Negative resist composition and method for producing resist pattern

Abstract

The present application relates to a negative resist composition and a method for producing a resist pattern. The present application provides a negative resist composition capable of forming a resist pattern with good shape. In addition, a method for producing a resist pattern using the negative resist composition is provided. The present application relates to a negative resist composition containing a resin (A1) containing a structural unit represented by formula (a2-1) and a structural unit represented by formula (a2-4), an acid generator (B), a crosslinking agent (E), and an aromatic compound (I) having a molecular weight of 2000 or less and having 3 or more phenolic hydroxyl groups, and a method for producing a resist pattern using the composition.

Description

Technical Field

[0001] This invention relates to a negative resist composition and a method for manufacturing a resist pattern. Background Technology

[0002] Patent document 1 describes a negative resist composition containing partially ethyl etherified polyvinylphenol and m-cresol phenolic resin.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2001-42529 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] The negative resist composition described in Patent Document 1 sometimes results in an undesirable resist pattern due to the influence of standing waves generated by the reflection of light used for exposure from the substrate.

[0008] Therefore, the objective of this invention is to provide a negative resist composition capable of forming well-shaped resist patterns. Furthermore, another objective of this invention is to provide a method for manufacturing resist patterns using this negative resist composition.

[0009] means for solving problems

[0010] To address the aforementioned problems, the inventors conducted in-depth research and discovered that by preparing a negative resist composition containing a resin (A1), an acid-generating agent (B), a crosslinking agent (E), and an aromatic compound (I), wherein the aromatic compound (I) comprises a compound with a molecular weight of less than 2000 and having three or more phenolic hydroxyl groups, the problems could be solved. Further research led to the completion of this invention.

[0011] That is, the present invention relates to the following negative resist composition and a method for manufacturing a resist pattern using the composition.

[0012] [1] A negative resist composition, wherein the negative resist composition comprises: a resin (A1) containing structural units of formula (a2-1) and formula (a2-4), an acid-producing agent (B), a crosslinking agent (E), and an aromatic compound (I) having a molecular weight of less than 2000 and having more than 3 phenolic hydroxyl groups.

[0013]

[0014] In equations (a2-1) and (a2-4), Ra7 and R a13 They can be used to represent hydrogen atoms or methyl groups independently.

[0015] R a10 and R a14 Alkyl groups having 1 to 6 carbon atoms can be represented independently.

[0016] R a15 It represents a hydrocarbon group with 1 to 12 carbon atoms.

[0017] m 1 Represents any integer from 0 to 4. When m 1 When the value is 2 or higher, multiple R a10 They can be the same or different.

[0018] m 2 It represents any integer from 1 to 4.

[0019] Where, m 1 With m 2 The total is less than 5.

[0020] m 3 Represents any integer from 0 to 4. When m 3 When the value is 2 or higher, multiple R a14 They can be the same or different.

[0021] m 4 Represents any integer from 1 to 4. When m 4 When the value is 2 or higher, multiple R a15 They can be the same or different.

[0022] Where, m 3 With m 4 The total is less than 5.

[0023] [2] According to the negative resist composition of [1], wherein the aromatic compound (I) is a compound represented by formula (I0).

[0024]

[0025] In equation (I0), L 0 and L 1 These can be independently represented as hydrocarbon groups with 1 to 20 carbon atoms that may have substituents, wherein the methylene group contained in the hydrocarbon group can be replaced by an oxygen atom or a carbonyl group.

[0026] R h12 R h13 and R h14 Independently representing halogen atoms or hydrocarbon groups having 1 to 20 carbon atoms that may have substituents, or Rh12 With R h13 R h12 With R h14 R h13 With R h14 Or R h12 R h13 or R h14 With L 0 or L 1 They can bond together to form rings that can have substituents.

[0027] k0 represents any integer from 0 to 6. When k0 is 2 or higher, the groups within the parentheses can be the same or different.

[0028] k1 represents any integer from 1 to 6. When k1 is 2 or higher, the groups within the parentheses can be the same or different from each other.

[0029] h1 and h2 represent any integer from 0 to 5 independently.

[0030] h5 represents any integer from 0 to 4.

[0031] h3 and h4 independently represent any integer from 0 to 5. When h3 is greater than 2, multiple R... h12 They can be the same or different. When h4 is 2 or more, multiple Rs h13 They can be the same or different.

[0032] h6 represents any integer from 0 to 4. When h6 is 2 or higher, multiple R... h14 They can be the same or different.

[0033] Among them, the sum of h1, h2, and h5 is 3 or more; the sum of h1 and h3 is 5 or less; the sum of h2 and h4 is 5 or less; and the sum of h5 and h6 is 4 or less.

[0034] [3] The negative resist composition according to [1] or [2], wherein the aromatic compound (I) is a compound of formula (I1).

[0035]

[0036] In equation (I1), Xi represents a single bond or an oxygen atom.

[0037] A represents an alkyldiyl group with 1 to 6 carbon atoms that can have substituents, wherein the methylene group contained in the alkyldiyl group can be replaced by an oxygen atom or a carbonyl group. Specifically, when Xi is an oxygen atom, the methylene group bonded to Xi is not replaced by an oxygen atom.

[0038] i1 and i2 independently represent any integer from 0 to 4. The sum of i1 and i2 is 3 or more.

[0039] R i12 and R i13 The halogen atom or the alkyl group having 1 to 12 carbon atoms that may have substituents can be represented independently.

[0040] i3 and i4 independently represent any integer from 0 to 4. When i3 is 2 or higher, multiple R... i12 They can be the same or different. When i4 is 2 or higher, multiple Rs... i13 They can be the same or different.

[0041] R i1 R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms that may have substituents, or, in the case of A being an alkyldiyl group, R i1 It can bond with A to form a ring that can have substituents.

[0042] Among them, the sum of i1 and i3 is less than 4, and the sum of i2 and i4 is less than 5.

[0043] [4] The negative resist composition according to any one of [1] to [3], wherein the crosslinking agent (E) is a glycourea crosslinking agent.

[0044] [5] A manufacturing method for a resist pattern, wherein the manufacturing method comprises the following steps: (1) The process of coating the negative resist composition described in any one of [1] to [4] onto a substrate; (2) A process of drying the coated composition to form a composition layer; (3) The process of exposing the composite layer; and (4) The process of heating and developing the exposed composite layer.

[0045] Invention Effects

[0046] According to the present invention, a negative resist composition with good resist pattern shape can be obtained. Attached Figure Description

[0047] Figure 1 It is a diagram that schematically represents the cross-sectional shape of the lines and spaces in a resist pattern. Detailed Implementation

[0048] In this specification, unless otherwise stated, in the description of the structural formula of a compound, "hydrocarbon group" refers to a linear or branched chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and groups composed of these. "Alicyclic hydrocarbon group" refers to a group obtained by removing a number of hydrogen atoms equivalent to the valence from the ring of an alicyclic hydrocarbon. "Aromatic hydrocarbon group" also includes groups with chain hydrocarbon groups and alicyclic hydrocarbon groups bonded to an aromatic ring. In the presence of stereoisomers, all stereoisomers are included.

[0049] 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".

[0050] In this specification, groups that can take both straight-chain and branched structures are to be interpreted in a way that includes both of their meanings.

