Negative resist film laminate and patterning method

Abstract

The present invention provides a negative resist film laminate comprising a thermoplastic film as a first support and a negative resist film, wherein the negative resist film comprises: (A) an alkali-soluble resin having phenolic hydroxyl groups, (B) a plasticizer comprising polyester, (C) a photoacid-generating agent, (D) an epoxy compound containing an average of more than 4 epoxy groups per molecule, and (E) a benzotriazole compound and / or an imidazole compound.

Description

Technical Field

[0001] This invention relates to negative resist film laminates and a method for forming patterns thereon. Background Technology

[0002] In semiconductor manufacturing processes, resist materials are typically used to form resist films on supports such as films, wafers, metal substrates, and ceramic substrates. However, the surface of these supports often develops step-like elevation differences as the circuit is formed. Therefore, the resist materials used in the latter stages of semiconductor manufacturing require uniform coating on surfaces with these elevation differences and the absence of voids or other defects. Applying liquid resist materials to the surface of such unevenly textured supports makes it difficult to achieve a uniform coating thickness, and voids easily form near the elevation differences. Therefore, liquid resist materials are insufficient to meet these requirements; resist films are more suitable.

[0003] Furthermore, for negative resist films that meet such requirements, Patent Document 1 describes the use of organosiloxane-based resins to maintain the flexibility of the film material. Regarding development, organic solvent development is used, which differs from alkaline aqueous solution development, thus requiring changes to the development equipment. Additionally, Patent Document 2 describes a negative resist film that suppresses voids on substrates with stepped height differences, but it suffers from low chemical resistance after curing, and improvements are desired.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2011-145664

[0007] Patent Document 2: Japanese Patent Application Publication No. 2019-128438 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] The present invention was made in view of the above circumstances, and its object is to provide a negative resist film laminate and a pattern forming method, wherein the negative resist film laminate can transfer a negative resist film without creating voids on a support with a stepped height difference, and has excellent chemical resistance after curing.

[0010] Methods for solving problems

[0011] In order to achieve the above-mentioned objectives, the inventors conducted in-depth research and found that a negative resist film laminate comprising a thermoplastic film and a negative resist film containing an alkali-soluble resin having phenolic hydroxyl groups, a plasticizer containing polyester, a photoacid-generating agent, an epoxy compound containing an average of 4 or more epoxy groups in one molecule, a benzotriazole compound and / or an imidazole compound can solve the above-mentioned problems, and thus the present invention was completed.

[0012] That is, the present invention provides the following negative resist film laminate and pattern formation method.

[0013] 1. A negative resist film laminate comprising a thermoplastic film serving as a first support and a negative resist film, wherein the negative resist film comprises:

[0014] (A) An alkali-soluble resin with phenolic hydroxyl groups.

[0015] (B) Plasticizers containing polyester,

[0016] (C) Photoacid-producing agents

[0017] (D) Epoxy compounds containing an average of more than 4 epoxy groups per molecule, and

[0018] (E) Benzotriazole compounds and / or imidazole compounds.

[0019] 2. The laminate according to 1, wherein the polyester is a polycarboxylic acid polyester having 2 to 6 carboxyl groups.

[0020] 3. A method for forming a pattern, which includes:

[0021] (1) The process of transferring a negative resist film of the laminate according to 1 or 2 onto the second support.

[0022] (2) The process of exposing the resist film, and

[0023] (3) The process of developing the resist film using an alkaline aqueous solution.

[0024] 4. The pattern forming method according to 3, wherein in step (1), heat treatment is performed after transfer.

[0025] 5. The pattern forming method according to 3 or 4, wherein in step (2), a heat treatment is performed after exposure.

[0026] The effects of the invention

[0027] According to the negative resist film laminate of the present invention, even on a support with a stepped height difference, a negative resist film can be transferred without gaps, and after curing, a pattern with high chemical resistance can be formed. Detailed Implementation

[0028] [Negative resist film laminate]

[0029] The negative resist film laminate of the present invention comprises a thermoplastic film serving as a first support and a negative resist film transferable onto a second support.

[0030] [Thermoplastic film]

[0031] Since the thermoplastic film serving as the first support is to become the release substrate, there are no particular limitations as long as it can be peeled off from the negative resist film without damaging its morphology. Such a film can be a single-layer film composed of a single polymer film or a multilayer film composed of multiple polymer films stacked together. Specifically, examples include nylon films, polyethylene (PE) films, polyethylene terephthalate (PET) films, polyethylene naphthalate (PET) films, polyphenylene sulfide (PPS) films, polypropylene (PP) films, polystyrene films, polymethylpentene (TPX) films, polycarbonate films, fluorinated films, special polyvinyl alcohol (PVA) films, and polyester films that have undergone release treatment, among other plastic films.

[0032] Among these, PET or PP films, which possess moderate flexibility, mechanical strength, and heat resistance, are preferred as the first support. Additionally, these films can also be those that have undergone various treatments such as corona treatment or coating with a release agent. Commercially available thermoplastic films can be used as the aforementioned thermoplastic films, for example: Cerapeel (registered trademark) WZ(RX), BX8(R) (manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (manufactured by Toyobo Co., Ltd.), Purex (registered trademark) G31, G71T1 (manufactured by Teijin Film Solution Co., Ltd.), PET38×1-A3, PET38×1-V8, PET38×1-X08 (manufactured by Nippa Co., Ltd.), etc. It should be noted that in this invention, flexibility refers to the property of the film to exhibit softness at room temperature and pressure and not cracking upon deformation.

[0033] [Negative resist film]

[0034] The aforementioned negative resist film comprises: (A) an alkali-soluble resin having phenolic hydroxyl groups, (B) a plasticizer containing polyester, (C) a photoacid-generating agent, (D) an epoxy compound containing an average of more than 4 epoxy groups in one molecule, and (E) a benzotriazole compound and / or an imidazole compound.

[0035] [(A) Alkali-soluble resin with phenolic hydroxyl groups]

[0036] Examples of alkali-soluble resins containing phenolic hydroxyl groups used as the base resin for the aforementioned negative resist film include phenolic varnish resins formed by the condensation polymerization of phenols and aldehydes in the presence of an acid catalyst, polyhydroxystyrene resins, and resins copolymerized with hydroxystyrene and other free radical polymerizable monomers (methyl acrylate, methyl methacrylate and other acrylic monomers, styrene, etc.). Among these, phenolic varnish resins are preferred.

[0037] Examples of the aforementioned phenols include phenol; xylenephenols such as m-cresol, o-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, and 3,4-xylenol; and xylenephenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, and 6-tert-butyl-3-methylphenol. Alkylphenols such as phenol; alkoxyphenols such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, and 2-ethyl-4-isopropenylphenol; polyhydroxyphenols such as 4,4'-dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, hydroquinone, and pyrogallol; and hydroxynaphthols such as α-naphthol, β-naphthol, and dihydroxynaphthol. Preferably, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, and / or 3,5-xylenol are used as raw materials, and more preferably m-cresol and / or p-cresol are used.

[0038] Examples of aldehydes mentioned above include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexylformaldehyde, furfural, furanylpropionaldehyde, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, and p-chlorobenzaldehyde. They can be used individually or in combination of two or more. Among these aldehydes, formaldehyde is preferred due to its ease of availability.

[0039] The aforementioned phenolic varnish resin, preferably obtained by using 40 mol% or more of p-cresol as the phenolic raw material, more preferably by using 45 mol% or more of p-cresol. In this case, the upper limit of the amount of p-cresol used is 100 mol% of the phenolic raw material. If other phenols besides p-cresol are used, the upper limit of the amount of p-cresol used is preferably 80 mol%, more preferably 70 mol%. As the aforementioned other phenols, m-cresol, 2,5-xylenol, and 3,5-xylenol are preferred, and m-cresol is more preferred.

