WO2009145153A1 - Composition de résine photosensible - Google Patents

Composition de résine photosensible Download PDF

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Publication number
WO2009145153A1
WO2009145153A1 PCT/JP2009/059543 JP2009059543W WO2009145153A1 WO 2009145153 A1 WO2009145153 A1 WO 2009145153A1 JP 2009059543 W JP2009059543 W JP 2009059543W WO 2009145153 A1 WO2009145153 A1 WO 2009145153A1
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group
general formula
photosensitive resin
resin composition
compound
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PCT/JP2009/059543
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English (en)
Japanese (ja)
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智史 渋井
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旭化成イーマテリアルズ株式会社
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Priority to KR1020107025831A priority Critical patent/KR101288640B1/ko
Priority to JP2010514468A priority patent/JP5260646B2/ja
Priority to CN200980118983.6A priority patent/CN102047178B/zh
Publication of WO2009145153A1 publication Critical patent/WO2009145153A1/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
    • C08G73/22—Polybenzoxazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • 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
    • G03F7/004—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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a positive photosensitive resin composition that is a precursor of a heat resistant resin used as a surface protective film or an interlayer insulating film of a semiconductor device, and a heat-resistant curing using the positive photosensitive resin composition.
  • the present invention relates to a method for manufacturing a relief pattern and a semiconductor device having the cured relief pattern.
  • Polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like are widely used for surface protection films and interlayer insulating films of semiconductor devices.
  • This polyimide resin is currently often provided in the form of a photosensitive polyimide precursor composition.
  • the precursor composition is applied to a substrate such as a silicon wafer, patterned with actinic rays, developed, and subjected to a thermal imidization treatment to become a part of the semiconductor device.
  • a surface protective film, an interlayer insulating film, or the like can be easily formed.
  • the manufacturing process of a semiconductor device using a photosensitive polyimide precursor composition is a manufacturing process using a conventional non-photosensitive polyimide precursor composition that needs to be patterned by a lithography method after forming a surface protective film or the like. Compared with the process, it has the feature that the process can be greatly shortened.
  • this photosensitive polyimide precursor composition needs to use an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the developing process. Countermeasures are being sought.
  • various proposals have been made on heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution, as with photoresists.
  • a PBO precursor composition in which an alkaline aqueous solution-soluble hydroxypolyamide, such as polybenzoxazole (hereinafter, also referred to as “PBO”) precursor, which becomes a heat-resistant resin after curing, is mixed with a photoacid generator such as a naphthoquinonediazide compound.
  • Patent Document 1 The method of using a product as a positive photosensitive resin composition is disclosed in the following Patent Document 1 and Patent Document 2, and has attracted attention in recent years.
  • the development mechanism of this positive photosensitive resin composition is that the naphthoquinone diazide compound and PBO precursor in the unexposed area have a low dissolution rate in an alkaline aqueous solution, whereas the photosensitive diazoquinone compound is converted to indenecarboxylic acid by exposure. This is based on the fact that the dissolution rate of the exposed portion in the alkaline aqueous solution is increased by chemical change to the compound.
  • a relief pattern composed of the unexposed portion can be created.
  • the above-mentioned PBO precursor composition can form a positive relief pattern by exposure and development with an alkaline aqueous solution. Further, heat generates an oxazole ring, and the cured PBO film has the same thermosetting film characteristics as a polyimide film. Therefore, the PBO precursor composition is a promising organic solvent development type polyimide precursor composition. Has attracted attention as an alternative material.
  • the PBO precursor composition has a lower sensitivity than the photosensitive polyimide precursor composition due to the problem associated with the absorption wavelength of the photosensitive agent, and therefore there is a demand for a more sensitive composition.
  • these cured films are used for surface protective films and the like, they require good thermal and mechanical properties and good adhesion to a substrate such as Si as a base.
  • Patent Document 3 discloses a heat resistant resin composition containing a compound having a triazine skeleton and / or a vinyl group and a PBO precursor resin as essential components.
  • a curable organic compound having two or more unsaturated groups and / or epoxy groups together with at least one imide group in the molecule, and a resin binder having a carbonyl group bonded to a hetero atom in the main chain are bisallylnaphthal.
  • Patent Document 4 proposes a heat resistant resin composition containing a compound having a triazine skeleton and / or a vinyl group and a PBO precursor resin as essential components.
  • a curable organic compound having two or more unsaturated groups and / or epoxy groups together with at least one imide group in the molecule, and a resin binder having a carbonyl group bonded to a hetero atom in the main chain are bisallylnaphthal.
  • Patent Document 4 A method for improving sensitivity and thermomechanical characteristics by using a diimide compound or a
  • the problem to be solved by the present invention is a positive photosensitive resin composition having a positive lithography performance with excellent pattern shape after curing of the resin, high sensitivity and high adhesion, and curing using the composition A relief pattern manufacturing method and a semiconductor device having the cured relief pattern are provided.
  • the present inventor has found that a photosensitive resin composition that solves the above problems can be obtained by combining a specific compound with a heat-resistant alkaline aqueous solution-soluble polymer having a specific structure, and has led to the present invention. It was.
  • aqueous alkali-soluble polymer having a hydroxyamide structure represented by the formula (B) 1 to 50 parts by weight of a photoacid generator, (C) the following general formula (2): ⁇ Wherein, D 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, having at least one alkenyl group, and a functional group selected from the group consisting of organic radicals capable of crosslinking, M 1 is, -CH 2 represents a group selected from the group consisting of —O— and —S—, Z 1 is a divalent organic group, n 1 is an integer of 0 to 4, and D 1 is When there are a plurality, D 1 may be the same or different.