[0051] In this specification, "solid component of negative resist composition" means the total of the components after removing the solvent (D) described later from the total amount of negative resist composition.

[0052] 1. Negative resist composition

[0053] The negative resist composition of the present invention contains: a resin having phenolic hydroxyl groups (hereinafter sometimes referred to as "resin (A1)"), an acid-generating agent (hereinafter sometimes referred to as "acid-generating agent (B)"), a crosslinking agent (hereinafter sometimes referred to as "crosslinking agent (E)"), and an aromatic compound having a molecular weight of 2000 or less and having 3 or more phenolic hydroxyl groups (hereinafter sometimes referred to as "compound (I)" or "aromatic compound (I)").

[0054] Furthermore, the negative resist composition of the present invention may contain, as needed, a resin other than resin (A1), a quencher (hereinafter sometimes referred to as "quencher (C)"), a solvent (hereinafter sometimes referred to as "solvent (D)"), and other components (hereinafter sometimes referred to as "other components (F)").

[0055] In the negative resist composition of the present invention, examples of resins other than resin (Al) include alkali-soluble resins. Alkali-soluble resins are resins that have acidic groups (sometimes also called hydrophilic groups) and are soluble in alkaline developing solutions. Acidic groups include, for example, carboxyl groups, sulfonyl groups, and hydroxyl groups (phenolic hydroxyl groups, etc.).

[0056] Examples of alkali-soluble resins include: alkali-soluble resins known in the field of resists, such as: phenolic varnish resins (hereinafter sometimes referred to as "phenolic varnish resin (A2)"), resins containing structural units (a2-1) but not structural units (a2-4), resins containing structural units derived from (meth)acrylates, and polyalkylene glycols, etc.

[0057] <Resin (A1)>

[0058] The resin (A1) contains structural units having phenolic hydroxyl groups, preferably a resin containing structural units (a2-1) and structural units (a2-4).

[0059]

[0060] In equations (a2-1) and (a2-4), R a7 and R a13 They can be used to represent hydrogen atoms or methyl groups independently.

[0061] R a10 and R a14 Alkyl groups having 1 to 6 carbon atoms can be represented independently.

[0062] R a15 It represents a hydrocarbon group with 1 to 12 carbon atoms.

[0063] m 1 Represents any integer from 0 to 4. When m 1 When the value is 2 or higher, multiple R a10 They can be the same or different.

[0064] m 2 It represents any integer from 1 to 4.

[0065] Where, m 1 With m 2 The total is less than 5.

[0066] m 3 Represents any integer from 0 to 4. When m 3 When the value is 2 or higher, multiple R a14 They can be the same or different.

[0067] m 4 Represents any integer from 1 to 4. When m 4 When the value is 2 or higher, multiple R a15 They can be the same or different.

[0068] Where, m 3 With m 4 The total is less than 5.

[0069] R a15 The hydrocarbon groups with 1 to 12 carbon atoms shown do not include groups where the carbon atom bonded to the oxygen atom is a tertiary carbon atom. The methylene group contained in the hydrocarbon group with 1 to 12 carbon atoms may be replaced by an oxygen atom or a carbonyl group. Among them, the methylene group bonded to the oxygen atom and the methylene group bonded to the methylene group in formula (a2-4) are not replaced by oxygen atoms.

[0070] As R a15 Preferably, it is an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably methyl, ethyl, and propyl.

[0071] In resin (A1), the content of structural unit (a2-1) is preferably 10 mol% to 90 mol% relative to all structural units of resin (A1), and more preferably 20 mol% to 85 mol%.

[0072] In resin (A1), the content of structural unit (a2-4) is preferably 5 mol% to 40 mol% relative to all structural units of resin (A1), more preferably 10 mol% to 30 mol%, and even more preferably 15 mol% to 30 mol%.

[0073] The resin (A1) may contain structural units other than structural units (a2-1) and structural units (a2-4). Examples of such structural units include: structural units of monomers in which the hydroxyl groups of hydroxystyrene are replaced by other groups, and structural units of monomers having α,β-unsaturated double bonds.

[0074] In addition, examples of monomers that form this structural unit include: styrene monomers such as styrene, chlorostyrene, and α-methylstyrene; acrylic monomers such as acrylic acid, methacrylic acid, methyl acrylate, and methyl methacrylate; and vinyl acetate monomers such as vinyl acetate and vinyl benzoate.

[0075] The resin (A1) can be manufactured, for example, by the method described in Japanese Patent Application Publication No. 7-295220.

[0076] The weight-average molecular weight of the resin (A1) is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, preferably 10000 or less, more preferably 8000 or less, and even more preferably 5000 or less. The weight-average molecular weight is determined by gel permeation chromatography analysis as a conversion value based on standard polystyrene. Detailed analytical conditions for this analysis are described in the embodiments of this application.

[0077] The content of resin (Al) is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 100% by mass or less, relative to the total amount of resin contained in the negative resist composition of the present invention.

[0078] <Phenolic varnish resin (A2)>

[0079] Phenolic varnish resin (A2) is a resin obtained by condensing phenolic compounds with aldehydes in the presence of a catalyst, for example, a resin containing the structural unit shown in the following formula (a4).

[0080]

[0081] In equation (a4), R a45 It can represent a halogen atom, a carboxyl group, an alkyl group with 1 to 6 carbon atoms, a haloalkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, an alkoxyalkyl group with 2 to 12 carbon atoms, an alkoxyalkoxy group with 2 to 12 carbon atoms, an alkyl carbonyl group with 2 to 4 carbon atoms, an alkyl carbonyloxy group with 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group.

[0082] na4 represents any integer from 1 to 4.

[0083] na41 represents any integer from 0 to 3. When na41 is 2 or higher, multiple R... a45 They can be the same or different. Among them, 1 ≤ na⁴ + na⁴¹ ≤ 4.

[0084] In equation (a4), as R a45 Halogen atoms can be listed as: fluorine, chlorine, bromine and iodine.

[0085] As R a45 Alkyl groups having 1 to 6 carbon atoms can be straight-chain or branched, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.

[0086] As R a45 The alkyl halogroup having 1 to 6 carbon atoms can be exemplified by groups obtained by replacing the hydrogen atoms in the alkyl halogroup with the halogen atoms, such as fluoroalkyl halogroups having 1 to 6 carbon atoms, chloroalkyl halogroups having 1 to 6 carbon atoms, bromoalkyl halogroups having 1 to 6 carbon atoms, or iodoalkyl halogroups having 1 to 6 carbon atoms, wherein, preferably, perfluoroalkyl halogroups having 1 to 3 carbon atoms.

[0087] As R a45Alkoxy groups having 1 to 6 carbon atoms can be exemplified by: methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, and tert-butoxy. The alkoxy group preferably has 1 to 4 carbon atoms, more preferably 1 to 3, further preferably methoxy or ethoxy, and even more preferably methoxy.

[0088] As R a45 The alkoxyalkyl group having 2 to 12 carbon atoms can be exemplified by: methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl, and tert-butoxymethyl. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably methoxymethyl or ethoxyethyl, and even more preferably methoxymethyl.