[0040] (A) The weight-average molecular weight (Mw) of the resin component is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. It should be noted that in this invention, Mw is a converted value of polystyrene determined by gel permeation chromatography using tetrahydrofuran as a solvent.

[0041] (A) The resin of component (A) can be used alone or in combination of two or more.

[0042] [(B) Plasticizer]

[0043] (B) The plasticizer in component B contains polyester. The polyester is a condensation product of a polycarboxylic acid and a polyol, or a condensation product of a polycarboxylic anhydride and a polyol.

[0044] As the aforementioned polycarboxylic acids, polycarboxylic acids having 2 to 6 carboxyl groups are preferred. Specifically, examples include oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, citraconic acid, fumaric acid, maleic acid, methylmaleic acid, mesoconic acid, pentenic acid, itaconic acid, allylmalonic acid, beconic acid, mucoconic acid, 2-butynediacid, aconitic acid, malic acid, tartaric acid, gluconic acid, citric acid, oxomalacic acid, oxosuccinic acid, thiomalic acid, glutamic acid, ethylenediaminetetraacetic acid, 1,2-cyclopropanedicarboxylic acid, cocaic acid, camphoric acid, phthalic acid, isophthalic acid, terephthalic acid, phenylsuccinic acid, 2-(3-carboxyphenyl)-2-oxoacetic acid, mucoconic acid, and cyclobutanedicarboxylic acid. Furthermore, their anhydrides can be used. Dicarboxylic acids are preferred. One of the aforementioned polycarboxylic acids may be used alone, or two or more may be used in combination.

[0045] In addition, examples of polyols include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,4-butanediol, 1,4-cyclohexanediol, 1,2-pentanediol, 1,3-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, neopentanediol, glycerol, and pentaglycerol. Diols are preferred. The above polyols can be used alone or in combination of two or more.

[0046] Using the above-mentioned raw materials, polyester is obtained by polycondensation according to known methods. The amount of raw materials used can be adjusted appropriately according to the molecular weight of the obtained polymer. Generally, the amount of polyol is about 0.5 to 3 moles relative to 1 mole of polycarboxylic acid. Alternatively, esterification can be carried out using known methods, employing acidic catalysts such as sulfuric acid, metals such as titanium compounds, tin compounds, zinc compounds, germanium compounds, and antimony compounds, and heating at approximately 150 to 300°C as needed to induce a condensation reaction.

[0047] Commercially available products can be used as the aforementioned polyesters, such as Polysizer (registered trademark) W-2050, W-2310, W-230-H, W-1020-EL, W-1410-EL, W-705 (manufactured by DIC Corporation), and ADK. Cizer (registered trademark) PN-150, PN-170, PN-230, PN-280, PN-7230, PN-1010, PN-1020, PN-1030, P-200, PN-260, PN-650, PN-7650, PN-1430, HPN-3130, PN-446, PN-7310 (manufactured by ADEKA Co., Ltd.), D620, D621, D623, D643, D64, D633, D620N, D623N, D643D, D640A (manufactured by J-Plus Co., Ltd.), etc.

[0048] The Mw of the aforementioned polyester is preferably 700 to 50,000, more preferably 1,500 to 45,000. If the Mw is within the above range, the development speed is good, and therefore it is preferred.

[0049] (B) is a component of the negative resist film, and is therefore preferably alkali-soluble, and particularly preferably soluble in an aqueous solution of tetramethylammonium hydroxide (TMAH).

[0050] (B) The plasticizer in component (B) may contain only the polyester, but may also contain other plasticizers besides the polyester. Conventionally known plasticizers may be used as other plasticizers. The content of other plasticizers is not particularly limited as long as it does not impair the effects of the invention.

[0051] Regarding the content of component (B), it is preferably 5 to 100 parts by weight relative to 100 parts by weight of resin of component (A), more preferably 10 to 60 parts by weight, and even more preferably 15 to 50 parts by weight. If the content is within the above range, no voids will be generated when the above-mentioned negative resist film is transferred onto the second support. The polyester of component (B) can be used alone or in combination of two or more types.

[0052] [(C) Photoacid-producing agents]

[0053] As a photoacid-producing agent for component (C), there are no particular limitations as long as it is a compound that produces acid through irradiation with high-energy rays. Examples of such high-energy rays include ultraviolet rays, far-ultraviolet rays, and electron beams (EB). Specifically, examples include gamma rays, h-rays, i-rays, KrF excimer lasers, ArF excimer lasers, EB, and synchrotron radiation.

[0054] Preferred photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide type photoacid generators, benzoin sulfonate type photoacid generators, pyrogallol trisulfonate type photoacid generators, nitrobenzyl sulfonate type photoacid generators, sulfone type photoacid generators, O-arylsulfonyl oxime compounds or O-alkylsulfonyl oxime compounds (sulfonate oxime esters) type photoacid generators, etc.

[0055] The aforementioned sulfonium salts are salts of sulfonium cations and sulfonate anions. Examples of such sulfonium cations include triphenylsulfonium, (4-tert-butoxyphenyl)diphenylsulfonium, bis(4-tert-butoxyphenyl)phenylsulfonium, tris(4-tert-butoxyphenyl)sulfonium, (3-tert-butoxyphenyl)diphenylsulfonium, bis(3-tert-butoxyphenyl)phenylsulfonium, tris(3-tert-butoxyphenyl)sulfonium, (3,4-di-tert-butoxyphenyl)diphenylsulfonium, bis(3,4-di-tert-butoxyphenyl)phenylsulfonium, tris(3,4-di-tert-butoxyphenyl)sulfonium, and diphenylsulfonium. (4-Thiophenoxyphenyl)sulfonium, (4-tert-butoxycarbonylmethoxyphenyl)diphenylsulfonium, tris(4-tert-butoxycarbonylmethoxyphenyl)sulfonium, (4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium, tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium, dimethyl2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, etc. Examples of sulfonate anions include trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctanoate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octylsulfonate, dodecylbenzenesulfonate, butyrate, and methanesulfonate. Preferably, the matte salt is composed of a combination of these.

[0056] The aforementioned iodonium salts are salts of an iodonium cation and a sulfonate anion. Examples of iodonium cations include diphenyliodonium, bis(4-tert-butylphenyl)iodonium, 4-tert-butoxyphenylphenyliodonium, and 4-methoxyphenylphenyliodonium, among other aryl iodonium cations. Examples of sulfonate anions include trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctanoate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanoate, dodecylbenzenesulfonate, butyrate, and methanesulfonate. Preferably, the iodonium salt is composed of a combination of these.

[0057] Examples of sulfonyl diazonium methanes include bis(ethylsulfonyl)diazonium methane, bis(1-methylpropylsulfonyl)diazonium methane, bis(2-methylpropylsulfonyl)diazonium methane, bis(1,1-dimethylethylsulfonyl)diazonium methane, bis(cyclohexylsulfonyl)diazonium methane, bis(perfluoroisopropylsulfonyl)diazonium methane, bis(phenylsulfonyl)diazonium methane, bis(4-methylphenylsulfonyl)diazonium methane, and bis(2,4-dimethylphenyl)diazonium methane. Bis(2-naphthylsulfonyl)diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthyldiazomethane, methylsulfonylbenzoyldiazomethane, tert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane, etc., are bis(sulfonyl)diazomethane or sulfonylcarbonyldiazomethane.

