CN115718406A - Photosensitive resin composition for forming resist, resin film, cured film, and semiconductor device - Google Patents
Photosensitive resin composition for forming resist, resin film, cured film, and semiconductor device Download PDFInfo
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- CN115718406A CN115718406A CN202211513979.3A CN202211513979A CN115718406A CN 115718406 A CN115718406 A CN 115718406A CN 202211513979 A CN202211513979 A CN 202211513979A CN 115718406 A CN115718406 A CN 115718406A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
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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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G03F7/075—Silicon-containing compounds
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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
- G03F7/16—Coating processes; Apparatus therefor
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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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Abstract
The invention provides a photosensitive resin composition for forming a resist, a resin film, a cured film and a semiconductor device. The photosensitive resin composition for forming a resist of the present invention comprises a phenol resin (a) having a biphenol structure, a photoacid generator (B), and a solvent.
Description
The application date of the present case is11/9/2017Application No. is201780059665.1The invention is named asPhotosensitive tree Resin composition, resin film, cured film, method for producing semiconductor device, and semiconductor deviceDivisional application of the patent application.
Technical Field
The invention relates to a photosensitive resin composition, a method for manufacturing a semiconductor device, a resin film, a cured film and a semiconductor device. More specifically, the present invention relates to a photosensitive resin composition which can be used as a resist used for manufacturing a semiconductor device or as a precursor of a heat-resistant resin used for a semiconductor element surface protective film or an interlayer insulating film.
This application claims priority based on Japanese application No. 2016-220584 filed on 11/2016, the contents of which are incorporated herein by reference.
Background
Conventionally, various resin compositions and photosensitive compositions have been proposed as materials used for forming surface protective films, interlayer insulating films, and the like used for semiconductor elements in electronic components (for example, patent document 1).
Patent document 1 describes a photosensitive resin composition containing, in a solvent: a phenolic resin (A) having a biphenyldiyl structure in the main chain; a photoacid generator (B); and a compound (C) capable of reacting with the compound (A) by utilizing an acid or heat generated from the compound (B). Patent document 1 describes a phenol resin containing an unsubstituted biphenyldiyl structure as the phenol resin (a).
Documents of the prior art
Patent literature
Patent document 1: japanese laid-open patent publication No. 2012-123378
Disclosure of Invention
Technical problem to be solved by the invention
A cured resin film for forming a surface protective film, an interlayer insulating film, and the like of a semiconductor device can be obtained by: a photosensitive resin composition is applied to a substrate to obtain a resin film, the resin film is exposed and developed to form a pattern, and the patterned resin film is heated and cured. In the conventional photosensitive resin composition, the resin film obtained has a low softening point and thus low heat resistance, and the pattern shape is deformed by heating, and thus the resin film cannot be suitably used as a surface protective film or an interlayer insulating film of a semiconductor device in some cases.
According to the present invention for solving the above-described technical problems, it is possible to provide a photosensitive resin composition capable of forming a resin film and a cured film having excellent heat resistance, a resin film composed of the photosensitive resin composition, a cured film of the resin film and a semiconductor device including the cured film, and a method for manufacturing a semiconductor device using the photosensitive resin composition.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have completed the present invention including the following modes.
[ 1] A photosensitive resin composition comprising:
a phenol resin (A) having a diphenol structure;
a photoacid generator (B); and
and (3) a solvent.
The photosensitive resin composition according to the above [ 1], wherein the phenol resin (A) has a structural unit derived from a diphenol compound and at least 1 compound selected from the group consisting of aldehyde compounds, dimethylol compounds, dimethoxymethyl compounds and dihaloalkyl compounds.
[ 3 ] the photosensitive resin composition according to the above [ 1] or [ 2], wherein the phenol resin (A) is a resin having a structural unit represented by the formula (1).
(in the formula (1),
R 11 and R 12 Each independently represents a 1-valent substituent selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkylether group having 1 to 20 carbon atoms, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure having 6 to 20 carbon atoms, and these may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond,
p and q are each independently an integer of 0 to 3,
X 1 and Y 1 Each independently a single bond or a 2-valent substituent selected from the group consisting of an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an alicyclic group having 3 to 20 carbon atoms and an organic group having an aromatic structure having 6 to 20 carbon atoms,
wherein, Y 1 Bonded to any of the 2 benzene rings).
The photosensitive resin composition according to any one of [ 1] to [ 3 ] above, wherein the phenol resin (A) has a repeating structural unit represented by formula (2).
(in the formula (2),
m is an integer of 2 to 10000,
R 11 and R 12 Each independently represents a 1-valent substituent selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkylether group having 1 to 20 carbon atoms, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure having 6 to 20 carbon atoms, and these may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond,
p and q are each independently an integer of 0 to 3,
X 1 and Y 1 Each independently a single bond or a 2-valent substituent selected from the group consisting of an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an alicyclic group having 3 to 20 carbon atoms and an organic group having an aromatic structure having 6 to 20 carbon atoms,
wherein, Y 1 Bonded to any of 2 benzene rings).
The photosensitive resin composition according to any one of [ 1] to [4 ], wherein the photoacid generator (B) is a compound that generates an acid upon irradiation with radiation having a wavelength of 200 to 500nm.
The photosensitive resin composition according to any one of [ 1] to [5 ] above, further comprising a crosslinking agent (C) having a group capable of reacting with the phenol resin (A).
The photosensitive resin composition according to any one of [ 1] to [ 6 ], wherein the weight average molecular weight of the phenol resin (A) in terms of polystyrene is 1000 to 100000.
The photosensitive resin composition according to any one of [ 1] to [ 7 ] above, which further comprises a silane coupling agent (D).
The photosensitive resin composition according to any one of [ 1] to [ 8 ] above, which further comprises a nonionic surfactant (E).
[ 10 ] the photosensitive resin composition according to any one of [ 1] to [ 9 ] above, which further comprises a reaction accelerator (F).
[ 11 ] A method for manufacturing a semiconductor device, comprising the steps of:
a step of applying the photosensitive resin composition according to any one of [ 1] to [ 10 ] above onto a semiconductor substrate;
a step of obtaining a photosensitive resin layer by heating and drying the photosensitive resin composition;
exposing the photosensitive resin layer with an activating light;
a step of obtaining a patterned resin layer by developing the exposed photosensitive resin layer; and
and heating the patterned resin layer to obtain a cured resin layer.
[ 12 ] A resin film comprising the photosensitive resin composition according to any one of [ 1] to [ 10 ].
[ 13 ] a cured film of the resin film according to [ 12 ] above.
A semiconductor device comprising the cured film according to [ 13 ] above.
Effects of the invention
According to the present invention, a photosensitive resin composition capable of forming a resin film or a cured film having excellent heat resistance, a resin film composed of the photosensitive resin composition, a cured film of the resin film, a semiconductor device including the cured film, and a method for manufacturing a semiconductor device using the photosensitive resin composition can be provided.
Detailed Description
Embodiments of the present invention will be described below.
(photosensitive resin composition)
The photosensitive resin composition according to the present embodiment includes a phenol resin (a) having a diphenol structure, a photoacid generator (B), and a solvent.
