WO2001075525A1 - Composition de resine polyimide photosensible positive - Google Patents

Composition de resine polyimide photosensible positive Download PDF

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Publication number
WO2001075525A1
WO2001075525A1 PCT/JP2001/002502 JP0102502W WO0175525A1 WO 2001075525 A1 WO2001075525 A1 WO 2001075525A1 JP 0102502 W JP0102502 W JP 0102502W WO 0175525 A1 WO0175525 A1 WO 0175525A1
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Prior art keywords
acid
group
polyimide resin
resin composition
carboxylic acid
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PCT/JP2001/002502
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English (en)
Japanese (ja)
Inventor
Tomonari Nakayama
Takayasu Nihira
Hiroyoshi Fukuro
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Nissan Chemical Industries, Ltd.
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Publication of WO2001075525A1 publication Critical patent/WO2001075525A1/fr

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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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
    • 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
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • 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
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides

Definitions

  • the present invention relates to a photosensitive material suitable for use in an electric / electronic device, particularly a semiconductor device, and more particularly to a positive photosensitive polyimide resin composition excellent in adhesion to a substrate, developability, and the like.
  • JP-A-54-116162 and JP-A-54-116162 Techniques for imparting photosensitivity to the polyimide resin are described, for example, in JP-A-54-116162 and JP-A-54-116162.
  • a method of chemically linking a crosslinkable group to a soluble polyimide precursor, a method disclosed in JP-A-54-145794, and a method disclosed in JP-A-57-168942 is disclosed. There is a method of mixing the crosslinkable monomers described.
  • the above method is a negative type in which the exposed area is cross-linked and insolubilized by light.
  • there is a problem in safety because an organic solvent is used during development. It is difficult to process.
  • JP-A-64-66030 discloses a composition obtained by mixing an orthoquinonediazide compound with an organic solvent-soluble polyimide resin having a hydroxyl group introduced therein.
  • Japanese Patent Application Laid-Open No. 2009-478 discloses a high-resolution photosensitive resin composition in which an orthoquinonediazide compound is mixed with a polyimide having extremely excellent transparency.
  • Japanese Patent Application Laid-Open No. 08-221118 and Japanese Patent Application Laid-Open No. 11-84653 disclose an aqueous solution, a polyamide or a solvent which is soluble in an organic solvent.
  • a photosensitive resin composition whose sensitivity has been increased by adding an alkali-soluble polyimide precursor to the polyimide is disclosed.
  • bisphenol is added to a soluble polyamide.
  • a photosensitive polyimide resin composition has been disclosed in which high sensitivity has been achieved by adding a low-molecular compound such as mono-tris-funol.However, high sensitivity can be achieved with a small amount of polyamic acid and phenol compound Poor effect. Of course, higher sensitivity can be achieved by increasing the amount of addition, but in the former case, the film thickness decreases during development, and in the latter case, the film thickness decreases during post-curing, resulting in a problem that the resolution decreases when the film is thick. become.
  • the conventional positive-type photosensitive heat-resistant resin achieves high sensitivity and high resolution at the time of thin film, but when trying to obtain a pattern with sufficient sensitivity at the time of thick film, a large amount of additives are added. Therefore, there is a problem that the film thickness is reduced. Disclosure of the invention
  • the present invention has been made in view of the above circumstances, and an alkali developing property is improved by arbitrarily adding a small amount of a low-molecular compound having a high alkali affinity to a soluble polyimide and a photosensitive agent.
  • a photosensitive polyimide resin composition that is excellent in sensitivity and resolution even in the case of a thick film, and that provides a heat-resistant resin pattern with a small decrease in film thickness after development and post-baking. It is assumed that.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found the present invention.
  • the present invention provides a compound represented by the general formula (1):
  • the present invention relates to a positive-type photosensitive polyimide resin composition characterized by containing a) a photosensitive ortho-quinonediazide compound.
  • the present invention will be described in detail.
  • composition of the present invention can be easily etched with an aqueous alkali solution, and can easily form a polyimide resin coating film having a fine and highly dimensional accurate relief pattern by exposing using a mask having a predetermined pattern. Obtainable.
  • the method for obtaining the solvent-soluble polyimide of the present invention is not particularly limited. Usually, it is obtained by reacting and polymerizing a tetracarboxylic acid or a derivative thereof with a diamine. Particularly, it is possible to react and polymerize a tetracarboxylic dianhydride (hereinafter, abbreviated as an acid anhydride) with a diamine.
  • a tetracarboxylic dianhydride hereinafter, abbreviated as an acid anhydride
  • R 1 in the general formula (1) is a divalent organic group constituting diamine
  • R 2 is a tetravalent organic group constituting acid anhydride.
  • R 1 represents at least one group selected from the group consisting of a phenolic hydroxyl group, a hydroxyl group, a thiophenol group and a sulfonic acid group in an amount of 1 to 100 mol%.