  • a photosensitive resin composition comprising 1 to 40 parts by mass of a compound represented by the formula:
  • the compound represented by the general formula (2) is represented by the following general formula (3):
  • An aqueous alkaline solution-soluble polymer having a hydroxyamide structure represented by the general formula (1) is represented by the following general formula (4): ⁇ In the formula, X 3 represents a single bond and the following general formula (5): And L 1 , L 2 , and L 3 each independently represent a hydrogen atom or a methyl group, and L 4 represents a hydrogen atom, a methyl group, or a methyl group. Represents a group or a hydroxyl group.
  • [6] (1) A step of forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [5] on a substrate, and (2) exposure with actinic radiation through a mask. Or a step of directly irradiating a light beam, an electron beam or an ion beam, (3) a step of eluting or removing the exposed portion or the irradiated portion, and (4) a step of heat-treating the obtained relief pattern. And a method for producing a cured relief pattern.
  • a positive photosensitive resin composition having a positive lithography performance with excellent pattern shape at the time of curing of the resin, high sensitivity and high adhesion, and curing using the positive photosensitive resin composition
  • a method for producing a relief pattern and a semiconductor device having the cured relief pattern are provided.
  • FIG. 1 shows a cross section of a 50 ⁇ m line of a post-cure relief pattern, observed using an Hitachi S-2400 type Hitachi scanning electron microscope.
  • X 1 is a tetravalent organic group having at least 2 carbon atoms
  • Y 1 is a divalent organic group having at least 2 carbon atoms
  • m 1 is 1 It is an integer of ⁇ 1000.
  • M 1 is an integer of 1 to 1000
  • m 2 is an integer of 1 to 500
  • X 1 and The arrangement order of m 1 units including Y 1 and m 2 units including X 2 and Y 2 is not limited. ⁇
  • X 3 represents a single bond and at least one structure selected from the group consisting of structures represented by the following general formula (5), and L 1 , L 2 , and L 3 are each independently , Represents a hydrogen atom or a methyl group, and L 4 represents a hydrogen atom, a methyl group or a hydroxyl group.
  • the tricyclodecane moiety is preferably at least one selected from the structural group represented by the following general formula (8).
  • the dihydroxydiamide unit has a structure obtained by polycondensation of a dicarboxylic acid having a Y 1 (COOH) 2 structure and a bisaminophenol having a X 1 (NH 2 ) 2 (OH) 2 structure.
  • the two amino groups and hydroxy groups of the bisaminophenol are in ortho positions with each other, and the hydroxypolyamide is closed by heating to about 250 to 400 ° C. to form polybenz, which is a heat-resistant resin. Change to oxazole.
  • X 1 is preferably a tetravalent organic group having 2 or more and 30 or less carbon atoms.
  • Y 1 is preferably a divalent organic group having 2 or more and 30 or less carbon atoms.
  • m 1 is in the range of 1 to 1000, preferably in the range of 2 to 100, and more preferably in the range of 3 to 60.
  • the hydroxy polyamide may have m 2 diamide units of the general formula (7) as necessary.
  • the diamide unit has a structure obtained by polycondensing a diamine having a structure of X 2 (NH 2 ) 2 and a dicarboxylic acid having a structure of Y 2 (COOH) 2 .
  • m 2 is preferably in the range of 1 to 500, and more preferably in the range of 1 to 10.
  • the higher the ratio of the dihydroxydiamide unit in the hydroxypolyamide the better the solubility in an alkaline aqueous solution used as a developer. Therefore, m 1 / (m 1 + m
  • the value of 2 ) is preferably 0.5 or more, more preferably 0.7 or more, and most preferably 0.8 or more.
  • Examples of the bisaminophenol having the structure of X 1 (NH 2 ) 2 (OH) 2 include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 4,4 ′.
  • X 1 is preferably an aromatic group selected from the following.
  • a compound having a structure of X 1 (NH 2 ) 2 (OH) 2 two pairs of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other (hereinafter referred to as “PBO precursor structure in the molecule”).
  • PBO precursor structure in the molecule two pairs of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other.
  • PBO precursor structure in the molecule two pairs of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other
  • PBO precursor structure in the molecule two pairs of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other
  • PBO precursor structure in the molecule two pairs of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other.
  • PBO precursor structure in the molecule two pairs of diamines having an amide bond and a phenolic
  • the dicarboxylic acid dichloride having the structure of Y 3 (COCl) 2 is reacted with two molecules of nitroaminophenol for reduction, and the following general formula: ⁇
  • Y 3 is a divalent organic group having at least 2 carbon atoms, and is an at least one organic group selected from the group consisting of preferable organic groups represented by Y 1 described later.
  • Y 1 is an organic group selected from the group consisting of preferable organic groups represented by
  • Examples of the diamine having the structure of X 2 (NH 2 ) 2 include aromatic diamine and silicon diamine.
  • aromatic diamine examples include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino.
  • Diphenyl ether 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2'-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy)
  • silicon diamine can be selected as part or all of the diamine having the structure of X 2 (NH 2 ) 2 in order to enhance the adhesion to the substrate.
  • Examples of the dicarboxylic acid having Y 1 (COOH) 2 and Y 2 (COOH) 2 structures include dicarboxylic acids in which Y 1 and Y 2 are each an aromatic group or an aliphatic group selected from the following. ⁇ Wherein A 1 is selected from the group consisting of —CH 2 —, —O—, —S—, —SO 2 —, —CO—, —NHCO—, —C (CF 3 ) 2 —, and a single bond.
  • L 7 represents a selected divalent group, each L 7 independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an unsaturated group, and a halogen atom, and k is an integer of 0 to 4 Indicates. ⁇
  • L 8 , L 9 and L 10 each independently represent a hydrogen atom or a methyl group
  • L 11 represents a hydrogen atom, a methyl group or a hydroxyl group.
