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WO2025134631A1 - Composition de résine photosensible, feuille de résine photosensible utilisant ladite composition de résine photosensible, produit durci, procédé de production de film de produit durci, et dispositif à semi-conducteur et dispositif d'affichage comprenant ledit produit durci - Google Patents

Composition de résine photosensible, feuille de résine photosensible utilisant ladite composition de résine photosensible, produit durci, procédé de production de film de produit durci, et dispositif à semi-conducteur et dispositif d'affichage comprenant ledit produit durci Download PDF

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Publication number
WO2025134631A1
WO2025134631A1 PCT/JP2024/040768 JP2024040768W WO2025134631A1 WO 2025134631 A1 WO2025134631 A1 WO 2025134631A1 JP 2024040768 W JP2024040768 W JP 2024040768W WO 2025134631 A1 WO2025134631 A1 WO 2025134631A1
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Prior art keywords
photosensitive resin
resin composition
group
carbon atoms
formula
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English (en)
Japanese (ja)
Inventor
進 田中
洸平 山岡
智之 弓場
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Toray Industries Inc
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Toray Industries Inc
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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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • 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
    • 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

Definitions

  • the present invention relates to a photosensitive resin composition suitable for use in semiconductor devices, and also to a photosensitive resin sheet, semiconductor device, and display device that use the photosensitive resin composition or its cured product.
  • Polyimide resins and polybenzoxazole resins which have excellent heat resistance, electrical insulation, and mechanical properties, are widely used for surface protection films and interlayer insulating films used in semiconductor devices, insulating layers in organic electroluminescent devices, and planarizing films for thin film transistor (TFT) substrates.
  • TFT thin film transistor
  • photosensitive resin compositions in which these resins themselves or their precursors are given photosensitivity have been used (hereinafter, these photosensitive resin compositions will be referred to as "polyimide resin or other photosensitive resin compositions").
  • polyimide resin or other photosensitive resin compositions By using polyimide resin or other photosensitive resin compositions, the pattern processing process can be simplified, and the complicated manufacturing process can be shortened.
  • Positive-type photosensitive resin compositions such as polyimide resins have been proposed, in which the exposed areas are easily soluble in developer and can be patterned, and negative-type materials in which the composition itself is easily soluble and the exposed areas are insoluble in developer.
  • positive-type photosensitive resin compositions such as polyimide resins have superior resolution compared to negative-type compositions, so positive-type photosensitive resin compositions are used in applications that require fine processing.
  • Known positive-type photosensitive resin compositions such as polyimide resins include those in which a quinone diazide compound is added to polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor (see, for example, Patent Document 1), those in which a photoacid generator is added to a polyamide containing a protecting group that can be removed in the presence of an acid (see, for example, Patent Document 2), and those in which an aliphatic hydrocarbon group with low light absorption is introduced into the polyamide structure (see, for example, Patent Document 3).
  • Patent Document 1 combines an alkali-soluble resin with a quinone diazide compound.
  • the quinone diazide compound interacts with the alkali-soluble resin to reduce the solubility of the composition in an alkaline developer.
  • a photochemical reaction upon exposure turns it into an indene carboxylic acid compound, which acts as a dissolution promoter in an alkaline developer, resulting in a difference in dissolution rate between the unexposed and exposed areas, allowing pattern processing.
  • the sensitivity depends on the amount of quinone diazide compound added, but if the amount of quinone diazide compound added is increased, the photochemical reaction rate decreases due to the light absorption of the quinone diazide itself, so there is a limit to how much sensitivity can be improved.
  • Patent Document 2 substitutes the hydrogen atoms of the hydroxyl groups in an alkali-soluble polyamide with protective groups that can be removed in the presence of acid to produce an alkali-insoluble resin, which is then combined with a photoacid generator.
  • This technology uses acid generated from the photoacid generator in the exposed area to remove the protective groups from the polyamide, changing the resin from an alkali-insoluble to an alkali-soluble resin. As a result, a difference in dissolution rate occurs between the exposed and unexposed areas, making positive-tone pattern processing possible.
  • this technology has the problem of insufficient sensitivity improvement due to the low acid generation efficiency of the photoacid generator hindered by the light absorption of the polyamide.
  • R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-decomposable group having 1 to 120 carbon atoms.
  • X represents a divalent linking group.
  • V represents a linear or branched divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or a divalent aliphatic hydrocarbon group represented by formula (9).
  • R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-decomposable group having 1 to 120 carbon atoms.
  • Y represents a divalent linking group.
  • U represents a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms containing an alicyclic skeleton, or a straight-chain or branched divalent aliphatic hydrocarbon group having 4 to 20 carbon atoms (excluding groups corresponding to the divalent aliphatic hydrocarbon group represented by the above formula (9)).
  • the present invention also provides various improved aspects of the photosensitive resin composition of the present invention, as well as a cured product of the photosensitive resin composition of the present invention, and aspects of use of the photosensitive resin composition of the present invention and the cured product thereof.
  • the photosensitive resin composition of the present invention is highly sensitive and enables the formation of patterns with minimal shrinkage by suppressing reflow during curing.
  • FIG. 4 is a schematic cross-sectional view illustrating a taper angle.
  • R 1 and R 2 are independently an alkyl group having 1 to 6 carbon atoms or a monovalent acid-decomposable group having 1 to 120 carbon atoms.
  • R 1 and R 2 when present as both, are each independently a monovalent acid-decomposable group having 1 to 120 carbon atoms.
  • monovalent acid-decomposable groups having 1 to 120 carbon atoms include, but are not limited to, t-butoxycarbonyl, t-butyl, tetrahydropyranyl, and ( ⁇ -oxyalkyl)alkylene groups.
  • An ( ⁇ -oxyalkyl)alkylene group is a group (R is hydrogen or an alkyl group) that forms an —O—CR 2 —O— bond together with the oxygen to which the group is bonded.
