WO2021187481A1 - Composition filmogène isolante photosensible - Google Patents

Composition filmogène isolante photosensible Download PDF

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Publication number
WO2021187481A1
WO2021187481A1 PCT/JP2021/010607 JP2021010607W WO2021187481A1 WO 2021187481 A1 WO2021187481 A1 WO 2021187481A1 JP 2021010607 W JP2021010607 W JP 2021010607W WO 2021187481 A1 WO2021187481 A1 WO 2021187481A1
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WIPO (PCT)
Prior art keywords
group
insulating film
forming composition
photosensitive insulating
composition according
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PCT/JP2021/010607
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English (en)
Japanese (ja)
Inventor
雅久 遠藤
和宏 澤田
高広 岸岡
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日産化学株式会社
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Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to KR1020227023703A priority Critical patent/KR20220155258A/ko
Priority to CN202180021724.2A priority patent/CN115298616A/zh
Priority to JP2022508378A priority patent/JP7444239B2/ja
Publication of WO2021187481A1 publication Critical patent/WO2021187481A1/fr

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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
    • 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
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to a photosensitive insulating film forming composition, a photosensitive resin film obtained from the composition, a photosensitive resin film obtained from the composition, a substrate with a cured relief pattern using the composition, and a method for producing the same. , And a semiconductor device having the cured relief pattern.
  • a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties has been used as an insulating material for electronic components, a passivation film, a surface protective film, an interlayer insulating film, and the like of a semiconductor device.
  • these polyimide resins those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern film by coating, exposing, developing, and thermally imidizing the precursor. be able to.
  • Such a photosensitive polyimide precursor has a feature that it enables a significant process shortening as compared with a conventional non-photosensitive polyimide resin.
  • the method of mounting a semiconductor device on a printed wiring board has changed from the viewpoint of improving the degree of integration and calculation function and reducing the chip size.
  • the polyimide film comes into direct contact with the solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable higher density mounting from the conventional mounting method using metal pins and lead-tin eutectic solder. Structures are being used. When forming such a bump structure, the coating is required to have high heat resistance and chemical resistance.
  • Patent Document 1 introduces an aliphatic group having an ethylene glycol structure and having 5 to 30 carbon atoms in a part of the side chain of the polyimide precursor, thereby containing the polyimide precursor.
  • a photosensitive resin composition is disclosed in which the transparency when the sex resin composition is formed is improved, and the Young ratio of the cured film is further improved after heat curing.
  • the photosensitive resin composition composed of the polyimide precursor described in Patent Document 1 gives a cured product having high transparency and a high Young's modulus after heat curing, but when used in the above-mentioned applications, it is dielectrically tangent. Further reduction and suppression of changes in dielectric loss tangent with time have been required.
  • the present invention is a photosensitive resin composition, which not only reduces the dielectric loss tangent, but also provides a cured film in which the change over time of the dielectric loss tangent after being left for a certain period of time in a normal environment is suppressed to a small extent. It is an object of the present invention to provide a substrate with a cured relief pattern using the above, a method for manufacturing the same, and a semiconductor device provided with the cured relief pattern.
  • the present inventors have adopted a polymer having a repeating unit structure containing a specific aromatic heterocycle and a crosslinkable substituent, thereby achieving a low dielectric loss tangent.
  • a photosensitive resin composition that provides a cured film that can be maintained even after long-term storage under normal circumstances can be obtained, and the present invention has been completed.
  • the present invention includes the following.
  • Group B 2 represents an organic group having 6 to 40 carbon atoms which does not have a crosslinkable substituent and may contain at least one heteroatom selected from N, S and O, and may contain a halogen atom.
  • n 1 and n 2 are independently numbers of 0 or more and 1 or less, respectively.
  • m 1 and m 2 are independently numbers of 0 or more and 1 or less, respectively.
  • n is a number greater than or equal to 1
  • group A 1 is Represents an aromatic heterocycle represented by, and the aromatic heterocycle may have a crosslinkable substituent.
  • Group A 2 is as well as Represents at least one aromatic heterocycle selected from the group consisting of aromatic heterocycles represented by, and any of these aromatic heterocycles may have a crosslinkable substituent.
