Negative-type resist composition and method for manufacturing resist pattern

Abstract

The present invention provides a negative-type resist composition capable of forming a resist pattern with good resolution, and a method for manufacturing a resist pattern using the negative-type resist composition. [Solution] The present invention relates to a negative-type resist composition containing a resin (A1) having phenolic hydroxyl groups, an acid generator (B), a crosslinking agent (E), and a quencher (C), wherein the acid generator (B) contains a compound (B4) having an amide skeleton, and to a method for producing a resist pattern using the negative-type resist composition.

Description

[Technical Field]

[0001] The present invention relates to a negative-type resist composition and a method for producing a resist pattern. [Background technology]

[0002] Patent Document 1 describes a negative-type resist composition containing partially ethyl etherified polyvinylphenol and m-cresol novolac resin. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2001-42529 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, negative-type resist compositions such as those described in Patent Document 1 sometimes lacked sufficient resolution. Therefore, the object of the present invention is to provide a negative-type resist composition that can form a resist pattern with good resolution. Another object is to provide a method for manufacturing a resist pattern using the negative-type resist composition. [Means for solving the problem]

[0005] The inventors conducted diligent research to solve the above problems and found that the problems could be solved by providing a negative-type resist composition containing a resin (A1), an acid generator (B), and a crosslinking agent (E), wherein the acid generator (B) is a compound having a predetermined group (chemical structure). Further investigation led to the completion of the present invention. In other words, the present invention relates to the following negative-type resist composition and method for producing the same. [1] A negative-type resist composition comprising a resin having phenolic hydroxyl groups (A1), an acid generator (B), a crosslinking agent (E), and a quencher (C), wherein the acid generator (B) comprises a compound having an amide skeleton (B4). [2] The negative resist composition according to [1], wherein the compound having an amide skeleton (B4) is a compound having a group represented by formula (q1). TIFF2026093329000001.tif29170[In formula (q1), * represents a coupling.] [3] The negative resist composition according to [1] or [2], wherein the compound having an amide skeleton (B4) is a compound having a group represented by formula (q11). TIFF2026093329000002.tif33170[In formula (q11), R b06 This represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. * represents a bond. [4] A negative-type resist composition according to any one of [1] to [3], wherein the compound having an amide skeleton (B4) is a compound represented by formula (b4). TIFF2026093329000003.tif42170[In formula (b4), R b1 This represents a hydrocarbon group having 1 to 18 carbon atoms that may contain a fluorine atom, and the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom or a carbonyl group. R b5 Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Ring W b2 This represents an aromatic hydrocarbon ring with 6 to 14 carbon atoms, or an aromatic heterocycle with 6 to 14 carbon atoms. R b6 This represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. x4 represents an integer between 0 and 6. If x4 is 2 or greater, multiple R b5 They may be the same or different. [5] The negative resist composition according to any one of [1] to [4], wherein the resin (A1) having a phenolic hydroxyl group is a resin (A1) containing a structural unit represented by formula (a2-1) and a structural unit represented by formula (a2-4). TIFF2026093329000004.tif44170In formula (a2-1) and formula (a2-4), R a7 and R a13 each independently represents a hydrogen atom or a methyl group. R a10 and R a14 each independently represents an alkyl group having 1 to 6 carbon atoms. R a15 represents a hydrocarbon group having 1 to 12 carbon atoms. m 1 represents any integer from 0 to 4. When m 1 is 2 or more, the plurality of R a10 may be the same or different from each other. m 2 represents any integer from 1 to 4. However, the sum of m 1 and m 2 is 5 or less. m 3 represents any integer from 0 to 4. When m 3 is 2 or more, the plurality of R a14 may be the same or different from each other. m 4 represents any integer from 1 to 4. When m 4 is 2 or more, the plurality of R a15 may be the same or different from each other. However, the sum of m 3 and m 4 [[ID=5⑧]]and is 5 or less.] [6] The negative resist composition according to any one of [1] to [5], wherein the crosslinking agent (E) is a melamine-based crosslinking agent. [7] A method for producing a resist pattern, comprising: (1) A step of applying the negative resist composition according to any one of [1] to [6] onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) Heating and developing the composition layer after exposure. A manufacturing method that includes [details omitted]. [Effects of the Invention]

[0006] According to the present invention, a negative-type resist composition with good resolution can be obtained. [Brief explanation of the drawing]

[0007] [Figure 1] This diagram schematically represents the criteria for evaluating the shape of a hole pattern. [Modes for carrying out the invention]

[0008] In this specification, unless otherwise specified, in the description of the structural formula of a compound, "hydrocarbon group" means a linear or branched chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by combining these. "Alicyclic hydrocarbon group" means a group obtained by removing a number of hydrogen atoms corresponding to the valence from the ring of an alicyclic hydrocarbon. If stereoisomers exist, "hydrocarbon group" includes all stereoisomers. In this specification, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid," and "(meth)acrylate" means "at least one of acrylate and methacrylate." In this specification, groups that can exist in both linear and branched structures are interpreted to include both. In this specification, "solid content of negative-type resist composition" means the total amount of the components of the negative-type resist composition excluding the solvent (D) described later.

[0009] 1. Negative type resist composition The negative-type resist composition of the present invention contains a resin having phenolic hydroxyl groups (hereinafter sometimes referred to as "resin (A1)"), an acid generator (hereinafter sometimes referred to as "acid generator (B)"), a crosslinking agent (hereinafter sometimes referred to as "crosslinking agent (E)"), and a quencher (hereinafter sometimes referred to as "quencher (C)"). Furthermore, the negative resist composition of the present invention may optionally contain a novolac resin (hereinafter sometimes referred to as "novolac resin (A2)"), a solvent (hereinafter sometimes referred to as "solvent (D)"), and other components (hereinafter sometimes referred to as "other components (F)").

[0010] The negative resist composition of the present invention contains an alkali-soluble resin. An alkali-soluble resin is a resin that has acidic groups (sometimes called hydrophilic groups) and is soluble in an alkaline developer. Examples of acidic groups include carboxyl groups, sulfo groups, and hydroxyl groups (such as phenolic hydroxyl groups). Examples of alkali-soluble resins include alkali-soluble resins known in the resist field, such as novolac resin (A2), resins containing structural unit (a2-1) but not containing structural unit (a2-4), resins containing structural units derived from (meth)acrylic acid esters, and polyalkylene glycols.