  • the diamine having a phenolic hydroxyl group, a carboxyl group, a thiophenol group, and a sulfonic acid group used for obtaining the solvent-soluble polyimide of the present invention is not particularly limited, but specific examples thereof include:
  • diamines having a phenolic acid group examples include 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, and 2,5-diaminophenol.
  • Droquinone bis (3—Amino 4— Hydroxyphenyl ether, bis (4-amino-3-hydroxyphenyl ether, bis (4-amino-1,3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3) —Hydroxyphenyl) methane, Bis (4-amino-3,5-dihydroxyphenyl) methane, Bis (3-amino-4-hydroxyphenyl) sulfone, Bis (4-amino3-Hydroxyphenyl) sulfone, Bis (4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) Nil) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphen
  • diamine having a carboxyl group examples include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino 1,3-monobenzenedicarboxylic acid, 2,5 —Diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3_carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4-amino-3-carboxyphenyl) ether Phenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4'diamino 3,3'-dicarboxybiphenyl, 4,4'diamino 3,3'-dicarboxy-5 , 5'-Dimethylbiphenyl, 4,4'-Diamino 3,3'-Dicarboxy-1,
  • diamines having a thiophenol group examples include 1,3-diamino-4-mercaptobenzene, 1,3-diamino-15-mercaptobenzene, 1,4 diamino-12-mercaptobenzene, and bis (4-amino-3-mercaptobenzene).
  • diamine having a sulfonic acid group examples include 1,3-diaminobenzene-14-sulfonic acid, 1,3-diaminobenzene-15-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis ( 4—Aminobenzene-1,3-sulfonic acid) ether,, 4 'diamino biphenyl) 3,3'-disulfonic acid, 4, 4' diamino- 3,3'-dimethyl biphenyl 2,6'-disulfonic acid No.
  • To 5-Hydroxyphenyl) sulfone, 2,2-bis (4-amino-3 -carboxy-1-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3 -carboxy-1-5-hydroxyphenyl) Xafluoropropane and the like are preferred, but not limited thereto.
  • diamine having a carboxyl group and a sulfonic acid group is preferable for obtaining a solvent-soluble polyimide resin that can be easily produced by catalyst imidization.
  • diamines having a phenolic hydroxyl group, a carboxyl group, a thiophenol group or a sulfonic acid group can be used alone or in combination of two or more.
  • Diamines having no phenolic hydroxyl group, carboxyl group, thiophenol group or sulfonic acid group used for obtaining the solvent-soluble polyimide of the present invention are particularly limited.
  • dare examples include 4,4,1-methylene-bis (2,61-ethylanilinine), 4,4,1-methylene-bis (2_isopropyl-16-methylaniline) 4, 4'-Methylene-bis (2,6-diisopropylpropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4- Phenylenediamine, 0-trizine, m-trizine, 3,3 ', 5,5'-tetramethylbenzidine, bis [4- (3-aminophenol) phenyl] sulfone, 2,2-bis [ 4- (3-Aminophenoxy) phenyl] pu-pan, 2,2-bis [4- (3-aminophenoxy) phenyl
  • siloxane-containing diamines are preferred from the viewpoint of polyimide adhesion.
  • siloxane-containing diamine component As the siloxane-containing diamine component,
  • diamines having no phenolic hydroxyl group, carboxyl group, thiophenol group or sulfonic acid group can be used alone or in combination of two or more.
  • diamines having no phenolic hydroxyl group, carboxyl group, thiophenol group, or sulfonic acid group cannot be used.
  • the acid anhydride used to obtain the solvent-soluble polyimide of the present invention is not particularly limited, but specific examples thereof include pyromellitic dianhydride, 3, 3 ′, 4, 4′-bif Enyltetracarboxylic dianhydride, 3, 3 ', 4, 4' benzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4' diphenyl tertetracarboxylic dianhydride, 3, 3 ', 4,4'diphenylsulfonetetracarponic acid 2,3,4-bis (3,4-dicarboxyphenyl) hexafluoropropane 2,3,3', Aromatic tetracarboxylic anhydrides such as 4,4'-diphenylsulfonetetracarboxylic acid anhydride can be mentioned.
  • 1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2-di Methyl 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride Anhydride, 2,3,5-tricarboxylic acid ruboxyl-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] oct-1 7-ene-2,3,5,6—tetracarboxylic acid Anhydrides, 2,3,4,5-tetrahydrofurante tracarboxylic acid dianhydride;!
  • 1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1'2,3,4—Cyclopentanetetracarbonic dianhydride, 1,2,4,5— Cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4—tetrahidro 1-naphthalenesuccinic dianhydride, 2,3,5—tricarboxy-2-cyclopentaneacetic acid None; ⁇ Mate, bicyclo [2.2.2] oct-1-ene-1,2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic acid Acid dianhydride, 3, 5, 6-tric
  • 1,2,3,4-cyclobutanetetracarboxylic dianhydride is preferred.