  • group B 1 is at least one selected from the following, (In the formula, G represents either a direct bond or one of the following formulas.
  • L and M independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group, respectively.
  • Group B 1 The photosensitive insulating film forming composition according to any one of [1] to [4] represented by.
  • Group B 2 is at least one selected from the following. (In the formula, G represents either a direct bond or one of the following formulas.
  • L and M independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group, respectively.
  • Group B 2 The photosensitive insulating film forming composition according to any one of [1] to [6] represented by.
  • [8] The photosensitive insulating film-forming composition according to any one of [1] to [7], wherein the crosslinkable substituent contains a radical crosslinkable group.
  • m 0.
  • a photosensitive resin film which is a fired product of a coating film of the photosensitive insulating film forming composition according to any one of [1] to [10].
  • the photosensitive resin film according to [11] which has a dielectric loss tangent of 0.01 or less.
  • a semiconductor device comprising a semiconductor element and a cured film provided on the upper or lower portion of the semiconductor element, wherein the cured film has the cured relief pattern according to [14].
  • a photosensitive resin composition that gives a cured product having a low dielectric loss tangent, a photosensitive resin film obtained from the composition, a photosensitive resin film obtained from the composition, and a cured relief using the composition. It is possible to provide a patterned substrate, a method for producing the same, and a semiconductor device having the cured relief pattern.
  • the photosensitive insulating film forming composition of the present invention is The following formula (1): [In equation (1) Group A 1 is Represents a 5- to 8-membered aromatic heterocycle represented by The aromatic heterocycle may have a crosslinkable substituent and may have a crosslinkable substituent. Group A 2 is Represents a 5- to 8-membered aromatic heterocycle represented by The aromatic heterocycle may have a crosslinkable substituent and may have a crosslinkable substituent.
  • Group B 1 represents an organic group having a crosslinkable substituent and having 6 to 40 carbon atoms, which may contain at least one heteroatom selected from N, S and O, and may contain a halogen atom.
  • Group B 2 represents an organic group having 6 to 40 carbon atoms and which does not have a crosslinkable substituent, which may contain at least one heteroatom selected from N, S and O, and may contain a halogen atom.
  • n 1 and n 2 are independently numbers of 0 or more and 1 or less, respectively.
  • m 1 and m 2 are independently numbers of 0 or more and 1 or less, respectively.
  • n is a number greater than or equal to 1
  • the polymer according to the present invention has a repeating unit structure represented by the above formula (1).
  • Group A 1 represents a heteroatom-free 5- to 8-membered aromatic heterocycle in the shortest series of covalent bonds between two bonds, the aromatic heterocycle having a crosslinkable substituent. May be good.
  • the group A 1 is Represents an aromatic heterocycle represented by, and the aromatic heterocycle may have a crosslinkable substituent.
  • the group A 1 may be one kind or a combination of two or more kinds.
  • the group A 2 represents a 5- to 8-membered aromatic heterocycle containing a nitrogen atom in the shortest series of covalent bonds between two bonds, and the aromatic heterocycle is crosslinkable. It may have a substituent.
  • the group A 2 is as well as Represents at least one aromatic heterocycle selected from the group consisting of aromatic heterocycles represented by, and any of these aromatic heterocycles may have a crosslinkable substituent.
  • the group A 2 may be one kind or a combination of two or more kinds.
  • the crosslinkable substituent contains a radical crosslinkable group.
  • the crosslinkable substituent contains a (meth) acrylate group, a maleimide group, or an allyl group.
  • Examples of the crosslinkable substituent containing the (meth) acrylate group include the following general formula (2): (In the formula, R 3 , R 4 and R 5 are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, and m is an integer of 1 to 10. * Is an integer of 1 to 10. Examples thereof include a group represented by the group A 1 , the group A 2 , or the group B 1 of the general formula (1).
  • R 3 in the above general formula (2) is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but when the photosensitive insulating film forming composition is a negative type, it is not limited. From the viewpoint of photosensitive characteristics, it is preferably a hydrogen atom or a methyl group.
  • R 4 and R 5 in the above general formula (2) are not limited as long as they are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, but the photosensitive insulating film forming composition is negative. In the case of a mold, it is preferably a hydrogen atom from the viewpoint of its photosensitive characteristics.