  • L 8 , L 9 , L 10 and L 11 are most preferably hydrogen atoms in that the mechanical properties of the resulting resin film are good.
  • Representative compounds as the dicarboxylic acid having a tricyclodecane skeleton, and a bis (carboxy) tricyclo [5,2,1,0 2,6] decane can be synthesized by the synthesis method according to Production Example A of JP-A No. 58-110538, the synthesis method according to Example 1 of JP-T-2002-504891, or the synthesis by Synthesis Example 2 of JP-A No. 09-15846. Can be obtained according to the method. However, in this method, since a heavy metal is used as an oxidizing agent, the following manufacturing method is more preferable in that no heavy metal is used. That is, tricyclo (5,2,1,0) decanedimethanol (catalog No.
  • Catalyst No. T0850 2,2,6,6-tetramethylpiperidine-1-oxyl
  • dicarboxylic acid compounds having the structure of the above structural group (11) are methylcyclopentadiene dimer (catalog No. M0920 manufactured by Tokyo Chemical Industry), 1-methyldicyclopentadiene (Tokyo Chemical Industry). Catalog No. M0910) and 1-hydroxydicyclopentadiene (Tokyo Chemical Industry catalog No. H0684) as raw materials. Org. Chem. , 45, 3527 (1980), hydrogen bromide or hydrogen chloride is added to the unsaturated bond site of the raw material. Am. Chem. Soc.
  • a derivative of 5-aminoisophthalic acid may be used for a part or all of the dicarboxylic acid having the Y 1 (COOH) 2 and Y 2 (COOH) 2 structures.
  • Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivative include 5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3, 6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, -Cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthal
  • a dicarboxylic acid having a Y 1 (COOH) 2 or Y 2 (COOH) 2 structure a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol or a monoamine can also be used.
  • monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol and the like
  • monoamine include butylamine and aniline.
  • said tetracarboxylic dianhydride the compound shown by following Chemical formula is mentioned.
  • a 2 is selected from the group consisting of —CH 2 —, —O—, —S—, —SO 2 —, —CO—, —NHCO—, and —C (CF 3 ) 2 —.
  • a divalent group is meant. ⁇ .
  • tetracarboxylic dianhydride can be reacted with bisaminophenol or diamine, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.
  • trimellitic acid chloride is reacted with bisaminophenol to produce tetracarboxylic dianhydride, and ring-opened in the same manner as the above tetracarboxylic dianhydride and used as dicarboxylic acid You can also.
  • the tetracarboxylic dianhydride obtained here has the following chemical formula: ⁇ In the formula, X 5 represents a divalent organic group represented by X 1 (OH) 2 (NH—) 2 , and X 1 has the same meaning as in the general formula (1). ⁇ Is given.
  • diacid chloride and thionyl chloride are used to form diacid chloride, and then bisaminophenol (diamine) is used.
  • bisaminophenol (diamine) is used as a method of polycondensation of dicarboxylic acid and bisaminophenol (diamine) with dicyclohexylcarbodiimide.
  • hydroxybenztriazole can be allowed to act simultaneously.
  • the end group is preferably sealed with an organic group (hereinafter referred to as “sealing group”).
  • an organic group hereinafter referred to as “sealing group”.
  • a compound having an amino group or a hydroxyl group is used as the sealing group. Is preferred.
  • Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, hydroxyethyl acrylate and the like.
  • the sealing group has an acid anhydride, carboxylic acid, acid chloride, isocyanate group, etc. It is preferable to use a compound.
  • Examples of such compounds include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methyl cyclohexane dicarboxylic anhydride Products, cyclohexene dicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, tosylic chloride and the like.
  • the base polymer of the photosensitive resin composition may be used only with the above-mentioned hydroxypolyamide, but it can be obtained by cyclocondensing tetracarboxylic dianhydride and an aromatic diamine having a phenolic hydroxyl group.
  • a polyimide structure having a phenolic hydroxyl group can be copolymerized as necessary.
  • the tetracarboxylic dianhydride used when synthesizing a polyimide containing a phenolic hydroxyl group includes aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms and 6 to 34 carbon atoms from the viewpoint of solvent solubility.
  • aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms and 6 to 34 carbon atoms from the viewpoint of solvent solubility.
  • Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) is preferred
  • 5- (2,5-dioxotetrahydro-3-furyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride and bis (3,4-dicarboxyphenyl) ether dianhydride are mercury lamps. From the viewpoint of transparency to i-line, solubility in an aqueous alkali solution, and photosensitivity.
  • 2,2-bis (3-amino-4-hydroxyphenyl) propane is more preferable from the viewpoint of high photosensitivity of the resin composition.
  • the dehydration condensation reaction when synthesizing an imide unit having a phenolic hydroxyl group is carried out by, for example, following the method described in International Publication No. 01/034679 pamphlet with the above tetracarboxylic dianhydride and the above phenolic diamine. It can be carried out by heating to 30 ° C. to 220 ° C., preferably 170 ° C. to 200 ° C. in the presence of a base catalyst.
  • the acid catalyst it is possible to use an inorganic acid such as sulfuric acid or an organic acid such as p-toluenesulfonic acid that is usually used in the production of polyimide. ⁇ -valerolactone and pyridine may be used.
  • Examples of the base catalyst include pyridine, triethylamine, dimethylaminopyridine, 1,8-diazabicyclo (5,4,0) undecene-7, 1,3,5,7-tetraazatricyclo (3,3,1,1, 3,7) Decane, triethylenediamine or the like may be used.
  • the temperature of the reaction solution is maintained at a temperature higher than the temperature at which the imidization reaction occurs, and the water generated by the dehydration reaction is removed from the reaction system using an azeotropic solvent with water such as toluene.
  • the imidation dehydration condensation reaction may be completed.