  • acid anhydrides can be used alone or in combination of two or more.
  • the polyimide is reacted with tetracarboxylic dianhydride and diamin in a polar solvent such as ⁇ -methylpyrrolidone and dimethylacetamide.
  • a polar solvent such as ⁇ -methylpyrrolidone and dimethylacetamide.
  • the reaction temperature of the tetracarboxylic acid dianhydride with the diamine can be selected from any temperature of from 120 to 150 ° (preferably from 15 to 100 ° C).
  • the polyimide precursor may be heated at 150 to 250 ° C in a solution state, and water generated by dehydration ring closure is removed. It is also possible to add toluene, xylene, or the like, and perform azeotropic dehydration.
  • Another simpler method for converting polyamic acid to polyimide is catalyst imidization.
  • acetic anhydride and a tertiary amine such as triethylamine, pyridine, isoquinoline, imidazole, etc. are added to the polyimide precursor solution, and imidization is performed at any temperature between 0 ° C and 250 ° C. be able to.
  • the diamine constituting R 1 in the general formula (1) has at least one or more groups selected from the group consisting of a carboxy group and a sulfonic acid group.
  • this method can be adopted only when it has neither a phenolic hydroxyl group nor a thiophenol group.
  • the repeating unit a in the general formula (1) of the polyimide in the present invention is an integer of 3 or more and 1000 or less, and if a is less than 3, the mechanical properties of a film formed from the obtained composition When the strength is reduced and a is larger than 1000, the viscosity of the obtained composition is remarkably increased, and the workability for use thereof is extremely reduced.
  • the carboxylic acid or carboxylic acid derivative represented by the above general formula (2) constituting the positive photosensitive resin composition of the present invention can be added from a small amount to the positive photosensitive resin by adding it to the soluble resin. Easier etching of resin with aqueous solution And has the effect of improving the sensitivity.
  • b and c are 0 or 1 or more, and are integers satisfying b + c ⁇ 1, and R 3 is composed of a b + 2c-valent organic group. It is not particularly limited as long as it is a carboxylic acid or a carboxylic acid derivative.
  • the carboxylic acid or carboxylic acid derivative represented by the general formula (2) of the present invention can be used alone or as a mixture of two or more.
  • carboxylic acid used in the present invention include benzoic acid, 4-hydroxybenzoic acid, 4-nitrobenzoic acid, biphenylcarboxylic acid, phthalic acid, 3-hydroxyphthalic acid, and 4-hydroxyphthalic acid.
  • propionic acid, valeric acid, hexanoic acid, malonic acid maleic acid, fumaric acid, succinic acid, butanetetracarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid 1,1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,6-tetrahi Drophthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2-cyclopentanedicarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,1-cyclopentanediacetic acid, 2,3,5-tricarboxy-2-cyclopentenoic acetic acid, 1-cyclopentene-1-1 carboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid,
  • phthalic anhydride pyromellitic dianhydride, 3,34,4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarbonic acid dianhydride None;! K product, bis (3,4-dicarboxyphenyl) ether difree product, 2,2_bis (3,4-dicarboxyphenyl) hexafluoropropane 3,4-dicarboxyphenyl) sulfone dianhydride and aromatic tetracarboxylic acid derivatives such as trimellitic anhydride.
  • maleic anhydride glutaric anhydride, butanetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3 1,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3 1,4,5,6-tetrahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, 1,1-cyclopentanedi Acetic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid, 1,2,, 5-cyclohexane He
  • 1,2,3,4-cyclobutanetetracarboxylic acid and 1,2,3,4-butanetetracarboxylic acid are required in order to obtain sufficient sensitivity as a photosensitive polyimide in terms of solubility and the like.
  • medium R 3 is aromatic
  • the compounding amount of the carboxylic acid or the carboxylic acid derivative is 0.5 to 50 parts by weight based on 100 parts by weight of the organic solvent-soluble polyimide, and when the compounding amount is less than 0.5 part by weight, No effect of improving sensitivity at the time of exposure of the obtained composition is observed. On the other hand, if the amount is more than 50 parts by weight, the film thickness of the unexposed portion during development is greatly reduced, and a favorable positive pattern cannot be obtained.
  • the orthoquinonediazide compound constituting the positive photosensitive polyimide resin composition of the present invention is not particularly limited as long as it is a compound containing an orthoquinonediazide group in a molecule.
  • Examples thereof include orthobenzoquinone diazide compounds, orthonaphthoquinone diazide compounds, and orthoquinoline quinone diazide compounds, which are used in the so-called phenol nopolak-based positive photosensitive composition. It is common to use
  • the above-mentioned orthoquinone diazide compound is usually used as an orthoquinone diazide sulfonyl compound.