[0011] <Resin (A1)> The resin (A1) contains structural units having phenolic hydroxyl groups, and preferably contains structural units (a2-1) and (a2-4). TIFF2026093329000005.tif44170[In formula (a2-1) and formula (a2-4), R a7 , and R a13 These elements independently represent either a hydrogen atom or a methyl group. R a10 , and R a14 These terms independently represent alkyl groups having 1 to 6 carbon atoms. R a15This represents a hydrocarbon group having 1 to 12 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced by an oxygen atom or a carbonyl group. m 1 m represents an integer between 0 and 4. 1 When there are 2 or more R a10 They may be the same or different from one another. m 2 This represents an integer between 1 and 4. However, m 1 and m 2 The sum of these is 5 or less. m 3 m represents an integer between 0 and 4. 3 When there are 2 or more R a14 They may be the same or different from one another. m 4 m represents an integer between 1 and 4. 4 When there are 2 or more R a15 They may be the same or different from one another. However, m 3 and m 4 The sum of these is 5 or less.

[0012] R a10 and R a14 Examples of C1-C6 alkyl groups represented by include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. The C1-C6 alkyl group is preferably C1-C4, and more preferably C1-C3. R a10 and R a14 Preferably, each of these groups is an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, even more preferably a methyl group or an ethyl group, and even more preferably a methyl group. m 1 and m 3 These are mutually independent integers, preferably any integer between 0 and 2, and more preferably 0 or 1. R a15Examples of C1-C12 hydrocarbon groups represented by this formula include C1-C12 chain hydrocarbon groups (alkyl groups, alkenyl groups, and alkynyl groups, etc.), C3-C12 alicyclic hydrocarbon groups, C6-C12 aromatic hydrocarbon groups, and C4-C12 groups formed by combining these. Examples of alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group. Examples of alkenyl groups having 2 to 12 carbon atoms include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups. Examples of alkynyl groups having 2 to 12 carbon atoms include ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, tert-butynyl, pentynyl, hexynyl, octinyl, and noninyl groups. The chain-like hydrocarbon group having 1 to 12 carbon atoms is preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms. Alicyclic hydrocarbon groups having 3 to 12 carbon atoms may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bond). TIFF2026093329000006.tif23170 The alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferably having 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms. Examples of aromatic hydrocarbon groups having 6 to 12 carbon atoms include phenyl groups and naphthyl groups. Preferably, the aromatic hydrocarbon group has 6 to 10 carbon atoms. Examples of groups with 4 to 12 carbon atoms formed by combining the above groups include groups (groups with 4 to 12 carbon atoms) that combine alkyl groups and alicyclic hydrocarbon groups, such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, and norbornylethyl group. Examples of groups combining an alkyl group and an aromatic hydrocarbon group (groups having 7 to 12 carbon atoms) include aralkyl groups and aromatic hydrocarbon groups having an alkyl group. Specifically, these include benzyl groups, phenethyl groups, phenylpropyl groups, trityl groups, naphthylmethyl groups, naphthylethyl groups, p-methylphenyl groups, p-tert-butylphenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, 2,6-diethylphenyl groups, and 2-methyl-6-ethylphenyl groups. Examples of groups (groups with 9 to 12 carbon atoms) that combine an alicyclic hydrocarbon group and an aromatic hydrocarbon group include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group. Specifically, examples include p-cyclohexylphenyl groups and phenylcyclohexyl groups. R a15 The hydrocarbon groups having 1 to 12 carbon atoms represented by exclude groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. The methylene groups contained in the hydrocarbon groups having 1 to 12 carbon atoms may be substituted with an oxygen atom or a carbonyl group. However, the methylene group bonded to the oxygen atom in formula (a2-4) and the methylene group bonded to said methylene group are not substituted with an oxygen atom. Also, R a15 It does not contain acid-unstable groups. Acid-unstable groups refer to groups that can be removed upon contact with an acid (sometimes called leaving groups). R a15 Preferably, the group is an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group having 6 to 10 carbon atoms formed by a combination of these. More preferably, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is even more preferred, and a methyl group, an ethyl group, or a propyl group is even more preferred. R a7 and R a13As such, hydrogen atoms are preferred, independently of each other. m 2 and m 4 Each of these is preferably an integer from 1 to 3, and more preferably 1 or 2, independently of the others.

[0013] In resin (A1), the content of structural units (a2-1) is preferably 2 to 99 mol%, more preferably 5 to 98 mol%, even more preferably 10 to 90 mol%, even more preferably 20 to 85 mol%, even more preferably 40 to 85 mol%, and even more preferably 75 to 85% relative to the total structural units of resin (A1). In resin (A1), the content of structural units (a2-4) is preferably 1 to 98 mol%, more preferably 2 to 95 mol%, even more preferably 3 to 40 mol%, even more preferably 5 to 30 mol%, even more preferably 10 to 25 mol%, and still more preferably 15 to 25 mol% relative to the total structural units of resin (A1).

[0014] The resin (A1) may contain structural units other than structural units (a2-1) and (a2-4). Examples of such structural units include structural units of monomers in which the hydroxyl group of hydroxystyrene is replaced with another group, and structural units of monomers having an α,β-unsaturated double bond. Furthermore, examples of monomers that form such structural units include styrene monomers such as styrene, chlorostyrene, and α-methylstyrene; acrylic acid monomers such as acrylic acid, methacrylic acid, methyl acrylate, and methyl methacrylate; and vinyl acetate monomers such as vinyl acetate and vinyl benzoate.

[0015] The resin (A1) can be manufactured, for example, by a method described in Japanese Patent Publication No. 7-295220.

[0016] The resin (A1) has a weight-average molecular weight of preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 5,000 or less. The weight-average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. The detailed analytical conditions for this analysis are described in the examples of this application.

[0017] The content of resin (A1) is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less, based on the total amount of resin contained in the negative-type resist composition of the present invention.

[0018] <Novolac resin (A2)> Novolac resin (A2) is a resin obtained by condensing a phenol compound and an aldehyde in the presence of a catalyst, and is, for example, a resin containing a structural unit represented by the following formula (a4). TIFF2026093329000007.tif29170[In formula (a4), R a45 This represents a halogen atom, a carboxyl group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. na4 represents an integer between 1 and 4. na41 represents an integer between 0 and 3, and when na41 is 2 or greater, multiple R a45 These elements may be identical or different from each other, provided that 1 ≤ na4 + na41 ≤ 4.