[0058] Examples of N-sulfonyloxyimide-type photoacid-generating agents include compounds in which the hydrogen atom bonded to the nitrogen atom of imides such as succinimide, naphthalenedicarboximide, phthalimide, cyclohexyldicarboximide, 5-norbornene-2,3-dicarboximide, and 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboximide is replaced by sulfonyloxy groups such as trifluoromethanesulfonyloxy, nonafluorobutyryloxy, heptadecafluorooctyloxy, 2,2,2-trifluoroethanesulfonyloxy, pentafluorobenzenesulfonyloxy, 4-trifluoromethylbenzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, toluenesulfonyloxy, benzenesulfonyloxy, naphthalenesulfonyloxy, camphorsulfonyloxy, octylsulfonyloxy, dodecylbenzenesulfonyloxy, butylsulfonyloxy, and methanesulfonyloxy.

[0059] Examples of benzoin sulfonate-type photoacid generators include benzoin toluene sulfonate, benzoin methane sulfonate, and benzoin butyrate sulfonate.

[0060] As photoacid-generating agents of pyrogallol trisulfonate type, examples include compounds in which all the hydroxyl groups of pyrogallol, resorcinol, catechol, resorcinol, or hydroquinone are replaced by trifluoromethanesulfonyloxy, nonafluorobutyryloxy, heptadecanofluorooctyloxy, 2,2,2-trifluoroethanesulfonyloxy, pentafluorobenzenesulfonyloxy, 4-trifluoromethylbenzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, toluenesulfonyloxy, benzenesulfonyloxy, naphthalenesulfonyloxy, camphorsulfonyloxy, octylsulfonyloxy, dodecylbenzenesulfonyloxy, butylsulfonyloxy, methanesulfonyloxy, etc.

[0061] Examples of photoacid-generating agents of the nitrobenzyl sulfonate type include esters of nitrobenzyl alcohol such as 2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, and 2,6-dinitrobenzyl sulfonate, and sulfonic acids such as trifluoromethanesulfonic acid, nonafluorobutyric acid, heptadecafluorooctyl sulfonic acid, 2,2,2-trifluoroethanesulfonic acid, pentafluorobenzenesulfonic acid, 4-trifluoromethylbenzenesulfonic acid, 4-fluorobenzenesulfonic acid, toluenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, camphorsulfonic acid, octylsulfonic acid, dodecylbenzenesulfonic acid, butyric acid, and methanesulfonic acid. Furthermore, compounds formed by replacing the nitro group with a trifluoromethyl group can also be used as photoacid-generating agents.

[0062] Examples of sulfone-type photoacid-generating agents include bis(phenylsulfonyl)methane, bis(4-methylphenylsulfonyl)methane, bis(2-naphthylsulfonyl)methane, 2,2-bis(phenylsulfonyl)propane, 2,2-bis(4-methylphenylsulfonyl)propane, 2,2-bis(2-naphthylsulfonyl)propane, 2-methyl-2-(p-toluenesulfonyl)phenylacetone, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, and 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one.

[0063] Examples of photoacid-generating agents of the O-arylsulfonyl oxime or O-alkylsulfonyl oxime (sulfonate oxime ester) type include: dioxime derivative type, sulfonate oxime ester type via the conjugation system of thiophene and cyclohexadiene, sulfonate oxime ester type with increased stability of the compound by electron-withdrawing groups such as trifluoromethyl, sulfonate oxime ester type using acetonitrile derivatives substituted with phenylacetonitrile, and sulfonate dioxime ester type, etc.

[0064] Examples of photoacid-producing agents derived from dioxime include bis-O-(p-toluenesulfonyl)-α-dimethyldioxime, bis-O-(p-toluenesulfonyl)-α-diphenyldioxime, bis-O-(p-toluenesulfonyl)-α-dicyclohexyldioxime, bis-O-(p-toluenesulfonyl)-2,3-pentanedione dioxime, bis-O-(n-butanesulfonyl)-α-dimethyldioxime, and bis-O-( (n-Butanesulfonyl)-α-diphenylglyoxime, bis-O-(n-Butanesulfonyl)-α-dicyclohexylglyoxime, bis-O-(methanesulfonyl)-α-dimethylglyoxime, bis-O-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-O-(2,2,2-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-O-(10-camphorsulfonyl)-α-dimethylglyoxime, bis-O-(benzenesulfonyl)-α-dimethylglyoxime, bis-O-(4-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-O-(4-trifluoromethylbenzenesulfonyl)-α-dimethylglyoxime, bis-O-(xylenesulfonyl)-α-dimethylglyoxime, bis-O-(trifluoromethanesulfonyl)-1,2-cyclohexanedione dioxime, bis-O-(2,2,2-trifluoroethanesulfonyl)-1 , 2-cyclohexanedione dioxime, bis-O-(10-camphorsulfonyl)-1,2-cyclohexanedione dioxime, bis-O-(benzenesulfonyl)-1,2-cyclohexanedione dioxime, bis-O-(4-fluorobenzenesulfonyl)-1,2-cyclohexanedione dioxime, bis-O-(4-(trifluoromethyl)benzenesulfonyl)-1,2-cyclohexanedione dioxime, bis-O-(dimethylbenzenesulfonyl)-1,2-cyclohexanedione dioxime, etc.

[0065] Examples of oxime sulfonate-type photoacid-generating agents that incorporate the conjugated system of thiophene and cyclohexadiene include (5-(p-toluenesulfonyl)oxyimino-5H-thiophen-2-yl)phenylacetonitrile, (5-(10-camphorsulfonyl)oxyimino-5H-thiophen-2-yl)phenylacetonitrile, (5-n-octanesulfonyloxyimino-5H-thiophen-2-yl)phenylacetonitrile, and (5-(p-toluenesulfonyl)oxyimino-5H-thiophen-2-yl)(2-methylphenyl) Acetonitrile, (5-(10-camphorsulfonyl)oxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)acetonitrile, (5-n-octanesulfonyloxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)acetonitrile, (5-(4-(p-toluenesulfonyloxy)benzenesulfonyl)oxyimino-5H-thiophen-2-ylidene)phenylacetonitrile, (5-(2,5-bis(p-toluenesulfonyloxy)benzenesulfonyl)oxyimino-5H-thiophen-2-ylidene)phenylacetonitrile, etc.