In the resin composition of the present embodiment, a resin having a biphenol structure, that is, a phenol resin having a biphenyldiyl structure in which each of phenyl groups has at least 1 hydroxyl group is used as the phenol resin (a), whereby the heat resistance of a resin film made of the above composition is improved. Therefore, when a resin film made of the photosensitive resin composition is exposed to light and developed to form a pattern, a high-resolution pattern can be formed on the resin film.
(phenol resin (A))
In one embodiment, the phenol resin (a) has a structural unit derived from a diphenol compound and at least 1 compound selected from the group consisting of an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound. In other words, the phenol resin (a) can be obtained by the reaction of a diphenol compound with at least 1 compound selected from the group consisting of aldehyde compounds, dimethylol compounds, dimethoxymethyl compounds and dihaloalkyl compounds.
In the present specification, the term "structure derived from (substance)" refers to a structure produced using the above-mentioned substance, and includes both a case where the above-mentioned structure can be confirmed by a method generally used in the art and a case where the above-mentioned structure cannot be confirmed by a method generally used in the art.
Since such a phenol resin (a) can be produced using a commercially available raw material monomer without requiring a complicated step, the obtained photosensitive resin composition can be produced at low cost.
The phenol resin (a) can be produced by any known method. Examples of the production method include a condensation reaction of a diphenol compound with an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound or a dihaloalkyl compound.
Examples of the diphenol compound that can be used for the production of the phenolic resin (a) include 2,2 '-diphenol, 4' -diphenol and isomers thereof. These diphenol compounds may have a substituent, and examples of the substituent include a hydroxyl group, a halogen, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkylether group having 1 to 20 carbon atoms, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, an organic group having an aromatic structure having 6 to 20 carbon atoms, and the like.
Such biphenol compounds are exemplified by the following compounds, but are not limited thereto.
Examples of the aldehyde compound which reacts with the diphenol compound to produce the phenolic resin (a) include formaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, trioxane, glyoxal, cyclohexanal, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, cinnamaldehyde, diphenylacetaldehyde, methyl benzoate, 3-methyl-2-butenal, glyoxylic acid, 5-norbornene-2-formaldehyde, malonaldehyde, succinaldehyde, glutaraldehyde, naphthaldehyde, and terephthalaldehyde.
<xnotran> (A) , 2,2- ( ) ,1,3- ,2- -1,3- ,2,2- -1,3- ,2,2- -1,3- , ,2- -2- -1,3- ,5- -2,2- ,5- -2,3- , ,2- -1,3- , , ,3,6- ( ) ,2- - ,1, 10- ,1, 12- ,1,4- ( ) ,1,4- ( ) ,1,6- ( ) ,1,4- ,1,3- ,2,6- ( ) -1,4- ,2,6- ( ) - ,2,3- ( ) ,2,6- ( ) ,1,8- ( ) ,2,2' - ( ) , </xnotran> 4,4 '-bis (hydroxymethyl) diphenyl ether, 4' -bis (hydroxymethyl) diphenyl sulfide, 4 '-bis (hydroxymethyl) benzophenone 4' -hydroxymethylphenyl 4-hydroxymethylbenzoic acid, 4 '-hydroxymethylaniline 4-hydroxymethylbenzoic acid, 4' -bis (hydroxymethyl) phenylurea 4,4 '-bis (hydroxymethyl) phenylurethane, 1, 8-bis (hydroxymethyl) anthracene, 4' -bis (hydroxymethyl) biphenyl, 2 '-dimethyl-4, 4' -bis (hydroxymethyl) biphenyl, 2-bis (4-hydroxymethylphenyl) propane, and the like.
Examples of the dimethoxymethyl compound which forms the phenol resin (A) by the reaction with the above-mentioned diphenol compound include 2, 2-bis (methoxymethyl) butyric acid, 1, 3-dimethoxymethylpropane, 2-benzyloxy-1, 3-dimethoxymethylpropane, 2-dimethyl-1, 3-dimethoxymethylpropane, 2-diethyl-1, 3-dimethoxymethylpropane, 2, 3-dimethoxy-1-propanol acetate, 2-methyl-2-nitro-1, 3-dimethoxymethylpropane, 5-norbornene-2, 2-dimethoxymethyl ester, 5-norbornene-2, 3-dimethoxymethyl ester, tetrakis (methoxymethyl) methane, 2-phenyl-1, 3-dimethoxymethylpropane, trimethoxyethane, trimethoxypropane, 3, 6-bis (methoxymethyl) durene, 2-nitro-1, 4-bis (methoxymethyl) benzene, 1, 10-dimethoxydecane, 1, 12-dimethoxydodecane, 1, 4-bis (methoxymethyl) cyclohexane, 1, 4-bis (methoxymethyl) cyclohexene, 1, 6-bis (methoxymethyl) adamantane, 1, 4-bis (methoxymethyl) benzene, 1, 3-dimethoxymethylbenzene, 2, 6-bis (methoxymethyl) -1, 4-dimethoxybenzene, 2, 6-bis (methoxymethyl) -p-cresol, 2, 3-bis (methoxymethyl) naphthalene, 2, 6-bis (methoxymethyl) naphthalene, 1, 8-bis (methoxymethyl) anthracene, 2 '-bis (methoxymethyl) diphenyl ether, 4' -bis (methoxymethyl) diphenyl sulfide, 4 '-bis (methoxymethyl) benzophenone, 4-methoxymethylbenzoic acid-4' -methoxymethylphenyl group, 4-methoxymethylbenzoic acid-4 '-methoxymethylaniline, 4' -bis (methoxymethyl) phenylurea, 4 '-bis (methoxymethyl) phenylurethane, 1, 8-bis (methoxymethyl) anthracene, 4' -bis (methoxymethyl) biphenyl, 2 '-dimethyl-4, 4' -bis (methoxymethyl) biphenyl, 2-bis (4-methoxymethylphenyl) propane, and the like.
Examples of the dihaloalkyl compound which forms the phenol resin (a) by the reaction with the above-mentioned diphenol compound include dichloroxylene, dichloromethyl dimethoxybenzene, dichloromethyl durene, dichloromethyl biphenyl carboxylic acid, dichloromethyl biphenyl dicarboxylic acid, dichloromethyl methyl biphenyl, dichloromethyl dimethyl biphenyl, dichloromethyl anthracene, ethylene glycol bis (chloroethyl) ether, diethylene glycol bis (chloroethyl) ether, triethylene glycol bis (chloroethyl) ether, and tetraethylene glycol bis (chloroethyl) ether.
The above compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.
The phenol resin (a) can be obtained by dehydrating or dehydrohalogenating condensing the above diphenol compound with the above polymerization component, and a catalyst can be used for the polymerization. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfuric acid, diethylsulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1, 1' -diphosphonic acid, zinc acetate, boron trifluoride, a boron trifluoride phenol complex, a boron trifluoride ether complex, and the like. Examples of the basic catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, piperazine, 1, 4-diazabicyclo [2.2.2] octane, 1, 8-diazabicyclo [5.4.0] -7-undecene, 1, 5-diazabicyclo [4.3.0] -5-nonene, ammonia, and hexamethylenetetramine.
When the synthesis reaction of the phenol resin (a) is carried out, an organic solvent may be used as necessary. Specific examples of the organic solvent that can be used include, but are not limited to, bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene, γ -butyrolactone, and N-methyl-2-pyrrolidone.