[0019] In equation (a4), R a45Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. R a45 The alkyl group having 1 to 6 carbon atoms may be linear or branched, and examples include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. R a45 Examples of C1-C6 haloalkyl groups include groups in which the hydrogen atoms contained in the above alkyl group are replaced by the above halogen atoms, such as C1-C6 alkyl fluorides, C1-C6 alkyl chlorides, C1-C6 alkyl bromides, or C1-C6 alkyl iodides, with C1-C3 perfluoroalkyl groups being preferred. R a45 Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, and tert-butoxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 4, more preferably 1 to 3, even more preferably methoxy or ethoxy, and even more preferably methoxy. R a45 Examples of alkoxyalkyl groups having 2 to 12 carbon atoms include methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl, and tert-butoxymethyl groups. The alkoxyalkyl group is preferably a alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl or ethoxyethyl group, and even more preferably a methoxymethyl group. R a45 Examples of alkoxyalkoxy groups having 2 to 12 carbon atoms include methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, sec-butoxymethoxy, and tert-butoxymethoxy. The alkoxyalkoxy group is preferably a alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy or ethoxyethoxy group. R a45Examples of alkylcarbonyl groups having 2 to 4 carbon atoms include acetyl, propionyl, and butyryl groups. A alkylcarbonyl group having 2 to 3 carbon atoms is preferred, and an acetyl group is more preferred. R a45 Examples of alkylcarbonyloxy groups having 2 to 4 carbon atoms include acetyloxy groups, propionyloxy groups, and butyryloxy groups. Alkylcarbonyloxy groups having 2 to 3 carbon atoms are preferred, and acetyloxy groups are more preferred. In equation (a4), Ra 45 The group is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, even more preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and even more preferably a methyl group or a methoxy group.

[0020] na4 is preferably 1 or 2, and more preferably 1. na41 is preferably 0, 1, or 2, and more preferably 0 or 1.

[0021] The novolac resin (A2) has a weight-average molecular weight of preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, even more preferably 6,000 or more, preferably 100,000 or less, more preferably 50,000 or less, even more preferably 20,000 or less, even more preferably 15,000 or less, and even more preferably 10,000 or less. By setting the weight-average molecular weight within this range, thinning and residue retention after development can be effectively prevented. The weight-average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. The detailed analytical conditions for this analysis are described in the examples of this application.

[0022] The content of resin (A2) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less, based on the total amount of resin contained in the negative-type resist composition of the present invention.

[0023] <Other resins (A3)> The negative-type resist composition of the present invention may contain resins other than resin (A1) and resin (A2) (hereinafter sometimes referred to as "resin (A3)"). Examples of resin (A3) include resins containing structural units derived from (meth)acrylic acid esters, polyalkylene glycols, and the like. <(Meth)acrylic acid ester-derived structural units in resins> Examples of resins containing structural units derived from (meth)acrylic acid esters include those obtained by polymerizing one or more of the following monomers using conventional methods. Monomers having a carboxyl group, such as (meth)acrylic acid; monomers having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; monomers having multiple ether links, such as polyethylene glycol monomethyl ether (meth)acrylates (polyalkylene glycol monoalkyl ether (meth)acrylates), including diethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, pentaethylene glycol monomethyl ether (meth)acrylate, hexaethylene glycol monomethyl ether (meth)acrylate, heptaethylene glycol monomethyl ether (meth)acrylate, octaethylene glycol monomethyl ether (meth)acrylate, and nonaethylene glycol monomethyl ether (meth)acrylate.

[0024] The above monomers may be used in combination with alkyl (meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, tert-butyl (meth)acrylate, and hexyl (meth)acrylate; monocyclic (meth)acrylate esters such as cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate; polycyclic (meth)acrylate esters such as adamantyl (meth)acrylate and norbornyl (meth)acrylate; aryl (meth)acrylate esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; ethylene glycol monoalkyl ether (meth)acrylates (alkylene glycol monoalkyl ether (meth)acrylates) such as ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monopropyl ether (meth)acrylate, and ethylene glycol monobutyl ether (meth)acrylate. In addition to the monomers mentioned above, styrenes such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, and 4-isopropoxystyrene; carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and hydroxystyrenes exemplified in the resin containing the hydroxystyrene-derived structural units mentioned above may also be used in combination. Structural units derived from the monomers mentioned above include those represented by formulas (a2-1) to (a2-4).

[0025] <Polyalkylene glycol> Polyalkylene glycols are polymers obtained by addition polymerization of alkylene oxides to alcohols. Examples of alcohols include butanol, ethylene glycol, propylene glycol, glycerin, and pentaerythritol. Examples of alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide. Examples of polyalkylene glycols include polyethylene glycol, polypropylene glycol, and polybutylene glycol.

[0026] The content of resin (A3) is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total amount of resin contained in the negative-type resist composition of the present invention.

[0027] <Acid Generator (B)> The acid generator (B) is a compound that can decompose and generate acid upon light irradiation (exposure). The generated acid acts as an acid catalyst to promote the crosslinking reaction, allowing the crosslinking agent to bond with the reactive groups in the resin and form a crosslink. In other words, by exposing a negative-type resist composition containing resin (A) to light, it can be made insoluble in the resist developer (alkaline aqueous solution).

[0028] The acid generator (B) includes a compound having an amide skeleton (hereinafter sometimes referred to as "compound (B4)"). In this specification, an amide skeleton is a skeleton in which one carbonyl group (-CO-) is bonded to a nitrogen atom, while an imide skeleton is a skeleton in which two carbonyl groups (-CO-) are bonded to a nitrogen atom; the two are distinct.

[0029] Compounds having an amide skeleton (B4) include compounds having a group represented by formula (q0). TIFF2026093329000008.tif31170[In expression (q0), * represents a bond.] The group represented by formula (q0) is preferably the group represented by formula (q01). TIFF2026093329000009.tif37170[In formula (q01), R b06 This represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. * represents a bond.

[0030] Compound (B4) is preferably a compound having an amide sulfonate group. In this specification, an amide sulfonate group is a group in which one carbonyl group (-CO-) and one sulfonyloxy group (-O-SO2-) are bonded to a nitrogen atom, while an imidosulfonate group is a group in which two carbonyl groups (-CO-) and one sulfonyloxy group (-O-SO2-) are bonded to a nitrogen atom; the two are distinct. Compounds having an amide sulfonate group (B4) include compounds having a group represented by formula (q1). TIFF2026093329000010.tif30170[In formula (q1), * represents a coupling.] The group represented by formula (q1) is preferably the group represented by formula (q11). TIFF2026093329000011.tif33170[In formula (q11), R b06 This represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. * represents a bond.

[0031] Compound (B4) is represented by the compound (b4). TIFF2026093329000012.tif42170[In formula (b4), R b1 This represents a hydrocarbon group having 1 to 18 carbon atoms that may contain a fluorine atom, and the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom or a carbonyl group. R b5 These independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Ring W b2 This represents an aromatic hydrocarbon ring with 6 to 14 carbon atoms, or an aromatic heterocycle with 6 to 14 carbon atoms. R b6 This represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. x4 represents an integer between 0 and 6. If x4 is 2 or greater, multiple R b5 They may be the same or different.