[0066] Examples of oxime sulfonate-type photoacid-generating agents that enhance compound stability with electron-withdrawing groups such as trifluoromethyl groups include 2,2,2-trifluoro-1-phenylethyl ketone = O-(methylsulfonyl) oxime, 2,2,2-trifluoro-1-phenylethyl ketone = O-(10-camphorsulfonyl) oxime, 2,2,2-trifluoro-1-phenylethyl ketone = O-(4-methoxybenzenesulfonyl) oxime, 2,2,2-trifluoro-1-phenylethyl ketone = O-(1-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1-phenylethyl ketone = O-(2-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1-phenylethyl ketone = O-(2,4,6-trimethylphenylsulfonyl) oxime, and 2,2,2-trifluoro-1-(4-methylphenyl) oxime. Ketones = O-(10-camphorsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methylphenyl) ethyl ketone = O-(methylsulfonyl) oxime, 2,2,2-trifluoro-1-(2-methylphenyl) ethyl ketone = O-(10-camphorsulfonyl) oxime, 2,2,2-trifluoro-1-(2,4-dimethylphenyl) ethyl ketone = O-(10-camphorsulfonyl) oxime, 2,2,2-trifluoro-1-(2,4-dimethylphenyl) ethyl ketone = O-(1-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1-(2,4-dimethylphenyl) ethyl ketone = O-(2-naphthylsulfonyl) oxime, 2, 2,2-Trifluoro-1-(2,4,6-trimethylphenyl) ethyl ketone = O-(1-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1-(2,4,6-trimethylphenyl) ethyl ketone = O-(2-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methoxyphenyl) ethyl ketone = O-(methylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methylthiophenyl) ethyl ketone = O-(methylsulfonyl) oxime, 2,2,2-trifluoro-1-(3,4-dimethoxyphenyl) ethyl ketone = O-(methylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methoxyphenyl) ethyl ketone = O-(4-methylphenylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methoxyphenyl) ethyl ketone =O-(4-methoxyphenylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methoxyphenyl) ethyl ketone =O-(4-dodecylphenylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methoxyphenyl) ethyl ketone =O-(octylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methylthiophenyl) ethyl ketone =O-(4-methoxyphenylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methylthiophenyl) ethyl ketone =O-(4-dodecylphenylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methylthiophenyl) ethyl ketone =O-(octylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methylthiophenyl) ethyl ketone =O-(2-naphthylsulfonyl) oxime, 2,2,2-Trifluoro-1-(2-methylphenyl)ethyl ketone = O-(methylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methylphenyl)ethyl ketone = O-(phenylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-chlorophenyl)ethyl ketone = O-(phenylsulfonyl) oxime, 2,2,3,3,4,4,4-heptafluoro-1-phenylbutanone = O-(10 -camphorsulfonyl) oxime, 2,2,2-trifluoro-1-(1-naphthyl) ethyl ketone = O-(methylsulfonyl) oxime, 2,2,2-trifluoro-1-(2-naphthyl) ethyl ketone = O-(methylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-benzylphenyl) ethyl ketone = O-(methylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-(phenyl-1, 4-Dioxa-but-1-yl)phenyl)ethyl ketone = O-(methylsulfonyl) oxime, 2,2,2-trifluoro-1-(1-naphthyl)ethyl ketone = O-(propylsulfonyl) oxime, 2,2,2-trifluoro-1-(2-naphthyl)ethyl ketone = O-(propylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-benzylphenyl)ethyl ketone = O-(propylsulfonyl) oxime 2,2,2-Trifluoro-1-(4-methylsulfonylphenyl) ethyl ketone = O-(propylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methylsulfonyloxyphenyl) ethyl ketone = O-(propylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methylcarbonyloxyphenyl) ethyl ketone = O-(propylsulfonyl) oxime, 2,2,2-trifluoro-1-(6H,7H-5,8-dioxonaphthoyl-2-yl) ethyl ketone = O-(propylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-methoxycarbonylmethoxyphenyl) ethyl ketone = O-(propylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-(methoxycarbonyl)-(4-amino-1-oxa-pent-1-yl) ... Acyl) oxime, 2,2,2-trifluoro-1-(3,5-dimethyl-4-ethoxyphenyl) ethyl ketone = O-(propylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-benzyloxyphenyl) ethyl ketone = O-(propylsulfonyl) oxime, 2,2,2-trifluoro-1-(2-thienyl) ethyl ketone = O-(propylsulfonate) oxime, and 2,2,2-trifluoro-1 -(1-dioxathiophene-2-yl)ethyl ketone = O-(propylsulfonate) oxime, 2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(trifluoromethanesulfonyloxyimino)ethyl)phenoxy)propoxy)phenyl)ethyl ketone = O-(trifluoromethanesulfonyl) oxime, 2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(1-propanesulfonyloxyimino)ethyl)phenoxy)propoxy)phenyl)ethyl ketone = O-(propylsulfonyl) oxime, 2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(1-butanesulfonyloxyimino)ethyl)phenoxy)propoxy)phenyl)ethyl ketone = O-(butanesulfonyl) oxime, 2,2,2-Trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)ethyl)phenoxy)propoxy)phenyl)ethyl ketone = O-(4-(4-methylphenylsulfonyloxy)phenylsulfonyl)oxime, 2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-((2,5-bis(4-methylphenylsulfonyloxy)phenylsulfonyloxy)phenylsulfonyloxyimino)ethyl)phenoxy)propoxy)phenyl)ethyl ketone = O-((2,5-bis(4-methylphenylsulfonyloxy)phenylsulfonyloxy)phenylsulfonyl)oxime, etc.

[0067] Examples of oxime sulfonate-type photoacid generators that utilize substituted acetonitrile derivatives include α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(p-chlorobenzenesulfonyloxyimino)-phenylacetonitrile, α-(4-nitrobenzenesulfonyloxyimino)-phenylacetonitrile, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-4-chlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(benzenesulfonyloxyimino)-2-thienylacetonitrile, and α-(4- Dodecylbenzenesulfonyloxyimino)-phenylacetonitrile, α-((4-toluenesulfonyloxyimino)-4-methoxyphenyl)acetonitrile, α-((dodecylbenzenesulfonyloxyimino)-4-methoxyphenyl)acetonitrile, α-(toluenesulfonyloxyimino)-3-thienylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(n-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(n-butylsulfonyloxyimino)-1-cyclohexenylacetonitrile, etc.

[0068] In addition, examples of bis(α-(p-toluenesulfonyloxy)imino)-p-phenylene diacetonitrile, bis(α-(benzenesulfonyloxy)imino)-p-phenylene diacetonitrile, bis(α-(methanesulfonyloxy)imino)-p-phenylene diacetonitrile, bis(α-(butanesulfonyloxy)imino)-p-phenylene diacetonitrile, bis(α-(10-camphorsulfonyloxy)imino)-p-phenylene diacetonitrile, bis(α-(trifluoromethanesulfonyloxy)imino)-p-phenylene diacetonitrile, bis(α-(4-methoxybenzenesulfonyloxy)imino) -p-Phenylidene diacetonitrile, bis(α-(p-toluenesulfonyloxy)imino)-m-Phenylidene diacetonitrile, bis(α-(benzenesulfonyloxy)imino)-m-Phenylidene diacetonitrile, bis(α-(methanesulfonyloxy)imino)-m-Phenylidene diacetonitrile, bis(α-(butanesulfonyloxy)imino)-m-Phenylidene diacetonitrile, bis(α-(10-camphorsulfonyloxy)imino)-m-Phenylidene diacetonitrile, bis(α-(trifluoromethanesulfonyloxy)imino)-m-Phenylidene diacetonitrile, bis(α-(4-methoxybenzenesulfonyloxy)imino)-m-Phenylidene diacetonitrile, etc.

[0069] In addition, the oxime sulfonate esters shown in the following formula (C1) can also be used as photoacid-generating agents.

[0070] [Chemistry 1]

[0071]

[0072] In equation (C1), R 1 It is a substituted or unsubstituted haloalkylsulfonyl group or halobenzenesulfonyl group with 1 to 10 carbon atoms. R 2 It is a haloalkyl group having 1 to 11 carbon atoms. R 3 It is a substituted or unsubstituted aryl or heteroaryl group.

[0073] Examples of oxime sulfonates represented by formula (C1) include 2-(2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxyimino)pentyl)fluorene, 2-(2,2,3,3,4,4-pentafluoro-1-(nonafluorobutylsulfonyloxyimino)butyl)fluorene, and 2-(2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutylsulfonyloxyimino)hexyl)fluorene. Fluorene, 2-(2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxyimino)pentyl)-4-biphenyl, 2-(2,2,3,3,4,4-pentafluoro-1-(nonafluorobutylsulfonyloxyimino)butyl)-4-biphenyl, 2-(2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutylsulfonyloxyimino)hexyl)-4-biphenyl, etc.