[0089] As R a45 Alkoxyalkyl groups having 2 to 12 carbon atoms can be listed as follows: methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, sec-butoxymethoxy, and tert-butoxymethoxy. Preferably, the alkoxyalkyl group has 2 to 8 carbon atoms, and more preferably, it is methoxyethoxy or ethoxyethoxy.

[0090] As R a45 The alkyl carbonyl group having 2 to 4 carbon atoms can be exemplified by acetyl, propionyl, and butyryl groups. Preferably, the alkyl carbonyl group has 2 to 3 carbon atoms, and more preferably, it has acetyl.

[0091] As R a45 The alkyl carbonyloxy group having 2 to 4 carbon atoms can be exemplified by acetoxy, propionyloxy, and butyryloxy. Preferably, the alkyl carbonyloxy group has 2 to 3 carbon atoms, and more preferably, it has acetoxy.

[0092] In equation (a4), Ra is... 45 Preferably, it is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group or an alkoxy group having 1 to 3 carbon atoms, further preferably methyl, ethyl, methoxy or ethoxy, and even more preferably methyl or methoxy.

[0093] na4 is preferably 1 or 2, more preferably 1.

[0094] na41 is preferably 0, 1 or 2, more preferably 0 or 1.

[0095] The weight-average molecular weight of the phenolic varnish resin (A2) is preferably 3000 or more, more preferably 4000 or more, further preferably 5000 or more, even more preferably 6000 or more, preferably 100000 or less, more preferably 50000 or less, even more preferably 10000 or less, even more preferably 9000 or less, and even more preferably 8000 or less. By adjusting the weight-average molecular weight to this range, film formation and residue residue can be effectively prevented after development. The weight-average molecular weight is determined by gel permeation chromatography analysis as a conversion value based on standard polystyrene. Detailed analytical conditions for this analysis are described in the embodiments of this application.

[0096] Relative to the total amount of resin contained in the negative resist composition of the present invention, 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.

[0097] <Other Resins (A3)>

[0098] The negative resist composition of the present invention may contain a resin other than resin (A1) and resin (A2) (hereinafter, sometimes referred to as "resin (A3)"). Examples of resin (A3) include: resins containing structural units (a2-1) but not structural units (a2-4), resins containing structural units derived from (meth)acrylates, polyalkylene glycols, etc.

[0099] <Resins containing structural units derived from (meth)acrylates>

[0100] Examples of resins comprising structural units derived from (meth)acrylates include resins obtained by polymerizing one or more of the following monomers using conventional methods, employing compounds described below as monomers. Examples of resins comprising structural units derived from (meth)acrylates include resins comprising structural units derived from monomers described below.

[0101] Monomers containing carboxyl groups, such as (meth)acrylic acid; monomers containing hydroxyl groups, such as 2-hydroxyethyl (meth)acrylic acid and 2-hydroxypropyl (meth)acrylic acid; monomers containing multiple ether bonds, such as 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, nonaethylene glycol monomethyl ether (meth)acrylate, etc., of polyethylene glycol monomethyl ether (meth)acrylate (polyalkylene glycol monoalkyl ether (meth)acrylate) and other monomers.

[0102] The above monomers can be used in combination with alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, tert-butyl methacrylate, and hexyl methacrylate; monocyclic methacrylates such as cyclopentyl methacrylate and cyclohexyl methacrylate; polycyclic methacrylates such as adamantyl methacrylate and norborneol methacrylate; aryl methacrylates such as phenyl methacrylate and benzyl methacrylate; and ethylene glycol monoalkyl ether methacrylates such as ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether methacrylate, ethylene glycol monopropyl ether methacrylate, and ethylene glycol monobutyl ether methacrylate (alkylene glycol monoalkyl ether methacrylates). In addition to the monomers mentioned above, styrene derivatives such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, and 4-isopropoxystyrene can also be used in combination; carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, zeaxanthinic acid, and itaconic acid can also be used; and hydroxystyrene derivatives exemplified in the resins containing structural units derived from hydroxystyrene. Structural units derived from the monomers described above can also be listed as those shown in formulas (a2-1) to (a2-4).

[0103] <Polyalkylene glycols>

[0104] Polyalkylene glycols are polymers obtained by addition polymerization of alkylene oxides and alcohols. Examples of alcohols include butanol, butanediol, ethylene glycol, propylene glycol, glycerol, and pentaerythritol. Examples of alkylene oxides include ethylene oxide, propylene oxide, and butane oxide. Examples of polyalkylene glycols include polyethylene glycol, polypropylene glycol, and polybutanediol.

[0105] Relative to the total amount of resin contained in the negative resist composition of the present invention, 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.

[0106] <Acid-producing agent (B)>

[0107] The acid-generating agent (B) is a compound that can decompose upon light irradiation (exposure) to produce acid. The produced acid acts as an acid catalyst that promotes the crosslinking reaction, allowing the crosslinking agent to bond with reactive groups in the resin to form crosslinks. That is, by exposing the negative resist composition containing resin (A), it can be made insoluble in the resist developer (alkaline aqueous solution).

[0108] Acid-generating agent (B) can be either nonionic or ionic.

[0109] Examples of nonionic acid-generating agents include: organohalides, sulfonates (e.g., 2-nitrobenzyl ester, aromatic sulfonates, oxime sulfonates, N-sulfonyloxyimides, sulfonyloxyketones, diazonoquinone-4-sulfonates), and sulfones (e.g., disulfones, ketone sulfones, sulfonyldiazomethane). Examples of ionic acid-generating agents include those containing... Cations Salts (e.g., diazonium salts, Salt, matte salt, iodine Salt is used as a representative example. Anions of salts can be listed as: sulfonate anion, sulfonamide anion, and sulfonyl methyl anion.

[0110] As the acid-generating agent (B), compounds that generate acid through radiation as described in Japanese Patent Application Publication Nos. 63-26653, 55-164824, 62-69263, 63-146038, 63-163452, 62-153853, 63-146029, US Patent Nos. 3,779,778 and 3,849,137, German Patent No. 3,914,407, and European Patent No. 126,712 can be used. Alternatively, compounds manufactured by known methods can also be used. The acid-generating agent (B) can be used alone or in combination of two or more.

[0111] As a nonionic acid-generating agent, it is preferable to have a group represented by formula (B1). Compounds that indicate the bonding sites.

[0112]

[0113] In equation (B1), R b1 This refers to a hydrocarbon group with 1 to 18 carbon atoms that can contain fluorine atoms, wherein the methylene group contained in this hydrocarbon group with 1 to 18 carbon atoms can be replaced by an oxygen atom or a carbonyl group. It should be noted that nitrogen atoms can also have double bonds.

[0114] As R b1 The hydrocarbon groups that have fluorine atoms and have 1 to 18 carbon atoms include: linear or branched chain hydrocarbon groups with 1 to 18 carbon atoms, alicyclic hydrocarbon groups with 3 to 18 carbon atoms, aromatic hydrocarbon groups with 6 to 18 carbon atoms, and groups with 4 to 18 carbon atoms formed by combining these groups.

[0115] As a linear or branched chain hydrocarbon group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms is preferred, and examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. Among them, a linear hydrocarbon group is preferred.

[0116] Examples of alicyclic hydrocarbon groups with 3 to 18 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl.

[0117] As an aromatic hydrocarbon group having 6 to 18 carbon atoms, aryl groups having 6 to 18 carbon atoms are preferred, such as phenyl, naphthyl, anthracene, biphenyl, phenanthrene and other aryl groups.