  • the alkyl group and alkylene group in the ( ⁇ -oxyalkyl)alkylene group may have hydrogen in the alkyl group or alkylene group (excluding hydrogen when the atom bonded to the ⁇ -position is hydrogen) replaced with an oxyalkyl group, or a ring structure may be formed between two or more alkyl groups or between an alkyl group and an alkylene group. Specific examples of the structure include the structure shown in the formula below.
  • R 7 to R 12 and R 14 represent monovalent organic groups
  • R 13 and R 15 represent divalent organic groups.
  • * represents a bonding point with oxygen.
  • the number of carbon atoms contained in R 1 and R 2 is preferably 3 to 20.
  • divalent organic groups examples include propane-1,3-diyl, butane-1,3-diyl, and pentane-1,3-diyl groups, as well as groups in which the hydrogen atoms of a group selected from the group consisting of propane-1,3-diyl, butane-1,3-diyl, and pentane-1,3-diyl groups are substituted with a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkoxyalkyl groups having 2 to 8 carbon atoms.
  • R 16 represents an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms.
  • R 17 and R 18 represent an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an alkoxycyclic alkyl group having 6 to 16 carbon atoms.
  • R 19 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an alkoxycyclic alkyl group having 6 to 16 carbon atoms.
  • the hydrogen atom portion may be replaced by a direct bond to form a ring structure.
  • * represents a bond point with oxygen.
  • alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl.
  • cyclic alkyl groups having 5 to 10 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclopentylethyl, cyclohexylethyl, cycloheptylethyl, cyclopentylpropyl, cyclohexylpropyl, and cycloheptylpropyl.
  • alkoxy cyclic alkyl groups having 6 to 16 carbon atoms include, for example, methoxypentyl group, ethoxypentyl group, propoxypentyl group, dimethoxypentyl group, diethoxypentyl group, dipropoxypentyl group, trimethoxypentyl group, triethoxypentyl group, tripropoxypentyl group, methoxyhexyl group, ethoxyhexyl group, propoxyhexyl group, dimethoxyhexyl group, diethoxyhexyl group, dipropoxyhexyl group, trimethoxyhexyl group, triethoxyhexyl group, tripropoxyhexyl group, methoxyheptyl group, ethoxyheptyl group, propoxyheptyl group, dimethoxyheptyl group, diethoxyheptyl group, dipropoxyheptyl group, trimethoxyheptyl
  • R 1 and R 2 of -OR 1 and -OR 2 are ( ⁇ -oxyalkyl) alkylene groups
  • the carbon at the ⁇ position i.e., the carbon to which R 17 to R 19 are bonded
  • the activation energy for converting -OR 1 and -OR 2 to a phenolic hydroxyl group, i.e., deprotection can be reduced. Therefore, even if only a small amount of acid is generated in the photosensitive composition by exposure, deprotection can be performed, and a highly sensitive photosensitive resin composition can be obtained.
  • groups represented by any of formulas (5) to (7) are preferably used as R 1 and R 2 , and groups represented by formula (7) can be particularly preferably used.
  • the structure of a hydroxyl group protected by an acid-decomposable group can be obtained by reacting a resin having a hydroxyl group, including a phenolic hydroxyl group, with a protecting agent.
  • the resin having a hydroxyl group and the protecting agent can be reacted in the presence of an acid or a base at a reaction temperature of ⁇ 20 to 50° C. without a solvent or in a solvent such as toluene, hexane, propylene glycol monomethyl ether acetate, or cyclopentanone, to obtain component (a) in which —OR 1 and —OR 2 are hydroxyl groups protected by an acid-decomposable group.
  • the protecting agent used in the present invention is a compound capable of protecting a hydroxyl group, and the protecting group introduced thereby can be deprotected by the action of an acid or a base. Any known protecting agent capable of protecting a hydroxyl group can be used as the protecting agent.
  • ethyl vinyl ether can be used when R 1 and R 2 are 1-ethoxyethyl groups
  • isobutyl vinyl ether can be used when R 1 and R 2 are 1-isobutylethyl groups
  • 3,4-dihydro-2H-pyran can be used when R 1 and R 2 are 2-tetrahydropyranyl groups
  • di-tert-butyl dicarbonate can be used when R 1 and R 2 are t-butoxycarbonyl groups.
  • An acid or base catalyst can be used in the reaction to react a resin having a hydroxyl group, including phenolic hydroxyl groups, with a protecting agent to obtain a resin containing a hydroxyl group structure protected by an acid-decomposable group.
  • acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid.
  • organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid.
  • Organic acid salts such as pyridinium p-toluenesulfonate can also be preferably used.
  • base catalysts include amine compounds such as pyridine, N,N-diethyl-4-aminopyridine, triethylamine, and diisopropylamine.
  • X is a divalent linking group.
  • the divalent linking group refers to a direct bond, a divalent hydrocarbon group, and a divalent group chemically equivalent thereto, which connect two adjacent phenyl groups.
  • the divalent aromatic hydrocarbon group, the divalent aliphatic hydrocarbon group, and the divalent heterocycle may be bonded to a monovalent functional group containing a heteroatom, such as an oxyalkyl group, an oxyaryl group, a thioalkyl group, a thioaryl group, an aminocarbonylalkyl group, a cyano group, or a halogen group.
  • a monovalent functional group containing a heteroatom such as an oxyalkyl group, an oxyaryl group, a thioalkyl group, a thioaryl group, an aminocarbonylalkyl group, a cyano group, or a halogen group.
  • the meaning of "chemically equivalent” is that the photosensitive resin composition of the present invention is as stable as a direct bond or a divalent hydrocarbon group in the process until it is cured, that is, the structure does not change, and is chemically inactive.