The phenol resin (a) may be obtained by further polymerizing phenol compounds other than the above-mentioned diphenol compounds within a range not to impair the effects of the present invention.
In one embodiment, the phenolic resin (a) obtained from the above compound may have a structural unit represented by formula (1).
In the formula (1), the acid-base catalyst,
R 11 and R 12 Each independently represents a 1-valent substituent selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkylether group having 1 to 20 carbon atoms, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure having 6 to 20 carbon atoms, and these may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond,
p and q are each independently an integer of 0 to 3,
X 1 and Y 1 Each independently a single bond or a 2-valent substituent selected from the group consisting of an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an alicyclic group having 3 to 20 carbon atoms and an organic group having an aromatic structure having 6 to 20 carbon atoms,
wherein, Y 1 Bonded to any of the 2 benzene rings.
The structural unit of formula (1) that the phenol resin (a) may have includes a biphenol structure, that is, a biphenyldiyl structure having at least 1 hydroxyl group in each phenyl group, and thereby the heat resistance of a resin film composed of the composition including the phenol resin (a) is improved. Therefore, when a resin film made of the photosensitive resin composition is exposed to light and developed to form a pattern, a high-resolution pattern can be formed on the resin film.
Preferably R 11 And R 12 Each independently is a hydroxyl group.
Preferably, p and q are each independently an integer of 0 to 2.
Preferably X 1 And Y 1 Each independently a single bond or a 2-valent substituent selected from an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond and an organic group having an aromatic structure having 6 to 20 carbon atoms.
X 1 And Y 1 The "aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond" in (1) may be a straight chain or a branched chain. The number of carbon atoms may be 1 to 7, 1 to 5, or 1 to 3. When the aliphatic group is an aliphatic hydrocarbon group, examples thereof include an alkylene group, an alkenylene group, and an alkynylene group, and among them, an alkylene group is preferable, and examples thereof include a methylene group, an ethylene group, and a propylene group.
X 1 And Y 1 The "organic group having an aromatic structure and having 6 to 20 carbon atoms" in (1) may have 6 to 14 carbon atoms, 6 to 12 carbon atoms, 6 to 9 carbon atoms, or 6 to 8 carbon atoms. Examples of the "aromatic structure" include phenylene, biphenyldiyl, naphthalenediyl and the like, and among them, phenylene is preferable.
X 1 And Y 1 The "organic group having an aromatic structure and having 6 to 20 carbon atoms" in (1) may be a 2-valent substituent in which the "aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond" and the "aromatic structure" are bonded to each other.
More preferably X 1 And Y 1 Each independently is the following organic group.
In the above formula, n is 0 to 20, preferably 0 to 10.
The structural unit represented by the above formula (1) can be obtained by the reaction of the above-mentioned diphenol compound with at least 1 compound selected from the group consisting of aldehyde compounds, dimethylol compounds, dimethoxymethyl compounds and dihaloalkyl compounds.
In the present embodiment, the phenolic resin (a) substantially has a repeating unit represented by formula (2).
Wherein in the formula (2), m is an integer of 1 to 10000, R 11 And R 12 P and q and X 1 And Y 1 The same as defined in formula (1).
The resin having a repeating unit structure represented by formula (2) may be, for example, a resin having a structure represented by formula (3).
In the formula (3), l and m represent a composition ratio, l + m =1, 0. Ltoreq.1, 0. Ltoreq. M.ltoreq.1,
R 11’ 、R 12’ 、R 11” and R 12” Each independently a 1-valent substituent selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkylether group having 1 to 20 carbon atoms, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure having 6 to 20 carbon atoms, which may be bonded through an ester bond, an ether bond, an amide bond, or a carbonyl bond,
p and q are each independently an integer of 0 to 3,
X 1’ 、Y 1’ 、X 1” and Y 1” Each independently represents a single bond or is selected from the group consisting of 1 to 1 carbon atoms which may have an unsaturated bond0, an alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure and having 6 to 20 carbon atoms.
The above structure of the phenol resin (a) can be understood by those skilled in the art from the kinds of the diphenol compound and the polymerizable compound used.
In one embodiment, the weight average molecular weight (in terms of polystyrene) of the phenolic resin (a) is in the range of 1000 to 100000, preferably in the range of 2000 to 50000, and more preferably in the range of 3000 to 30000. The phenolic resin (a) having a weight average molecular weight in the above range is excellent in solubility in a solvent, and the obtained resin film is excellent in mechanical properties.
(photoacid Generator (B))
The photosensitive resin composition of the present embodiment is not particularly limited as long as it is a composition capable of forming a resin pattern by being irradiated with radiation such as ultraviolet rays, electron beams, and X-rays, and may be a negative or positive photosensitive resin composition. The resin composition of the present embodiment, which contains the photoacid generator (B) and has photosensitivity, can be used as a resist used for manufacturing a semiconductor device, for example.
The photoacid generator (B) used in the photosensitive resin composition of the present embodiment is a compound that generates an acid upon being irradiated with radiation, and is a compound that generates an acid upon being irradiated with radiation having a wavelength of preferably 200 to 500nm, particularly preferably 350 to 450 nm. Specific examples thereof include onium salts such as a photosensitive diazobenzoquinone compound, a photosensitive diazonaphthoquinone compound, a diaryliodonium salt, a triarylsulfonium salt, and a sulfonium borate, a 2-nitrobenzyl ester compound, an N-iminosulfonate compound, an imidosulfonate compound, a 2, 6-bis (trichloromethyl) -1,3, 5-triazine compound, and a dihydropyridine compound. These may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Among them, a photosensitive diazoquinone compound and a photosensitive diazonaphthoquinone compound which are excellent in sensitivity and solvent solubility are preferable. Specific examples thereof include 1, 2-benzoquinone diazide-4-sulfonate ester, 1, 2-naphthoquinone diazide-4-sulfonate ester, and 1, 2-naphthoquinone diazide-5-sulfonate ester of phenol compounds.
The photoacid generator (B) is used in an amount of 1 to 100% by weight, preferably 3 to 50% by weight, based on 100% by weight of the phenol resin (a).
(solvent)
The photosensitive resin composition of the present embodiment can be used in the form of a varnish obtained by dissolving the above components in a solvent. Examples of the solvent used include N-methyl-2-pyrrolidone, γ -butyrolactone, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1, 3-butanediol acetate, 1, 3-butanediol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, and methyl 3-methoxypropionate, and the like, and they may be used alone or in a mixture.
The amount of the solvent used is 50 to 1000 wt%, preferably 100 to 500 wt%, based on 100 wt% of the phenol resin (a). By using the solvent in the above range, a varnish having excellent handling properties in which the resin is sufficiently dissolved can be produced.
(crosslinking agent (C))
The photosensitive resin composition of the present embodiment may contain a crosslinking agent (C) having a group capable of reacting with the phenol resin (a). When a resin film is produced using the photosensitive resin composition of the present embodiment containing the crosslinking agent (C), and the resin film is exposed, developed, patterned, and then cured by heating, the crosslinking agent (C) is crosslinked with the phenol resin (a) by the action of acid or heat generated from the photoacid generator (B). The resin film obtained from the photosensitive resin composition containing a crosslinking agent is inhibited from being deformed by the patterned resin film when cured by heating by containing the phenol resin (a) having the above-described structure. Furthermore, the obtained cured film has excellent heat resistance, electrical characteristics, and mechanical characteristics, and thus can be used as a surface protective film and an interlayer insulating film used in a semiconductor device.