[0032] R b1 Examples of C1-C18 hydrocarbon groups that may have a fluorine atom include linear or branched chain hydrocarbon groups with C1-C18, alicyclic hydrocarbon groups with C3-C18, aromatic hydrocarbon groups with C6-C18, and groups with C4-C18 formed by combining these groups. As linear or branched chain hydrocarbon groups having 1 to 18 carbon atoms, alkyl groups having 1 to 18 carbon atoms are preferred, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Of these, linear groups are preferred. Examples of alicyclic hydrocarbon groups having 3 to 18 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl groups. As aromatic hydrocarbon groups having 6 to 18 carbon atoms, aryl groups having 6 to 18 carbon atoms are preferred, and examples include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups.

[0033] Among the groups with 4 to 18 carbon atoms formed by combining the above groups, examples of groups (groups with 4 to 18 carbon atoms) that combine a chain-type hydrocarbon group and an alicyclic hydrocarbon group include the methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, isobornyl group, 2-alkyladamantan-2-yl group, and 1-(adamantan-1-yl)alkane-1-yl group. Examples of groups (groups with 7 to 18 carbon atoms) that combine a chain-like hydrocarbon group and an aromatic hydrocarbon group include aralkyl groups and alkyl groups. Specifically, these include benzyl groups, phenethyl groups, phenylpropyl groups, trityl groups, naphthylmethyl groups, naphthylethyl groups, p-methylphenyl groups, p-tert-butylphenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, 2,6-diethylphenyl groups, and 2-methyl-6-ethylphenyl groups. Groups (groups with 9 to 18 carbon atoms) that combine an alicyclic hydrocarbon group and an aromatic hydrocarbon group include, for example, aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group. Specifically, examples include p-cyclohexylphenyl group, p-adamantylphenyl group, and phenylcyclohexyl group. R b1 Of the hydrocarbon groups having 1 to 18 carbon atoms represented by , preferably an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0034] R b1 Examples of groups in which a methylene group in a cycloaliphatic hydrocarbon group having 3 to 18 carbon atoms is substituted with an oxygen atom or a carbonyl group include the groups represented by formulas (Y1) to (Y12). Preferably, the groups are represented by formulas (Y7) to (Y9), and more preferably, the group is represented by formula (Y9). TIFF2026093329000013.tif53170

[0035] Examples of hydrocarbon groups having 1 to 18 carbon atoms and containing a fluorine atom include groups in which one or more hydrogen atoms in the above-mentioned hydrocarbon groups having 1 to 18 carbon atoms are substituted with a fluorine atom. Specifically, examples include fluoroalkyl groups such as fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, fluoropentyl, fluorohexyl, fluoroheptyl, fluorooctyl, fluorononyl, and fluorodecyl; fluorocycloalkyl groups such as fluorocyclopropyl, fluorocyclobutyl, fluorocyclopentyl, fluorocyclohexyl, fluorocycloheptyl, fluorooctyl, and fluoroadamantyl; and fluoroaryl groups such as fluorophenyl, fluoronaphthyl, and fluoroanthryl.

[0036] The hydrocarbon group having 1 to 18 carbon atoms and containing a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms and containing a fluorine atom, or an aromatic hydrocarbon group having 6 to 10 carbon atoms and containing a fluorine atom, more preferably a perfluoroalkyl group having 1 to 8 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

[0037] Examples of alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, propyl, butyl, and pentyl groups, with methyl being preferred. Examples of alkoxy groups having 1 to 8 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentyloxy groups, with methoxy being preferred.

[0038] Examples of aromatic hydrocarbon rings having 6 to 14 carbon atoms include benzene rings, naphthalene rings, and anthracene rings. Examples of aromatic heterocycles having 6 to 14 carbon atoms include rings with 6 to 14 atoms constituting the ring, and preferably the following rings. TIFF2026093329000014.tif38170 Ring W b2 This is preferably a naphthalene ring. x4 is preferably an integer from 0 to 4, and more preferably an integer from 0 to 2, independently of each other.

[0039] Examples of compounds represented by formula (b4) include those represented by the following formula. TIFF2026093329000015.tif99170

[0040] The acid generator (B) may further contain other acid generators, to the extent that they do not adversely affect the effects of the present invention. Other acid generators may be either nonionic or ionic. Examples of nonionic acid generators include organic halides, sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxiimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), and sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane). Typical ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of onium salt anions include sulfonate anions, sulfonylimide anions, and sulfonylmethide anions.

[0041] Other acid-generating agents include compounds that generate acid by radiation as described in Japanese Patent Publication Nos. 63-26653, 55-164824, 62-69263, 63-146038, 63-163452, 62-153853, 63-146029, U.S. Patent Nos. 3,779,778 and 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. Furthermore, other acid-generating agents, which may be compounds produced by known methods, may be used individually or in combination of two or more.

[0042] Among other acid generators, examples of nonionic acid generators include compounds represented by formulas (b1) to (b3). TIFF2026093329000016.tif88170[In formulas (b1), (b2), and (b3), R b1 represents the same meaning as described above. R b2 , R b3 and R b4 represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Ring W b1 represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms or an aromatic heterocyclic ring having 6 to 14 carbon atoms. x1 represents any integer from 0 to 6. When x1 is 2 or more, the plurality of R b2 may be the same or different. s x2 represents any integer from 0 to 5. When x2 is 2 or more, the plurality of R b3 may be the same or different. x3 represents any integer from 0 to 5. When x3 is 2 or more, the plurality of R b4 may be the same or different.]

[0043] As the compound represented by formula (b1), a compound represented by any of formulas (b5) to (b8) is preferable, and a compound represented by formula (b5) is more preferable. TIFF2026093329000017.tif98170[In formulas (b5) to (b8), R b1 and R b2 represent the same meaning as described above. x represents any integer from 0 to 6, y represents any integer from 0 to 4, and z represents any integer from 0 to 2. When x is 2 or more, the plurality of R b2 may be the same or different. When y is 2 or more, the plurality of R b2 may be the same or different. When z is 2, the two R b2 may be the same or different. Xb1 and X b2 each independently represents -O-, -S- or -CO-.]

[0044] Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc., and a methyl group is preferable. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, etc., and a methoxy group is preferable.

[0045] Examples of the compound represented by the formula (b1) include compounds represented by the formula (b1-1) to the formula (b1-17). Preferably, they are compounds represented by the formula (b1-6), the formula (b1-7), the formula (b1-10), the formula (b1-13) and the formula (b1-15).

[0046] TIFF2026093329000018.tif190170

[0047] Examples of the compound represented by the formula (b2) include compounds represented by the following formula. TIFF2026093329000019.tif51170

[0048] Examples of the compound represented by the formula (b3) include compounds represented by the following formula. TIFF2026093329000020.tif18170

[0049] Among other acid generators, as ionic acid generators, compounds represented by the formula (b9) or the formula (b10) are preferable. TIFF2026093329000021.tif30170[In the formula (b9) and the formula (b10), A b1 and A b2 each independently represents an oxygen atom or a sulfur atom. R b8 、R b9 、R b10 and R b11Each of these independently represents an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. X1 - and X2 - This represents an organic anion.