[0074] Preferred photoacid-generating agents include sulfonium salts, disulfonyldiazomethane, N-sulfonyloxyimide, and sulfonyl oxime compounds.

[0075] Depending on the fragility of the unstable acid groups used in the polymer, the optimal anion for generating the acid varies, but generally, anions with non-volatile properties and low diffusivity are chosen. In this case, preferred anions include benzenesulfonic acid anion, toluenesulfonic acid anion, 4-(4-toluenesulfonyloxy)benzenesulfonic acid anion, pentafluorobenzenesulfonic acid anion, 2,2,2-trifluoroethanesulfonic acid anion, nonafluorobutyric acid anion, heptadecafluorooctanoic acid anion, and camphorsulfonic acid anion.

[0076] Regarding the content of the photoacid generator (C), it is preferably 0.2 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, relative to 100 parts by weight of the resin of component (A). If the content is within the above range, practically acceptable photosensitivity and pattern shape can be obtained. The photoacid generator of component (C) can be used alone or in combination of two or more. Alternatively, a photoacid generator with low transmittance at the exposure wavelength can be used, and the light transmittance in the resist film can be controlled by the amount added.

[0077] [(D) Epoxy compounds containing an average of more than 4 epoxy groups per molecule]

[0078] Component (D) is an epoxy compound containing an average of four or more epoxy groups per molecule, which functions as a crosslinking agent. Examples of such compounds include any one of the compounds shown in formulas (D1) to (D3) below, but are not limited to these.

[0079] [Chemistry 2]

[0080]

[0081] In formula (D1), m is an integer from 0 to 2. n is an integer greater than 2, preferably an integer from 2 to 10.

[0082] In equation (D1), R 11 It is a saturated hydrocarbon group with 1 to 6 carbon atoms. The saturated hydrocarbon group can be saturated or unsaturated, and can be straight-chain, branched, or cyclic. Specific examples include alkyl groups with 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl; and cyclic saturated hydrocarbon groups with 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0083] In equation (D1), L 1Each is an independently saturated alkylene group having 1 to 10 carbon atoms. The alkylene group can be linear, branched, or cyclic. Specific examples include alkylene groups such as methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, and butane-1,4-diyl; and cyclic saturated alkylene groups such as cyclopropylene, cyclopentane-1,2-diyl, and cyclohexane-1,2-diyl. Among these, methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, and propane-2,2-diyl are preferred.

[0084] In equations (D2) and (D3), p is an integer from 4 to 8. q is an integer from 2 to 4. R 12 It is a p-valent hydrocarbon group with 6 to 30 carbon atoms, and may contain at least one selected from nitrogen, oxygen, and sulfur atoms. R 13 It is a hydrocarbon group with a carbon number of 6 to 20 and a q valence, and may contain at least one selected from nitrogen, oxygen and sulfur atoms.

[0085] Examples of compounds represented by formula (D2) include, but are not limited to, those shown below.

[0086] [Chemistry 3]

[0087]

[0088] Examples of compounds represented by formula (D3) include, but are not limited to, those shown below.

[0089] [Chemistry 4]

[0090]

[0091] As for the compound represented by any one of formulas (D1) to (D3), compounds containing an aromatic ring are particularly preferred.

[0092] Regarding the content of component (D), it is preferably 10 to 200 parts by mass relative to 100 parts by mass of component (A), and more preferably 30 to 100 parts by mass. The epoxy compound of component (D) can be used alone or in combination of two or more.

[0093] [(E) Benzotriazole compounds, imidazole compounds]

[0094] Benzotriazole compounds that are components of (E) can be listed as compounds represented by the following formulas (E1) or (E2).

[0095] [Chemistry 5]

[0096]

[0097] In equations (E1) and (E2), R 21 and R 23 Each of the following is independently a hydrogen atom, hydroxyl group, amino group, alkyl group with 1 to 6 carbon atoms that may have substituents, phenyl group that may have substituents, substituent with sulfonyl group, or -A group. 1 -A 2 A 1 It is a carbonyl group, a saturated hydrocarbon group with 1 to 12 carbon atoms, or -A. 11 -O-,A 11 It is a saturated hydrocarbon group with 1 to 12 carbon atoms. A 2 It is a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a saturated alkyloxy group with 1 to 6 carbon atoms, a carboxyl group, or a dialkylamino group with 1 to 6 carbon atoms in each hydrocarbon group. The hydrocarbon group of the above-mentioned saturated alkylene group, saturated alkyloxy group, and dialkylamino group can be any of the following: straight-chain, branched, or cyclic.

[0098] In equations (E1) and (E2), R 22 and R 24 Each of the following is independently a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 6 carbon atoms that may have substituents, a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, a substituent having a sulfonyl group, or an organic group represented by the following formula (E3).

[0099] [Chemistry 6]

[0100]

[0101] (where R is in the formula) 25 It is a hydrogen atom or a saturated hydrocarbon group with 1 to 12 substituted carbon atoms. 'a' is 0 or 1. The dashed line represents the bond end.

[0102] Preferably, the following compounds are used as benzotriazole compounds: benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-hydroxymethylbenzotriazole, 1-ethylbenzotriazole, 1-(1-hydroxyethyl)benzotriazole, 1-(2-hydroxyethyl)benzotriazole, 1-propylbenzotriazole, 1-(1-hydroxypropyl)benzotriazole, 1-(2-hydroxypropyl)benzotriazole, 1-(3-hydroxypropyl)benzotriazole, and 4-hydroxy-1H-benzotriazole. 5-Methyl-1H-benzotriazole, benzotriazole-5-carboxylic acid, 1-methylbenzotriazole-5-carboxylic acid, 1-ethylbenzotriazole-5-carboxylic acid, 1-tert-butylbenzotriazole-5-carboxylic acid, 1-(2-cyclopentylethyl)benzotriazole-5-carboxylic acid, 1H-benzotriazole-4-sulfonic acid, 1H-benzotriazole-1-acetonitrile, 1H-benzotriazole-1-formaldehyde, 2-methyl-2H-benzotriazole, 2-ethyl-2H-benzotriazole, etc.

[0103] Next, as an imidazole compound of component (E), examples include compounds represented by the following formulas (E4) to (E9).

[0104] [Chemistry 7]

[0105]

[0106] In equations (E4) to (E9), R 31 It is a hydrogen atom, or a saturated hydrocarbon group with 2 to 20 carbon atoms having at least one polar functional group selected from hydroxyl, carbonyl, ester, ether, thioether, carbonate, cyano, and acetal. R 32 R 33 and R 34 Each of the following groups is independently a hydrogen atom, a saturated hydrocarbon group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an aralkyl group with 7 to 10 carbon atoms. R 35 R 37 R 39 and R 43 Each is an independent saturated hydrocarbon group with 1 to 10 carbon atoms. R 36 and R 38 Each group is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 15 carbon atoms, and the saturated hydrocarbon group may include at least one selected from hydroxyl, carbonyl, ester, ether, thioether, carbonate, cyano, and acetal groups. 40 It is a saturated hydrocarbon group having 1 to 15 carbon atoms, and may contain at least one selected from hydroxyl, carbonyl, ester, ether, thioether, carbonate, cyano, and acetal groups. R 41 It is a hydrocarbon group with 2 to 10 carbon atoms in the (b+1) valence. R 42 Each is independently a saturated hydrocarbon group having 1 to 15 hydrogen atoms or carbon atoms. The saturated hydrocarbon group may contain at least one selected from hydroxyl, carbonyl, ester, ether, thioether, carbonate, cyano, and acetal groups. Additionally, the two R groups... 42 They can combine to form a ring. b can be 2, 3, 4, or 5.