  • orthoquinonediazidosulfonyl compounds are generally obtained by a condensation reaction of an orthoquinonediazidosulfonyl compound and a compound having a phenolic hydroxyl group or an amino group.
  • the orthoquinone diazide sulfonyl chloride constituting the orthoquinone diazide sulfonyl chloride includes, for example, 1,2-naphthoquinone-12-diazide-14-sulfonyl, 1,2-naphthoquinone-12-diazido 5-sulfonyl, 2-naphthoquinone-1-diazido 6-sulfonyl and the like.
  • orthoquinonediazidosulfonyl chloride are, for example, phenol, hydroquinone, resorcinol, catechol, phloroglucinol, 2, '4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2', 4 , 4'-tetrahydric mouth "xybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 3,4,4,1-pentahydroxybenzophenone , 2,, 4 'dihydroxyacetophenone, 2,, 5, dihydroxyacetophenone, 2,, 6' dihydroxyacetophenone, 3,, 5, dihydroxyacetophenone, 2,, 3 ', 4,- 2,4-, 6-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy) 2,3-, 4-bis (4-hydroxyphenyl) propane (Ciphenyl) hexafluoropropane, bis (4-hydroxyphenyl)
  • aromatic amines such as aniline, m-phenylenediamine, p-phenylenediamine, 4,4, diaminodiphenyl ether and 4,4 ′ diaminodiphenyl methane can be mentioned.
  • 4-aminophenol 3-aminophenol, 1,3-diamino-4-hydroxybenzene, 1,3-diamino-15-hydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene
  • aminophenols such as 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
  • orthoquinonediazide compounds include 1,2-naphthoquinone-2-diazide-14-sulfonic acid ester, 1,2-naphthoquinone-12-diazido-5-sulfonic acid ester, and 1,2— Naphthoquinone-12-diazide-16-sulfonate is preferred. These compounds may be used alone or in combination of two or more.
  • the amount of the orthoquinonediazide compound is 1 to 100 parts by weight based on 100 parts by weight of the total amount of the organic solvent-soluble polyimide and the polyimide precursor, and the amount is less than 1 part by weight. And the sensitivity at the time of exposure of the resulting composition is extremely low. And the pattern cannot be formed. On the other hand, if the amount is more than 100 parts by weight, the mechanical properties, electrical properties, and the like of the film formed from the obtained composition are reduced.
  • the positive photosensitive polyimide resin composition of the present invention is used for an electric / electronic device or the like, it is used as a solution dissolved in an organic solvent.
  • the organic solvent is not particularly limited as long as it can uniformly dissolve the polyimide, carboxylic acid or carboxylic acid derivative, and orthoquinone diazide compound. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, m-cresol, 7 -Butyrolactone.
  • organic solvents may be mixed and used as long as the solubility of the composition is not inhibited according to the purpose.
  • organic solvents include ethyl sorb, butyl sorb, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, ethyl lactate, butyl lactate, and cyclohexane.
  • the method for obtaining the present composition is not particularly limited, but a carboxylic acid or a carboxylic acid derivative, an orthoquinone diazide compound may be dissolved in a solution obtained by reacting and polymerizing an organic solvent-soluble polyimide, and a poor solvent is used. It may be dissolved in the organic solvent together with the organic solvent-soluble polyimide resin, carboxylic acid or carboxylic acid derivative, or orthoquinone diazide compound recovered by precipitation.
  • the concentration of the above-mentioned positive photosensitive polyimide resin composition in the organic solvent is not particularly limited as long as the polyimide, the orthoquinone diazide compound, and the carboxylic acid or carboxylic acid derivative are uniformly dissolved in the organic solvent. Not done. Ease of working surface, the range of 1 to 5 0 wt 0/0 is common.
  • the positive photosensitive polyimide resin composition of the present invention can be spin-coated on a substrate such as a silicon wafer, and then pre-dried at 50 to 130 ° C. to form a film. At this time, it is of course preferable to use a substrate treated with a silane coupling agent or the like.
  • an ultra-high pressure mercury lamp is used as the light source.
  • the method of transferring the mask pattern to the photosensitive polyimide resin composition of the present invention can be adhesion exposure using a contact liner, proximity exposure, or reduced projection exposure using a stepper.
  • the developing solution used in the development may be any aqueous solution of alkali metal, such as aqueous solution of alkali metal hydroxide such as caustic lithium, caustic soda, tetramethylammonium hydroxide, Examples of quaternary ammonium hydroxides such as tetraethylammonium hydroxide and choline; 7 solutions and aqueous amine solutions such as ethanolamine, propylamine and ethylenediamine can be given as examples. Further, a surfactant or the like can be added to these developers.