[0050] Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of aromatic hydrocarbon groups having 6 to 12 carbon atoms include phenyl groups, naphthyl groups, anthryl groups, biphenyl groups, phenanthryl groups, and other aryl groups. Aromatic hydrocarbon groups may also have substituents. Examples of substituted aromatic hydrocarbon groups include aralkyl groups and alkyl groups. Specifically, examples include benzyl groups, phenethyl groups, phenylpropyl groups, trityl groups, naphthylmethyl groups, naphthylethyl groups, p-methylphenyl groups, p-tert-butylphenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, 2,6-diethylphenyl groups, and 2-methyl-6-ethylphenyl groups. R b8 , R b9 , R b10 and R b11 Each of these is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a phenyl group.

[0051] X1 - and X2 - Examples of organic anions represented by the formula include sulfonic acid anions, bis(alkylsulfonyl)amide anions, tris(alkylsulfonyl)methide anions, and the like, with sulfonic acid anions being preferred, and more preferably sulfonic acid anions represented by formula (b11). TIFF2026093329000022.tif19170[In formula (b11), R b12 This represents a hydrocarbon group having 1 to 18 carbon atoms, which may contain a fluorine atom, and the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. R b12 For example, R in equation (B1) b1 Similar bases can be cited.

[0052] Examples of compounds represented by formula (b9) include the following: TIFF2026093329000023.tif98170

[0053] Examples of compounds represented by formula (b10) include the following compounds. TIFF2026093329000024.tif59170

[0054] In the resist composition of the present invention, the content of the acid generator (B) is preferably 0.1 parts by mass or more and 40 parts by mass or less, more preferably 0.5 parts by mass or more and 30 parts by mass or less, even more preferably 1 part by mass or more and 20 parts by mass or less, and even more preferably 1 part by mass or more and 5 parts by mass or less, per 100 parts by mass of resin (A). The resist composition of the present invention may contain one type of acid generator (B) alone, or may contain multiple types. Furthermore, the content of compound (B4) in the acid generator (B) is 10 to 100% by mass, preferably 30 to 100% by mass, and more preferably 40 to 100% by mass, relative to the total mass of the acid generator (B).

[0055] <Crosslinking agent (E)> The crosslinking agent (E) is a compound that bonds with the resin (A1) through the action of the acid generated when the acid generator (B) decomposes due to light irradiation (exposure). A crosslinked structure is formed by bonding with the resin. Examples of crosslinking agents include melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, and glycoluryl-based crosslinking agents.

[0056] Examples of melamine-based crosslinking agents include compounds represented by formula (e1). TIFF2026093329000025.tif30170[In formula (e1), R e1Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R e2 These are, independently of each other, a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or -CH2-OR e1 It represents. R e3 This represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a group represented by formula (e1-1). TIFF2026093329000026.tif15170[In formula (e1-1), R e1 , and R e2 This represents a base similar to that in equation (e1).

[0057] Specific examples of melamine-based crosslinking agents include N,N,N,N,N,N-hexakis(methoxymethyl)melamine, N,N,N,N,N,N-hexakis(ethoxymethyl)melamine, N,N,N,N,N,N-hexakis(propoxymethyl)melamine, N,N,N,N,N,N-hexakis(isopropoxymethyl)melamine, N,N,N,N,N,N-hexakis(butoxymethyl)melamine, and N,N,N,N,N,N -Hexakis(t-butoxymethyl)melamine, N,N,N,N,N,N-Hexakis(cyclohexyloxymethyl)melamine, N,N,N,N,N,N-Hexakis(cyclopentyloxymethyl)melamine, N,N,N,N,N,N-Hexakis(adamantyloxymethyl)melamine, N,N,N,N,N,N-Hexakis(norbornyloxymethyl)melamine, N,N,N,N,-Tetrakis(methoxy) Methyl) acetoguanamine, N,N,N,N-tetrakis(ethoxymethyl)acetoguanamine, N,N,N,N-tetrakis(propoxymethyl)acetoguanamine, N,N,N,N-tetrakis(isopropoxymethyl)acetoguanamine, N,N,N,N-tetrakis(butoxymethyl)acetoguanamine, N,N,N,N-tetrakis(t-butoxymethyl)acetoguanamine, N,N,N,N-tetrakis Examples include (methoxymethyl)benzoguanamine, N,N,N,N-tetrakis(ethoxymethyl)benzoguanamine, N,N,N,N-tetrakis(propoxymethyl)benzoguanamine, N,N,N,N-tetrakis(isopropoxymethyl)benzoguanamine, N,N,N,N-tetrakis(butoxymethyl)benzoguanamine, N,N,N,N-tetrakis(t-butoxymethyl)benzoguanamine, etc.

[0058] Examples of urea-based crosslinking agents include compounds represented by formula (e2). TIFF2026093329000027.tif20170[In formula (e2), R e1 , and R e2 This represents a base similar to that in equation (e1). Specific examples of urea-based crosslinking agents include, for example, N,N-di(methoxymethyl)urea, N,N-di(ethoxymethyl)urea, N,N-di(propoxymethyl)urea, N,N-di(isopropoxymethyl)urea, N,N-di(butoxymethyl)urea, N,N-di(t-butoxymethyl)urea, N,N-di(cyclohexyloxymethyl)urea, N,N-di(cyclopentyloxymethyl)urea, N,N-di(adamantyloxymethyl)urea, and N,N-di(norbornyloxymethyl)urea.

[0059] Examples of alkylene urea-based crosslinking agents include compounds represented by formula (e3). TIFF2026093329000028.tif28170[In formula (e2), R e1 This represents a base similar to that in equation (e1). R e3 Each of these independently represents a hydrogen atom, a hydroxyl group, a hydrocarbon group with 1 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms. xe represents an integer between 0 and 2.

[0060] Specific examples of alkylene urea-based crosslinking agents include, for example, N,N-di(methoxymethyl)-4,5-di(methoxymethyl)ethyleneurea, N,N-di(ethoxymethyl)-4,5-di(ethoxymethyl)ethyleneurea, N,N-di(propoxymethyl)-4,5-di(propoxymethyl)ethyleneurea, N,N-di(isopropoxymethyl)-4,5-di(isopropoxymethyl)ethyleneurea, N,N-di(butoxymethyl)-4,5-di(butoxymethyl)ethyleneurea, and N,N-di(t-butoxymethyl) Examples include N,N-(cyclohexyloxymethyl)-4,5-di(t-butoxymethyl)ethyleneurea, N,N-(cyclohexyloxymethyl)-4,5-di(cyclohexyloxymethyl)ethyleneurea, N,N-(cyclopentyloxymethyl)-4,5-di(cyclopentyloxymethyl)ethyleneurea, N,N-(adamantyloxymethyl)-4,5-di(adamantyloxymethyl)ethyleneurea, and N,N-(norbornyloxymethyl)-4,5-di(norbornyloxymethyl)ethyleneurea.