  • Specific examples include a direct bond, a sulfonyl group, an alkylene group, a divalent condensed polycyclic structure, a divalent hydrocarbon group containing an ether bond, a direct bond, an ether bond, a sulfide bond, a carbonyl group, a carboxylate bond, an amide bond, a urea bond, a urethane bond, a carbonate ester bond, a cycloalkylene group, an arylene group, a divalent condensed polycyclic heterocyclic structure, a divalent hydrocarbon group containing a carbonyloxy group, or a divalent hydrocarbon group containing a carbonylamide group.
  • X is preferably a sulfonyl group, an alkylene group, an ether bond, a sulfide bond, or a cycloalkylene group, and more preferably an alkylene group.
  • V represents a linear or branched divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or a divalent aliphatic hydrocarbon group represented by formula (9).
  • n represents an integer of 0 to 11
  • m represents an integer of 1 to 12, provided that n+m is 1 to 12.
  • R20 and R21 each represent a hydrocarbon group having 2 to 4 carbon atoms
  • n ⁇ 0 each represents a hydrocarbon group having 1 to 4 carbon atoms.
  • * represents a bonding point with an amide group.
  • the divalent aliphatic hydrocarbon group represented by formula (9) may be in the form of -CH 2 -C(CH 3 ) 2 -CH 2 - (in this case, n is 2 and m is 1).
  • V in formula (1) contains a divalent aliphatic hydrocarbon group as shown in formula (9), it is possible to suppress the fluidity of the polymer during curing and reduce the shrinkage of the pattern.
  • n+m is preferably an integer from 1 to 6, and more preferably an integer from 1 to 3.
  • * indicates the point of attachment to the amide group.
  • V is a linear or branched divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.
  • linear or branched divalent aliphatic hydrocarbon groups having 1 to 3 carbon atoms include residues of malonic acid, dimethylmalonic acid, succinic acid, methylsuccinic acid, and glutaric acid.
  • V is most preferably a divalent group represented by formula (3).
  • R5 and R6 each independently represent a hydrogen atom or a methyl group. * represents the point of attachment to the amide group.
  • At least one of R5 and R6 is a methyl group, and it is more preferable that both are methyl groups.
  • the component (a) used in the photosensitive resin composition of the present invention preferably contains a repeating unit represented by formula (2) in addition to the repeating unit represented by formula (1).
  • R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-decomposable group having 1 to 120 carbon atoms.
  • -OR3 and -OR4 are bonded to the ortho position relative to an amide bond bonded to the same aromatic ring, or to a carbon adjacent to the carbon to which the amide bond is bonded.
  • R3 and R4 are the same as those explained for R1 and R2 , and therefore the explanation is incorporated herein.
  • the meaning of the acid-decomposable group and the meaning of the terms used when an acid-decomposable group is used are the same as those explained for formula (1).
  • Y represents a divalent linking group and has the same meaning as the divalent linking group used for X in formula (1), so the explanation therefor is incorporated herein.
  • U represents a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms and containing an alicyclic skeleton, or a straight-chain or branched divalent aliphatic hydrocarbon group having 4 to 20 carbon atoms (excluding groups corresponding to the divalent aliphatic hydrocarbon group represented by formula (9) above).
  • U is preferably a divalent aliphatic hydrocarbon group having 3 to 10 carbon atoms and containing an alicyclic structure, and more preferably a divalent aliphatic hydrocarbon group having 3 to 5 carbon atoms and containing an alicyclic structure.
  • alicyclic structures include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, dimethylcyclohexane, dimethylcyclobutane, and tetramethylcyclohexane.
  • the component (a) used in the present invention preferably contains 1 mol% or more of the repeating units represented by formula (2), more preferably 20 mol% or more, and even more preferably 30 mol% or more. Also, from the viewpoint of increasing sensitivity, when the sum of the repeating units represented by formula (1) and the repeating units represented by formula (2) is taken as 100 mol%, the component (a) preferably contains 80 mol% or less of the repeating units represented by formula (2), more preferably 70 mol% or less.
  • R 24 and R 25 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-decomposable group having 1 to 120 carbon atoms.
  • -OR 24 and -OR 25 are bonded to the ortho position relative to an amide bond bonded to the same aromatic ring, or to a carbon adjacent to the carbon to which the amide bond is bonded.
  • W represents a divalent linking group and has the same meaning as the divalent linking group used for X in formula (1), so the explanation therefor is incorporated herein.
  • * indicates the point of attachment to the amide group.
  • the (a) component used in the present invention preferably contains 1 mol % or more of the repeating units represented by formula (11), more preferably 2 mol % or more, and even more preferably 5 mol % or more.
  • the (a) component preferably contains less than 15 mol %, more preferably 12 mol % or less, and even more preferably 10 mol % or less of the repeating units represented by formula (11).
  • the polybenzoxazole precursor used in the present invention can be synthesized by a known method. For example, it can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester, or the like.
  • the repeating units represented by formula (1), formula (2), and formula (11) are 70 mol% or more, preferably 80 mol% or more, particularly preferably 90 mol% or more of the total repeating units, with the upper limit being 100 mol% (note that here, the repeating units represented by formula (2) and the repeating units represented by formula (11) may not be included).
  • polybenzoxazole precursor (a) may contain other ⁇ -hydroxy (alkyl or hydrogen) arylamide structures in addition to the repeating units represented by formula (1), the repeating units represented by formula (2), and the repeating units represented by formula (11).
  • copolymerizable repeating units other than the ⁇ -hydroxy (alkyl or hydrogen) aryl amide structure may be included in the range of less than 30 mol %, preferably 20 mol % or less, and more preferably 10 mol % or less of the total repeating units.
  • the photosensitive resin composition of the present invention may contain polybenzoxazole precursors other than component (a) and other polymer components within the scope of not impairing the object of the present invention, but the amount is preferably 35% by mass or less, more preferably 25% by mass or less, and even more preferably 15% by mass or less, when the mass of the solid content of the photosensitive resin composition is taken as 100% by mass.