  • M in the above general formula (2) is an integer of 1 or more and 10 or less, and is preferably an integer of 1 or more and 4 or less from the viewpoint of photosensitive characteristics.
  • the monovalent organic group having 1 to 3 carbon atoms include a linear alkyl group such as a methyl group, an ethyl group and a propyl group; a branched alkyl group such as an isopropyl group; and a fat such as a cyclopropyl group.
  • Cyclic alkyl group alkenyl group such as vinyl group and allyl group; alkynyl group such as ethynyl group; alkoxy group such as methoxy group, ethoxy group and propoxy group; acyl group such as acetyl group; ester group such as methoxycarbonyl group; Examples thereof include a heterocyclic group such as a formyl group; a haloformyl group; a carbamoyl group; a cyano group; an oxylanyl group, an aziridinyl group, a thietanyl group, a triazinyl group, an oxathiolanyl group, a dihydroazetyl group and a dihydrothiazolyl group.
  • the group B 1 may contain at least one heteroatom selected from N, S and O, and may contain a halogen atom, and has 6 to 40 carbon atoms having a crosslinkable substituent. Represents an organic group of.
  • the group B 1 is at least one selected from the following: (In the formula, G represents either a direct bond or one of the following formulas. L and M independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group, respectively. )
  • the group B 1 is It is represented by.
  • the group B 2 may contain at least one hetero atom selected from N, S and O, may contain a halogen atom, and has 6 carbon atoms having no crosslinkable substituent. Represents 40 to 40 organic groups.
  • the group B 2 is at least one selected from the following: (In the formula, G represents either a direct bond or one of the following formulas. L and M independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group, respectively. )
  • the group B 2 is It is represented by.
  • the polymer having a repeating unit structure represented by the formula (1) can be prepared by a known method.
  • a compound represented by HO-A 1- OH, a compound represented by HO-A 2- OH, a compound represented by X-B 1- X, and a compound represented by X-B 2- X. can be prepared by appropriately selecting and condensing (in the formula, A 1 , A 2 , B 1 and B 2 are synonymous with the above, and X is a halogen atom).
  • a compound represented by HO-A 1- OH, a compound represented by HO-A 2- OH, a compound represented by X-B 1- X, and a compound represented by X-B 2- X. May be used alone or in combination of two or more.
  • the compound represented by X-B 1- X and X total 0.1 to 10 moles of -B compound represented by 2 -X, it can be preferably used by setting the proportion of 0.1 to 2 moles.
  • a basic or acidic catalyst can be used, but it is preferable to use a basic catalyst.
  • the basic catalyst include a solid base catalyst, and examples thereof include calcium hydroxide, strontium hydroxide octahydrate, barium hydroxide octahydrate, magnesium hydroxide, sodium carbonate, potassium carbonate and the like.
  • acidic catalysts include mineral acids such as sulfuric acid, phosphoric acid and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate and methanesulfonic acid, formic acid and oxalic acid.
  • the carboxylic acids of can be used.
  • the amount of the catalyst varies depending on the kind of the catalyst used, relative to total 100 parts by weight of HO-A 1 compound represented by -OH and HO-A compound represented by 2 -OH, usually 0. It is 001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass.
  • the condensation reaction is carried out without a solvent, but usually it is carried out with a solvent.
  • the solvent is not particularly limited as long as it can dissolve the reaction substrate and does not inhibit the reaction.
  • 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, dioxane and the like can be mentioned.
  • the condensation reaction temperature is usually 40 ° C. to 200 ° C., preferably 50 ° C. to 180 ° C.
  • the reaction time varies depending on the reaction temperature, but is usually 5 minutes to 500 hours, preferably 5 minutes to 200 hours.
  • the weight average molecular weight of the polymer having the repeating unit structure represented by the formula (1) is usually 500 to 100,000, preferably 600 to 80,000, 800 to 60,000, or 1,000 to 50,000. be.
  • solvent it is preferable to use an organic solvent from the viewpoint of solubility in a polymer having a repeating unit structure represented by the formula (1).
  • organic solvent N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, ⁇ -butyrolactone.