[0061] An example of a glycoluryl crosslinking agent is formula (e4). TIFF2026093329000029.tif36170[In formula (e4), R e1 This represents a base similar to that in equation (e1). R e4 These terms independently represent a hydrogen atom, a hydroxyl group, a hydrocarbon group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 6 carbon atoms.

[0062] Specific examples of glycoluryl crosslinking agents include, for example, N,N,N,N-tetra(methoxymethyl) glycoluryl, N,N,N,N-tetra(ethoxymethyl) glycoluryl, N,N,N,N-tetra(propoxymethyl) glycoluryl, N,N,N,N-tetra(isopropoxymethyl) glycoluryl, N,N,N,N-tetra(butoxymethyl) glycoluryl, N,N,N,N-tetra(t-butoxymethyl) glycoluryl, N,N,N,N-tetra(cyclohexyloxymethyl) glycoluryl, N,N,N,N-tetra(cyclopentyloxymethyl) glycoluryl, N,N,N,N-tetra(adamantyloxymethyl) glycoluryl, and N,N,N,N-tetra(norbornyloxymethyl) glycoluryl.

[0063] Among the above, melamine-based crosslinking agents or glycoluryl-based crosslinking agents are preferred as the crosslinking agent (E). Crosslinking agent (E) may be used alone or in combination of two or more types.

[0064] In the negative resist composition of the present invention, the content of the crosslinking agent (E) is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and even more preferably 3 to 30 parts by mass, per 100 parts by mass of resin.

[0065] <Solvent (D)> The content of solvent (D) in the negative resist composition is usually 40% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, and usually 99.9% by mass or less, preferably 99% by mass or less, and more preferably 90% by mass or less. The content of solvent (D) can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0066] Examples of solvent (D) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; and cyclic esters such as γ-butyrolactone. The solvent (D) may contain one type alone, or two or more types.

[0067] <Quencher (C)> The negative resist composition of the present invention may contain a quencher (hereinafter sometimes referred to as "quencher (C)"). Quencher (C) is a compound that captures the acid generated from the acid generator upon exposure. Examples of quencher (C) include basic nitrogen-containing organic compounds. Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. Examples of amines include aliphatic amines (including primary, secondary, and tertiary amines) and aromatic amines.

[0068] Examples of amines include compounds represented by formula (C1) or formula (C2). TIFF2026093329000030.tif20170[In formula (C1), R c1 , R c2 and R c3Each of these independently represents a hydrogen atom, a C1-C6 alkyl group, a C3-C10 alicyclic hydrocarbon group, or a C6-C10 aromatic hydrocarbon group. The C1-C6 alkyl group and the C3-C10 alicyclic hydrocarbon group may have at least one selected from the group consisting of a hydroxyl group, an amino group, and a C1-C6 alkoxy group. The C6-C10 aromatic hydrocarbon group may have at least one selected from the group consisting of a C1-C6 alkyl group, a C1-C6 alkoxy group, and a C3-C10 alicyclic hydrocarbon group.

[0069] The alkyl groups having 1 to 6 carbon atoms, alicyclic hydrocarbon groups having 3 to 10 carbon atoms, aromatic hydrocarbon groups having 6 to 10 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms in formula (C1) are the same as those described above.

[0070] Compounds represented by formula (C1) include, for example, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, dibutylmethylamine, Examples include dichloromethylamine, dihexylmethylamine, dicyclohexylmethylamine, diheptylmethylamine, methyldioctylamine, methyldinonylamine, didecylmethylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyl didecylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, and 4,4'-diamino-3,3'-diethyldiphenylmethane. Diisopropylaniline is preferred, and 2,6-diisopropylaniline is particularly preferred.

[0071] TIFF2026093329000031.tif17170[In formula (C2), Ring W 1 This represents a heterocycle containing a nitrogen atom among the atoms constituting the ring, or a benzene ring having a substituted or unsubstituted amino group, and the heterocycle and the benzene ring may have at least one selected from the group consisting of a hydroxyl group and an alkyl group having 1 to 4 carbon atoms. A 1 This represents a phenyl group or a naphthyl group. nc represents 2 or 3, and multiple A 1They may be the same or different.

[0072] The aforementioned substituted or unsubstituted amino groups are -N(R 4 )(R 5 ) is represented as R 4 and R 5 These terms independently represent a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms. Examples of chain-like hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. As an alicyclic hydrocarbon group having 3 to 10 carbon atoms, R in formula (10) is a1 ~R a3 Similar to those in [the relevant context], the same types of bases can be cited. As an aromatic hydrocarbon group having 6 to 14 carbon atoms, R in formula (20) is a1’ ~R a3’ Similar to those in [the relevant context], the same types of bases can be cited.

[0073] A heterocycle containing a nitrogen atom as one of its constituent atoms may be either an aromatic or non-aromatic ring, and may also contain other heteroatoms (e.g., oxygen or sulfur atoms) along with the nitrogen atom. The number of nitrogen atoms in the heterocycle is, for example, 1 to 3. Examples of such heterocycles include rings represented by any of the formulas (Y13) to (Y28). When one of the hydrogen atoms in the ring is removed, A 1 This forms a combined joint. TIFF2026093329000032.tif53170

[0074] Ring W 1 Preferably, the ring is a heterocycle containing nitrogen atoms among the atoms constituting the ring, more preferably a five-membered or six-membered aromatic heterocycle containing nitrogen atoms among the atoms constituting the ring, and even more preferably a ring represented by any of formulas (Y20) to (Y25).

[0075] Examples of compounds represented by formula (C2) include those represented by any of formulas (C2-1) to (C2-11). Preferably, the compound is one of formulas (C2-2) to (C2-8). TIFF2026093329000033.tif81170

[0076] The quencher (C) content is preferably 0.0001 to 5% by mass, more preferably 0.0001 to 4% by mass, even more preferably 0.001 to 3% by mass, even more preferably 0.01 to 1.0% by mass, and even more preferably 0.1 to 0.7% by mass, in the solid content of the negative-type resist composition. Quencher (C) may contain one type alone, or two or more types.

[0077] <Other ingredients> The negative-type resist composition of the present invention may optionally contain components other than those described above (hereinafter sometimes referred to as "other components (F)"). There are no particular limitations on other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, adhesion improvers, etc., can be used. If other components (F) are used, their content should be appropriately selected depending on the type of other component (F). Other ingredients may be present individually or in combination of two or more.