[0107] As the aforementioned imidazole compound, preferably imidazole, 2-methylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-methoxymethylimidazolium, N-tert-butoxycarbonylimidazolium, 1-(2-cyanoethyl)-2-methylimidazolium, 1-(2-hydroxyethyl)imidazolium, 1-(carboxymethyl)imidazolium, 2-methyl-1-vinylimidazolium, etc.

[0108] Regarding the content of component (E), it is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of component (A), more preferably 0.02 to 5 parts by mass. If the content of component (E) is within the above range, a pattern can be formed with practical photosensitivity. The compound of component (E) can be used alone or in combination of two or more.

[0109] [(F) Surfactant]

[0110] The aforementioned negative resist film may also contain (F) surfactants. Examples of (F) surfactants include nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene oil-based ether, etc.; polyoxyethylene alkyl allyl ether, such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc.; polyoxyethylene polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, etc.; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate; polyether silicone; polyoxyethylene sorbitan trioleate; polyoxyethylene sorbitan tristearate, etc.; and nonionic surfactants of polyoxyethylene sorbitan fatty acid esters. EFTOP (registered trademark) EF301, EF303, EF352 (Tohkem Co., Ltd.) Products (manufactured), MEGAFAC (registered trademark) F171, F172, F173 (manufactured by DIC Co., Ltd.), FLUORAD (registered trademark) FC-4430, FC-430, FC-431 (manufactured by 3M Corporation), Surflon (registered trademark) E1004 (manufactured by Nissin Chemical Industry Co., Ltd.), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, KH-10, KH-20, KH-30, KH-40 (AGC Fluorinated surfactants such as those manufactured by Semichemical Co., Ltd.; organosiloxane polymers KP-341, X-70-092, and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.); and acrylic or methacrylic surfactants such as Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.). Among these, FLUORAD FC-4430, KP-341, and X-70-093 are preferred. They can be used alone or in combination of two or more.

[0111] Regarding the content of surfactant in component (F), it is 0 to 5 parts by mass relative to 100 parts by mass of resin in component (A), and preferably 0.01 to 2 parts by mass if it is present. The surfactant in component (F) can be used alone or in combination of two or more.

[0112] [Other ingredients]

[0113] Furthermore, without impairing the effects of the present invention, other known additives may be added to the aforementioned negative resist film. Examples of such additives include various photo-induced alkali-generating agents, sensitizers, solubility promoters such as water-soluble cellulose, stress relievers such as polyvinyl alcohol and polyvinyl alkyl ether compounds, azo compounds, dyes such as curcumin, and shape improvers such as oxalic acid. The content of these additives is arbitrary, as long as it does not impair the effects of the present invention.

[0114] [Manufacturing method of negative resist film laminate]

[0115] The method for manufacturing the negative resist film laminate of the present invention will be described. First, components (A), (B), (C), (D), and (E), as well as component (F) and other components as needed, are simultaneously or in any order dissolved in an organic solvent to prepare a homogeneous negative resist solution. If necessary, the obtained homogeneous solution may also be filtered using a filter.

[0116] The aforementioned organic solvents are not particularly limited as long as they possess sufficient solubility for other components and good film-forming properties. Examples of such organic solvents include cellosolve agents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; propylene glycol-based solvents such as propylene glycol and dipropylene glycol; propylene glycol alkyl ether-based solvents such as propylene glycol monomethyl ether and propylene glycol monobutyl ether; propylene glycol alkyl ether acetate-based solvents such as propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, and propylene glycol monoethyl ether acetate; and butyl acetate, amyl acetate, methyl lactate, and methyl lactate. Ester solvents such as ethyl ester, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; alcohol solvents such as methanol, ethanol, isopropanol, butanol, hexanol, and diacetone alcohol; ketone solvents such as acetone, cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl amyl ketone, and methyl isobutyl ketone; ether solvents such as methyl phenyl ether and diethylene glycol dimethyl ether; highly polar solvents such as N,N-dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide; and mixed solvents thereof.

[0117] Particularly preferred organic solvents include propylene glycol alkyl ether acetate solvents, alkyl lactate esters, and alkyl ketones. The alkyl group in the aforementioned propylene glycol alkyl ether acetates can be alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, and propyl, with methyl and ethyl being preferred. Furthermore, propylene glycol alkyl ether acetates can have 1,2-substituted and 1,3-substituted derivatives, and can have three isomers depending on the combination of substitution positions; these can also be mixtures. Similarly, the alkyl group in alkyl lactate esters can be alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, and propyl, with methyl and ethyl being preferred. The alkyl group in alkyl ketones can be alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isobutyl, cyclopentyl, and cyclohexyl, with isobutyl, cyclopentyl, and cyclohexyl being particularly preferred.

[0118] When preparing the above-mentioned negative resist solution, the amount of organic solvent used is preferably 20 to 1000 parts by mass relative to 100 parts by mass of resin of component (A), more preferably 30 to 200 parts by mass. If the amount of organic solvent used is within the above range, a film with uniform film thickness can be manufactured without defects in the film. In this invention, once the constituent components are uniformly dissolved in excess organic solvent, the target negative resist film laminate is produced through the drying process described later. Therefore, the amount of organic solvent used in dissolving the constituent components can be appropriately adjusted according to the film thickness of the produced film.

[0119] The aforementioned negative resist solution is applied to a thermoplastic film (release substrate) serving as the first support in a cleanroom with a cleanliness level of 1000 or lower using a forward roller coater, reverse roller coater, corner roller coater, compression coater, lip coater, gravure coater, dip coater, air knife coater, capillary coater, R&R (raising and rising) coater, doctor blade coater, bar coater, coater, extruder, or similar machine, provided the area is maintained at a temperature of 5–45°C, preferably 15–35°C, and a humidity of 5–90%, preferably 10–70%. The coating speed is preferably 0.05–1000 m / min, more preferably 0.1–500 m / min. Then, the thermoplastic film coated with the negative resist solution is dried in an online dryer (hot air circulating oven) at 40–130°C for 1–40 minutes, more preferably at 50–120°C for 2–30 minutes, to remove organic solvents and volatile components, thus forming a negative resist film laminate. Alternatively, multiple drying methods can be used instead of an online dryer, such as solvent removal based on infrared irradiation, or a method using both an online dryer and infrared irradiation, to remove solvent and form the negative resist film laminate. Furthermore, if necessary, a protective film (release substrate) can be pressed onto the negative resist film laminate using a roller laminator for lamination.

[0120] Furthermore, in this invention, by delivering the negative resist solution to the production line using specific molding conditions and a molding machine, the thermoplastic film can be continuously rolled and processed into a roll film of the desired shape. The same applies when a protective film is formed on the negative resist film laminate.

[0121] For example, when the support film is rolled out from the roll-out shaft of the film coating machine and passed through the film coating head, a negative resist solution is coated on the support film at a specified thickness. After drying on the support film in a hot air circulating oven at a specified temperature and for a specified time, it is passed through a laminating roller together with a protective film rolled out from another roll-out shaft of the film coating machine at a specified pressure. After being bonded to the negative resist layer on the support film, it is wound onto the winding shaft of the film coating machine. Using this method, a negative resist film laminate can be manufactured in roll form.

[0122] Similar to thermoplastic films, as the aforementioned protective film, there are no particular limitations as long as it does not damage the morphology of the negative resist film and can be peeled off from the negative resist film; a single film or a multilayer film consisting of multiple polymer films can be used. Specifically, examples include nylon films, polyethylene (PE) films, polyethylene terephthalate (PET) films, polyethylene naphthalate (PET) films, polyphenylene sulfide (PPS) films, polypropylene (PP) films, polystyrene films, polymethylpentene (TPX) films, polycarbonate films, fluorinated films, special polyvinyl alcohol (PVA) films, and polyester films that have undergone mold release treatment, among other plastic films.