  • the solvent is, for example, 30 parts by mass to 1500 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1), depending on the desired coating film thickness and viscosity of the photosensitive insulating film forming composition. It can be used in the range of parts by mass, preferably 40 parts by mass to 1000 parts by mass, and more preferably 50 parts by mass to 300 parts by mass.
  • the photosensitive insulating film forming composition may further contain components other than the polymer and the solvent having the repeating unit structure represented by the above formula (1).
  • other components include resin components other than polymers having a repeating unit structure represented by the formula (1), photopolymerization initiators, adhesion aids, hindered phenol compounds, carboxylic acid compounds or anhydrides thereof, and crosslinks. Examples include sex compounds, sensitizers, thermal polymerization inhibitors, azole compounds, fillers and the like.
  • the photosensitive insulating film forming composition may further contain a resin component other than the polymer having the repeating unit structure represented by the formula (1).
  • the resin component that can be contained in the photosensitive insulating film forming composition include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin.
  • the blending amount of the resin component is preferably in the range of 0.01 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1). Is.
  • the photosensitive insulating film-forming composition of the present invention may contain a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as it is a compound having absorption in the light source used during photocuring, but for example, tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis (benzoyl).
  • the photopolymerization initiator is available as a commercially available product.
  • IRGACURE registered trademark
  • KAYACURE registered trademark] DETX, MBP, same DMBI, EPA, OA (above, Nippon Kayaku Co., Ltd.), VICURE-10, 55 (above, STAUFFER Co.
  • the blending amount of the photopolymerization initiator is usually 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1), which is preferable from the viewpoint of photosensitivity characteristics. It is 0.5 parts by mass to 15 parts by mass.
  • 0.1 part by mass or more of the photopolymerization initiator is blended with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1), the photosensitivity of the photosensitive insulating film forming composition is likely to be improved.
  • 20 parts by mass or less is blended, the thick film curability of the photosensitive insulating film forming composition is likely to be improved.
  • a cross-linking agent can be added to the photosensitive insulating film forming composition in order to improve the resolution of the relief pattern.
  • a cross-linking agent a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is not particularly limited to the following, but ethylene such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate.
  • the blending amount of the cross-linking agent is preferably 1 part by mass to 100 parts by mass, and more preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1). be.
  • thermal cross-linking agent examples include hexamethoxymethyl melamine, tetramethoxymethyl glycol uryl, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis (methoxymethyl) glycoluryl, 1,3,4,6-tetrakis (butoxymethyl).
  • filler examples include inorganic fillers, and specific examples thereof include sol such as silica, aluminum nitride, boron nitride, zirconia, and alumina.
  • an adhesive auxiliary may be optionally added to the photosensitive insulating film forming composition in order to improve the adhesiveness between the film formed by using the photosensitive insulating film forming composition and the substrate.
  • the adhesion aid include ⁇ -aminopropyldimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, and the like.
  • the blending amount of the adhesive aid is preferably in the range of 0.5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1).
  • a hindered phenol compound can be optionally added to the photosensitive insulating film-forming composition in order to suppress discoloration on copper or as a polymerization inhibitor at a radical cross-linking site.
  • the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl).
  • 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) ) -Trione is particularly preferred.
  • the blending amount of the hindered phenol compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1), from the viewpoint of light sensitivity characteristics. More preferably, it is 0.5 parts by mass to 10 parts by mass.
  • the blending amount of the hindered phenol compound with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1) is 0.1 parts by mass or more, for example, a photosensitive insulating film forming composition on copper or a copper alloy. When an object is formed, discoloration and corrosion of copper or a copper alloy are prevented, while when the amount is 20 parts by mass or less, the light sensitivity is excellent, which is preferable.
  • a sensitizer can be optionally added to the photosensitive insulating film forming composition in order to improve the photosensitivity.
  • the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal).
  • the blending amount of the sensitizer is preferably 0.1 part by mass to 25 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1).
  • a thermal polymerization inhibitor can be optionally added in order to improve the stability of the viscosity and photosensitivity of the photosensitive insulating film-forming composition, especially when stored in a solution containing a solvent. ..