  • a reaction solvent for performing the dehydration condensation reaction it is preferable to use a polar organic solvent for dissolving an alkali-soluble resin soluble in an aqueous alkali solution in addition to toluene, which is a solvent for azeotropically distilling water.
  • polar solvents ⁇ -butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, sulfolane and the like are used.
  • the solubility and physical properties in an alkaline aqueous solution may be controlled by copolymerizing the above-mentioned non-phenolic diamine in addition to the above-mentioned phenolic diamine as necessary.
  • a block copolycondensate using a sequential reaction may be used, or a raw material having three or more components is charged.
  • the raw materials may be charged into the reaction system at the same time to form a random copolycondensate.
  • the base polymer of the positive photosensitive resin composition of the present invention may copolymerize the above-mentioned hydroxypolyamide and polyimide unit, but the copolymerization ratio at the time of copolymerization is arbitrarily selected, but polybenzoxazole
  • the ratio of the precursor unit: polyimide unit is preferably in the range of 10:90 to 100: 0 from the viewpoint of photosensitivity.
  • the terminal of the aqueous alkali solution-soluble polymer is preferably at least one terminal group selected from the group consisting of terminal groups represented by the following general formula (9).
  • L 5 represents a group selected from the group consisting of —CH 2 —, —O—, and —S—
  • L 6 represents a hydrogen atom or an alkyl group.
  • Examples of methods for modifying the terminal include maleic anhydride, succinic anhydride, cinnamic anhydride, 5-norbornene anhydride, 4-ethynylphthalic anhydride, phenylethynylphthalic anhydride, 3,6- Epoxy-1,2,3,6-tetrahydrophthalic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, cyclohexane-1,2-dicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic An appropriate amount of acid anhydride, 4-aminostyrene, 4-ethynylaniline, 3-ethynylaniline, 4-aminophenol, 3-aminophenol, 2-aminophenol or the like may be added during the synthesis of the alkali-soluble resin. Moreover, you may leave the dicarboxylic acid used by this invention as
  • the polystyrene-equivalent weight average molecular weight of the aqueous alkali-soluble polymer by gel permeation chromatography (hereinafter also referred to as “GPC”) is preferably 3,000 to 50,000, preferably 6,000 to 30,000. Is more preferable.
  • the weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the cured relief pattern. Moreover, from a viewpoint of resolution, 50,000 or less is preferable.
  • GPC gel permeation chromatography
  • THF tetrahydrofuran
  • NMP N-methyl-2-pyrrolidone
  • the molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene.
  • the standard monodisperse polystyrene is recommended to be selected from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko.
  • Photoacid generator As the photoacid generator, a naphthoquinonediazide compound, an onium salt, a halogen-containing compound, and the like can be used. From the viewpoint of solvent solubility and storage stability, a naphthoquinonediazide structure is used. (Hereinafter, also referred to as “naphthoquinone diazide compound”) is preferable.
  • Examples of the onium salt include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, and diazonium salts, and onium salts selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, and trialkylsulfonium salts are preferable.
  • Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferable.
  • the naphthoquinone diazide compound is a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure.
  • the naphthoquinonediazide structure includes 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinonediazide-5-sulfonic acid ester of the polyhydroxy compound.
  • At least one compound selected from the group consisting of hereinafter also referred to as “NQD compound”.
  • the NQD compound is obtained by subjecting a naphthoquinone diazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride and subjecting the resulting naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound according to a conventional method.
  • a predetermined amount of polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone, or tetrahydrofuran, and a basic such as triethylamine can be obtained by reacting in the presence of a catalyst for esterification and washing the resulting product with water and drying.
  • NQD compounds of polyhydroxy compounds represented by the following general formula (10) ⁇ Wherein n 2 to n 5 each independently represents 1 or 2, and R 1 to R 10 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, And at least one monovalent group selected from the group consisting of an acyl group, and Y 4 to Y 6 each independently represents a single bond, —O—, —S—, —SO—, —SO 2 —.
  • R 11 and R 12 each independently represent at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an allyl group, and a substituted allyl group.
  • R 13 to R 16 each represent a hydrogen atom or an alkyl group, which may be the same or different, and m 3 represents an integer of 1 to 5.
  • R 17 to R 20 each represent a hydrogen atom or an alkyl group, and may be the same or different. ⁇ .
  • NQD compounds of polyhydroxy compounds described in [Chemical Formula 18] to [Chemical Formula 32] of JP-A No. 2001-109149 are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.
  • NQD compounds of polyhydroxy compounds represented by the following general formula (11) NQD compounds of polyhydroxy compounds represented by the following general formula (11) ⁇
  • X 6 represents at least one tetravalent group selected from organic groups represented by the following chemical formula;
  • R 21 to R 24 each independently represents a monovalent organic group;
  • m 4 to m 7 each independently represents an integer of 0 to 3
  • n 6 to n 9 each independently represents an integer of 0 to 2.
  • NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.
  • m 8 represents an integer of 3 to 8
  • m 8 ⁇ j L 14s each independently represents a monovalent organic group having one or more carbon atoms
  • j represents 1 to 5 of an integer
  • m 8 pieces of L 12 and m 8 pieces of L 13 each independently represent a monovalent group selected from the group consisting of a hydrogen atom or a monovalent organic group.
  • NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.
  • p is an integer of 0 to 9.
  • NQD compounds of polyhydroxy compounds represented by the following general formula (13) wherein M 2 represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and A 3 represents at least one divalent group selected from the groups represented by the following chemical formulas: Indicates. ⁇
  • NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.
  • L 15 represents a group selected from the group consisting of —CH 2 —, —O—, and —S—
  • L 16 represents a hydrogen atom or an alkyl group.