[0118] Among the groups with 4 to 18 carbon atoms formed by combining the above groups, groups formed by combining chain hydrocarbon groups and alicyclic hydrocarbon groups (groups with 4 to 18 carbon atoms) can be listed as follows: methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, isobornyl, 2-alkyladamantane-2-yl, 1-(adamantane-1-yl)alkane-1-yl, etc.

[0119] As a group composed of a chain hydrocarbon group and an aromatic hydrocarbon group (a group with 7 to 18 carbon atoms), such as aralkyl groups and aromatic hydrocarbon groups containing alkyl groups, specifically, examples include: benzyl, phenethyl, phenylpropyl, triphenylmethyl, naphthylmethyl, naphthylethyl, p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, isopropylphenyl, mesitylene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.

[0120] As a group composed of an alicyclic hydrocarbon group and an aromatic hydrocarbon group (a group with 9 to 18 carbon atoms), for example, an aromatic hydrocarbon group having an alicyclic hydrocarbon group or an alicyclic hydrocarbon group having an aromatic hydrocarbon group. Specifically, examples include p-cyclohexylphenyl, p-adamantylphenyl, phenylcyclohexyl, etc.

[0121] In R b1 Among the hydrocarbon groups with 1 to 18 carbon atoms shown, alkyl groups with 1 to 10 carbon atoms or aromatic hydrocarbon groups with 6 to 10 carbon atoms are preferred, alkyl groups with 1 to 8 carbon atoms are more preferred, and alkyl groups with 1 to 4 carbon atoms are even more preferred.

[0122] As R b1 The group in which the methylene group of an alicyclic hydrocarbon group with 3 to 18 carbon atoms is replaced by an oxygen atom or a carbonyl group, for example, the groups shown in formulas (Y1) to (Y12). Preferably, the groups shown in formulas (Y7) to (Y9) are preferred, and more preferably the group shown in formula (Y9).

[0123]

[0124] As a hydrocarbon group having 1 to 18 carbon atoms and containing fluorine atoms, it is a group in which one or more hydrogen atoms in the aforementioned hydrocarbon group having 1 to 18 carbon atoms are replaced by fluorine atoms. Specifically, examples include: fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, fluoropentyl, fluorohexyl, fluoroheptyl, fluorooctyl, fluorononyl, fluorodecyl and other fluoroalkyl groups; fluorocyclopropyl, fluorocyclobutyl, fluorocyclopentyl, fluorocyclohexyl, fluorocycloheptyl, fluorocyclooctyl, fluoroadamantyl and other fluorocycloalkyl groups; fluorophenyl, fluoronaphthyl, fluoroanthrayl and other fluoroaryl groups, etc.

[0125] The hydrocarbon group having 1 to 18 carbon atoms containing fluorine atoms is preferably an alkyl group having 1 to 10 carbon atoms containing fluorine atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms containing fluorine atoms, more preferably a perfluoroalkyl group having 1 to 8 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

[0126] Examples of compounds having the group shown in formula (B1) include compounds shown in formulas (b1) to (b4). Compounds shown in formulas (b1), (b2), and (b4) are preferred, and compounds shown in formulas (b1) and (b4) are more preferred.

[0127]

[0128] In equations (b1) to (b4), R b1 It means the same as above.

[0129] Rb2 They can be used independently to represent alkyl groups having 1 to 8 carbon atoms or alkoxy groups having 1 to 8 carbon atoms.

[0130] Ring W b1 and ring W b2 They can be used to represent aromatic hydrocarbon rings with 6 to 14 carbon atoms or aromatic heterocycles with 6 to 14 carbon atoms, which are independent of each other.

[0131] x represents any integer from 0 to 6. When x is 2 or higher, multiple R... b2 They can be the same or different.

[0132] x1 represents any integer from 0 to 5. When x1 is 2 or higher, multiple R... b2 They can be the same or different.

[0133] R b6 This refers to alkyl groups having 1 to 8 hydrogen atoms or carbon atoms.

[0134] Examples of alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, propyl, butyl, and pentyl, with methyl being preferred.

[0135] Examples of alkoxy groups with 1 to 8 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentoxy, with methoxy being the most preferred.

[0136] Examples of aromatic hydrocarbon rings with 6 to 14 carbon atoms include benzene rings, naphthalene rings, and anthracene rings.

[0137] Examples of aromatic heterocycles having 6 to 14 carbon atoms include rings having 6 to 14 atoms, with the following rings being preferred.

[0138]

[0139] Ring W b1 and ring W b2 Naphthalene rings are preferred.

[0140] The compound represented by formula (b1) is preferably a compound represented by any one of formulas (b5) to (b8), and more preferably a compound represented by formula (b5).

[0141]

[0142] In equations (b5) to (b8), R b1 R b2 And x represents the same meaning as above.

[0143] y represents any integer from 0 to 4. When y is greater than or equal to 2, multiple R... b2They can be the same or different.

[0144] z represents any integer from 0 to 2. When z is 2, the two R... b2 They can be the same or different.

[0145] X b1 and X b2 Each can be independently represented as -O-, -S-, or -CO-.

[0146] Examples of compounds represented by formula (b1) include compounds represented by formulas (b1-1) to (b1-17). Compounds represented by formulas (b1-6), (b1-7), (b1-10), (b1-13), and (b1-15) are preferred.

[0147]

[0148] Examples of compounds represented by formula (b2) include compounds represented by the following formulas.

[0149]

[0150] Examples of compounds represented by formula (b3) include compounds represented by the following formulas.

[0151]

[0152] Examples of compounds represented by formula (b4) include compounds represented by the following formulas.

[0153]

[0154] As an ionic acid-producing agent, the compound shown in formula (b9) or formula (b10) is preferred.

[0155]

[0156] In equations (b9) and (b10), R b2 It means the same as above.

[0157] z1 represents any integer from 0 to 5. When z1 is 2 or higher, multiple R... b2 They can be the same or different.

[0158] z2 represents any integer from 0 to 4. When z2 is greater than or equal to 2, multiple R... b2 They can be the same or different.

[0159] z3 represents any integer from 0 to 3. When z3 is 2 or higher, multiple R...b2 They can be the same or different.

[0160] X b3 It represents an oxygen atom or a sulfur atom.

[0161] X b4 and X b5 They can be used to represent oxygen atoms, sulfur atoms, or -CO- independently.

[0162] R b8 and R b9 They can be used to represent alkyl groups with 1 to 10 carbon atoms or aromatic hydrocarbon groups with 6 to 12 carbon atoms, independently of each other.

[0163] X1 - This indicates an organic anion.

[0164] Examples of alkyl groups with 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc.

[0165] Aromatic hydrocarbon groups with 6 to 12 carbon atoms include, for example, phenyl, naphthyl, anthraceneyl, biphenyl, phenanthrene, and other aryl groups. Aromatic hydrocarbon groups may also have substituents. Examples of aromatic hydrocarbon groups with substituents include aralkyl groups and aromatic hydrocarbon groups containing alkyl groups, specifically including: benzyl, phenethyl, phenylpropyl, triphenylmethyl, naphthylmethyl, naphthylethyl, p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, isopropylphenyl, mesitylene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.