  • thermal polymerization inhibitor examples include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, and 2 , 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-) N-Sulphopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.
  • the blending amount of the thermal polymerization inhibitor is preferably in the range of 0.005 parts by mass to 12 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1).
  • an azole compound can be optionally added to the photosensitive insulating film forming composition in order to suppress discoloration of the substrate.
  • the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, and 4-t-butyl.
  • the blending amount of the azole compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1), and is 0. It is more preferably 5 parts by mass to 5 parts by mass.
  • the photosensitive insulating film forming composition is placed on copper or a copper alloy. When it is formed in, discoloration of the surface of copper or a copper alloy is suppressed, while when it is 20 parts by mass or less, it is preferable because it has excellent light sensitivity.
  • Step of applying the photosensitive insulating film forming composition according to the present invention on a substrate and forming a photosensitive resin layer on the substrate the photosensitive insulating film forming composition according to the present invention is used. It is applied onto a substrate and, if necessary, dried thereafter to form a photosensitive resin layer.
  • a coating method a method conventionally used for coating a photosensitive insulating film forming composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or spraying with a spray coater.
  • a coating method or the like can be used.
  • the coating film composed of the photosensitive insulating film-forming composition can be dried, and as the drying method, for example, air drying, heat drying in an oven or a hot plate, vacuum drying and the like are used.
  • the coating film is dried by air drying or heat drying, it can be dried at 20 ° C. to 200 ° C. for 1 minute to 1 hour.
  • the film is formed by prebaking in a relatively low temperature range of the above temperature range, baking in a medium temperature range, and further baking in a high temperature range. You can also do it.
  • the photosensitive resin layer (film) can be formed on the substrate.
  • Step of exposing the photosensitive resin layer the photosensitive resin layer formed in the above step (1) is exposed to a photomask having a pattern using an exposure device such as a contact aligner, a mirror projection, or a stepper. Alternatively, it is exposed through a reticle or directly with an ultraviolet light source or the like.
  • Light sources used for exposure include, for example, g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser.
  • the exposure amount is preferably 25 mJ / cm 2 to 1000 mJ / cm 2 .
  • post-exposure bake (PEB) and / or pre-development bake at any combination of temperature and time may be applied, if necessary, for the purpose of improving light sensitivity and the like.
  • the range of the baking conditions is preferably a temperature of 50 ° C. to 200 ° C. and a time of preferably 10 seconds to 600 seconds, but as long as it does not interfere with various properties of the photosensitive insulating film forming composition. Not limited to this range.
  • Step of developing the photosensitive resin layer after exposure to form a relief pattern the unexposed portion of the exposed photosensitive resin layer is developed and removed.
  • a developing method for developing the photosensitive resin layer after exposure any of conventionally known photoresist developing methods, for example, a rotary spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, etc. The method can be selected and used.
  • post-development baking may be performed at an arbitrary combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern.
  • Examples of the developing solution used for development include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, ⁇ -butyrolactone, and ⁇ -acetyl- ⁇ .
  • -Butyrolactone and the like are preferable.
  • two or more kinds of each solvent for example, several kinds can be used in combination.
  • Step of heat-treating the relief pattern to form a substrate with a cured relief pattern the relief pattern obtained by the above development is heated and converted into a cured relief pattern.
  • various methods can be selected, for example, a method using a hot plate, a method using an oven, a method using a temperature-increasing oven in which a temperature program can be set, and the like.
  • the heating can be performed, for example, at 130 ° C. to 250 ° C. for 30 minutes to 5 hours.
  • Air may be used as the atmospheric gas at the time of heat curing, or an inert gas such as nitrogen or argon may be used. From the above, a substrate with a cured relief pattern can be manufactured.
  • the cured relief pattern according to the present invention thus obtained has a dielectric loss tangent of 0.01 or less immediately after formation, and an increase in dielectric loss tangent is formed after exposure to a 23 ° C. and 50% RH environment for 24 hours. It is less than 0.004, preferably 0.003 or less, as compared with immediately after.
  • the relative ratio of the dielectric loss tangent of the cured relief pattern to the dielectric loss tangent of the cured relief pattern immediately after formation after exposure to 23 ° C. and 50% RH environment for 24 hours is usually within ⁇ 80%, preferably within ⁇ 70%. Yes, more preferably within ⁇ 60%.