  • L 17 represents a group selected from the group consisting of —CH 2 —, —O—, and —S—
  • L 18 represents a hydrogen atom or an alkyl group.
  • R 25 to R 27 represent a monovalent organic group represented by the following general formula, and may be the same or different, and m 9 to m 11 are each independently , An integer from 0 to 2. ⁇
  • each R 28 independently represents at least one monovalent organic group selected from a hydrogen atom, an alkyl group, and a cycloalkyl group
  • m 12 each independently represents an integer of 0 to 2 It is. ⁇ .
  • NQD compounds of polyhydroxy compounds described in [Chemical Formula 17] to [Chemical Formula 22] of JP-A No. 2004-109849 are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.
  • NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.
  • R 30 represents a monovalent organic group represented by the following general formula, which may be the same or different, and m 13 to m 15 are each independently 0 to 2 R 31 to R 33 represent one selected from a hydrogen atom, an alkyl group, or a cycloalkyl group. ⁇
  • each R 34 independently represents at least one monovalent organic group selected from a hydrogen atom, an alkyl group and a cycloalkyl group; and m 16 represents an integer of 0 to 2. ⁇ .
  • NQD compounds of polyhydroxy compounds described in [Chemical 15] and [Chemical 16] of JP-A-2005-008626 are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.
  • the naphthoquinone diazide sulfonyl group in the NQD compound either a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group is preferably used.
  • the 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • the 5-naphthoquinonediazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
  • a naphthoquinone diazide sulfonyl ester compound can be obtained by using a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination.
  • the blending amount of the naphthoquinone diazide compound with respect to the alkaline aqueous solution-soluble polymer is 1 to 50 parts by mass, preferably 5 to 30 parts by mass with respect to 100 parts by mass of the alkaline aqueous solution-soluble polymer. If the blending amount of the photosensitive diazoquinone compound is 1 part by mass or more, the patterning property of the resin is good. (Scum) is low.
  • (C) As a compound represented by following General formula (2), a bisallyl nadiimide compound, a bisnorbornene imide compound, etc. are mentioned. From the viewpoint of sensitivity, a compound consisting of the following general formula (3) is more preferable. Specific examples of these compounds include general formula (3) (manufactured by Maruzen Petrochemical Co., Ltd .: trade names BANI-M, BANI-X, BANI-H, BANI-D). Of the compounds represented by the general formula (3), BANI-X is most preferable from the viewpoint of the curing shape and sensitivity.
  • D 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, having at least one alkenyl group, and a functional group selected from the group consisting of organic radicals capable of crosslinking
  • M 1 is
  • -CH 2 represents a group selected from the group consisting of —O— and —S—
  • Z 1 is a divalent organic group
  • n 1 is an integer of 0 to 4
  • D 1 is When there are a plurality, D 1 may be the same or different.
  • a compound may be used individually or may be used in mixture of 2 or more.
  • the compounding amount of the compound (C) is 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and still more preferably 4 to 20 parts by mass with respect to 100 parts by mass of the (A) alkaline aqueous solution-soluble polymer.
  • the compounding amount of the compound is 1 part by mass or more, the cured shape at the time of curing is improved.
  • the compounding amount is 40 parts by mass or less, the tensile elongation of the film after curing is good and the adhesiveness and litho performance are good. Show.
  • (D) Organic solvent In the present invention, these components are preferably dissolved in a solvent to form a varnish and used as a solution of the photosensitive resin composition.
  • solvents include N-methyl-2-pyrrolidone, ⁇ -butyrolactone (hereinafter also referred to as “GBL”), cyclopentanone, cyclohexanone, isophorone, N, N-dimethylacetamide (hereinafter also referred to as “DMAc”).
  • DMDG diethylene glycol dimethyl ether
  • DMDG diethylene glycol diethyl ether
  • diethylene glycol dibutyl ether propylene glycol monomethyl
  • non-amide solvents are preferred because they have little influence on the photoresist.
  • Specific preferred examples include ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofurfuryl alcohol and the like.
  • These organic solvents may be used alone or in combination of two or more.
  • the blending amount in the case of blending the solvent is 100 to 2000 parts by mass with respect to 100 parts by mass of the (A) alkaline aqueous solution-soluble polymer, and the viscosity can be controlled by changing the addition amount of the organic solvent. .
  • the addition amount of the solvent within the above range can be set to a viscosity suitable for the coating apparatus and the coating thickness. It is preferable because the manufacturing can be facilitated.
  • the photosensitive resin composition is known as an additive for a hydroxyl group-containing compound (excluding a phenol compound that appears later) and a positive photosensitive resin composition, if necessary. It is also possible to add a phenol compound, a dye, a surfactant, a stabilizer, at least one kind of an adhesion assistant for enhancing the adhesion to the silicon wafer. More specifically, the hydroxyl group-containing compound preferably has 4 to 14 carbon atoms. Addition of a hydroxyl group-containing compound to the photosensitive resin composition of the present invention is preferable from the viewpoints of sensitivity and resolution.
  • hydroxyl group-containing compound examples include cyclopropylcarbinol, 2-cyclohexen-1-ol, cyclohexanemethanol, 4-methyl-1-cyclohexanemethanol, 3,4-dimethylcyclohexanol, and 4-ethylcyclohexanol.
  • tanol 3-ethyl-2-methyl-3-pentanol
  • glycerol- ⁇ , ⁇ '-diallyl ether are particularly preferred.
  • These hydroxyl group-containing compounds may be used alone or in combination of two or more.
  • the blending amount in the case of blending the above hydroxyl group-containing compound is preferably 0 to 70 parts by weight, more preferably 0.1 to 50 parts by weight, and more preferably 1 to 40 parts by weight with respect to 100 parts by weight of the aqueous alkali solution-soluble polymer. Part is more preferable, and 5 to 25 is particularly preferable.