As the crosslinking agent (C) that can be used in the photosensitive resin composition of the present embodiment, a compound that can be thermally crosslinked with the phenol resin (a) is preferably used. Examples of the crosslinking agent (C) that can be used include the following compounds:
(1) A compound containing 1 or more crosslinkable groups selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group: for example, benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl; <xnotran> , CYMEL 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 ( (Mitsui Cytec Co., ltd.) ), NIKALAC MX-270, -280, -290, NIKALAC MS-11, NIKALAC MW-30, -100, -300, -390, -750 ( (Sanwa Chemical Co., ltd.) ), 1,4- ( ) ,4,4'- ,4,4' - ( ) , 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A ( (ASAHI YUKIZAI CORPORATION) ), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, -Bis-C, -BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP, 2,6- -4- ,2,6- - ,2,6- - , triML-P, triML-35XL, </xnotran> TriML-TrisCR-HAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (produced by HONSHU CHEMICAL INDUSTRY CO., LTD.), etc. These compounds may be used alone or in admixture thereof.
(2) Compound having epoxy group: for example, n-butyl glycidyl ether, 2-ethoxyhexylglycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ethers of bisphenol A (or F) and the like, diglycidyl adipate, glycidyl esters of phthalic acid diglycidyl ester and the like, 3, 4-epoxycyclohexylmethyl (3, 4-epoxycyclohexane) carboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl (3, 4-epoxy-6-methylcyclohexane) carboxylate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentane diene oxide, bis (2, 3-cyclopentyl) ether, CEILOXIDE 2021, CEILOXIDE XI2081, ILOXIDE 2083, XICELLODE 2085, EPILLODE 8000, bis (2-epoxy) 2- (2-phenyl) ethylene oxide (-) ((2, 4-epoxyphenyl) 1, bis (3, 4-epoxycyclohexylmethyl) adipate), bis (3, 4-epoxycyclohexylmethyl) adipate, dicyclopentane oxide, bis (2, 3-cyclopentyl) ether, epoxy-2' -epoxy-2-bis (2-epoxyphenyl) 1, bis (epoxyphenyl) ethylene oxide) (401, bis (2-epoxyphenyl) ethylene oxide) (2, bis (4-epoxyphenyl) oxide) (2, bis (epoxyphenyl) oxide) (401, bis (epoxyphenyl) ether), techmore VG3101L (manufactured by Printec Corporation)), aliphatic polyglycidyl ethers such as Epolite 100MF (manufactured by Kyoeisha CHEMICAL Co., ltd., ltd.), epiol TMP (manufactured by NOF CORPORATION) and the like, 1,3, 5-hexamethyl-1, 5-bis (3- (oxiran-2-ylmethoxy) propyl) trisiloxane (e.g., DMS-E09 (manufactured by Gelest, inc.));
(3) Compound having isocyanate group: for example, 4 '-diphenylmethane diisocyanate, tolylene diisocyanate, 1, 3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate;
(4) Compounds having bismaleimide group: for example, 4' -diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3' -dimethyl-5, 5' -diethyl-4, 4' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1,6' -bismaleimide- (2, 4-trimethyl) hexane, 4' -diphenyl ether bismaleimide, 4' -diphenylsulfone bismaleimide, 1, 3-bis (3-maleimidophenoxy) benzene, 1, 3-bis (4-maleimidophenoxy) benzene.
The amount of the crosslinking agent (C) in the photosensitive resin composition is 1 to 100% by weight, preferably 5 to 50% by weight, based on 100% by weight of the phenol resin (a). When the compounding amount is 1% by weight or more, the mechanical strength of the thermosetting film is good, and when the compounding amount is 100% by weight or less, the stability of the composition in a varnish state is good, and the mechanical strength of the obtained thermosetting film is good.
(silane coupling agent (D))
The photosensitive resin composition of the present embodiment may contain a silane coupling agent (D). When the photosensitive resin composition is applied to a substrate to obtain a resin film, the adhesion to the substrate is improved by containing the silane coupling agent (D).
Examples of the silane coupling agent (D) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and silicon compounds obtained by reacting a silicon compound having an amino group with an acid dianhydride or an acid anhydride, but are not limited thereto. The silane coupling agents may be used alone or in combination.
The amount of the silane coupling agent (D) incorporated in the photosensitive resin composition is 0.1 to 30% by weight, preferably 1 to 20% by weight, based on 100% by weight of the phenolic resin (a). By using the silane coupling agent (D) within the above range, both the adhesion to the substrate and the storage stability of the photosensitive resin composition can be achieved.
(nonionic surfactant (E))
The photosensitive resin composition of the present embodiment may contain a nonionic surfactant (E). By containing the nonionic surfactant (E), the coating property when the photosensitive resin composition is coated on a substrate to obtain a resin film is improved, and a coating film having a uniform thickness can be obtained. Further, it is possible to prevent residues or pattern floating when the coating film is developed.
The nonionic surfactant (E) used in the photosensitive resin composition is, for example, a compound containing a fluorine group (e.g., a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a main skeleton. In the present embodiment, as the nonionic surfactant (E), a nonionic surfactant containing a fluorine-based surfactant or a silicone-based surfactant is more preferably used, and a fluorine-based surfactant is particularly preferably used. Examples of the fluorine-based surfactant include, but are not Limited to, magafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F-554, F-556 and F-557 manufactured by DIC CORPORATION, and Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited.
When a surfactant is used, the amount of the surfactant to be added is preferably 0.01 to 10% by weight based on 100 parts by mass of the alkali-soluble phenol resin.
(reaction Accelerator (F))
The photosensitive resin composition of the present embodiment may contain a reaction accelerator (F). By including the reaction accelerator (F), thermal crosslinking between the phenol resin (a) and the crosslinking agent contained in the photosensitive resin composition can be accelerated.
As the reaction accelerator (F), for example, a nitrogen-containing five-membered heterocyclic compound or a compound which generates an acid by heat can be used. These may be used alone or in combination of two or more. Examples of the nitrogen-containing five-membered heterocyclic compound which can be used as the reaction accelerator (F) include pyrrole, pyrazole, imidazole, 1,2, 3-triazole and 1,2, 4-triazole. Examples of the compound that generates an acid by heat, which can be used as the reaction accelerator (F), include sulfonium salts, iodonium salts, sulfonates, phosphates, borates, and salicylates. From the viewpoint of more effectively improving curability at low temperatures, the compound that generates an acid by heat more preferably contains one or both of a sulfonate and a borate, and particularly preferably contains a borate in consideration of heat resistance of cured film characteristics.
(other additives)
In the photosensitive resin composition of the present embodiment, additives such as a dissolution accelerator, an antioxidant, a filler, a photopolymerization initiator, a capping agent, and a sensitizer may be further used as necessary within a range not to impair the effects of the present invention.
(method for producing cured film)
Another embodiment of the present invention provides a method for manufacturing a semiconductor device, including the steps of:
a step of applying the photosensitive resin composition of the present invention on a semiconductor substrate;
a step of obtaining a photosensitive resin layer by heating and drying the photosensitive resin composition;
exposing the photosensitive resin layer with an activating light;
a step of obtaining a patterned resin layer by developing the exposed photosensitive resin layer; and
and heating the patterned resin layer to obtain a cured resin layer.