[0166] R b8 and R b9 Each is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a phenyl group.

[0167] As X1 - The organic anions shown may include, for example, sulfonate anions, bis(alkylsulfonyl)amine anions, bis(alkylsulfonyl)imine anions, tri(alkylsulfonyl)methyl anions, etc., preferably sulfonate anions, more preferably sulfonate anions shown in formula (b11).

[0168]

[0169] In equation (b11), R b10 This refers to a hydrocarbon group with 1 to 18 carbon atoms that can contain fluorine atoms, wherein the methylene group can be replaced by an oxygen atom or a carbonyl group. As R b10 Examples include: R in equation (B1) b1The same group.

[0170] Examples of compounds represented by formula (b9) include the following compounds.

[0171]

[0172] Examples of compounds represented by formula (b10) include the following compounds.

[0173]

[0174] In the resist composition of the present invention, the content of the acid-generating agent relative to 100 parts by weight of resin (A1) is preferably 0.1 parts by weight or more and 40 parts by weight or less, more preferably 0.5 parts by weight or more and 30 parts by weight or less, even more preferably 1 part by weight or more and 20 parts by weight or less, and even more preferably 1 part by weight or more and 5 parts by weight or less. The resist composition of the present invention may contain only one of the acid-generating agents (B), or it may contain multiple acid-generating agents (B).

[0175] <Crosslinking agent (E)>

[0176] The crosslinking agent (E) is a compound that bonds to the resin (A1) through the acid produced by the decomposition of the acid-producing agent (B) under light irradiation (exposure). A crosslinked structure is formed by the bonding between the crosslinking agent (E) and the resin.

[0177] Examples of crosslinking agents include: melamine crosslinking agents, urea crosslinking agents, alkylene urea crosslinking agents, and glycourea crosslinking agents.

[0178] Examples of melamine-based crosslinking agents include compounds represented by formula (e1).

[0179]

[0180] In equation (e1), R e1 These are hydrocarbon groups that can be represented independently of each other, either by hydrogen atoms or by carbon atoms, and have a number of 1 to 6.

[0181] R e2 Independently representing hydrogen atoms, hydrocarbon groups with 1 to 6 carbon atoms, or -CH2-OR e1 .

[0182] R e3 This refers to a hydrocarbon group containing 1 to 6 hydrogen atoms or carbon atoms, or a group represented by formula (e1-1).

[0183] In equation (e-1), R e1 and Re2 [This represents the same group as in formula (e1)]

[0184] Specific examples of melamine-based crosslinking agents include: N,N,N,N,N,N-hexa(methoxymethyl)melamine, N,N,N,N,N,N-hexa(ethoxymethyl)melamine, N,N,N,N,N,N-hexa(propoxymethyl)melamine, N,N,N,N,N,N-hexa(isopropoxymethyl)melamine, N,N,N,N,N,N-hexa(butoxymethyl)melamine, N,N,N,N,N,N-hexa(tert-butoxymethyl)melamine, N,N,N,N,N,N-hexa(cyclohexyloxymethyl)melamine, N,N,N,N,N,N-hexa(cyclopentyloxymethyl)melamine, N,N,N,N,N,N-hexa(adamantyloxymethyl)melamine, and N,N,N,N,N,N-hexa(norberine). Melamine, N,N,N,N-Tetra(methoxymethyl)methylguanidine, N,N,N,N-Tetra(ethoxymethyl)methylguanidine, N,N,N,N-Tetra(propoxymethyl)methylguanidine, N,N,N,N-Tetra(isopropoxymethyl)methylguanidine, N,N,N,N-Tetra(butoxymethyl)methylguanidine, N,N,N,N-Tetra(tert-butoxymethyl)methylguanidine, N,N,N,N-Tetra(methoxymethyl)phenylguanidine, N,N,N,N-Tetra(ethoxymethyl)phenylguanidine, N,N,N,N-Tetra(propoxymethyl)phenylguanidine, N,N,N,N-Tetra(isopropoxymethyl)phenylguanidine, N,N,N,N-Tetra(butoxymethyl)phenylguanidine, N,N,N,N-Tetra(tert-butoxymethyl)phenylguanidine, etc.

[0185] Examples of urea crosslinking agents include compounds represented by formula (e2).

[0186]

[0187] In equation (e2), R e1 and R e2 [This represents the same group as in formula (e1)]

[0188] Specific examples of urea crosslinking agents include: 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(tert-butoxymethyl)urea, N,N-di(cyclohexyloxymethyl)urea, N,N-di(cyclopentyloxymethyl)urea, N,N-di(adamantyloxymethyl)urea, and N,N-di(norbornyloxymethyl)urea.

[0189] Examples of alkylene urea crosslinking agents include compounds represented by formula (e3).

[0190]

[0191] In equation (e3), R e1 It represents the same group as in formula (e1).

[0192] R e3 These groups independently represent hydrogen atoms, hydroxyl groups, hydrocarbon groups with 1 to 6 carbon atoms, or alkoxy groups with 1 to 6 carbon atoms. xe represents any integer from 0 to 2.

[0193] Specific examples of alkylene urea crosslinking agents include: N,N-di(methoxymethyl)-4,5-di(methoxymethyl)ethylene, N,N-di(ethoxymethyl)-4,5-di(ethoxymethyl)ethylene, N,N-di(propoxymethyl)-4,5-di(propoxymethyl)ethylene, N,N-di(isopropoxymethyl)-4,5-di(isopropoxymethyl)ethylene, and N,N-di(butoxymethyl)-4,5-di(butoxymethyl)ethylene. N,N-Di(tert-butoxymethyl)-4,5-Di(tert-butoxymethyl) ethylurea, N,N-Di(cyclohexyloxymethyl)-4,5-Di(cyclohexyloxymethyl) ethylurea, N,N-Di(cyclopentyloxymethyl)-4,5-Di(cyclopentyloxymethyl) ethylurea, N,N-Di(adamantyloxymethyl)-4,5-Di(adamantyloxymethyl) ethylurea, N,N-Di(norbornyloxymethyl)-4,5-Di(norbornyloxymethyl) ethylurea, etc.

[0194] Examples of glycourea crosslinking agents include: Formula (e4).

[0195]

[0196] In equation (e4), R e1 It represents the same group as in formula (e1).

[0197] R e4 These can be used independently to represent hydrogen atoms, hydroxyl groups, hydrocarbon groups with 1 to 6 carbon atoms, and alkoxy groups with 1 to 6 carbon atoms.

[0198] Specific examples of glycourea crosslinking agents include: N,N,N,N-tetra(methoxymethyl)glycourea, N,N,N,N-tetra(ethoxymethyl)glycourea, N,N,N,N-tetra(propoxymethyl)glycourea, N,N,N,N-tetra(isopropoxymethyl)glycourea, N,N,N,N-tetra(butoxymethyl)glycourea, N,N,N,N-tetra(tert-butoxymethyl)glycourea, N,N,N,N-tetra(cyclohexyloxymethyl)glycourea, N,N,N,N-tetra(cyclopentyloxymethyl)glycourea, N,N,N,N-tetra(adamantyloxymethyl)glycourea, and N,N,N,N-tetra(norbornyloxymethyl)glycourea, etc.