  • the compounding amount of the hydroxyl group-containing compound is 0.01 parts by mass or more, the development residue in the exposed part is reduced, while when it is 70 parts by mass or less, the tensile elongation of the film after curing is good.
  • phenol compound examples include ballast agents used in the photosensitive diazoquinone compound, linear phenol compounds such as paracumylphenol, bisphenols, resorcinols, MtrisPC and MtetraPC (manufactured by Honshu Chemical Industry Co., Ltd .: trade name), TrisP -Non-linear phenol compounds such as HAP, TrisP-PHBA, TrisP-PA (Honshu Chemical Industry Co., Ltd .: trade name), compounds in which 2 to 5 hydrogen atoms of the phenyl group of diphenylmethane are substituted with hydroxyl groups, 2, 2 -A compound in which 1 to 5 hydrogen atoms of the phenyl group of diphenylpropane are substituted with a hydroxyl group.
  • linear phenol compounds such as paracumylphenol, bisphenols, resorcinols, MtrisPC and MtetraPC (manufactured by Honshu Chemical Industry Co., Ltd .: trade name
  • a ballast agent means the phenol compound currently used as a raw material for the above-mentioned photosensitive diazoquinone compound which is a phenol compound in which a part of the phenolic hydrogen atom is converted to naphthoquinonediazide sulfonic acid ester.
  • the blending amount when the phenol compound is blended is preferably 0 to 50 parts by weight, and preferably 1 to 30 parts by weight with respect to 100 parts by weight of the aqueous alkali-soluble polymer. When the addition amount is within 50 parts by mass, the heat resistance of the film after thermosetting is good.
  • the dye examples include methyl violet, crystal violet, and malachite green.
  • the blending amount when the dye is blended is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the aqueous alkali-soluble polymer. When the addition amount is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.
  • the surfactant examples include polypropylene glycol, polyglycols such as polyoxyethylene lauryl ether, and nonionic surfactants made of derivatives thereof. Further, fluorine-based surfactants such as Fluorard (manufactured by Sumitomo 3M: trade name), MegaFac (manufactured by Dainippon Ink & Chemicals, Inc .: trade name), or Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.) can be used.
  • Fluorard manufactured by Sumitomo 3M: trade name
  • MegaFac manufactured by Dainippon Ink & Chemicals, Inc .
  • Lumiflon trade name, manufactured by Asahi Glass Co., Ltd.
  • organosiloxane surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), DBE (manufactured by Chisso Corporation: trade name), granol (manufactured by Kyoeisha Chemical Co., Ltd .: trade name), and the like can be mentioned.
  • the surfactant By adding the surfactant, it is possible to make it less likely to cause repellency of the coating film at the wafer edge during coating.
  • the blending amount is preferably 0 to 10 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the aqueous alkali-soluble polymer.
  • the adhesion assistant include various silane coupling agents such as alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy polymer, and epoxy silane.
  • silane coupling agent examples include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name: Silaace S810), 3-mercaptopropyltriethoxysilane.
  • the blending amount in the case of blending the above adhesion assistant is preferably 0 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 8 parts by weight with respect to 100 parts by weight of the aqueous alkali soluble polymer. Part is more preferable, and 1 to 6 parts by mass is particularly preferable.
  • the compounding amount of the silicon-based coupling agent is 0.01 parts by mass or more, there is no development residue in the exposed part, and the adhesiveness with the silicon substrate is good. Good stability. Further, the following compounds may be used in combination.
  • the compounding amount of the above compound with respect to the aqueous alkali-soluble polymer is preferably 0 to 10 parts by weight, more preferably 0.1 to 6 parts by weight, and more preferably 1 to 4 parts by weight with respect to 100 parts by weight of the aqueous alkali-soluble polymer. Particularly preferred. When it is 0.1 part by mass or more, there is no development residue in the exposed part and the adhesiveness to the silicon substrate is good, while when it is 10 parts by mass or less, the temporal stability in the adhesiveness is good.
  • the photosensitive resin composition can contain a crosslinking agent.
  • a crosslinking agent a compound that causes a crosslinking reaction with the alkali-soluble resin by heat is used.
  • the temperature for causing the crosslinking reaction is preferably 150 to 350 ° C.
  • the crosslinking reaction occurs during the heat treatment after pattern formation by development. For the purpose of improving chemical resistance and physical properties, it is preferable to add the following compounds.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol AD type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, glycidylamine type epoxy resin, polysulfide type epoxy resin, MX270 (Sanwa) Chemical Co., Ltd.), MX280 (manufactured by Sanwa Chemical Co., Ltd.), dimethylol urea, trimethylol melamine, hexamethylol melamine, dimethylol ethylene urea, dimethylol propylene urea, 1,4-bis (methoxyphenoxy) benzene, trimethoxymethyl melamine , Hexamethoxymethyl melamine, diethylene glycol diallyl ether, diallyl chlorendate, diallyl hexahydrophthalate, and the like.
  • a compound having an alkoxymethyl group is used as a cyclized resin as a base polymer used in the photosensitive resin composition. This is most preferable in terms of the effect of reducing deformation during the process.
  • the blending amount is 0.5 to 50 with respect to 100 parts by mass of the aqueous alkali-soluble polymer from the viewpoint of deformation of the pattern in the heat treatment of development and the allowable range of residues generated during development. Mass parts are preferred, and 5 to 20 parts by mass are more preferred.
  • a step of forming a photosensitive resin layer made of a photosensitive resin composition on a substrate (first step).
  • the photosensitive resin composition solution is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spinner or a coater such as a die coater or a roll coater. This is dried by applying heat at 50 to 140 ° C., preferably 100 to 140 ° C., using an oven or a hot plate to remove the solvent (hereinafter also referred to as “soft baking” or “pre-baking”).