Next, an example of the present embodiment will be described.
(method of Forming coating film)
First, the photosensitive resin composition of the present embodiment is applied to a support or a substrate, for example, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, or the like. Here, the substrate includes, for example, a substrate having a semiconductor element or a display element formed on a surface thereof, in addition to a raw substrate. In this case, an adhesion aid such as a silane coupling agent may be applied to the support or the substrate in advance in order to secure water-resistant adhesion between the formed pattern and the support. The photosensitive resin composition can be applied by spin coating using a spin coater, spray coating using a spray coater, dipping, printing, roll coating, or the like.
Then, the coating film of the photosensitive resin composition is formed by prebaking at 80 to 140 ℃ for about 30 to 600 seconds to remove the solvent. The thickness of the coating film after removal of the solvent is preferably 1 to 500. Mu.m.
(Exposure Process)
Next, the coating film obtained as described above is exposed to light. The activating light for exposure may be, for example, X-rays, electron beams, ultraviolet rays, visible rays, or the like, and preferably has a wavelength of 200 to 500nm. In view of pattern resolution and handling property, the light source wavelength is preferably in the g-ray, h-ray or i-ray region of the mercury lamp, and may be used alone or in combination of 2 or more kinds of light. As the exposure device, a contact alignment exposure apparatus, a mirror projection alignment exposure apparatus, or a stepper exposure apparatus is particularly preferable. After the exposure, the coating film may be heated again at 80 to 140 ℃ for about 10 to 300 seconds, if necessary.
(developing step)
Next, the coating film after the exposure is developed to form a relief pattern (reliefpattern). In the developing step, development can be performed by a method such as a dipping method, a puddle (dip method), or a spin coating method using an appropriate developer. By development, the exposed portion (in the case of a positive type) or the unexposed portion (in the case of a negative type) is eluted and removed from the coating film, and a relief pattern can be obtained.
As the developer, for example, there can be used:
inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia;
organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine;
an aqueous solution of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide;
an organic solvent such as cyclopentanone, propylene glycol monomethyl ether, or propylene glycol monomethyl ether acetate, and a water-soluble organic solvent such as methanol or ethanol, or a surfactant may be added to these developer solutions.
Among them, aqueous tetramethylammonium hydroxide is preferred. The concentration of tetramethylammonium hydroxide in the aqueous solution is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass.
After the development, the developing solution is washed with a rinse solution to remove the developing solution, whereby a relief pattern can be obtained. Examples of the rinse solution include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether, which may be used alone or in combination of 2 or more.
(heating step)
Finally, by heating the relief pattern obtained as described above, a cured relief pattern (cured film) can be obtained. The heating temperature is preferably 150 to 500 ℃ and more preferably 150 to 400 ℃. The heating time may be 15 to 300 minutes. The heat treatment may be performed by a hot plate, an oven, a temperature-raising oven capable of setting a temperature program, or the like. As an atmosphere gas in the heat treatment, air may be used, or an inert gas such as nitrogen or argon may be used. In the case where the heat treatment needs to be performed at a lower temperature, heating may be performed under reduced pressure using a vacuum pump or the like.
The relief pattern obtained from the photosensitive resin composition of the present embodiment has little or no deformation in the heating step, and can retain the shape of the relief pattern before heating, and a cured relief pattern with high resolution can be obtained.
(semiconductor device)
The cured relief pattern can be used as a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip-chip device protective film, or a protective film for a device having a bump structure, and can be combined with steps in a known method for manufacturing a semiconductor device. As described above, the cured relief pattern of the present embodiment can be produced with high resolution, and therefore, a semiconductor device using the cured relief pattern is excellent in electrical reliability.
Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than the above-described configurations may be adopted. The present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within a range in which the object of the present invention can be achieved are included in the present invention.
Examples
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.
(Synthesis example 1)
< Synthesis of phenol resin (A-1) >
After adding 186.2g (1.00 mol) of 4,4' -biphenol, 134.6g (0.8 mol) of 2, 6-bis (hydroxymethyl) -p-cresol, 6.3g (0.05 mol) of oxalic acid dihydrate and 327g of gamma-butyrolactone to a 4-necked glass round-bottomed flask having a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet, the polycondensation reaction was carried out at 100 ℃ for 6 hours while refluxing the reaction mixture by placing the round-bottomed flask in an oil bath while flowing nitrogen gas. Next, after the obtained reaction liquid was cooled to room temperature, 436g of acetone was added and mixed with stirring until it became homogeneous. Then, the reaction solution in the round-bottom flask was dropwise mixed with 10L of water to precipitate a resin component. Subsequently, the precipitated resin component was collected by filtration, and then vacuum-dried at 60 ℃ to obtain a phenol resin represented by the following formula (A-1). The weight-average molecular weight of the obtained phenol resin (A-1) was 9,800.
(in the formula (A-1), the bond bonding to the biphenol structure is bonded to any of the 2 benzene rings).
(Synthesis example 2)
< Synthesis of phenol resin (A-2) >
A4-necked glass round-bottomed flask having a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet was charged with 186.2g (1.00 mol) of 4,4' -biphenol, 133.0g (0.8 mol) of 1, 4-bis (methoxymethyl) benzene, 7.7g (0.05 mol) of diethyl sulfate and 327g of γ -butyrolactone, and then subjected to polycondensation reaction at 100 ℃ for 6 hours while refluxing the reaction mixture by passing nitrogen gas through the flask in an oil bath. Next, after the obtained reaction liquid was cooled to room temperature, 436g of acetone was added and mixed with stirring until it became homogeneous. Thereafter, the reaction mixture in the round-bottom flask was dropwise mixed with 10L of water to precipitate a resin component. Subsequently, the precipitated resin component was collected by filtration, and then vacuum-dried at 60 ℃ to obtain a phenol resin represented by the following formula (A-2). The weight-average molecular weight of the obtained phenol resin (A-2) was 12,300.
(in the formula (A-2), the bond bonding to the biphenol structure is bonded to any of 2 benzene rings).
(Synthesis example 3)
< Synthesis of phenol resin (A-3) >
A4-necked glass round bottom flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet was charged with 186.2g (1.00 mol) of 4,4 '-biphenol, 193.9g (0.8 mol) of 4,4' -bis (methoxymethyl) biphenyl, 7.7g (0.05 mol) of diethyl sulfate and 582g of gamma-butyrolactone, and then placed in an oil bath with nitrogen gas flowing therethrough, and polycondensation reaction was carried out at 100 ℃ for 6 hours. Next, after the obtained reaction liquid was cooled to room temperature, 323g of acetone was added and mixed with stirring until it became homogeneous. Thereafter, the reaction mixture in the round-bottom flask was dropwise mixed with 10L of water to precipitate a resin component. Subsequently, the precipitated resin component was collected by filtration, and then vacuum-dried at 60 ℃ to obtain a phenol resin represented by the following formula (a-3). The weight average molecular weight of the obtained phenol resin (A-3) was 7,000.
(in the formula (A-3), the bond bonded to the diphenol structure is bonded to any one of the 2 benzene rings).