[0199] As the crosslinking agent (E), melamine-based crosslinking agents or glycourea-based crosslinking agents are preferred among the above. The crosslinking agent (E) can be used alone or in combination of two or more.

[0200] In the negative resist composition of the present invention, the content of crosslinking agent (E) relative to 100 parts by weight of resin is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, and even more preferably 3 to 30 parts by weight.

[0201] <Aromatic Compounds (I)>

[0202] Compound (I) is an aromatic compound with a molecular weight of less than 2000 and having more than three phenolic hydroxyl groups in the molecule.

[0203] Compound (I) is preferably a compound that does not have a molecular weight distribution, and the molecular weight of compound (I) is not the average molecular weight.

[0204] The molecular weight of compound (I) is, for example, 100 or more, preferably 120 or more, more preferably 150 or more, further preferably 180 or more, and even more preferably 200 or more. Additionally, the molecular weight of compound (I) is, for example, 1500 or less, preferably 1200 or less, more preferably 1000 or less, further preferably 900 or less, further preferably 800 or less, even more preferably 700 or less, and even more preferably 600 or less. Specifically, the molecular weight of compound (I) is, for example, 100 or more and 2000 or less, preferably 100 or more and 1500 or less, more preferably 100 or more and 1200 or less, further preferably 100 or more and 1000 or less, further preferably 120 or more and 900 or less, even more preferably 150 or more and 800 or less, even more preferably 180 or more and 700 or less, and even more preferably 200 or more and 600 or less.

[0205] As described above, compound (I) is preferably a low molecular weight compound, and compound (I) does not contain resin.

[0206] Regarding compound (I), examples can be given such as the compound represented by the following formula (I0) (hereinafter sometimes referred to as "compound (I0)").

[0207]

[0208] In equation (I0), L 0 and L 1 These can be independently represented as hydrocarbon groups with 1 to 20 carbon atoms that may have substituents, wherein the methylene group contained in the hydrocarbon group can be replaced by an oxygen atom or a carbonyl group.

[0209] R h12 R h13 and R h14 Independently representing halogen atoms or hydrocarbon groups having 1 to 20 carbon atoms that may have substituents, or R h12 With R h13 R h12 With R h14 R h13 With R h14 Or R h12 R h13 or R h14 With L 0 or L 1 They can bond together to form rings that can have substituents.

[0210] k0 represents any integer from 0 to 6. When k0 is 2 or higher, the groups within the parentheses can be the same or different.

[0211] k1 represents any integer from 1 to 6. When k1 is 2 or higher, the groups within the parentheses can be the same or different from each other.

[0212] h1 and h2 represent any integer from 0 to 5 independently.

[0213] h5 represents any integer from 0 to 4.

[0214] h3 and h4 independently represent any integer from 0 to 5. When h3 is greater than 2, multiple R... h12 They can be the same or different. When h4 is 2 or more, multiple Rs h13 They can be the same or different.

[0215] h6 represents any integer from 0 to 4. When h6 is 2 or higher, multiple R... h14 They can be the same or different.

[0216] Among them, the sum of h1, h2, and h5 is 3 or more; the sum of h1 and h3 is 5 or less; the sum of h2 and h4 is 5 or less; and the sum of h5 and h6 is 4 or less.

[0217] Compound (I0) is preferably, for example, the compound shown in formula (I1) (hereinafter sometimes referred to as "compound (I1)").

[0218]

[0219] In equation (I1), Xi represents a single bond or an oxygen atom.

[0220] A represents an alkyldiyl group with 1 to 6 carbon atoms that can have substituents, wherein the methylene group contained in the alkyldiyl group can be replaced by an oxygen atom or a carbonyl group. Specifically, when Xi is an oxygen atom, the methylene group bonded to Xi is not replaced by an oxygen atom.

[0221] i1 and i2 independently represent any integer from 0 to 4. The sum of i1 and i2 is 3 or more.

[0222] R i12 and R i13 The halogen atom or the alkyl group having 1 to 12 carbon atoms that may have substituents can be represented independently.

[0223] i3 and i4 independently represent any integer from 0 to 4. When i3 is 2 or higher, multiple R... i12 They can be the same or different. When i4 is 2 or higher, multiple Rs... i13 They can be the same or different.

[0224] R i1 R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms that may have substituents, or, in the case of A being an alkyldiyl group, R i1 It can bond with A to form a ring that can have substituents.

[0225] Among them, the sum of i1 and i3 is 4 or less, and the sum of i2 and i4 is 5 or less.

[0226] Compound (I1) is preferably a compound represented by formula (Ia) or formula (Ib) (hereinafter sometimes referred to as "compound (Ia)" or "compound (Ib)").

[0227]

[0228] In equations (Ia) and (Ib), R i12 R i13 The meanings of i1 to i4 are the same as those described above.

[0229] A 1 It represents a carbonyl group or an alkyl diol with 1 to 6 carbon atoms.

[0230] R i6 It represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms that may have substituents.

[0231] R i8 R i9 R i10 and R i11 Independently representing hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, or R i8 With R i9 They can bond together to form rings that can have substituents, and R i10 With R i11 They can bond together to form rings that can have substituents.

[0232] The compound represented by formula (Ib) is preferably the compound represented by formula (Ib-1) (hereinafter sometimes referred to as "compound (Ib-1)").

[0233]

[0234] In equation (Ib-1), R i12 R i13 The meanings of i1 to i4 are the same as those described above.

[0235] R i14 and R i15 The terms can be used independently to represent alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 1 to 12 carbon atoms, cycloalkyl groups with 3 to 12 carbon atoms, or aryl groups with 5 to 18 carbon atoms.

[0236] i5 represents any integer from 0 to 4. When i5 is 2 or higher, multiple R... i15 They can be the same or different.

[0237] i6 represents any integer from 0 to 5. When i6 is 2 or higher, multiple R... i14 They can be the same or different.

[0238] In formula (I0), examples of halogen atoms include fluorine atoms, iodine atoms, chlorine atoms, and bromine atoms.

[0239] Examples of hydrocarbon groups with 1 to 20 carbon atoms include: chain hydrocarbon groups with 1 to 20 carbon atoms, alicyclic hydrocarbon groups with 3 to 20 carbon atoms, aromatic hydrocarbon groups with 6 to 20 carbon atoms, and groups with 4 to 20 carbon atoms formed by combining these groups. Chain hydrocarbon groups can be either straight-chain or branched. Alicyclic hydrocarbon groups and aromatic hydrocarbon groups can be either monocyclic or polycyclic.

[0240] Examples of chain hydrocarbon groups with 1 to 20 carbon atoms include: alkyl or alkyldiyl groups with 1 to 20 carbon atoms, such as: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.; methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1, Alkyl groups include 16-diyl and heptadecane-1,17-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl.

[0241] Examples of alicyclic hydrocarbon groups with 3 to 20 carbon atoms include: cycloalkyl or cycloalkyl dimethyl groups with 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl, etc.; and cycloalkyl dimethyl groups such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclooctane-1,5-diyl, norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl, etc.

[0242] As aromatic hydrocarbon groups with 6 to 20 carbon atoms, examples include: aryl or arylene groups with 6 to 20 carbon atoms, such as: phenyl, naphthyl, anthracene, biphenyl, phenanthryl, etc.; and arylene groups such as phenylene, naphthylene, anthracene, biphenylene, phenanthryl, etc.