  • alkali metal hydroxide such as caustic lithium, caustic soda, tetramethylammonium hydroxide
  • Examples of quaternary ammonium hydroxides such as tetraethylammonium hydroxide and choline
  • 7 solutions and aqueous amine solutions such as ethanolamine, propylamine and ethylenediamine can be given as examples.
  • a surfactant or the like can be
  • the composition has a high solubility of the exposed portion, the generic of two. 3 8 weight 0/0 tetraalkylammonium hydroxide ammonium Niu arm It can be easily developed at room temperature.
  • a polyimide having excellent heat resistance, chemical resistance, and electrical characteristics and having a good relief pattern is obtained.
  • a coated film can be obtained.
  • the composition of the present invention has high-sensitivity, high-resolution positive-type photosensitive characteristics, is easy to etch with an aqueous alkaline solution, and has a fine shape by being exposed using a mask having a predetermined pattern. Further, a polyimide resin coating film having a relief pattern with high dimensional accuracy can be easily obtained.
  • composition of the present invention has an improved development speed as compared with a mixture composition containing only a solvent-soluble polyimide and a perfor- quinone diazide compound, and can greatly improve the efficiency of the pattern forming process.
  • This positive photosensitive polyimide resin composition is an interlayer insulating film for semiconductor devices. It can be used as a substrate film, a buffer coat film, an insulating film for a multilayer printed circuit board, or the like.
  • DABA 1,3-diamino-5-benzoic acid
  • BAPS bis [4- (3-aminophenoxy) phenyl] sulfone
  • CB DA 1,22,3,4-Cyclobutanetetracarboxylic dianhydride
  • NMP N-methylpyrrolidone
  • the polyimide powder obtained in Synthesis Example 1 was dissolved in a peptide lactone to form a solution having a resin concentration of 20%. 20 g of this solvent-soluble polyimide resin solution was mixed with 0.12 g of 1,2,3,4-butanetetracarboxylic acid and completely dissolved.
  • This photosensitive polyimide solution is directly coated on a silicon wafer using a spin coater.
  • the coating was applied and heated on a hot plate at 80 ° C. for 3 minutes to obtain a coating having a thickness of 5 / m.
  • Ultraviolet light (365 nm light extracted using a filter) was passed through a test mask through a test mask and irradiated with ultraviolet light (PLA-501, manufactured by Canon Inc.) at a wavelength of 40 to 800 mJ / cm 2 . Irradiated in range.
  • the film was developed by immersing it in an alkaline developer (NMD-3, manufactured by Tokyo Ohka Co., Ltd.) at approximately 23 ° C for 120 seconds, and then rinsed with pure water for 20 seconds.
  • NMD-3 alkaline developer
  • pattern formation was confirmed in a portion irradiated with an exposure amount of 40 Om J / cm 2 or more.
  • the film thickness after development was about 4.7 m.
  • the pattern resolution was formed up to 8 m in line / space without pattern peeling.
  • the obtained film was heated in a circulating drying oven at 170 ° C. for 60 minutes and at 350 ° C. for 30 minutes to obtain a polyimide pattern having a film thickness of 3.6 m.
  • the polyimide powder obtained in Synthesis Example 1 was dissolved in 7 -butyrolactone to prepare a solution having a resin concentration of 20%.
  • 20 g of CBDA was mixed with 20 g of the solvent-soluble polyimide resin solution, and completely dissolved.
  • a naphthoquinone-based photosensitizer (4 moles of 1,2-naphthoquinone-12-diazido-4-sulfonic acid per mole of 2,3,4,4'-tetrahydroxybenzophenone).
  • a coating film having a thickness of 5 was obtained in accordance with Example 1.
  • pattern formation was confirmed exposure at 4 0 O m J Zc m 2 or more irradiated portion.
  • the film thickness after development was about 5 m.
  • the pattern resolution was formed up to 8 m in line / space without pattern peeling.
  • the obtained film was heated in a circulating drying oven at 170 ° C. for 60 minutes and at 350 ° C. for 30 minutes to obtain a polyimide film pattern having a film thickness of 3.8 m.
  • the polyimide powder obtained in Synthesis Example 1 was dissolved in y-butyrolactone to obtain a solution having a resin concentration of 20%.
  • 20 g of CB DA O was mixed with 20 g of the solvent-soluble polyimide resin solution, and completely dissolved.
  • a naphthoquinone-based positive photosensitive agent (2, 3 , 4,4'-Tetrahydroxybenzophenone (1 mol) is substituted with 1,2-naphthoquinone-12-diazido 4-sulfonic acid (4 mol).
  • a solution of the positive photosensitive polyimide resin composition of the present invention was obtained.
  • a coating film having a thickness of 5 / m was obtained in accordance with Example 1.
  • pattern formation was confirmed exposure at 2 8 O m J / cm 2 or more irradiated portion.