(Synthesis example 4)
< Synthesis of phenol resin (A-4) >
Into a 4-necked glass round bottom flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet were charged 186.2g (1.00 mol) of 2,2' -biphenol, 134.6g (0.8 mol) of 2, 6-bis (hydroxymethyl) -p-cresol, 6.3g (0.05 mol) of oxalic acid dihydrate and 327g of γ -butyrolactone, and then polycondensation reaction was carried out at 100 ℃ for 6 hours while refluxing the reaction mixture by placing the round bottom flask in an oil bath with nitrogen gas flowing therethrough. Next, after the obtained reaction liquid was cooled to room temperature, 436g of acetone was added and mixed with stirring until it became homogeneous. Thereafter, the reaction mixture in the round-bottom flask was dropwise mixed with 10L of water to precipitate a resin component. Subsequently, the precipitated resin component was collected by filtration, and then vacuum-dried at 60 ℃ to obtain a phenol resin represented by the following formula (A-4). The weight-average molecular weight of the obtained phenol resin (A-4) was 7,700.
(in the formula (A-4), the bond bonding to the biphenol structure is bonded to any of the 2 benzene rings).
(Synthesis example 5)
< Synthesis of phenol resin (A-5) >
234.2g (1.00 mol) of pentahydroxybiphenyl (phenyloglucide), 133.0g (0.8 mol) of 1, 4-bis (methoxymethyl) benzene, 7.7g (0.05 mol) of diethyl sulfate and 375g of gamma-butyrolactone were added to a 4-neck glass round bottom flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen inlet, and then the reaction mixture was refluxed and subjected to polycondensation reaction at 100 ℃ for 6 hours while passing through a nitrogen bath. Next, after the obtained reaction liquid was cooled to room temperature, 500g of acetone was added and mixed with stirring until it became homogeneous. Then, the reaction solution in the round-bottom flask was dropwise mixed with 10L of water to precipitate a resin component. Subsequently, the precipitated resin component was collected by filtration, and then vacuum-dried at 60 ℃ to obtain a phenol resin represented by the following formula (A-5). The weight average molecular weight of the obtained phenolic resin (A-5) was 22,000.
(in the formula (A-5), the bond bonding to the biphenol structure is bonded to any of the 2 benzene rings).
(Synthesis example 6)
< Synthesis of phenol resin (A-6) >
Into a 4-necked glass round-bottomed flask having a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet were added 186.2g (1.00 mol) of 4,4' -biphenol, 86.5g (0.8 mol) of p-cresol, 24.0g (0.8 mol) of formaldehyde, 11.3g (0.09 mol) of oxalic acid dihydrate and 308g of γ -butyrolactone, and then the reaction mixture was refluxed at 100 ℃ for 6 hours while passing nitrogen gas through the flask. Next, after the obtained reaction liquid was cooled to room temperature, 411g of acetone was added and mixed with stirring until it became homogeneous. Thereafter, the reaction mixture in the round-bottom flask was dropwise mixed with 10L of water to precipitate a resin component. Subsequently, the precipitated resin component was collected by filtration, and then vacuum-dried at 60 ℃ to obtain a phenol resin represented by the following formula (A-6). The weight average molecular weight of the obtained phenol resin (A-6) was 11,000.
(in the formula (A-6), the bond bonding to the biphenol structure is bonded to any of the 2 benzene rings).
(Synthesis example 7)
< Synthesis of phenol resin (A-2) >
A4-necked glass round-bottomed flask having a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet was charged with 186.2g (1.00 mol) of 4,4' -biphenol, 140.0g (0.8mo 1) of dichloroparaxylene, 7.7g (0.05 mol) of diethyl sulfate and 327g of γ -butyrolactone, and then the reaction mixture was refluxed in an oil bath with nitrogen gas flowing through the flask, and subjected to a polycondensation reaction at 100 ℃ for 6 hours. Next, after the obtained reaction liquid was cooled to room temperature, 436g of acetone was added and mixed with stirring until it became homogeneous. Thereafter, the reaction mixture in the round-bottom flask was dropwise mixed with 10L of water to precipitate a resin component. Subsequently, the precipitated resin component was collected by filtration, and then vacuum-dried at 60 ℃ to obtain a phenol resin represented by the following formula (A-2). The weight-average molecular weight of the obtained phenol resin (A-2) was 13,500.
(in the formula (A-2), the bond bonding to the biphenol structure is bonded to any of 2 benzene rings).
(preparation of photosensitive resin composition)
Photosensitive resin compositions were prepared in the following manner for examples 1 to 11 and comparative examples 1 to 2, respectively. First, each component blended in accordance with table 1 was dissolved in γ -butyrolactone (GBL), stirred under a nitrogen atmosphere so that the viscosity after the blending became about 500mpa.s, and then filtered with a polyethylene filter having a pore diameter of 0.2 μm, thereby obtaining a varnish-like photosensitive resin composition. The details of each component in table 1 are as follows. The units in table 1 are parts by mass.
< phenol resin (A) >
(A-1) the phenolic resin obtained in Synthesis example 1
(A-2) the phenol resin obtained in Synthesis example 2 or Synthesis example 7
(A-3) the phenol resin obtained in Synthesis example 3
(A-4) the phenol resin obtained in Synthesis example 4
(A-5) the phenol resin obtained in Synthesis example 5
(A-6) the phenol resin obtained in Synthesis example 6
(A-7) phenol novolac resin (PR-50731 produced by Sumitomo Bakelite Co., ltd., polystyrene-reduced weight average molecular weight (Mw) =11,000)
(A-8) phenol Biphenyl aralkyl resin (MEH-7851 produced by Meiwapatic Industries, LTD.), polystyrene-reduced weight-average molecular weight (Mw) =2,000)
[ photoacid Generator (B) ]
(B-1) naphthoquinone Compound having the Structure of the following formula (B-1)
(B-2) naphthoquinone Compound having the Structure of the following formula (B-2)
(B-3) CPI-210S (San-Apro Ltd. Production)
< crosslinking agent >
(C-1) NIKALAC MX-270 (manufactured by Sanhe chemical Co., ltd.)
(C-2) TML-BPA (produced by Kyoho chemical industry Co., ltd.)
(C-3) CELLOXIDE 2021P (produced by Dailu Co., ltd.)
[ silane coupling agent (D) ]
(D-1) KBM-403 (produced by Shin-Etsu Chemical Co., ltd.)
(D-2) KBM-503 (Shin-Etsu Chemical Co., ltd.)
(D-3) KBM-846 (Shin-Etsu Chemical Co., ltd.)
< surfactant (E) >
(E-1) F444 (produced by DIC corporation)
[ thermal acid-producing agent and thermal alkali-producing agent ]
(F-1) Sun-Aid SI-150 (manufactured by Sanshin Chemical Industry Co., ltd.)
(F-2) UCAT SA506 (San-Apro Ltd.)
< phenol Compound >
(G-1) Pentahydroxybiphenyl
(G-2) Biphenols
< solvent (H) >
(H-1) Gamma-butyrolactone
< evaluation of phenolic resin-1 (measurement of softening Point) >
The softening points of the phenolic resins (A-1) to (A-8) were measured in accordance with JIS K2207. The apparatus used was ASP-M2SP manufactured by Mingdaku of Kyowa Kagaku (Meitec CORPORATION). The results are shown in Table 1. From the viewpoint of pattern retention property at the time of final curing, the higher the softening point, the better.