[0243] Among the groups with 4 to 20 carbon atoms formed by combining the above groups, those that are groups formed by combining chain hydrocarbon groups and alicyclic hydrocarbon groups (groups with 4 to 20 carbon atoms) can be listed as follows: methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, isobornyl, 2-alkyladamantane-2-yl, 1-(adamantane-1-yl)alkane-1-yl, etc.

[0244] As a group composed of a chain hydrocarbon group and an aromatic hydrocarbon group (a group with 7 to 20 carbon atoms), such as aralkyl and aromatic hydrocarbon groups containing alkyl groups, specifically, examples include: benzyl, phenethyl, phenylpropyl, triphenylmethyl, naphthylmethyl, naphthylethyl, p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, isopropylphenyl, mesitylene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.

[0245] As a group composed of an alicyclic hydrocarbon group and an aromatic hydrocarbon group (a group with 9 to 20 carbon atoms), such as an aromatic hydrocarbon group having an alicyclic hydrocarbon group or an alicyclic hydrocarbon group having an aromatic hydrocarbon group, specifically, examples include: p-cyclohexylphenyl, p-adamantylphenyl, phenylcyclohexyl, etc.

[0246] Examples of substituents include: halogen atoms, alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 1 to 12 carbon atoms, cycloalkyl groups with 3 to 12 carbon atoms, or aryl groups with 5 to 18 carbon atoms.

[0247] Following formula (I1), the alkyl dienyllium having 1 to 6 carbon atoms can be either straight-chain or branched, for example: methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, etc.

[0248] Examples of halogen atoms include fluorine, iodine, chlorine, and bromine.

[0249] Examples of alkyl groups with 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl.

[0250] Examples of alkenyl groups with 1 to 12 carbon atoms include vinyl, allyl, butenyl, pentenyl, and hexenyl.

[0251] As cycloalkyl groups having 3 to 12 carbon atoms, they can be either monocyclic or polycyclic, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, cyclododecyl, etc.

[0252] Examples of aryl groups with 5 to 18 carbon atoms include phenyl, naphthyl, anthraceneyl, biphenyl, and phenanthrene.

[0253] R in equation (I0)h12 R h13 or R h14 With L 0 or L 1 They can bond together to form a ring, R in equation (I1) i1 It can bond with A and others to form a ring. The total number of carbon atoms in such a ring is preferably 3 to 24, more preferably 3 to 20. Examples of such a ring include the following groups. Although not listed below, other groups may also be included. Indicates the bonding site.

[0254]

[0255] A 1 Preferably, it is carbonyl or methylene.

[0256] The sum of i1 and i2 is preferably 3 to 6, more preferably 3 to 5, and even more preferably 3 or 4.

[0257] R i12 and R i13 The atoms are preferably halogen atoms or alkyl groups having 1 to 4 carbon atoms, and are preferably fluorine atoms, methyl or ethyl.

[0258] R i8 R i9 R i10 and R i11 The hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or rings formed by mutual bonding that can have substituents are preferred to be hydrogen atoms, methyl groups, or rings formed by mutual bonding that can have substituents. Methyl groups or rings formed by mutual bonding that can have substituents are even more preferred to be methyl groups or rings formed by mutual bonding that can have substituents.

[0259] In equation (Ia), i3 and i4 are preferably 0 to 2 independently of each other.

[0260] In formulas (Ib) and (Ib-1), i3 to i5 are preferably 0 or 1, more preferably 0, and i6 is preferably 0.

[0261] As compound (I), the following compounds can be listed.

[0262]

[0263] As compound (I), compounds described in Japanese Patent Application Publication Nos. 3-191351, 8-99922, 9-292714, and 2001-100406 may be used, for example. Furthermore, compound (I) may be synthesized by known methods, and may be a compound manufactured by known methods or a commercially available product.

[0264] As compound (I), it can be used alone or in combination of two or more.

[0265] In the negative resist composition of the present invention, the content of compound (I) relative to 100 parts by weight of resin is preferably 0.5 parts by weight to 20 parts by weight, more preferably 1 part by weight to 15 parts by weight, and even more preferably 2 parts by weight to 10 parts by weight.

[0266] Solvent (D)

[0267] In the negative resist composition, the solvent (D) content is typically 40% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, typically 99.9% by mass or less, preferably 99% by mass or less, more preferably 90% by mass or less. The solvent (D) content can be determined, for example, by known analytical methods such as liquid chromatography or gas chromatography.

[0268] Examples of solvents (D) include: glycol ether esters such as ethyl cellolytic acetate, methyl cellolytic 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.

[0269] Solvent (D) may contain only one type or two or more types.

[0270] <Quencher (C)>

[0271] The negative resist composition of the present invention may contain a quencher (hereinafter sometimes referred to as "quencher (C)").

[0272] Quencher (C) is a compound that captures acid generated by an acid-producing agent upon exposure. Examples of quenchers (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), aromatic amines, etc.

[0273] Examples of amines include compounds represented by formula (C1) or formula (C2).

[0274]

[0275] In equation (C1), R c1 R c2 and R c3The terms independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The alkyl group having 1 to 6 carbon atoms and the alicyclic hydrocarbon group having 3 to 10 carbon atoms may have at least one selected from the group consisting of a hydroxyl group, an amino group, and an alkoxy group having 1 to 6 carbon atoms. The aromatic hydrocarbon group having 6 to 10 carbon atoms may have at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alicyclic hydrocarbon group having 3 to 10 carbon atoms.

[0276] Regarding alkyl groups with 1 to 6 carbon atoms, alicyclic hydrocarbon groups with 3 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 10 carbon atoms, and alkoxy groups with 1 to 6 carbon atoms in formula (C1), the following groups can be listed: groups that are the same as the groups mentioned above.

[0277] Examples of compounds represented by formula (C1) include: 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-methylaniline, 3-methylaniline 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, methyldipentylamine, dihexylmethylamine, Dicyclohexylmethylamine, diheptylmethylamine, methyl dioctylamine, methyl dinonylamine, didecylmethylamine, ethyl dibutylamine, ethyl dipentylamine, ethyl dihexylamine, ethyl diheptylamine, ethyl dioctylamine, ethyl dinonylamine, ethyl didecylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, etc. Preferred examples include diisopropylaniline, and particularly preferred examples include 2,6-diisopropylaniline.

[0278]

[0279] In equation (C2), Ring W 1 This refers to a heterocycle containing a nitrogen atom in the atoms constituting the ring, or a benzene ring having a substituted or unsubstituted amino group, wherein 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.

[0280] A 1 It indicates phenyl or naphthyl.

[0281] nc represents 2 or 3, multiple A's 1 They can be the same or different.

[0282] The above-mentioned substituted or unsubstituted amino groups are composed of -N(R) 4 (R) 5 ) indicates that R 4 and R 5 They can be used to represent hydrogen atoms, chain hydrocarbon groups with 1 to 10 carbon atoms, alicyclic hydrocarbon groups with 3 to 10 carbon atoms, or aromatic hydrocarbon groups with 6 to 14 carbon atoms, independently of each other.

[0283] Examples of chain hydrocarbon groups with 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0284] Examples of alicyclic hydrocarbon groups with 3 to 10 carbon atoms include: monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornel.