  • a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern is also provided. Therefore, a semiconductor device having a base material which is a semiconductor element and a cured relief pattern (cured film) formed on the base material by the above-described cured relief pattern manufacturing method on the upper or lower part of the semiconductor element is provided. be able to.
  • the present invention can also be applied to a method for manufacturing a semiconductor device, which uses a semiconductor element as a base material and includes the above-mentioned method for manufacturing a cured relief pattern as a part of a process.
  • the semiconductor device of the present invention is a semiconductor device having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure of a cured relief pattern formed by the above-mentioned cured relief pattern manufacturing method. It can be manufactured by forming it as a protective film or the like and combining it with a known manufacturing method of a semiconductor device.
  • a display body device including a display body element and a cured film provided on the upper portion of the display body element
  • the cured film is a display body device having the above-mentioned cured relief pattern.
  • the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched between them.
  • examples of the cured film include a surface protective film, an insulating film, and a flattening film of a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a partition wall for an organic EL element cathode. ..
  • the photosensitive insulating film-forming composition of the present invention is applied to semiconductor devices as described above, as well as applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, and liquid crystal alignment films. Is also useful.
  • the weight average molecular weight shown in the following synthetic example of the present specification is a measurement result by gel permeation chromatography (hereinafter, abbreviated as GPC in the present specification).
  • GPC device HSC-8320GPC
  • HPC column TSKgelSuperH-RC, TSKgelSuperMultipore HZ-N, TSKgelSuperMultipore HZ-N (manufactured by Tosoh Corporation)
  • Column temperature 40 ° C
  • Solvent Tetrahydrofuran (Kanto Chemical Co., Inc., for high performance liquid chromatography)
  • Standard sample Polystyrene (manufactured by Shodex)
  • This polymer has a repeating unit structure represented by the following formula (2).
  • Example 1 6.557 g of the polymer obtained in Synthesis Example 1, IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 0.1311 g, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane ( A composition was prepared by dissolving 1.3115 g of (manufactured by Tokyo Chemical Industry Co., Ltd.) in 12.00 g of N-methyl-2-pyrrolidinone. Then, it was filtered using a microfilter made of PTFE having a pore size of 5 ⁇ m to prepare a negative photosensitive resin composition.
  • Example 2 The polymer obtained in Synthesis Example 1 was dissolved in 10.00 g and 14.99 g of N-methyl-2-pyrrolidinone, and then filtered using a microfilter made of PTFE having a pore size of 5 ⁇ m to prepare a resin composition.
  • Example 3 5.6609 g of the polymer obtained in Synthesis Example 1, IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 0.1311 g, trisocyanurate (2-acryloyloxyethyl) (manufactured by Tokyo Chemical Industry Co., Ltd.) A composition was prepared by dissolving 1.1202 g in 10.2496 g of N-methyl-2-pyrrolidinone. Then, it was filtered using a microfilter made of PTFE having a pore size of 5 ⁇ m to prepare a negative photosensitive resin composition.
  • Example 4 N2.6984 g of the polymer obtained in Synthesis Example 1, 0.7619 g of IRGACURE [registered trademark] OXE01 (manufactured by BASF, a photopolymerization initiator), and 2.5397 g of trimethylolpropane triacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.).
  • the composition was prepared by dissolving in 24.00 g of -methyl-2-pyrrolidinone. Then, it was filtered using a microfilter made of PTFE having a pore size of 5 ⁇ m to prepare a negative photosensitive resin composition.
  • N-DCP tricyclodecanedimethanol diacrylate
  • IRGACURE® OXE01 manufactured by BASF, photopolymerization initiator 0.7619 g
  • the composition was prepared by dissolving in 24.00 g of methyl-2-pyrrolidinone. Then, it was filtered using a microfilter made of PTFE having a pore size of 5 ⁇ m to prepare a negative photosensitive resin composition.