< evaluation of phenolic resin-2 (alkali solubility evaluation) >
The phenol resins (A-1) to (A-8) were dissolved in gamma-butyrolactone to obtain a resin solution. After the obtained solution was coated on a 4-inch silicon wafer using a spin coater, pre-baking was performed at 120 ℃ for 3 minutes using a hot plate, and a coating film having a film thickness of about 3 μm was obtained. The obtained coating film was immersed in a 2.38% aqueous tetramethylammonium hydroxide solution at 23 ℃ for 3 minutes, and the solubility of the coating film was confirmed. The results are shown in Table 1.
[ Table 1]
< evaluation of patterning-1 (examples 1 to 8, examples 10 to 11, and comparative examples 1 to 2) >
The photosensitive resin compositions obtained above were applied to 8-inch silicon wafers using a spin coater, and then prebaked at 120 ℃ for 3 minutes using a hot plate, to obtain a coating film having a thickness of about 9.0. Mu.m. The coating film was irradiated with varying exposure amount by using an i-ray stepper (NSR-4425 i produced by Nikon Corporation (Nikon Corporation)) through a mask (test chart No.1: drawn with a residual pattern and a hollow pattern having a width of 0.88 to 50 μm) produced by relief PRINTING Corporation (TOPPAN PRINTING co., ltd.).
Next, using a 2.38% tetramethylammonium hydroxide aqueous solution as a developing solution, a puddle (immersion) development (puddle development) was performed 2 times while adjusting the development time so that the difference between the film thickness after prebaking and the film thickness after development became 1.0 μm to dissolve and remove the exposed portion, and then the substrate was rinsed with pure water for 10 seconds. Minimum exposure amount +100mJ/cm using a square via pattern capable of forming 100 μm 2 The pattern obtained by exposure with the energy of (1) was evaluated for the resolution of the line pattern. The results are shown in Table 2 as pattern resolution (. Mu.m). In the production of fine wiringThe smaller the resolution, the better.
< evaluation of patterning-2 (example 9) >
The photosensitive resin compositions obtained above were applied to 8-inch silicon wafers by a spin coater, and then prebaked at 120 ℃ for 3 minutes by a hot plate, to obtain coating films having a film thickness of about 9.0. Mu.m. The coating film was irradiated with varying exposure amount through a mask (test pattern No.1: with a residual pattern and a hollow pattern having a width of 0.88 to 50 μm) produced by Kagaku, using an i-ray stepper (NSR-4425 i produced by Nikon K.K.).
Next, baking treatment was performed at 100 ℃ for 2 minutes using a hot plate. Next, the exposed portion was dissolved and removed by 30 seconds × 2 puddle (spin-on immersion) development using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer, and then the substrate was rinsed with pure water for 10 seconds. With the lowest exposure amount to be able to form a line of 5 μm +100mJ/cm 2 The pattern obtained by exposure with the energy of (2) was evaluated for the resolution of the line pattern. The results are shown in Table 2 as pattern resolution (. Mu.m). In the production of fine wiring, the smaller the resolution, the better.
< evaluation of resolution after curing (examples 1 to 11 and comparative examples 1 to 2) >
The patterned wafers obtained in the above-described patterning evaluations-1 and-2 were put into a heating oven, heated from room temperature to 200 ℃ at 5 ℃/min while flowing nitrogen gas, and then subjected to a heating treatment at 200 ℃ for 60 minutes in this state, and cooled to room temperature. The patterned wafer after heating was observed under a microscope to evaluate the line resolution. The results are shown in Table 2 as the resolution (. Mu.m) after curing. In forming a fine pattern, the smaller the resolution, the better.
< production of semiconductor device >
The photosensitive resin compositions of examples 1 to 11 and comparative examples 1 to 2 were applied to an analog device wafer having an aluminum circuit on the surface thereof so as to be 5 μm in the end, and then subjected to patterning and curing. Then, the chips were divided into individual chip sizes, mounted on a lead frame for 16Pin DIP (Dual Inline Package) using a conductive paste, and then sealed and molded with an epoxy resin for semiconductor encapsulation (EME-6300H manufactured by Sumitomo Corp.) to produce semiconductor devices.
< evaluation of reliability of semiconductor device-1 (Electrical connectivity) >
Electrical connection inspection of each of the 10 semiconductor devices obtained by the above-described method was performed,
all 10 semiconductor devices were evaluated as a without electrical connection failure,
the presence of electrical connection failure in 1 or more of the 10 semiconductor devices was evaluated as B.
< evaluation of reliability of semiconductor device-2 (moisture resistance) >
After each of 10 semiconductor devices obtained by the above-described method was treated under conditions of 85 ℃/85% humidity for 168 hours, the semiconductor devices were immersed in a solder bath at 260 ℃ for 10 seconds, and then subjected to autoclave treatment at high temperature and high humidity (125 ℃, 2.3atm, 100% relative humidity) to inspect electrical connection.
All 10 semiconductor devices were evaluated as a without electrical connection failure,
among the 10 semiconductor devices, 1 or more semiconductor devices in which poor electrical connection was observed were evaluated as B.
Table 2 describing examples and comparative examples is shown below.
The coating films formed from the phenolic resins (A-1) to (A-6) of the examples exhibited good alkali solubility. The softening point of the coating film is above 180 ℃. Thus, these phenolic resins can be used as, for example, resists used in the production of semiconductor devices.
The coating films formed from the photosensitive resin compositions containing the phenolic resins (A-1) to (A-6) of the examples had good pattern formability. A semiconductor device comprising the cured film has no defects in electrical connectivity, and also has no defects due to corrosion of an aluminum circuit after storage at high temperature and high humidity. Therefore, it is expected that the cured film can be used as an interlayer insulating film of a semiconductor device.
Industrial applicability
The present invention can provide a photosensitive resin composition capable of forming a resin film and a cured film having excellent heat resistance, a resin film composed of the photosensitive resin composition, a cured film of the resin film, a semiconductor device including the cured film, and a method for manufacturing a semiconductor device using the photosensitive resin composition.
Claims (10)
1. A photosensitive resin composition for forming a resist, which is used for a surface protective film or an interlayer insulating film of a semiconductor device, comprising:
a phenol resin (A) having a diphenol structure;
a photoacid generator (B); and
a solvent, a water-soluble organic solvent,
the phenolic resin (A) has a structural unit derived from a diphenol compound and at least 1 compound selected from the group consisting of aldehyde compounds, dimethylol compounds, dimethoxymethyl compounds and dihaloalkyl compounds,
the phenolic resin (A) has a repeating structural unit represented by formula (2),
the weight average molecular weight of the phenolic resin (A) in terms of polystyrene is 7000-30000,
in the formula (2), the reaction mixture is,
m is an integer of 2 to 10000,
R 11 and R 12 Each independently selected from a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkylether group having 1 to 20 carbon atoms, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms or an alicyclic group having 6 carbon atoms20 of 1-valent substituents in the organic group having an aromatic structure, which may be bonded via an ester bond, an ether bond, an amide bond or a carbonyl bond,
p and q are each independently an integer of 0 to 3,
X 1 and Y 1 Each independently a single bond or a 2-valent substituent selected from the group consisting of organic groups represented by the formula (3),
wherein, Y 1 Bonded to any of the 2 benzene rings,
in the formula (3), n is 0 to 20.