[0123] Among these, PET film and PE film with moderate flexibility are preferred as protective films. Commercially available products can be used. Examples of PET films include Cerapeel (registered trademark) WZ(RX), BX8(R) (manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (manufactured by Toyobo Co., Ltd.), PET38×1-A3, PET38×1-V8, PET38×1-X08 (manufactured by Nippa Co., Ltd.). Examples of PE films include GF-8 (manufactured by Tamapoly Co., Ltd.), PE film type 0 (manufactured by Nippa Co., Ltd.), Toretec (registered trademark) 7332, 7111, 7721 (manufactured by Toray Film Processing Co., Ltd.).

[0124] Regarding the thickness of the aforementioned thermoplastic film and protective film, from the viewpoint of manufacturing stability and preventing easy curling of the core, a thickness of 10 to 150 μm is preferred, and 25 to 100 μm is more preferred.

[0125] The roll-shaped negative resist film laminate manufactured in this way has excellent storage stability and can be used for a long time.

[0126] The aforementioned negative resist film is formed on the aforementioned thermoplastic film to enable transfer onto the second support. The thickness of the aforementioned negative resist film is preferably 5–250 μm, more preferably 10–180 μm. Furthermore, examples of the second support include plastic films or sheets, semiconductor substrates such as Si, Cu, SiO2, SiN, SiON, TiN, WSi, BPSG, and SOG, metal substrates such as Au, Ti, W, Cu, Ni-Fe, Ta, Zn, Co, and Pb, substrates such as organic antireflective films, and organic substrates. A step height difference (unevenness) caused by circuit formation through plating, sputtering, or the formation of insulating resin may also be formed on the surface of the second support. The step height difference is preferably in the range of approximately 0–200 μm, more preferably in the range of approximately 3–100 μm, and even more preferably in the range of approximately 10–50 μm.

[0127] The peel force of the protective film against the negative resist film manufactured in the above process is typically in the range of 0.1–500 gf / 24 mm, and the testing method is described below. The test method is conducted according to "Test method for adhesion force of peel lining relative to the adhesive surface of pressure-sensitive adhesive tape" as described in JIS Z0237. The test environment is under standard conditions (temperature 23±1℃, relative humidity 50±5%). The film width used in the test is 24 mm; variations in film width result in variations in peel force, which is therefore not preferred. After producing films of the specified size, the peel angle of the protective film is 180° and the peel speed is 5.0±0.2 mm / s when measured using a testing machine. It should be noted that, excluding the initial 25 mm of measurement, the average value of the next 50 mm is used as the test value.

[0128] [Pattern Formation Method]

[0129] Using various laminators such as vacuum laminators and roller laminators, the resist film of the negative resist film laminate of the present invention is adhered to a second support, particularly a semiconductor substrate, and the thermoplastic film is peeled off, thereby enabling the transfer of the negative resist film. The second support can have a stepped height difference structure. By using an appropriate negative resist film thickness according to the height of the stepped height difference, the negative resist film can be embedded within the stepped height difference. Supports with stepped height differences of approximately 0 to 200 μm are preferred. After transfer, there is no problem even if special heating is not performed, but from the viewpoint of improving the adhesion to the substrate, heat treatment is preferred. When heat treatment is performed, pre-baking can be carried out on a hot plate or in an oven at 60 to 150°C for 1 to 30 minutes, preferably at 80 to 130°C for 1 to 10 minutes.

[0130] Next, exposure is performed using radiation selected from ultraviolet, far ultraviolet, and EB sources, preferably with a wavelength of 300 nm or higher, and more preferably with a wavelength of 350–500 nm, through a prescribed mask. The exposure dose is preferably 10–5000 mJ / cm². 2 Around 30–2000 mJ / cm², more preferably 30–2000 mJ / cm² 2 Approximately. After exposure, from the perspective of improving photosensitivity, post-exposure baking (PEB) is performed on a hot plate, preferably at 60–150°C for 1–10 minutes, and more preferably at 80–120°C for 1–5 minutes.

[0131] Then, using a developer solution of 0.1–5% by mass, preferably 2–3% by mass, of an alkaline aqueous solution such as TMAH, and preferably for 0.1–60 minutes, more preferably 0.5–15 minutes, development is performed using known methods such as dip, puddle, or spray to form the target pattern on the second support. After the pattern is formed, the surface may be rinsed as needed.

[0132] Furthermore, after the development process, a metal plating layer can be formed by electroplating or electroless plating to create a plating pattern. Examples of electroplating or electroless plating include Cu electroplating, Cu electroless plating, Ni electroplating, Ni electroless plating, and Au electroplating, which can be performed under known plating bath and plating conditions. Moreover, the thickness of the plating layer is generally formed to be 80% to 100% of the thickness of the resist pattern. For example, if the seed layer is Cu, and a 1 μm thick resist pattern is formed on it, Cu plating is then performed to form a Cu plating pattern with a thickness of 0.8 to 1 μm.

[0133] Example

[0134] The present invention is illustrated below with synthetic examples, embodiments and comparative examples, but the present invention is not limited to the embodiments described below.

[0135] [1] Synthesis of phenolic varnish resin

[0136] [Synthesis example 1]

[0137] In a three-necked flask equipped with a stirrer, condenser, and thermometer, 54.1 g (0.5 mol) of p-cresol, 43.3 g (0.4 mol) of m-cresol, 12.2 g (0.1 mol) of 2,5-dimethylphenol, 52.3 g (0.549 mol) of 37% formaldehyde aqueous solution, and 0.30 g (2.40 × 10⁻⁶) of oxalic acid dihydrate as a polycondensation catalyst were added. -3The flask was immersed in an oil bath, and the temperature inside the flask was maintained at 100℃ for 80 minutes for polycondensation. After the reaction was completed, 500 mL of methyl isobutyl ketone (MIBK) was added, and the mixture was stirred for 30 minutes. The aqueous layer was then separated, and the product extracted to the MIBK layer was washed five times with 300 mL of pure water. The product was then separated and subjected to vacuum stripping at 150℃ using an evaporator at 4 mmHg to obtain 87 g of phenolic varnish resin with a weight-average molecular weight (Mw) of 6000. Furthermore, the Mw was determined using a GPC column (G-2000H6: 2 columns, G-3000H6: 1 column, G-4000H6: 1 column) manufactured by Tosoh Co., Ltd., at a flow rate of 1.5 mL / min, an elution solvent of THF, and a column temperature of 40℃.

[0138] [2] Fabrication of negative resist film laminate

[0139] [Examples 1-8, Comparative Examples 1-4]

[0140] According to the composition shown in Table 1 below, after mixing components (A) to (F) and other components to prepare a solution, filter it through a 1.0 μm membrane filter to prepare resist solutions 1 to 12.

[0141] It should be noted that the components in Table 1 are described below.

[0142] (A) Alkali-soluble resins with phenolic hydroxyl groups

[0143] ·NP1: The phenolic varnish resin synthesized in Example 1

[0144] ·EP6050G: Phenolic varnish resin manufactured by Asahi Organics Co., Ltd. (Mw=2500-4000)

[0145] (B) Polyester

[0146] PE1: PolysizerW-2050 (Adipic acid-based polyester manufactured by DIC Corporation, Mw = 3900)

[0147] ·PE2: ADK Cizer P-300 (Adipic acid-based polyester manufactured by ADEKA Corporation, Mw = 4900) (C) Photoacid-generating agent

[0148] ·PAG1: PAI-101 (manufactured by Midori Kagaku Co., Ltd.)