  • a step of exposing with actinic radiation through a mask or directly irradiating a light beam, an electron beam or an ion beam (second step). Subsequently, the photosensitive resin layer is exposed to actinic radiation through a mask using a contact aligner or a stepper, or directly irradiated with a light beam, an electron beam or an ion beam.
  • actinic ray g-line, h-line, i-line, or KrF laser can also be used.
  • a step of eluting or removing the exposed portion or irradiated portion (third step).
  • the exposed portion or the irradiated portion is dissolved and removed with a developer, and then rinsed with a rinse solution to obtain a desired relief pattern.
  • a developing method methods such as spray, paddle, dip, and ultrasonic can be used.
  • the rinsing liquid distilled water, deionized water or the like can be used.
  • the developer used for developing the film formed of the photosensitive resin composition dissolves and removes the alkali-soluble polymer, and needs to be an alkaline aqueous solution in which an alkali compound is dissolved.
  • the alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.
  • Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia and the like.
  • organic alkali compound examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine.
  • -N-propylamine isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine and the like.
  • a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol
  • a surfactant such as methanol, ethanol, propanol, or ethylene glycol
  • a storage stabilizer such as a surfactant, a storage stabilizer, a resin dissolution inhibitor, or the like
  • Step of heating the obtained relief pattern (fourth step)
  • the obtained relief pattern is heat-treated (hereinafter, this process is referred to as “cure”) to form a heat-resistant cured relief pattern made of a resin having a polybenzoxazole structure.
  • the heating device an oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, a pressure oven, or the like can be used.
  • a heating method heating by hot air, infrared rays, electromagnetic induction, or the like is recommended.
  • the temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C.
  • the heating time is preferably 15 minutes to 8 hours, more preferably 1 hour to 4 hours.
  • a semiconductor device prepared using the photosensitive resin composition of the present invention has a cured relief pattern made of the photosensitive resin composition, a surface protective film, an interlayer insulating film, an insulating film for rewiring, and a protective film for flip chip devices. Or it can manufacture by combining with the manufacturing method of a well-known semiconductor device as a protective film of the apparatus which has a bump structure.
  • the photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, and liquid crystal alignment films.
  • reaction solution After the reaction, the reaction solution is cooled to 12 ° C., an aqueous solution in which 75 g of sodium sulfite is dissolved in 300 mL of ion-exchanged water is added dropwise to the reaction solution, the excess sodium chlorite is deactivated, and then with 500 mL of ethyl acetate. Washed. Thereafter, 115 mL of 10% hydrochloric acid was added dropwise to adjust the pH of the reaction solution to 3 to 4, and the precipitate was collected by decantation. This precipitate was dissolved in 200 mL of tetrahydrofuran.
  • the aqueous layer was extracted twice with 500 mL of ethyl acetate and then washed with brine, and the precipitate was dissolved in a tetrahydrofuran solution.
  • the above tetrahydrofuran solution was mixed and dried over anhydrous sodium sulfate.
  • the solution concentrated in an evaporator, followed by drying, to obtain a bis (carboxy) tricyclo [5,2,1,0 2,6] white crystalline product with decane 58.4 g (71.1% yield).
  • the weight average molecular weight (Mw) by GPC is a single sharp curve of 14000 in terms of polystyrene and is a single composition.
  • the analysis conditions for GPC are described below. Column: Showa Denko Co., Ltd. Trade name: Shodex 805/804/803 in series Separation: Tetrahydrofuran 40 ° C Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI SE-61
  • Ethanol was added to the reaction solution to precipitate a polymer, and then recovered and dissolved in 350 mL of NMP. Subsequently, ion exchange was performed with 78 g of cation exchange resin (Amberlyst A21, manufactured by Organo) and 75 g of anion exchange resin (Amberlyst 15, manufactured by Organo). This solution is dropped into 3 L of ion-exchanged water under high-speed stirring, and the polymer is dispersed and precipitated, recovered, appropriately washed with water, dehydrated and then vacuum-dried, and an alkali-soluble resin (P-2) comprising a PBO precursor unit. Got.
  • cation exchange resin Amberlyst A21, manufactured by Organo
  • anion exchange resin Amberlyst 15, manufactured by Organo
  • the weight average molecular weight by GPC of the alkali-soluble resin thus synthesized is a single sharp curve of 36800 in terms of polystyrene, and is a single composition.
  • the analysis conditions for GPC are described below. Column: Trade name Shodex 805M / 806M series manufactured by Showa Denko Co., Ltd. Separation: N-methylpyrrolidone 40 ° C Flow rate: 1.0 ml / min Detector: Trade name RI-930, manufactured by JASCO Corporation
  • Ethanol was added to the reaction solution to precipitate a polymer, and then recovered and dissolved in 470 g of GBL.
  • ion exchange was performed with 78 g of cation exchange resin and 95 g of anion exchange resin.
  • This solution was dropped into 5 L of ion-exchanged water under high-speed stirring, and the polymer was dispersed and precipitated, recovered, appropriately washed with water, dehydrated and then vacuum-dried, and an aqueous alkali-soluble polymer (P- 3) was obtained.
  • the weight average molecular weight by GPC of the aqueous alkaline solution polymer synthesized in this way is a single sharp curve of 29300 in terms of polystyrene, and is a single composition.
  • the product is imidized, it not characteristic absorption of amide groups in the vicinity of 1540 cm -1 and 1650 cm -1 appear characteristic absorption of an imide group 1394Cm -1 and 1774 cm -1 in the IR spectrum is present and, NMR The spectrum was confirmed by the absence of amide and carboxylic acid proton peaks.
  • 65.9 g (0.1 mol) of the product, 53.7 g (0.2 mol) of 1,2-naphthoquinonediazide-4-sulfonyl chloride and 560 g of acetone were added and dissolved by stirring at 20 ° C.