2. The photosensitive resin composition for resist formation according to claim 1, wherein:
the photoacid generator (B) is a compound that generates an acid upon irradiation with radiation having a wavelength of 200 to 500nm.
3. The photosensitive resin composition for resist formation according to claim 1, wherein:
said X 1 And Y 1 Is an organic group represented by the following formula:
4. the photosensitive resin composition for resist formation according to claim 1 or 2, wherein:
further comprising a crosslinking agent (C) having a group capable of reacting with the phenolic resin (A).
5. The photosensitive resin composition for resist formation according to claim 1 or 2, wherein:
further comprising a silane coupling agent (D).
6. The photosensitive resin composition for resist formation according to claim 1 or 2, wherein:
further comprising a nonionic surfactant (E).
7. The photosensitive resin composition for resist formation according to claim 1 or 2, wherein:
further comprising a reaction promoter (F).
8. A resin film characterized in that:
the photosensitive resin composition for resist formation according to claim 1 or 2.
9. A cured film characterized by:
the cured film is a cured film of the resin film according to claim 8.
10. A semiconductor device, characterized in that:
comprising the cured film of claim 9.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2016220584 | 2016-11-11 | ||
| JP2016-220584 | 2016-11-11 | ||
| CN201780059665.1A CN109791356A (en) | 2016-11-11 | 2017-11-09 | Photosensitive polymer combination, resin film, cured film, the manufacturing method of semiconductor device and semiconductor device |
| PCT/JP2017/040412 WO2018088469A1 (en) | 2016-11-11 | 2017-11-09 | Photosensitive resin composition, resin film, cured film, semiconductor device production method, and semiconductor device |
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| CN202211513979.3A Pending CN115718406A (en) | 2016-11-11 | 2017-11-09 | Photosensitive resin composition for forming resist, resin film, cured film, and semiconductor device |
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| KR (1) | KR102004129B1 (en) |
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| JP7340329B2 (en) | 2018-12-17 | 2023-09-07 | 旭化成株式会社 | Method for manufacturing photosensitive resin laminate and resist pattern |
| WO2021241581A1 (en) * | 2020-05-29 | 2021-12-02 | 住友ベークライト株式会社 | Photosensitive resin composition |
| WO2023095785A1 (en) * | 2021-11-26 | 2023-06-01 | 東レ株式会社 | Photosensitive resin composition, cured article, organic el display device, semiconductor device, and method for producing cured article |
| WO2023182136A1 (en) * | 2022-03-24 | 2023-09-28 | 住友ベークライト株式会社 | Positive-type photosensitive resin composition, cured film, and semiconductor device |
| CN114957575A (en) * | 2022-04-22 | 2022-08-30 | 上海极紫科技有限公司 | Modified phenolic resin, preparation method thereof and positive photoresist |
| WO2024081174A1 (en) * | 2022-10-10 | 2024-04-18 | Lam Research Corporation | Oxymethylene copolymers for transient surface protection during chemical vapor deposition |
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| JP3575095B2 (en) * | 1994-12-28 | 2004-10-06 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition and protective film for optical device formed therefrom |
| US6768197B2 (en) * | 1999-12-27 | 2004-07-27 | Sumitomo Bakelite Company, Ltd | Hardening flux, soldering resist, semiconductor package reinforced by hardening flux, semiconductor device and method of producing semiconductor package and semiconductor device |
| EP1852451A1 (en) * | 2005-02-25 | 2007-11-07 | Nippon Kayaku Kabushiki Kaisha | Epoxy resin, hardenable resin composition containing the same and use thereof |
| JP4858714B2 (en) * | 2006-10-04 | 2012-01-18 | 信越化学工業株式会社 | Polymer compound, resist material, and pattern forming method |
| JP5377020B2 (en) * | 2009-03-23 | 2013-12-25 | 太陽ホールディングス株式会社 | Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them |
| JP6026097B2 (en) | 2010-11-17 | 2016-11-16 | 旭化成株式会社 | Photosensitive resin composition for semiconductor element surface protective film or interlayer insulating film |
| JP5698184B2 (en) * | 2011-09-02 | 2015-04-08 | 信越化学工業株式会社 | Positive resist material and pattern forming method |
| JP5904211B2 (en) * | 2011-12-13 | 2016-04-13 | 日立化成株式会社 | Photosensitive resin composition, method for producing patterned cured film, and electronic component |
| KR20150015443A (en) * | 2012-04-24 | 2015-02-10 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Epoxy resin composition, resin sheet, cured article, and phenoxy resin |
| TWI627222B (en) * | 2013-01-24 | 2018-06-21 | 日產化學工業股份有限公司 | Resist overlayer film forming composition for lithography and production method for semiconductor device using the same |
| JP6159548B2 (en) * | 2013-03-27 | 2017-07-05 | 新日鉄住金化学株式会社 | Epoxy resin composition, resin sheet and cured epoxy resin |
| JP5981465B2 (en) * | 2014-01-10 | 2016-08-31 | 信越化学工業株式会社 | Negative resist material and pattern forming method using the same |
| SG11201607444VA (en) * | 2014-03-13 | 2016-10-28 | Mitsubishi Gas Chemical Co | Compound, resin, material for forming underlayer film for lithography, underlayer film for lithography, pattern forming method, and method for purifying the compound or resin |
| CN103901719A (en) * | 2014-04-28 | 2014-07-02 | 无锡德贝尔光电材料有限公司 | Quick-drying-type carboxyl-containing photosensitive resin and preparation method thereof |
| JP6352853B2 (en) * | 2014-10-02 | 2018-07-04 | 信越化学工業株式会社 | Silicone skeleton-containing polymer compound and production method thereof, chemically amplified negative resist material, photocurable dry film and production method thereof, pattern formation method, laminate, and substrate |
| EP3266759B1 (en) * | 2015-03-06 | 2023-09-13 | Mitsubishi Gas Chemical Company, Inc. | Compound, resin, material for forming underlayer film for lithography, underlayer film for lithography, pattern forming method, and method for purifying compound or resin |
| WO2016158458A1 (en) * | 2015-03-30 | 2016-10-06 | 三菱瓦斯化学株式会社 | Resist base material, resist composition, and method for forming resist pattern |
| JP6605828B2 (en) * | 2015-03-30 | 2019-11-13 | 日鉄ケミカル＆マテリアル株式会社 | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof |
| WO2016158994A1 (en) * | 2015-03-31 | 2016-10-06 | 富士フイルム株式会社 | Pattern formation method, photomask manufacturing method, and electronic device manufacturing method |
| JP7176844B2 (en) * | 2015-10-19 | 2022-11-22 | 日産化学株式会社 | Composition for forming resist underlayer film containing long-chain alkyl group-containing novolak |
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| JP6489289B2 (en) | 2019-03-27 |
| KR102004129B1 (en) | 2019-07-25 |
| JP7111129B2 (en) | 2022-08-02 |
| TW201830138A (en) | 2018-08-16 |
| JP2020187368A (en) | 2020-11-19 |
| CN109791356A (en) | 2019-05-21 |
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| TWI765933B (en) | 2022-06-01 |
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