[0149] PAG2: HT-1CS (manufactured by San-Apro Ltd)

[0150] (D) Crosslinking agent

[0151] ·CL1: EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent 191-207

[0152] [Chemistry 8]

[0153]

[0154] ·CL2: TEPIC-UC (manufactured by Nissan Chemical Co., Ltd.), epoxy equivalent 185-205

[0155] [Chemistry 9]

[0156]

[0157] ·CL3: TEP-G (manufactured by Asahi Organic Materials Co., Ltd.), epoxy equivalent 160-180

[0158] [Chemistry 10]

[0159]

[0160] ·CL4: Nikalik MW-30HM (Methylated melamine manufactured by Sanwa Chemical Co., Ltd.)

[0161] (E) Benzotriazole compounds, imidazole compounds

[0162] BTA-1: Benzotriazole

[0163] ·4MI: 4-Methylimidazole

[0164] (F) Organic solvents

[0165] ·CP: Cyclopentanone

[0166] ·PGMEA: Propylene glycol monomethyl ether acetate

[0167] (Other ingredients)

[0168] KP-341: Manufactured by Shin-Etsu Chemical Co., Ltd.

[0169] NT-300P: Manufactured by Toyosei Kogyo Co., Ltd.

[0170] Curcumin: (Strain) Sanwa Chemical Co., Ltd.

[0171] TrisP-PA: Manufactured by Honshu Chemical Industry Co., Ltd.

[0172] [Table 1]

[0173]

[0174] Resist solutions 1-12 were coated onto a PET film (38 μm thick) as a thermoplastic film in a cleanroom with a cleanliness level of 1000, humidity of 40-45%, and temperature of 22-26°C using a molding coater. The coated films were then dried in a hot air circulating oven at the oven temperatures listed in Table 2 for 5 minutes to produce a negative resist film laminate with a film thickness of 40 μm. Then, a PE film (50 μm thick) as a protective film was laminated onto the surface of the prepared resist film under a pressure of 1 MPa, thus producing negative resist film laminates 1-12 in roll form.

[0175] [Table 2]

[0176]

[0177] [3] Evaluation of void generation

[0178] For the fabricated negative resist film laminates 1-12, firstly, the protective film was peeled off, and using a vacuum laminator TEAM-100M (manufactured by TAKATORI Co., Ltd.), the vacuum chamber was set to a vacuum level of 80 Pa, and the negative resist film on the thermoplastic film was transferred onto a 200 mm Cu substrate with a maximum step height difference of 50 μm. The temperature condition at this time was 60°C. After returning to normal pressure, the substrate was removed from the vacuum laminator, the thermoplastic film was peeled off, and the presence of voids on the substrate was evaluated using an optical microscope (manufactured by Nikon Co., Ltd.). Each example and comparative example was evaluated 5 times, and the average value was used for judgment. No voids were marked as ○. The results are shown in Table 3.

[0179] [Table 3]

[0180] Example 1 1 ○ Example 2 2 ○ Example 3 3 ○ Example 4 4 ○ Example 5 5 ○ Example 6 6 ○ Example 7 7 ○ Example 8 8 ○ Comparative Example 1 9 ○ Comparative Example 2 10 Cracks occur during stacking. Comparative Example 3 11 Cracks occur during stacking. Comparative Example 4 12 ○

[0181] [4] Evaluation of preservation stability

[0182] The negative resist film laminates 1–12 in roll form were stored at 23°C, and the film condition was confirmed after one month. The results are shown in Table 4.

[0183] [Table 4]

[0184] Example 1 1 No change Example 2 2 No change Example 3 3 No change Example 4 4 No change Example 5 5 No change Example 6 6 No change Example 7 7 No change Example 8 8 No change Comparative Example 1 9 No change Comparative Example 2 10 Cracks appeared during use. Comparative Example 3 11 Cracks appeared during use. Comparative Example 4 12 No change

[0185] [5] Evaluation of pattern formation

[0186] A negative resist film laminate of 1 to 12 layers was deposited onto an 8-inch silicon wafer that had been sputter-deposited with Cu using a vacuum laminator. The wafer was then pre-baked at 110°C for 5 minutes on a hot plate. Next, the resulting photosensitive resin film was exposed through an intermediate mask using an i-line stepper (Nikon NSR-2205i11D) for 2 minutes at 100°C using PEB. Following this, it was spray-developed for 5 minutes using a 2.38% TMAH aqueous solution (alkaline developer), and then dried to form a pattern.

[0187] The obtained patterns were analyzed using a scanning electron microscope (Hitachi High Technology Co., Ltd. S-4700) to determine the optimal exposure and resolution. It should be noted that the optimal exposure was set at 50 μm for a 50 μm aperture pattern, and the resolution was set at the mask size used for image processing of the smallest aperture pattern at the optimal exposure. The results are shown in Table 5.

[0188] [Table 5]

[0189]

[0190] [6] Evaluation of solvent resistance

[0191] Negative resist film laminates 1 to 12 were laminated onto 8-inch silicon wafers using a vacuum laminator. Following pre-baking at 110°C for 5 minutes on a hot plate, the wafers were then heat-treated in an oven at 190°C for 2 hours. The wafers were then immersed at 50°C in the various solvents listed in Table 6 below for 15 minutes. Undissolved wafers were marked as ○, partially dissolved wafers as △, and completely dissolved wafers as ×.

[0192] [Table 6]

[0193]

Claims

1. A negative resist film laminate comprising a thermoplastic film as a first support and a negative resist film, wherein the negative resist film comprises: (A) Alkali-soluble resins with phenolic hydroxyl groups, (B) Plasticizers containing polyester, (C) Photoacid-producing agents, (D) An epoxy compound containing an average of 4 or more epoxy groups per molecule, as shown in any of the following formulas (D1) to (D3), and (E) Benzotriazole compounds and / or imidazole compounds, (B) The content of component B is 15-50 parts by weight relative to 100 parts by weight of resin of component A; (C) The content of photoacid-producing agent is 0.3-10 parts by weight relative to 100 parts by weight of resin of component A; (D) The content of component D is 10-100 parts by weight relative to 100 parts by weight of resin of component A; (E) The content of component E is 0.02-5 parts by weight relative to 100 parts by weight of resin of component A. in, m is an integer from 0 to 2, n is an integer greater than 2, and R 11 It is a saturated or unsaturated hydrocarbon group with 1 to 6 carbon atoms, L 1 Each is independently a saturated hydrocarbon group with 1 to 10 carbon atoms. p is an integer from 4 to 8, R 12 It is a p-valent hydrocarbon group with 6 to 30 carbon atoms, optionally containing at least one selected from nitrogen, oxygen, and sulfur atoms. q is an integer from 2 to 4, R 13 It is a hydrocarbon group with a carbon number of 6 to 20 and a q-valence, optionally containing at least one selected from nitrogen, oxygen and sulfur atoms.

2. The laminated body according to claim 1, wherein, The polyester is a polycarboxylic acid polyester having 2 to 6 carboxyl groups.

3. A method for forming a pattern, which includes: (1) The process of transferring a negative resist film of the laminate according to claim 1 or 2 onto the second support. (2) The process of exposing the resist film, and (3) The process of developing the resist film using an alkaline aqueous solution.

4. The pattern forming method according to claim 3, wherein, In process (1), the transfer is followed by heat treatment.

5. The pattern forming method according to claim 3 or 4, wherein, In process (2), the product is heated after exposure.

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