  • a solution prepared by diluting 21.2 g (0.21 mol) of triethylamine with 106.2 g of acetone was added dropwise thereto at a constant rate over 30 minutes.
  • the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.
  • the mixture was allowed to stir at 20 ° C. for another 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once.
  • the reaction solution was then cooled in an ice water bath, and the precipitated solid was filtered off with suction. .
  • the filtrate obtained at this time was dropped into 5 L of a 0.5% by weight aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration.
  • the obtained cake-like recovered material was dispersed again in 5 L of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the obtained cake-like material was vacuum-dried at 40 ° C. for 24 hours to obtain a photosensitive diazoquinone compound (Q-1).
  • reaction vessel a glass separable three-necked flask equipped with a Teflon (registered trademark) vertical stirrer was used.
  • a reaction vessel was charged with 131.0 g of di-t-butyl dicarbonate and 780 g of ⁇ -butyrolactone, and slowly added a solution obtained by mixing 132.8 g of 3-aminopropyltriethoxysilane and 270 g of ⁇ -butyrolactone at room temperature. The solution was added dropwise at room temperature. The reaction solution exothermed to about 40 ° C as it was added dropwise. In addition, the generation of carbon dioxide gas was confirmed with the reaction.
  • This coating film was exposed by changing the exposure amount stepwise using a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern.
  • a stepper NSR2005i8A manufactured by Nikon Corporation
  • i-line 365 nm
  • the film thickness after development is 85% of the initial film thickness at 23 ° C.
  • the development time was adjusted so as to develop, followed by rinsing with pure water to form a positive relief pattern.
  • the developed film was cured at 320 ° C. for 1 hour using a temperature rising oven (VF200B manufactured by Koyo Thermo Systems Co., Ltd.) to prepare a cure film.
  • VF200B temperature rising oven
  • the photosensitive resin composition of the present invention includes a surface protective film for semiconductor devices, an interlayer insulating film, an insulating film for rewiring, a protective film for flip chip devices, a protective film for devices having a bump structure, and an interlayer insulating film for multilayer circuits It can be suitably used as a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film, and the like.

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Abstract

L'invention porte sur une composition de résine photosensible caractérisée par le fait qu'elle contient 1-50 parties en masse de (B) un générateur de photoacide et 1-40 parties en masse de (C) un composé représenté par la formule générale (2) (dans laquelle D1 représente au moins un groupe choisi parmi le groupe constitué par un atome d'hydrogène, les groupes alkyles ayant 1-6 atomes de carbone, les groupes alcényles et les groupes organiques réticulables ; M1 représente un groupe choisi dans le groupe constitué par -CH2-, -O- et -S- ; Z1 représente un groupe organique divalent ; n1 représente un entier de 0-4 ; et lorsqu'il y a une pluralité de D1, les D1 peuvent être les mêmes ou différents les uns des autres), pour 100 parties en masse de (A) un polymère soluble en solution aqueuse alcaline ayant une structure d'hydroxyamide représentée par la formule générale (1) (dans laquelle X1 représente un groupe organique tétravalent ayant au moins 2 atomes de carbone ; Y1 représente un groupe organique divalent ayant au moins 2 atomes de carbone ; et m1 représente un entier de 1-1 000).
PCT/JP2009/059543 2008-05-29 2009-05-25 Composition de résine photosensible WO2009145153A1 (fr)

Priority Applications (3)

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JP2020160338A (ja) * 2019-03-27 2020-10-01 太陽ホールディングス株式会社 感光性樹脂組成物、ドライフィルム、硬化物、及び、電子部品

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SG11201707976RA (en) * 2015-04-01 2017-10-30 Toray Industries Photosensitive colored resin composition
JP6502754B2 (ja) * 2015-06-08 2019-04-17 信越化学工業株式会社 光硬化性樹脂組成物及びこれを用いた光硬化性ドライフィルム
WO2017038828A1 (fr) * 2015-09-03 2017-03-09 東レ株式会社 Composition de résine photosensible de type positif, motif de résine non durci formé avec ladite composition de résine, motif de résine durci, dispositif semi-conducteur l'utilisant, et son procédé de fabrication
WO2017073481A1 (fr) * 2015-10-28 2017-05-04 東レ株式会社 Composition de résine photosensible positive, feuille photosensible, film durci, film isolant inter-couche, film protecteur semi-conducteur, procédé de fabrication de dispositif semi-conducteur, élément électronique semi-conducteur, et dispositif semi-conducteur
JP6555115B2 (ja) * 2015-12-18 2019-08-07 住友ベークライト株式会社 感光性樹脂材料
JP7008417B2 (ja) * 2016-03-31 2022-01-25 東京応化工業株式会社 層間絶縁膜形成用組成物、層間絶縁膜及び層間絶縁膜パターンの形成方法、並びにデバイス
CN110591094B (zh) * 2018-06-13 2020-11-20 北京大学 基于2,5-二烯丙氧基对苯二胺单体的聚苯并噁唑高分子材料及其制备方法
KR102337564B1 (ko) * 2018-09-28 2021-12-13 삼성에스디아이 주식회사 감광성 수지 조성물, 이를 이용한 감광성 수지막 및 전자 소자
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US9546802B2 (en) 2007-10-05 2017-01-17 Muovitech Ab Pipe collector for heat pump systems
WO2020183617A1 (fr) * 2019-03-12 2020-09-17 日立化成株式会社 Composition de résine photosensible, film durci à motifs et son procédé de production, élément semi-conducteur et dispositif électronique
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JPWO2009145153A1 (ja) 2011-10-13
KR101288640B1 (ko) 2013-07-22
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KR20100133494A (ko) 2010-12-21

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