following formula)
  • ⁇ (C) Component Compound represented by Formula (1)>
  • C1 Compound represented by the following formula (trade name “NCI-930” manufactured by ADEKA Corporation)
  • C2 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (manufactured by BASF Japan Ltd., trade name “IRUGCURE OXE 01”, represented by the following formula: Compound) ⁇ (C ′) component>
  • C′1 Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (trade name, manufactured by BASF Japan Ltd.) “IRUGCURE OXE 02”, a compound represented by the following formula)
  • the component (b ′) means a component different from the component (b) used in the present invention
  • the component (c ′) means a component different from the component (c) used in the present invention.
  • the photosensitive resin composition was spin-coated on a silicon substrate using a coating apparatus (manufactured by Tokyo Electron Ltd., trade name “Act8”), dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes. A photosensitive resin film having a dry film thickness of 7 to 15 ⁇ m was formed. The obtained photosensitive resin film was exposed (exposure amount: 400 mJ / cm 2 ) using an i-line stepper (trade name “FPA-3000iW” manufactured by Canon Inc.).
  • the development time is set to twice the time until complete dissolution, and the exposed resin film is paddle-developed in cyclopentanone, and PGMEA is used. Rinse washing was performed to obtain a patterned resin film.
  • the resolution was defined as the minimum diameter at which the round hole-shaped pattern could be patterned without peeling and residue.
  • Film thickness before exposure, film thickness after development, and film thickness after curing expose the substrate by scribing a part of the resin film or cured film, and contact the height from the exposed substrate surface to the film surface It measured using the type
  • formula profiler The product made from ULVAC, Inc., brand name "Dektak150").
  • the photosensitive resin composition was applied on a copper substrate and spin-coated so that the film thickness after curing was 10 ⁇ m. After drying at 100 ° C. for 2 minutes, it was dried at 110 ° C. for 2 minutes to form a photosensitive resin film.
  • the obtained photosensitive resin film was exposed using a mask aligner (trade name “MA8”, manufactured by SUSS MICROTECH). This resin film was heated at 173 ° C. for 1 hour under a nitrogen atmosphere using a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd.) to obtain a cured film. Next, a pressure cooker test (PCT) was performed on the obtained cured film.
  • the PCT conditions were 121 ° C., 100 RH%, 2 atm, and the test times were 100 hours, 200 hours, 300 hours, 400 hours, and 500 hours.
  • the adhesion of the cured film after PCT was measured by a stud pull evaluation method (stud tensile peel strength measurement) using a thin film adhesion strength measuring instrument (trade name “Romulus” manufactured by Quad Group). Specifically, each copper substrate on which a cured film is formed is cut into 1 cm squares to prepare sample pieces, and a stud pin with an epoxy resin is raised and fixed at the center with a clip, and is cured by heating in an oven at 150 ° C. for 1 hour. Then, the stud pin with epoxy resin was fixed to the cured film, and a sample for evaluation was produced.
  • This sample for evaluation was set on a thin film adhesion strength measuring machine (Romulus), the load was increased to 100 kg at 5 kg / sec, a tensile load was applied to the stud pin in the vertical direction, and the presence or absence of peeling of the cured film was observed. .
  • the adhesion was evaluated according to the following criteria.
  • Circle The cured film did not peel in the sample test piece for evaluation for 500 hours.
  • X The cured film peeled off in the sample piece for evaluation of 100 hours or 200 hours.
  • the photosensitive resin composition of the present invention was excellent in resolution, and the cured film obtained from the photosensitive resin composition had high adhesion to the copper substrate.
  • the photosensitive resin composition of the present invention can be used for the formation of heat-resistant relief patterns such as insulating materials for electronic parts and passivation films, buffer coat films, interlayer insulating films, cover coat layers, surface protective films and the like in semiconductor devices. it can.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

L'invention concerne une composition de résine photosensible contenant : (a) un précurseur de polyimide ; (b) un composé polymérisable par voie radicalaire ayant une structure cyclique aliphatique ; et (c) un composé représenté par la formule (1). (Dans la formule (1), R1 est un groupe organique représenté par la formule (2), R2 est un atome d'hydrogène ou un groupe alkyle en C1-C10, et R3 est un groupe alkyle en C1-C3, un groupe alcoxy en C1-C3, ou un groupe aryle en C6-C10. Dans la formule (2), R4 est un groupe organique monovalent, X est un atome de carbone, un atome de soufre ou un groupe carbonyle, et s est un nombre entier de 0 à 5.)
PCT/JP2017/013589 2017-03-31 2017-03-31 Composition de résine photosensible, procédé de fabrication de film durci à motifs, produit durci, film isolant intercalaire, couche de revêtement de couverture, film protecteur de surface et composant électronique Ceased WO2018179330A1 (fr)

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JP2019508103A JPWO2018179330A1 (ja) 2017-03-31 2017-03-31 感光性樹脂組成物、パターン硬化膜の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜、及び電子部品
PCT/JP2017/013589 WO2018179330A1 (fr) 2017-03-31 2017-03-31 Composition de résine photosensible, procédé de fabrication de film durci à motifs, produit durci, film isolant intercalaire, couche de revêtement de couverture, film protecteur de surface et composant électronique
TW107111419A TW201841992A (zh) 2017-03-31 2018-03-30 感光性樹脂組成物、圖案硬化膜的製造方法、硬化物、層間絕緣膜、覆蓋層、表面保護膜及電子零件

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TWI761897B (zh) * 2019-07-29 2022-04-21 日商旭化成股份有限公司 負型感光性樹脂組合物、聚醯亞胺之製造方法、硬化浮凸圖案之製造方法、及半導體裝置
US20230359122A1 (en) * 2020-04-20 2023-11-09 Hd Microsystems, Ltd. Photosensitive resin composition, method for producing patterned cured film, cured film, interlayer insulating film, cover coat layer, surface protection film, and electronic component
KR20240088588A (ko) 2022-12-12 2024-06-20 아티엔스 가부시키가이샤 수지 조성물, 적층 시트, 프리프레그, 경화물, 경화물 부착 기판 및 전자기기

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JP2003345012A (ja) * 2002-05-28 2003-12-03 Hitachi Chemical Dupont Microsystems Ltd 感光性組成物、及びこれを用いた電子部品
JP2004133435A (ja) * 2002-09-17 2004-04-30 Toray Ind Inc ネガ型感光性樹脂前駆体組成物およびそれを用いた電子部品ならびに表示装置
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TWI761897B (zh) * 2019-07-29 2022-04-21 日商旭化成股份有限公司 負型感光性樹脂組合物、聚醯亞胺之製造方法、硬化浮凸圖案之製造方法、及半導體裝置
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US20230359122A1 (en) * 2020-04-20 2023-11-09 Hd Microsystems, Ltd. Photosensitive resin composition, method for producing patterned cured film, cured film, interlayer insulating film, cover coat layer, surface protection film, and electronic component
KR20240088588A (ko) 2022-12-12 2024-06-20 아티엔스 가부시키가이샤 수지 조성물, 적층 시트, 프리프레그, 경화물, 경화물 부착 기판 및 전자기기

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