  • the component (a) used in the present invention preferably has a thermally crosslinkable group or a monovalent hydrocarbon group having a thermally crosslinkable group in its terminal structure, from the viewpoint of suppressing the fluidity of the polymer during curing and reducing pattern shrinkage during hardening.
  • thermally crosslinkable groups include, but are not limited to, methylol groups, alkoxymethyl groups, vinyl groups, ethynyl groups, epoxy groups, glycidyl groups, oxetanyl groups, acrylic groups, and methacrylic groups.
  • component (a) By having the end structure of component (a) contain a thermally crosslinkable group, deformation due to reflow during curing can be further reduced, and the taper angle of the cured pattern is significantly improved compared to when the end structure of a resin other than component (a) contains a thermally crosslinkable group.
  • the introduction ratio of the monoamine used as the terminal blocking agent is preferably 20 mol% or more, more preferably 40 mol% or more, even more preferably 60 mol% or more, and particularly preferably 75 mol% or more, when the amount of the terminal carboxyl groups contained in component (a) is taken as 100 mol%.
  • the introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound used as the terminal blocking agent is preferably 20 mol% or more, more preferably 40 mol% or more, even more preferably 60 mol% or more, especially preferably 75 mol% or more, and most preferably 80 mol% or more, when the amount of the terminal amino groups contained in component (a) is taken as 100 mol%.
  • a plurality of different terminal groups may be introduced by reacting multiple terminal blocking agents.
  • the weight average molecular weight of component (a), as measured by gel permeation chromatography, is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and even more preferably 7,000 to 60,000, in terms of polystyrene.
  • the weight average molecular weight of component (a) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and even more preferably 7,000 to 60,000, in terms of polystyrene.
  • photoacid generators include ester compounds of polyhydric phenol compounds and naphthoquinone diazide sulfonic acid compounds, onium salt-type ionic photoacid generators, and non-ionic photoacid generators.
  • An onium salt is a compound that is generated when a compound with an electron pair that is not involved in a chemical bond forms a coordinate bond with another cationic compound through that electron pair.
  • the cationic part of the onium salt determines the photochemical properties (molar absorption coefficient, absorption wavelength, quantum yield), and the anionic part determines the strength of the acid generated.
  • non-ionic photoacid generators are photoacid generators in which the part that absorbs light and the acid are connected via an ester bond.
  • triorganosulfonium salt compounds include, for example, the methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, 4-toluenesulfonate, and perfluoro-1-butanesulfonate of triphenylsulfonium ("SP-056", product name, manufactured by ADEKA Corporation); the sulfonate of dimethyl-1-naphthylsulfonium; the sulfonate of dimethyl(4-hydroxy-1-naphthyl)sulfonium; the sulfonate of dimethyl(4,7-dihydroxy-1-naphthyl)sulfonium; and the sulfonate of diphenyliodonium.
  • SP-056 triphenylsulfonium
  • diazomethane compounds diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylate compounds, sulfonimide compounds, phosphate compounds, sulfonebenzotriazole compounds, etc. can be used.
  • a specific example of a diazomethane compound is bis(4-methylphenylsulfonyl)diazomethane (product name "WPAG-199", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
  • sulfone compounds include ⁇ -ketosulfone compounds and ⁇ -sulfonylsulfone compounds.
  • Preferred sulfone compounds include 2-(p-toluenesulfonyl)acetophenone and bis(phenylsulfonyl)methane.
  • sulfonate ester compounds include alkylsulfonate esters, haloalkylsulfonate esters, arylsulfonate esters, and iminosulfonate ester compounds.
  • Preferred examples include benzoin-4-tolylsulfonate, pyrogallol tris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, and 2,6-(dinitrobenzyl)phenylsulfonate.
  • a specific example of a carboxylic acid ester compound is 2-nitrobenzyl ester of carboxylic acid.
  • the content of the photoacid generator (b) is preferably 1 to 100 parts by mass, and more preferably 1 to 40 parts by mass, per 100 parts by mass of component (a), in terms of the difference in dissolution speed between exposed and unexposed areas and the tolerance range of sensitivity.
  • the photosensitive resin composition of the present invention preferably contains a thermal crosslinking agent from the viewpoint of improving the taper angle of the pattern after curing and forming a high-density pattern.
  • a thermal crosslinking agent examples include those containing two or more thermal crosslinkable groups in the molecule.
  • the number of thermally crosslinkable groups contained in the molecule of the thermal crosslinking agent is 5 or more. In other words, it is preferable that all or a part of the thermal crosslinking agent is a thermal crosslinking agent having 5 or more thermally crosslinkable groups.
  • thermally crosslinkable groups include, for example, methylol groups, alkoxymethyl groups, vinyl groups, ethynyl groups, epoxy groups, glycidyl groups, and oxetanyl groups. Of these, it is preferable for the thermal crosslinking agent to have a methylol group or an alkoxymethyl group, and more preferably an alkoxymethyl group.
  • alkoxymethyl groups include methoxymethyl groups, ethoxymethyl groups, propoxymethyl groups, and butoxymethyl groups.
  • HMOM-TPPHBA HMOM-TPHAP
  • NIKALAC registered trademark MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM
  • VG3101L trade name, manufactured by Printec Co., Ltd.
  • Epicron N660, “Epicron” N695, HP7200 (all trade names, manufactured by Dainippon Ink Co., Ltd.), Chemical Industry Co., Ltd.), "Denacol” EX-321L (trade name, manufactured by Nagase Chemte
  • the content of the thermal crosslinking agent is preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the component (a).
  • the content of the thermal crosslinking agent 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, based on 100 parts by mass of the component (a)
  • pattern shrinkage during curing is reduced.
  • the content of the thermal crosslinking agent 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, based on 100 parts by mass of the component (a) a decrease in the elongation of the cured product can be prevented.
  • component (a) By using a thermal crosslinking agent in combination with component (a), deformation due to reflow during curing can be further reduced, and the taper angle of the cured pattern is significantly improved compared to when component (a) is not used in combination.