  • Example 6 6.355 g of the polymer obtained in Synthesis Example 2, IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 0.3810 g, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane ( 1.270 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 2.394 g of N-ethyl-2-pyrrolidinone and 9.600 g of cyclohexanone to prepare a composition. Then, it was filtered using a microfilter made of PTFE having a pore size of 5 ⁇ m to prepare a negative photosensitive resin composition.
  • IRGACURE registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 0.3810 g, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane ( 1.270 g (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • the prepared resin composition was applied onto a silicon wafer using a spin coater, prebaked at 115 ° C. for 270 seconds , and exposed at 500 mJ / cm 2 to form a film having a film thickness of about 10 ⁇ m. Then, after immersing the film in cyclohexanone for 1 minute for development, the film thickness after spin-drying and drying at 115 ° C. for 270 seconds was measured, and the film thickness before and after development with cyclohexanone was compared, and the residual film ratio was 50% or more. Was allowed, and less than that was not allowed.
  • a cured product having a low initial dielectric loss tangent and a small change with time is provided.

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Abstract

L'invention concerne : une composition de film isolant photosensible qui donne un corps durci pour lequel la tangente diélectrique initiale est faible et les modifications dans le temps sont réduites ; un procédé de fabrication d'un substrat à motif en relief durci utilisant la composition de film isolant photosensible négatif ; et un dispositif à semi-conducteur comportant le motif en relief durci. L'invention concerne une composition filmogène isolante photosensible contenant un polymère ayant une structure d'unité récurrente représentée par la formule (1) : [dans la formule (1), le groupe A1 représente un hétérocycle aromatique représenté par (A1) ; le groupe A2 représente un hétérocycle aromatique représenté par (A2) ; le groupe A1 et le groupe A2 peuvent avoir des substituants réticulables ; le groupe B1 représente un groupe organique ayant un substituant réticulable ; et le groupe B2 représente un groupe organique n'ayant pas de substituant réticulable.] et un solvant.
PCT/JP2021/010607 2020-03-18 2021-03-16 Composition filmogène isolante photosensible WO2021187481A1 (fr)

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CN202180021724.2A CN115298616A (zh) 2020-03-18 2021-03-16 感光性绝缘膜形成用组合物
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022210095A1 (fr) * 2021-04-02 2022-10-06 Jsr株式会社 Polymère, composition, produit durci, corps multicouche et composant électronique
WO2023047901A1 (fr) * 2021-09-21 2023-03-30 日産化学株式会社 Composition filmogène d'isolation non photosensible

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015168775A (ja) * 2014-03-07 2015-09-28 Dic株式会社 酸基含有（メタ）アクリレート樹脂、酸基含有（メタ）アクリレート樹脂の製造方法、硬化性樹脂材料、その硬化物、及びレジスト材料
WO2019044874A1 (fr) * 2017-09-01 2019-03-07 日産化学株式会社 Composition de résine photosensible
WO2020021827A1 (fr) * 2018-07-25 2020-01-30 Jsr株式会社 Composition de résine photosensible, procédé de production d'un film de résine à motifs, film de résine à motifs et substrat de circuit à semi-conducteurs

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5593418B2 (ja) 2013-05-08 2014-09-24 東京エレクトロン株式会社 処理容器およびプラズマ処理装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015168775A (ja) * 2014-03-07 2015-09-28 Dic株式会社 酸基含有（メタ）アクリレート樹脂、酸基含有（メタ）アクリレート樹脂の製造方法、硬化性樹脂材料、その硬化物、及びレジスト材料
WO2019044874A1 (fr) * 2017-09-01 2019-03-07 日産化学株式会社 Composition de résine photosensible
WO2020021827A1 (fr) * 2018-07-25 2020-01-30 Jsr株式会社 Composition de résine photosensible, procédé de production d'un film de résine à motifs, film de résine à motifs et substrat de circuit à semi-conducteurs

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022210095A1 (fr) * 2021-04-02 2022-10-06 Jsr株式会社 Polymère, composition, produit durci, corps multicouche et composant électronique
WO2023047901A1 (fr) * 2021-09-21 2023-03-30 日産化学株式会社 Composition filmogène d'isolation non photosensible

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TW202204472A (zh) 2022-02-01
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KR20220155258A (ko) 2022-11-22
JP7444239B2 (ja) 2024-03-06

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