[0078] 2. Preparation of Negative Resist Composition The negative resist composition of the present invention can be prepared by mixing a resin (A1), an acid generator (B), a crosslinking agent (E), and a quencher (C), and optionally a resin other than resin (A1), a solvent (D), and other components (F). The mixing order is arbitrary and not particularly limited. The mixing temperature can be between 10 and 40°C, and an appropriate temperature can be selected depending on the type of resin, the solubility of the resin in the solvent (D), etc. The mixing time can be selected from between 0.5 and 24 hours, depending on the mixing temperature. There are no particular restrictions on the mixing method, and stirring or other methods can be used. After mixing the components, it is preferable to filter the mixture using a filter with a pore size of approximately 0.003 to 50 μm.

[0079] 3. Method for manufacturing a resist pattern The method for manufacturing a resist pattern of the present invention is: (1) A step of coating the negative resist composition of the present invention onto a substrate, (2) A step of drying the negative-type resist composition after coating to form a composition layer, (3) The step of exposing the composition layer and (4) The process includes heating the composition layer after exposure and developing it.

[0080] The negative resist composition can be applied to a substrate using commonly used equipment such as a spin coater. Examples of substrates include inorganic substrates such as silicon wafers, and semiconductor elements (e.g., transistors, diodes, etc.) may be pre-formed on the substrate. The solvent is removed and a composition layer is formed by drying the coated composition. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a vacuum device. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 30 to 600 seconds. The pressure when drying under reduced pressure is 1 to 1.0 × 10⁻⁶. 5 It is preferable that the pressure be around Pa. After drying, the film thickness of the obtained composition is preferably 1 to 50 μm, and more preferably 1.5 to 30 μm.

[0081] The resulting composition layer is typically exposed using an exposure machine. Various light sources can be used for exposure, including light sources that emit light with wavelengths of 345 to 436 nm (g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), i-line (wavelength: 365 nm)), light sources that emit ultraviolet laser light such as KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), and F2 excimer laser (wavelength: 157 nm), light sources that emit laser light in the ultraviolet or vacuum ultraviolet region by wavelength conversion from laser light from a solid-state laser light source (such as YAG or semiconductor laser), electron beams, and light sources that irradiate with ultra-ultraviolet (EUV) light. Of these, those that use the i-line as the exposure light source are preferred.

[0082] In this specification, the irradiation of these radiations may be collectively referred to as "exposure." During exposure, exposure is usually performed through a mask corresponding to the desired pattern. If the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask.

[0083] The composition layer after exposure may be subjected to heat treatment (so-called post-exposure baking) to promote the crosslinking reaction between the resin and the crosslinking agent. The heating temperature is usually around 50 to 200°C, preferably around 70 to 150°C. The heating time is usually 40 to 400 seconds, preferably 50 to 350 seconds.

[0084] The heated composition layer is typically developed using a developing device and a developing solution. Development methods include the dip method, paddle method, spray method, and dynamic dispensing method. The development temperature is preferably, for example, 5 to 60°C, and the development time is preferably, for example, 5 to 600 seconds.

[0085] The negative resist composition of the present invention uses an alkaline developer as the developer. The alkaline developer can be any alkaline aqueous solution used in this field. For example, aqueous solutions of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline) can be used. The alkaline developer may also contain a surfactant. It is preferable to wash the resist pattern with ultrapure water after development, and then remove any remaining water on the substrate and pattern. After cleaning, it is preferable to remove any remaining rinse solution from the substrate and patterns.

[0086] By exposing a resist obtained using the negative-type resist composition of the present invention, a resist pattern with a highly accurate shape can be formed.

[0087] 4.Applications The negative-type resist composition of the present invention is useful for producing thick resist films. For example, it is useful for producing resist films with a thickness of 1 to 50 μm (more preferably 1.5 to 30 μm). [Examples]

[0088] The present invention will be described in more detail with reference to examples. In the examples, "%" and "parts" representing the content or amount used are based on mass unless otherwise specified. The weight-average molecular weight was determined by gel permeation chromatography under the following conditions. Equipment: HLC-8320GPC model (manufactured by Tosoh Corporation) Column: TSKgel Multipore H XL -M x 3 + guardcolumn (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

[0089] Synthesis Example 1 [Synthesis of Resin (A3)-1] 70 parts of ethyl acetate were added to a four-necked flask equipped with a reflux condenser, stirrer, and thermometer, and the temperature was raised to 80°C. A mixture of 20 parts methacrylic acid, 58 parts ethyl acrylate, 35 parts methyl methacrylate (molar ratio: methacrylic acid:ethyl acrylate:methyl methacrylate = 20:50:30), 4.91 parts 2,2′-azobis(2-methylbutyronitrile), and 100 parts ethyl acetate was added dropwise over 2 hours. The mixture was stirred for 3 hours while maintaining a temperature of 80°C to 85°C. The resulting mixture was cooled to below 40°C, diluted with 125 parts of ethyl acetate, poured into a large amount of deionized water and methanol mixture to precipitate the resin, and then filtered and recovered. To the obtained resin, 650 parts of propylene glycol monomethyl ether acetate were added, dissolved, and concentrated. Then, another 650 parts of propylene glycol monomethyl ether acetate were added, and the mixture was concentrated again to obtain 185 parts of a propylene glycol monomethyl ether acetate solution of resin (A3)-1 (49% solids, 80% yield). The weight-average molecular weight of resin (A3)-1 is 1.26 × 10⁶. 4 That was the case. TIFF2026093329000034.tif28170

[0090] Synthesis Example 2 [Synthesis of Resin (A3)-2] 70 parts of ethyl acetate were added to a four-necked flask equipped with a reflux condenser, stirrer, and thermometer, and the temperature was raised to 55°C. A mixture of 15 parts methacrylic acid, 58 parts ethyl acrylate, 41 parts methyl methacrylate (molar ratio: methacrylic acid:ethyl acrylate:methyl methacrylate = 15:50:35), 3.46 parts 2,2′-azobis(2,4-dimethylvaleronitrile), and 100 parts ethyl acetate was added dropwise over 2 hours. The mixture was stirred for 3 hours while maintaining the temperature at 50°C to 55°C. The resulting mixture was cooled to below 40°C, diluted with 125 parts of ethyl acetate, poured into a large amount of deionized water and methanol mixture to precipitate the resin, which was then filtered and recovered. To the obtained resin, 650 parts of propylene glycol monomethyl ether acetate were added, dissolved, and concentrated. Then, another 650 parts of propylene glycol monomethyl ether acetate were added, and the mixture was concentrated again to obtain 190 parts of a propylene glycol monomethyl ether acetate solution of resin (A3)-2 (45% solids, 75% yield). The weight-average molecular weight of resin (A3)-2 is 3.79 × 10⁻⁶. 4 That was the case. TIFF2026093329000035.tif29170

[0091] <Preparation of Negative Resist Composition> A negative-type resist composition was prepared by mixing and dissolving each component shown in Table 1, and then filtering the resulting mixture through a fluororesin filter with a pore size of 5 μm.