  • the photosensitive resin composition of the present invention preferably does not substantially contain the compound represented by formula (10), and even if it does contain it, the content is preferably 0.3 mass% or less when the total amount of the photosensitive resin composition is taken as 100 mass%.
  • the meaning of "substantially” means that it is below the detection limit in the measurement method described in the Examples section.
  • R 22 represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. From the viewpoint of the shrinkage of the film during curing, when R 22 is a methyl group or an ethyl group, the effect is significant, and when R 22 is a methyl group, the effect is even more significant.
  • R 23 is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group
  • the effect on the above-mentioned change in sensitivity is large, when R 23 is a methyl group or an ethyl group, the effect is more significant, and when R 23 is a methyl group, the effect is even more significant.
  • s is 2 or 3. In terms of compatibility with component (a) and the effect on film shrinkage during curing, the effect is greater when s is 2.
  • t is an integer satisfying 0 ⁇ t ⁇ (s+1). From the viewpoint of suppressing the shrinkage of the film during curing, it is preferable that t is 0.
  • Examples of compounds represented by formula (10) include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, and 1,5-dimethyl-2-piperidone.
  • the content of the compound represented by formula (10) contained in the photosensitive resin composition is 0.1% by mass or less, more preferably 0.01% by mass or less, even more preferably 0.005% by mass or less, and most preferably 0% by mass, when the total amount of the photosensitive resin composition is taken as 100% by mass.
  • the inventors have discovered that, since the compound represented by formula (10) is often used as a general-purpose solvent in polymer polymerization and the like, when the compound represented by formula (10) coexists with component (a) having reduced flexibility of the skeleton in order to suppress fluidity during curing, the change in sensitivity with respect to the time from exposure to development becomes greater than when the compound coexists with a flexible polymer.
  • the photosensitive resin composition of the present invention may contain components other than the component (a) and the photoacid generator (b) to the extent that the object of the present invention is not impaired and for the purpose of imparting additional functions.
  • Such components include resins other than the polybenzoxazole precursor or their precursors, solvents, amine compounds, dissolution promoters, sensitizers, silane coupling agents, and surfactants.
  • the positive photosensitive resin composition of the present invention preferably further contains a solvent (hereinafter, sometimes referred to as "(c) solvent”).
  • a solvent hereinafter, sometimes referred to as "(c) solvent”
  • the coating property becomes good, and a homogeneous positive photosensitive resin film can be obtained.
  • the (c) solvent any known solvent can be used as long as it does not impair the effects of the present invention.
  • the (c) solvent is not particularly limited as long as it can dissolve or disperse the (a) component and (b) photoacid generator, but suitable solvents include amide-based solvents, ester-based solvents, alcohol-based solvents, ether-based solvents, ketone-based solvents, and dimethyl sulfoxide.
  • amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyric acid amide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylpropylene urea.
  • ester solvents include gamma-butyrolactone, delta-valerolactone, propylene carbonate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetoacetate, and cyclohexanol acetate.
  • alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 3-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol, propylene glycol, etc.
  • ether solvents include diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether.
  • ketone solvents include methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, cyclopentanone, cyclohexanone, cycloheptanone, dicyclohexyl ketone, etc.
  • the solvent preferably contains an aprotic solvent having a relative dielectric constant in the range of 5 to 20, more preferably a relative dielectric constant of 6 to 19, and even more preferably a relative dielectric constant of 7 to 19.
  • the solvent contains an aprotic solvent with a dielectric constant in the range of 5 to 20, which improves the stability of the positive photosensitive resin composition as a solution during storage.
  • Aprotic solvents with a dielectric constant in the range of 5 to 20 include tetrahydrofuran (dielectric constant 7.6), propylene glycol monomethyl ether acetate (8.3), methyl isobutyl ketone (13.1), cyclopentanone (14.5), cyclohexanone (18.3), and methyl ethyl ketone (18.5).
  • the (c) solvent is preferably an aprotic solvent having 3 to 12 carbon atoms, and more preferably has 4 to 10 carbon atoms.
  • An aprotic solvent having 3 to 12 carbon atoms has excellent solubility for the component (a) used in the positive photosensitive resin composition of the present invention. Therefore, by using an aprotic solvent having 3 to 12 carbon atoms in the photosensitive resin composition of the present invention, the solids concentration of the photosensitive resin composition can be increased, and by applying a composition containing such a solvent, it becomes easy to obtain a film of the photosensitive resin composition having a large thickness, for example, 1 ⁇ m or more.
  • the content of (c) solvent is preferably 100 parts by mass or more per 100 parts by mass of component (a) in order to increase the stability of the solution, while it is preferably 1,500 parts by mass or less in order to form a thick film of the photosensitive resin composition, specifically a film with a thickness of 1 ⁇ m or more.
  • the photosensitive resin composition of the present invention preferably further contains an amine compound (hereinafter, sometimes referred to as "(d) amine compound").
  • an amine compound hereinafter, sometimes referred to as "(d) amine compound”
  • amine compound As the amine compound, it is preferable to use an amine compound whose conjugated acid has a pKa in the range of 4.5 to 10.8, it is more preferable to use an amine compound whose pKa is 5.0 to 10.0, and it is even more preferable to use an amine compound whose pKa is 6.0 to 9.0.
  • pKa of the conjugated acid of the amine compound is in the above range, deprotection during pre-baking is suppressed, and the acid generated during exposure is less likely to be neutralized, so that a pattern of the photosensitive resin composition with less loss of film upon development can be obtained.
  • the content of the (d) amine compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the (a) component.
  • the content of fluorine atoms contained in the resin is preferably less than 5 mass%.
  • the hydrophobicity of the photosensitive resin composition is reduced. This increases the affinity to the developer and suppresses the generation of residues, thereby achieving high sensitivity.
  • the content of fluorine atoms contained in the resin can be analyzed by the following method.