  • the film thickness after development was about 4.4 // m.
  • the pattern resolution was 8 ⁇ m / line / space without pattern peeling.
  • the obtained film was heated in a circulating drying oven at 170 ° C. for 60 minutes and at 350 ° C. for 30 minutes to obtain a 3.4-m thick polyimide pattern.
  • the polyimide powder obtained in Synthesis Example 1 was dissolved in y-butyrolactone to obtain a solution having a resin concentration of 20%. 0.20 g of 1,2,3,4-butanetetracarboxylic dianhydride was mixed with 20 g of this solvent-soluble polyimide resin solution, and completely dissolved. To this solution was added a naphthoquinone-based positive-type photosensitizer (an ester obtained by substituting 4 mol of 1,2-naphthoquinone-12-diazido-4-sulfonic acid per mol of 2,3,4,4'-tetrahydroxybenzophenone). Compound (1.0 g) was added, and the mixture was stirred at room temperature for 1 hour, and filtered through a 1.0 m filter to obtain a solution of the positive photosensitive polyimide resin composition of the present invention.
  • a naphthoquinone-based positive-type photosensitizer an ester obtained by substituting 4 mol of 1,2-naph
  • Example 2 Using the prepared positive photosensitive resin composition varnish, a coating film having a thickness of 5 / m was obtained in accordance with Example 1. As a result, pattern Ichin formation was confirmed in the portion irradiated with the exposure amount 5 2 O m JZ cm 2 or more. The film thickness after development was about 4.7 m. The pattern resolution was formed up to 8 / m in line space without pattern peeling.
  • the obtained film was heated in a circulating drying oven at 170 ° C. for 60 minutes and at 350 ° C. for 30 minutes to obtain a polyimide pattern having a thickness of 3.6 m.
  • the polyimide powder obtained in Synthesis Example 1 was dissolved in Arptyrolactone to prepare a solution having a resin concentration of 20%. 0.20 g of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was mixed with 20 g of this solvent-soluble polyimide resin solution,
  • a coating film having a thickness of 5 / m was obtained in accordance with Example 1.
  • pattern formation was confirmed in the portion where the exposure amount was irradiated at 400 mJ / cm 2 or more.
  • the film thickness after development was about 4.8 m.
  • the pattern resolution was formed without line peeling up to 8 m in line space.
  • the obtained film was heated in a circulating drying oven at 170 ° C. for 60 minutes and at 350 ° C. for 30 minutes to obtain a polyimide pattern having a film thickness of 3.7 m.
  • the polyimide powder obtained in Synthesis Example 1 was dissolved in y-butyrolactone to obtain a solution having a resin concentration of 2096.
  • a solution having a resin concentration of 2096 was obtained by g of this solvent-soluble polyimide resin solution.
  • 0.20 g of bicyclo [2.2.2] octane-7,2-ene-1,2,3,5,6-tetracarboxylic dianhydride was mixed and completely mixed. was dissolved.
  • a naphthoquinone-based positive photosensitive agent (4 moles of 1,2-naphthoquinone-12-diazido-4-sulfonic acid was replaced by 1 mole of 2,3,4,4, -tetrahydroxybenzophenone).
  • 1.0 Og was added, and the mixture was stirred at room temperature for 1 hour, and filtered through a 1.0 m filter to obtain a solution of the positive photosensitive polyimide resin composition of the present invention.
  • a coating film having a thickness of 5 / m was obtained in accordance with Example 1. As a result, it was confirmed that a pattern was formed in a portion irradiated with an exposure amount of 450 mJ / cm 2 or more. The film thickness after development was about 4.9 m. The pattern resolution was up to 8 m in line / space without pattern peeling.
  • the obtained film was heated in a circulating drying oven at 170 ° C. for 60 minutes and at 350 ° C. for 30 minutes to obtain a polyimide pattern having a film thickness of 3.7 m.
  • the polyimide powder obtained in Synthesis Example 1 was dissolved in y -butyrolactone to prepare a solution having a resin concentration of 20%. Add 3,5,6-tri to 20 g of this solvent-soluble polyimide resin solution. Carboxy-2-norbornaneacetic acid dianhydride (0.20 g) was mixed and completely dissolved. To this solution, add a naphthoquinone-based positive-type photosensitizer (1 mol of 2,3,4,4'-tetrahydroxybenzophenone to 4 mol of 1,2-naphthoquinone-12-diazido-4-sulfonic acid by adding 1 mol of ⁇ "). 1.0 g of the resulting ester compound was added, and the mixture was stirred at room temperature for 1 hour, and then filtered through a 1.0 m filter to obtain a solution of the positive photosensitive polyimide resin composition of the present invention.
  • a coating film having a thickness of 5 m was obtained in accordance with Example 1.