[0092] [Table 1]

[0093] <Resin> (A1)-1: Resin (A1)-1 A resin containing the following constituent units. Synthesized by the method described in Japanese Patent Publication No. 2001-42529. TIFF2026093329000037.tif43170 Weight average molecular weight: 3700 The percentage of poly-p-hydroxystyrene in which hydroxyl groups are substituted with ethoxy groups is 20.9%. (A2)-1: Resin (A2)-1 A resin containing the following constituent units. Synthesized by the method described in Japanese Patent Publication No. 2001-42529. TIFF2026093329000038.tif29170 Weight average molecular weight: 9250

[0094] <Acid Generator (B)> (B4)-1: Compound represented by the following formula (synthesized by the method described in publication WO2016 / 072049) TIFF2026093329000039.tif35170(B4)-2: Compound represented by the following formula (synthesized by the same method as described in WO2016 / 072049, but with (+)-10-camphorsulfonyl chloride replaced by 1-octanesulfonyl chloride) TIFF2026093329000040.tif25170(B1)-1: N-hydroxynaphthalimide triflate (Heraeus) TIFF2026093329000041.tif22170(B2)-1: Compound represented by the following formula (manufactured by BASF) TIFF2026093329000042.tif27170

[0095] <Crosslinking agent (E)> (E)-1: N,N,N,N,N,N-Hexakis(methoxymethyl)melamine (manufactured by Tokyo Chemical Industry Co., Ltd.) TIFF2026093329000043.tif41170

[0096] <Quencher (C)> (C)-1: N,N-dicyclohexylmethylamine (manufactured by Aldrich) (C)-2: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0097] <Solvent (D)> (D)-1: Propylene glycol monomethyl ether acetate

[0098] Examples 1-5, Comparative Examples 1, 2 (i-line exposure evaluation of negative-type resist compositions) The above negative-type resist composition was spin-coated onto a 4-inch silicon wafer substrate treated with hexamethylene disilazane (HMDS) to a pre-baked film thickness of 20 μm. Subsequently, the mixture was pre-baked on a direct hot plate at 120°C for 180 seconds to form the composition layer. Next, the composition layer formed on the wafer was exposed using an i-line stepper (NSR-2005i9C; manufactured by Nikon Corporation, NA=0.5) with the exposure amount gradually changed, through a mask to form a 1:1 contact hole pattern (hole diameter: 6 μm, 5 μm, pitch: 12 μm, 10 μm). After exposure, a post-exposure bake was performed on a hot plate at 110°C for 60 seconds, followed by paddle development with a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 180 seconds to obtain a resist pattern. The resist pattern obtained after development was observed with a scanning electron microscope, and the exposure level at which a 6 μm diameter hole pattern was obtained was defined as the effective sensitivity.

[0099] <Resolution Evaluation> The resist patterns obtained in the effective sensitivity test were observed using a scanning electron microscope. Patterns in which a 5 μm diameter hole pattern was resolved were marked with "○", and patterns in which the 5 μm diameter hole pattern was not resolved were marked with "×". The results are shown in Table 2.

[0100] <Shape evaluation> The 6 μm hole patterns obtained in the effective sensitivity test were observed using a scanning electron microscope. Those with a top and base shape that was close to rectangular and good [Figure 1(a)] were marked with "◎", those with a notch in the base shape [Figure 1(b)] were marked with "〇", and those with an inverted tapered shape [Figure 1(c)] were marked with "△". The results are shown in Table 2.

[0101] [Table 2] (*a) A hole pattern with a diameter of 5 μm was resolved. (*b) The 6 μm diameter hole pattern was resolved, but the 5 μm diameter hole pattern was not.

[0102] Examples 1-6 showed good resolution. On the other hand, Comparative Examples 1 and 2 resolved a 6 μm diameter hole pattern, but failed to resolve a 5 μm diameter hole pattern. [Industrial applicability]

[0103] The negative resist composition of the present invention has good resolution and is useful for microfabrication of semiconductors.

Claims

1. A negative-type resist composition comprising a resin having phenolic hydroxyl groups (A1), an acid generator (B), a crosslinking agent (E), and a quencher (C), wherein the acid generator (B) comprises a compound having an amide skeleton (B4).

2. The negative-type resist composition according to claim 1, wherein the compound having an amide skeleton (B4) is a compound having a group represented by formula (q1). [In equation (q1), * represents a bond.]

3. The negative-type resist composition according to claim 1, wherein the compound having an amide skeleton (B4) is a compound having a group represented by formula (q11). [In formula (q11), R ｂ０６ This represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. * represents a bonding operation.

4. The negative-type resist composition according to claim 1, wherein the compound (B4) having an amide skeleton is a compound represented by formula (b4). [In formula (b4), R ｂ１ This represents a hydrocarbon group having 1 to 18 carbon atoms that may contain a fluorine atom, and the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom or a carbonyl group. R ｂ５ Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Ring W ｂ２ This represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms, or an aromatic heterocycle having 6 to 14 carbon atoms. R ｂ６ This represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. x4 represents an integer between 0 and 6. If x4 is 2 or greater, multiple R ｂ５ They may be the same or different.

5. The negative-type resist composition according to claim 1, wherein the resin (A1) having a phenolic hydroxyl group is a resin (A1) containing a structural unit represented by formula (a2-1) and a structural unit represented by formula (a2-4). [In formula (a2-1) and formula (a2-4), R ａ７ and R ａ１３ These elements independently represent either a hydrogen atom or a methyl group. R ａ１０ and R ａ１４ each independently represents an alkyl group having 1 to 6 carbon atoms. R ａ１５ This represents a hydrocarbon group having 1 to 12 carbon atoms. I understand １ m represents an integer between 0 and 4. １ When there are 2 or more, multiple R ａ１０ They may be the same or different from one another. I understand ２ This represents an integer between 1 and 4. However, m １ Tom ２ The sum of these is 5 or less. I understand ３ m represents an integer between 0 and 4. ３ When there are 2 or more, multiple R ａ１４ They may be the same or different from one another. I understand ４ m represents an integer between 1 and 4. ４ When there are 2 or more, multiple R ａ１５ They may be the same or different from one another. However, m ３ Tom ４ The sum of these is 5 or less.

6. The negative-type resist composition according to claim 1, wherein the crosslinking agent (E) is a melamine-based crosslinking agent.

7. A method for manufacturing a resist pattern, (1) A step of coating a negative-type resist composition according to any one of claims 1 to 6 onto a substrate. (2) A step of drying the coated composition to form a composition layer, (3) A step of exposing the composition layer, (4) Heating and developing the composition layer after exposure. A manufacturing method that includes this.

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