  • the resin is separated from the photosensitive resin composition.
  • the separated resin is precisely weighed as a sample. It is burned in the combustion tube of the analyzer using an automatic sample combustion device, and the generated gas is absorbed into a solution, after which a portion of the absorbed liquid is analyzed by ion chromatography. 0.036% by mass of hydrogen peroxide water can be used as the absorbent liquid.
  • the specific measurement method is as explained in the Examples section.
  • the photosensitive resin composition of the present invention is not limited in its form, and may be, for example, in the form of a solution, a paste, or a sheet.
  • the photosensitive resin sheet of the present invention is formed by forming the photosensitive resin composition of the present invention into a film on a support.
  • the support used for the photosensitive resin sheet is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used.
  • PET polyethylene terephthalate
  • the contact surface between the support and the photosensitive resin composition may be surface-treated with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, etc. to improve adhesion and peelability.
  • the thickness of the support is not particularly limited, but is preferably in the range of 10 to 100 ⁇ m from the viewpoint of workability.
  • a protective film may be provided on the film surface. This makes it possible to protect the surface of the film-like photosensitive resin composition from contaminants such as dust and dirt in the air.
  • Methods for applying the photosensitive resin composition to a support include spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, and slit die coater.
  • the film thickness after application varies depending on the application method, solids concentration of the composition, viscosity, etc., but it is usually preferable to set the film thickness after drying to 0.5 ⁇ m or more and 100 ⁇ m or less from the viewpoint of coating film uniformity, etc.
  • One embodiment of the method for producing a cured film on a substrate of the present invention is to A step of preparing a substrate and forming the photosensitive resin composition of the present invention into a film on the substrate; a step of exposing the film of the photosensitive resin composition to light to form a latent image in the film; developing the exposed photosensitive resin composition film with an alkaline aqueous solution; and and curing the developed film of the photosensitive resin composition.
  • the method for producing a cured product of the present invention includes the steps of preparing a substrate and forming a film of the photosensitive resin composition of the present invention on the substrate.
  • the substrate on which the cured film is formed is preferably selected from the group consisting of glass, silicon wafers, ceramic deposition substrates, metal-plated substrates, sapphire, and gallium arsenide.
  • electrical components and elements such as electrical wiring, electrodes, semiconductor elements, and pixels made of light-emitting materials may be formed on these substrates.
  • a known method can be used to apply the photosensitive composition of the present invention onto a substrate.
  • Apparatuses used for application include full-surface application apparatuses such as spin coating, dip coating, curtain flow coating, spray coating, and slit coating, and printing apparatuses such as screen printing, roll coating, microgravure coating, and inkjet.
  • a drying process is carried out to remove the solvent, forming a film of the dried photosensitive resin composition.
  • a vacuum drying device or a heating device such as a hot plate or oven is used for drying. When using a heating device, it is preferable to perform drying at a temperature range of 50°C to 150°C for 30 seconds to 30 minutes.
  • the thickness of the film of the dried photosensitive resin composition is preferably 0.1 mm to 100 ⁇ m.
  • the method for producing a cured product of the present invention includes a step of exposing the film of the dried photosensitive resin composition to light to form a latent image within the film.
  • the photosensitive resin composition in the form of a film is exposed through a mask having a desired pattern to form a latent image.
  • the wavelength of the exposure light to be irradiated includes light having a wavelength of 300 to 450 nm, such as g-line (436 nm), i-line (365 nm), and h-line (405 nm). Of these, it is preferable to irradiate light having a wavelength of 365 nm.
  • Examples of light sources used in the exposure step include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, and metal halide lamps.
  • the wavelength of the irradiated light may be adjusted as necessary through spectral filters such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter.
  • post-exposure baking may be performed as necessary. By performing post-exposure baking, effects such as improved resolution after development or an increased tolerance for development conditions can be expected.
  • post-exposure baking an oven, hot plate, infrared, flash annealing device, laser annealing device, etc. can be used.
  • the post-exposure baking temperature is preferably 50 to 170°C, more preferably 60 to 150°C.
  • the post-exposure baking time is preferably 10 seconds to 1 hour, more preferably 30 seconds to 30 minutes.
  • the method for producing a cured product of the present invention includes a step of developing the exposed film of the photosensitive resin composition with an alkaline aqueous solution.
  • the developer used for development is typically an alkaline aqueous solution in which an alkaline compound is dissolved.
  • alkaline compounds include tetramethylammonium hydroxide, potassium hydroxide, and sodium carbonate.
  • polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone, and dimethylacrylamide
  • alcohols such as methanol, ethanol, and isopropanol
  • esters such as ethyl lactate and propylene glycol monomethyl ether acetate
  • ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination to these alkaline aqueous solutions.
  • a rinsing treatment with an organic solvent or water.
  • organic solvent examples of the developer include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc., in addition to the above-mentioned developer.
  • water a hydrophilic organic solvent such as alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the water for rinsing treatment.
  • the method for producing a cured product of the present invention includes a step of curing the developed film of the photosensitive resin composition.
  • a temperature of 150°C to 320°C is applied to convert the polybenzoxazole precursor to polybenzoxazole, and when a crosslinking agent is used, a thermal crosslinking reaction is caused to proceed, improving heat resistance and chemical resistance.
  • This heat treatment is carried out by selecting a temperature and gradually increasing the temperature, or by selecting a certain temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each.
  • the lower limit of the curing conditions in this invention is preferably 170°C or higher, but more preferably 180°C or higher to allow sufficient curing to proceed.
  • the upper limit of the curing conditions is preferably 280°C or lower.
  • Another embodiment of the method for producing a cured film on a substrate of the present invention is a step of pressing the photosensitive resin sheet of the present invention onto a substrate, and peeling off a support or a protective film used in the photosensitive resin sheet to transfer a film-like photosensitive resin composition onto the substrate; a step of exposing the transferred photosensitive resin composition to light to form a latent image in the film of the photosensitive resin composition; developing the exposed photosensitive resin composition film with an alkaline aqueous solution; and and curing the developed film of the photosensitive resin composition.