  • pattern formation was confirmed in a portion irradiated with an exposure amount of 450 mJ / cm 2 or more.
  • the film thickness after development was about 4.9 m.
  • the pattern resolution was 8 m in line / space without pattern peeling.
  • the obtained film was heated in a circulating drying oven at 170 ° C. for 60 minutes and at 350 ° C. for 30 minutes to obtain a polyimide pattern having a film thickness of 3.7 m.
  • the polyimide powder obtained in Synthesis Example 1 was dissolved in y-butyrolactone to prepare a solution having a resin concentration of 20%. 0.20 g of pyromellitic dianhydride was mixed with 20 g of the solvent-soluble polyimide resin solution and completely dissolved. To this solution was added a naphthoquinone-based positive photosensitive agent (1,2-naphthoquinone-12-diazido-4-sulfonic acid per mole of 2,3,4,4'-tetrahydroxybenzophenone). Addition of 1.0 g of a mole-substituted ester compound), stirring for 1 hour at room temperature, and filtration with a 1.0 m filter to obtain a solution of the positive photosensitive polyimide resin composition of the present invention. Was.
  • a coating film having a thickness of 5 m was obtained in accordance with Example 1.
  • pattern formation was confirmed in a portion irradiated with an exposure amount of 320 mJ / cm 2 or more.
  • the film thickness after development was about 4.5 m.
  • the pattern resolution was up to 8 m in line / space without pattern peeling.
  • the obtained film was heated in a circulating drying oven at 170 ° C. for 60 minutes and at 350 ° C. for 30 minutes to obtain a polyimide pattern having a thickness of 3.5 m.
  • the polyimide powder obtained in Synthesis Example 1 was dissolved in y-butyrolactone to obtain a solution having a resin concentration of 20%. 1, 2, 3, 4, and 20 g of this solvent-soluble polyimide resin solution 0.25 g of 5,6-cyclohexanetetracarboxylic trianhydride was mixed and completely dissolved.
  • a coating film having a thickness of 5 Zm was obtained in accordance with Example 1.
  • pattern formation was confirmed in a portion irradiated with an exposure amount of 320 mJZcm 2 or more.
  • the film thickness after development was about 4.8 / m.
  • the pattern resolution was formed up to 8 m in line Z space without pattern peeling.
  • the obtained film was heated in a circulating drying oven at 170 ° C. for 60 minutes and at 350 ° C. for 30 minutes to obtain a polyimide pattern having a film thickness of 3.7 m.
  • the polyimide powder obtained in Synthesis Example 1 was dissolved in Arptyrolactone to prepare a solution having a resin concentration of 20%.
  • a naphthoquinone-based positive photosensitive agent (1,2 to naphthoquinone 1-2-diazide 1-4 per mole of 2,3,4,4'-tetrahydroxybenzophenone) was added.
  • -20 g of an ester compound substituted with 3 moles of sulfonic acid stirred at room temperature for 1 hour, and filtered through a 1.0 m filter to obtain a solution of the positive photosensitive polyimide resin composition of the present invention.
  • Example 2 a coating film having a thickness of 5 m was obtained in accordance with Example 1. As a result, it was confirmed that pattern formation was observed in a portion irradiated with an exposure of 640 mJ / cm 2 or more. The film thickness after development was approximately 4.9 m. The pattern resolution was formed up to 10 m in line / space without pattern peeling.
  • the obtained film was heated in a circulating drying oven at 170 ° C. for 60 minutes and at 350 ° C. for 30 minutes to obtain a polyimide pattern having a thickness of 3.8 / m.
  • the polyimide powder obtained in Synthetic Example 1 was dissolved in rapture-open ratatone to prepare a solution having a resin concentration of 20%.
  • a solution having a resin concentration of 20% To 20 g of this solvent-soluble polyimide resin solution, 2, 2 ', 4, 4, -Tetrahydroxybenzophenone (hereinafter abbreviated as THBP) 0.12 g was mixed and completely dissolved.
  • THBP 2, 2 ', 4, 4, -Tetrahydroxybenzophenone
  • a coating film having a thickness of 5 / m was obtained in accordance with Example 1. As a result, it was confirmed that pattern formation was observed in a portion irradiated with an exposure amount of 6300 mJZcm 2 or more. The film thickness after development was about 4.9 m. The pattern resolution was up to 10 m in line space without pattern peeling.
  • the obtained film was heated in a circulating drying oven at 170 ° C. for 60 minutes and at 350 ° C. for 30 minutes to obtain a 3.8-m-thick polyimide pattern.