  • the support or protective film used in the photosensitive resin sheet may be peeled off after exposure.
  • the patterned cured product obtained in this way is a cured product that is mainly composed of polybenzoxazole, and therefore has excellent heat resistance, electrical insulation, and mechanical properties.
  • the substrate on which the cured film is formed there are no particular limitations on the substrate on which the cured film is formed, but it is the same as that described in the section on the manufacturing method of the patterned cured film (1), and examples thereof include silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and substrates on which circuit constituent materials are arranged.
  • organic circuit boards include glass-based copper-clad laminates such as glass cloth/epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven cloth/epoxy copper-clad laminates, heat-resistant/thermoplastic substrates such as polyetherimide substrates, polyetherketone substrates, and polysulfone substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates.
  • inorganic circuit boards include ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal substrates such as aluminum-based substrates and iron-based substrates.
  • circuit constituent materials include conductors containing metals such as silver, gold, and copper, resistors containing inorganic oxides, low dielectrics containing glass-based materials and/or resins, high dielectrics containing resins and high-dielectric-constant inorganic particles, and insulators containing glass-based materials.
  • thermocompression bonding is preferably used, and known methods can be used.
  • the support is peeled off while leaving the protective film, and the photosensitive resin composition with the protective film is placed opposite the substrate and bonded by thermocompression bonding.
  • Thermocompression bonding can be performed by heat pressing, heat lamination, thermal vacuum lamination, etc. Among these, heat lamination is preferred.
  • the bonding temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability.
  • the bonding temperature is preferably 150°C or lower to prevent the resin composition film from hardening during bonding, which would deteriorate the resolution of the pattern formation in the exposure and development process.
  • the photosensitive resin sheet pressed onto the substrate is subjected to a process in which the support and protective film, if any, remain thereon are peeled off, the process in which the film of the photosensitive resin composition on the substrate is exposed to light, the process in which the exposed portion of the film of the photosensitive resin composition is developed by dissolving or removing it with an alkaline aqueous solution, and the process in which the developed film of the photosensitive resin composition is cured.
  • these processes There are no particular limitations on these processes, but it is preferable to carry them out in the same manner as in the manufacturing method (1) of the patterned cured film.
  • the cured product of the present invention can be used, for example, in electronic components and electronic devices.
  • electronic components include semiconductor devices, antennas, display devices, metal-clad laminates, wiring boards, semiconductor packages, active components including semiconductor devices, and passive components.
  • display devices include organic EL displays, quantum dot displays, micro light-emitting diode (hereinafter, "LED”) displays, mini LED displays, and liquid crystal displays.
  • the cured product obtained by curing the photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices.
  • the semiconductor device in the present invention refers to any device that can function by utilizing the characteristics of a semiconductor element. Electro-optical devices and semiconductor circuit boards in which a semiconductor element is connected to a substrate, stacks of multiple semiconductor elements, and electronic devices including these are all included in the semiconductor device. Electronic components such as interposers for connecting semiconductor elements to a substrate are also included in the semiconductor device.
  • the cured product obtained by curing the photosensitive resin composition of the present invention is excellent in electrical insulation, mechanical strength, adhesion, and heat resistance, so that it is preferable for these to be used in semiconductor devices in which they are arranged as surface protective films such as passivation films and buffer coat films for semiconductor elements, interlayer insulating films between rewirings formed on the surface of semiconductor elements, insulating films between elements when multiple semiconductor elements are joined, and insulating films between wiring layers of multilayer wiring boards for high-density packaging and interposers.
  • surface protective films such as passivation films and buffer coat films for semiconductor elements, interlayer insulating films between rewirings formed on the surface of semiconductor elements, insulating films between elements when multiple semiconductor elements are joined, and insulating films between wiring layers of multilayer wiring boards for high-density packaging and interposers.
  • the display device of the present invention includes a first electrode formed on a substrate, an insulating layer formed so as to partition pixels provided on the first electrode, and a second electrode provided opposite the first electrode, the insulating layer being the cured product of the present invention.
  • the insulating layer can be formed by applying and drying the photosensitive resin composition of the present invention onto a substrate on which a first electrode has been formed, or by laminating a sheet-like photosensitive resin composition, and then carrying out the steps of exposure, development, and curing to form a pattern of the insulating layer produced from the cured product of the present invention.
  • the display device has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and either or both of the planarization layer and the insulating layer are the cured product of the present invention.
  • a driving circuit a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and either or both of the planarization layer and the insulating layer are the cured product of the present invention.
  • TFTs and wiring located on the sides of the TFTs and connected to the TFTs on a substrate such as glass or a resin film, a planarization layer is provided on top of the TFTs so as to cover the unevenness, and a display element is further provided on the planarization layer.
  • the display element and the wiring are connected via contact holes formed in the planarization layer.
  • the cured product obtained by curing the photosensitive resin composition of the present invention is excellent in planarization properties and pattern dimensional stability, so it is preferable to provide it as a planarization layer in a display device.
  • flexible display devices have become mainstream in recent years, and the display device may be one in which the substrate having the driving circuit described above is made of a resin film.
  • NQD-1 4,4'-(1-(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)ethane-1,1-diyl)diphenol ester of naphthoquinone diazide sulfonic acid.
  • Measuring device Waters 2695 (manufactured by Waters Corporation) Column temperature: 50 ° C. Flow rate: 0.4mL/min Detector: 2489 UV/Vis Detector (measurement wavelength 260 nm) Developing solvent: NMP (containing 0.21% by mass of lithium chloride and 0.48% by mass of phosphoric acid) Guard column: TOSOH TSK guard column (manufactured by Tosoh Corporation) Column: TOSOH TSK-GEL a-2500, TOSOH TSK-GEL a-4000 in series (both manufactured by Tosoh Corporation).