  • the polyimide powder obtained in Synthesis Example 1 was dissolved in Arptyrolactone to prepare a solution having a resin concentration of 20%. 0.20 g of THB P was mixed with 20 g of the solvent-soluble polyimide resin solution, and completely dissolved. To this solution was added a naphthoquinone-based positive-type photosensitizer (4 moles of 1,2-naphthoquinone-12-diazido-4-sulfonic acid per mole of 2,3,4,4'-tetrahydroxybenzophenone). (Substituted ester compound) 1.0 g was added, and the mixture was stirred at room temperature for 1 hour, and then filtered through a 1.0 m filter to obtain a solution of the positive photosensitive polyimide resin composition of the present invention.
  • a naphthoquinone-based positive-type photosensitizer (4 moles of 1,2-naphthoquinone-12-diazido-4-sulfonic acid per mole
  • a coating film having a thickness of 5 / m was obtained in accordance with Example 1.
  • pattern formation was confirmed in a portion where the exposure amount was 680 mJ / cm 2 or more.
  • the thickness after development was about 4.8 / m.
  • the pattern resolution was 8 m in lines space without pattern peeling.
  • the obtained film was heated in a circulating drying oven at 170 ° C for 60 minutes and at 350 ° C for 30 minutes to obtain a polyimide pattern having a film thickness of 3.7 m.

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  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

L'invention concerne une composition de résine polyimide photosensible positive qui peut être développée au moyen d'une solution alcaline aqueuse et qui présente une excellente sensibilité et une excellente capacité de développement. Ladite composition est caractérisée en ce qu'elle comprend un polyimide soluble dans un solvant représenté par la formule générale (1), un acide carboxylique ou un dérivé d'acide carboxylique, ainsi qu'un composé o-quinonediazide photosensible. (Dans la formule (1), a, qui indique un nombre de motifs répétés, vaut un entier de 3 à 10000; 1 à 100 mol % de R1 constituent un groupe organique divalent présentant un ou plusieurs groupes dont au moins un est sélectionné dans le groupe consistant en des groupes hydroxyle phénolique, carboxyle, thiophénol, et sulfo, et 0 à 99 mol % de celui-ci constitue un groupe organique divalent ne contenant aucun des groupes hydroxyle phénolique, carboxyle, thiophénol et sulfo; et R2 est un groupe organique tétravalent.)
PCT/JP2001/002502 2000-03-30 2001-03-27 Composition de resine polyimide photosensible positive WO2001075525A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003029899A1 (fr) * 2001-09-26 2003-04-10 Nissan Chemical Industries, Ltd. Composition de resine polyimide photosensible positive
JP2009157351A (ja) * 2007-12-06 2009-07-16 Jsr Corp 液晶配向剤および液晶表示素子
CN111630454A (zh) * 2018-01-29 2020-09-04 富士胶片株式会社 感光性树脂组合物、树脂、固化膜、层叠体、固化膜的制造方法及半导体器件

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009229652A (ja) * 2008-03-21 2009-10-08 Jsr Corp 液晶配向剤および液晶表示素子
CN109912618B (zh) * 2019-03-20 2020-12-25 浙江福斯特新材料研究院有限公司 一种多官能度有机酸酐及低介电常数超支化聚酰亚胺薄膜

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5240125A (en) * 1975-09-22 1977-03-28 Ibm Positive photoresist composition
JPH03209478A (ja) * 1989-10-27 1991-09-12 Nissan Chem Ind Ltd ポジ型感光性ポリイミド樹脂組成物
WO1993009470A1 (fr) * 1991-10-29 1993-05-13 E.I. Du Pont De Nemours And Company Photoresists positifs contenant des agents augmentant la solubilite
JP2000338664A (ja) * 1999-05-27 2000-12-08 Hitachi Chemical Dupont Microsystems Ltd 感光性樹脂組成物、パターンの製造法及び電子部品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5240125A (en) * 1975-09-22 1977-03-28 Ibm Positive photoresist composition
JPH03209478A (ja) * 1989-10-27 1991-09-12 Nissan Chem Ind Ltd ポジ型感光性ポリイミド樹脂組成物
WO1993009470A1 (fr) * 1991-10-29 1993-05-13 E.I. Du Pont De Nemours And Company Photoresists positifs contenant des agents augmentant la solubilite
JP2000338664A (ja) * 1999-05-27 2000-12-08 Hitachi Chemical Dupont Microsystems Ltd 感光性樹脂組成物、パターンの製造法及び電子部品

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003029899A1 (fr) * 2001-09-26 2003-04-10 Nissan Chemical Industries, Ltd. Composition de resine polyimide photosensible positive
US7026080B2 (en) 2001-09-26 2006-04-11 Nissan Chemical Industries, Ltd. Positive photosensitive polyimide resin composition
JP2009157351A (ja) * 2007-12-06 2009-07-16 Jsr Corp 液晶配向剤および液晶表示素子
CN111630454A (zh) * 2018-01-29 2020-09-04 富士胶片株式会社 感光性树脂组合物、树脂、固化膜、层叠体、固化膜的制造方法及半导体器件

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