  • the capping rate of the resin's main chain ends was measured using the same equipment, heavy solvent, and cumulative number of times as used to calculate the protection rate.
  • the capping rate of the main chain ends can be calculated using the following formula.
  • Capping rate of main chain ends (%) Q/P x 100.
  • the solid content concentration of the photosensitive resin composition was determined by the following method. 1.5 g of the solution was weighed out in an aluminum cup and heated at 180° C. for 30 minutes using a hot plate to evaporate the liquid. The mass of the solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration was calculated from the ratio to the mass before heating.
  • the photosensitive resin composition sample was subjected to GC-MS analysis using a GC-MS device (manufactured by Agilent) under the following conditions: column temperature: 40 to 300° C., carrier gas: helium (1.5 mL/min), and scan range: m/z 29 to 600.
  • a GC-MS device manufactured by Agilent
  • carrier gas helium (1.5 mL/min)
  • scan range m/z 29 to 600.
  • Each of the target compounds was subjected to GC-MS analysis under the same conditions as above to create a calibration curve, and the content of the compound in the sample was calculated.
  • the wafer was exposed to an exposure dose in the range of 5 to 300 mJ/cm2 at intervals of 5 mJ/ cm2 through a mask having a pattern of 10 ⁇ m contact holes.
  • the resist was left to stand for 10 minutes in an environment of 23° C. and 45% RH, and then developed for 10 to 80 seconds using the ACT-8 developing device with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH, manufactured by Tama Chemical Industries Co., Ltd.) as a developer.
  • TMAH tetramethylammonium hydroxide
  • the film thickness was measured using an optical interference film thickness measuring apparatus Lambda Ace STM-602 (manufactured by SCREEN Holdings Co., Ltd.) under the condition of a refractive index of 1.629. The sample was then immersed in the thinner for 60 seconds. The presence or absence of residue remaining on the silicon wafer was observed.
  • B + Sensitivity change y is 110 or more and less than 150.
  • tapeer angle A relief pattern was prepared in the above (6) using a 20 ⁇ m contact hole pattern instead of a 10 ⁇ m contact hole pattern, and the minimum exposure dose Eth(1)' at which the contact hole opening diameter reached 20 ⁇ m was determined in the same manner as in the above (7).
  • the relief pattern obtained with the minimum exposure dose was heat-treated at 250° C. for 30 minutes in a nitrogen stream (oxygen concentration 20 ppm or less) using a clean oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.).
  • a vertical cross section including the maximum opening diameter of the contact hole pattern was then cut out, and the cross section was observed with a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation) to measure the taper angle (see reference numeral 3 in FIG. 1).
  • S-4800 field emission scanning electron microscope
  • the results were rounded off to the nearest whole number and evaluated according to the following criteria, with A to D being considered as acceptable.
  • A being the most excellent.
  • Synthesis Example 1 Synthesis of polybenzoxazole precursor (PBO-01) Under a dry nitrogen gas flow, 25.83 g (100 mmol) of BAP was dissolved in 106 g of MPA in a three-neck flask, and then the temperature of the solution was cooled to ⁇ 15° C. After confirming that the temperature of the solution had reached ⁇ 15° C., 12.68 g (75 mmol) of glutaryl chloride (glutaric acid dichloride) was added together with 30 g of MPA. After stirring for 30 minutes at ⁇ 10° C., the solution was heated to 20° C. and stirred for another 2 hours.
  • PBO-01 polybenzoxazole precursor
  • Synthesis Examples 2 to 31 Synthesis of Polybenzoxazole Precursors (PBO-02 to PBO-31) Synthesis was performed in the same manner as in Synthesis Example 1, except that the diacid dichloride, diamine, acid chloride, and solvent were changed to the types and amounts shown in Table 1. The results are shown in Table 1.
  • Table 1 the "mass %" in parentheses in the polymerization solvent column indicates the proportion when the total amount of solvent is taken as 100 mass %.

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Abstract

La présente invention aborde le problème consistant à fournir une composition de résine photosensible qui a une sensibilité élevée et qui est capable de former des motifs qui ne subissent qu'un faible retrait pendant une réaction de durcissement effectuée après l'exposition et le développement. La présente invention concerne une composition de résine photosensible qui comprend : un précurseur de polybenzoxazole ayant un motif récurrent représenté par la formule (1) ; et un générateur de photoacide. (R1 et R2 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle en C1-C6, ou un groupe monovalent en C1-C120 qui est labile en milieu acide. X représente un groupe de liaison divalent. V représente un groupe hydrocarboné aliphatique divalent linéaire ou ramifié en C1-C3 ou un groupe hydrocarboné aliphatique divalent représenté par la formule (9).) (n représente un nombre entier compris entre 0 et 11 et m représente un nombre entier compris entre 1 et 12. Ici, n + m est compris entre 1 et 12. R20 et R21 représentent chacun un groupe hydrocarboné en C2-C4 lorsque n = 0, et un groupe hydrocarboné en C1-C4 lorsque n ≠ 0. * représente un point de liaison à un groupe amide.)
PCT/JP2024/040768 2023-12-20 2024-11-18 Composition de résine photosensible, feuille de résine photosensible utilisant ladite composition de résine photosensible, produit durci, procédé de production de film de produit durci, et dispositif à semi-conducteur et dispositif d'affichage comprenant ledit produit durci Pending WO2025134631A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2016035819A1 (fr) * 2014-09-04 2016-03-10 富士フイルム株式会社 Composition de résine photosensible, procédé de fabrication de film durci, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage à électroluminescence organique, et panneau tactile

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016035819A1 (fr) * 2014-09-04 2016-03-10 富士フイルム株式会社 Composition de résine photosensible, procédé de fabrication de film durci, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage à électroluminescence organique, et panneau tactile

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