[0285] Aromatic hydrocarbon groups having 6 to 14 carbon atoms include, for example, phenyl, naphthyl, anthraceneyl, biphenyl, phenanthrene, and other aryl groups. Aromatic hydrocarbon groups may also have substituents, such as aryloxy groups having 6 to 10 carbon atoms.

[0286] A heterocycle containing nitrogen atoms in its ring can be an aromatic ring, a non-aromatic ring, or it can contain other heteroatoms (e.g., oxygen or sulfur atoms) in addition to nitrogen atoms. The number of nitrogen atoms in this heterocycle is, for example, 1 to 3. Examples of such heterocycles include rings shown in any of formulas (Y13) to (Y28). Removing one hydrogen atom from the ring results in a ring similar to A. 1 The bonding sites.

[0287]

[0288] Ring W 1 Preferably, it is a heterocycle containing nitrogen atoms in the atoms constituting the ring; more preferably, it is an aromatic heterocycle of a 5-membered or 6-membered ring containing nitrogen atoms in the atoms constituting the ring; and even more preferably, it is a ring represented by any one of formulas (Y20) to (Y25).

[0289] Examples of compounds represented by formula (C2) include compounds represented by any one of formulas (C2-1) to (C2-11). Preferably, compounds represented by any one of formulas (C2-2) to (C2-8) are preferred.

[0290]

[0291] In the solid component of the negative resist composition, the content of quencher (C) 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.

[0292] <Other Ingredients (F)>

[0293] The negative resist composition of the present invention may contain other components besides those described above (hereinafter sometimes referred to as "other components (F)"). Other components (F) are not particularly limited and may utilize additives known in the field of resists, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, adhesion enhancers, etc.

[0294] When using other ingredients (F), their content should be appropriately selected according to the type of other ingredients (F).

[0295] 2. Preparation of negative resist composition

[0296] The negative resist composition of the present invention can be prepared by mixing a resin (A1), an acid-generating agent (B), a crosslinking agent (E), and an aromatic compound (I), as well as, as needed, other resins besides the resin (A1), a quencher (C), a solvent (D), and other components (F). The mixing order is arbitrary and not particularly limited. Examples of mixing temperatures include 10°C to 40°C, and an appropriate temperature can be selected based on the type of resin, the solubility of the resin in the solvent (D), etc. The mixing time can be selected appropriately from 0.5 hours to 24 hours depending on the mixing temperature. It should be noted that the mixing method is also not particularly limited; stirring or mixing can be used.

[0297] After mixing the components, it is preferable to use a filter with a pore size of about 0.003 μm to about 50 μm for filtration.

[0298] 3. Method for manufacturing resist patterns

[0299] The method for manufacturing the resist pattern of the present invention includes the following steps: (1) The process of coating the negative resist composition of the present invention onto a substrate; (2) The process of drying the coated negative resist composition to form a composition layer; (3) The process of exposing the composite layer; and (4) The process of heating and developing the exposed composite layer.

[0300] To apply the negative resist composition onto a substrate, a commonly used apparatus such as a spin coater can be used. Examples of substrates include inorganic substrates such as silicon wafers, on which semiconductor elements (such as transistors, diodes, etc.) can be pre-formed.

[0301] The coated composition is dried to remove the solvent, forming a composition layer. 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 depressurization device. The heating temperature is preferably 50°C to 200°C, and the heating time is preferably 30 seconds to 600 seconds. Furthermore, the pressure during depressurization drying is preferably about 1 Pa to about 1.0 × 10⁻⁶ Pa. 5 Pa.

[0302] After drying, the film thickness of the resulting composition is preferably 10 nm to 3 μm, more preferably 100 nm to 1 μm.

[0303] The resulting composite layer is typically exposed using an exposure machine. As the exposure light source, various light sources can be used, including those emitting light in the ultraviolet region (g-line (wavelength: 436nm), h-line (wavelength: 405nm), i-line (wavelength: 365nm)), KrF excimer laser (wavelength: 248nm), ArF excimer laser (wavelength: 193nm), F2 excimer laser (wavelength: 157nm), etc.; light sources that convert the wavelength of laser light from solid-state laser sources (YAG or semiconductor lasers, etc.) to emit high-order harmonic lasers in the far ultraviolet or vacuum ultraviolet regions; irradiation electron beams; and extreme ultraviolet (EUV) light sources. Among these, the i-line is preferred as the exposure light source.

[0304] It should be noted that, in this specification, the irradiation of these rays is sometimes collectively referred to as "exposure." During exposure, it is usually performed through a mask corresponding to the desired pattern. However, when the exposure source is an electron beam, exposure can also be performed by direct drawing without using a mask.

[0305] To promote the crosslinking reaction between the resin and the crosslinking agent, the exposed composition layer can be subjected to heat treatment (so-called post-exposure baking). The heating temperature is typically about 50°C to about 200°C, preferably about 70°C to about 150°C. The heating time is typically 40 seconds to 400 seconds, preferably 50 seconds to 350 seconds.

[0306] The heated composite layer is typically developed using a developing apparatus with a developing solution. Examples of developing methods include immersion, swirling immersion, spraying, and dynamic distribution. The developing temperature is preferably 5°C to 60°C, and the developing time is preferably 5 seconds to 600 seconds.

[0307] 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. Examples include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may contain a surfactant.

[0308] After development, it is preferable to use ultrapure water to clean the resist pattern, and then remove the water remaining on the substrate and the pattern.

[0309] After cleaning, it is preferable to remove the rinsing solution remaining on the substrate and pattern.

[0310] By exposing the resist obtained using the negative resist composition of the present invention, a resist pattern with high precision can be formed.

[0311] 4. Applications

[0312] The negative resist composition of the present invention can be used, for example, in the manufacture of resist films with a thickness of less than 1 μm.

[0313] Example

[0314] The invention is illustrated in more detail by way of examples. In these examples, unless otherwise stated, “%” and “parts” indicating the content or amount used are based on mass.

[0315] The weight-average molecular weight is the value obtained by gel permeation chromatography under the following conditions.

[0316] Device: HLC-8320GPC type (manufactured by Tosoh Corporation)

[0317] Column: TSKgel Multipore H XL -M × 3 + guardcolumn (manufactured by Tosoh Corporation)

[0318] Eluent: Tetrahydrofuran

[0319] Flow rate: 1.0 mL / min

[0320] Detector: RI detector

[0321] Column temperature: 40℃

[0322] Injection volume: 100 μl

[0323] Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

[0324] <Preparation of Negative Corrosion Resist Compositions>

[0325] A negative resist composition was prepared by filtering the mixture obtained by mixing and dissolving the components shown in Table 1 using a fluorinated resin filter with a pore size of 0.5 μm.

[0326] [Table 1]

[0327] <Resin>

[0328] (A1)-1: Resin (A1)-1

[0329] A resin containing the following structural units. Synthesized using the method described in Japanese Patent Application Publication No. 2001-42529.

[0330]

[0331] Weight-average molecular weight: 3700

[0332] The ratio of hydroxyl groups to ethoxy groups in poly(p-hydroxystyrene) is 20.9%.

[0333] (A1)-2: Resin (A1)-2

[0334] A resin containing the following structural units. Synthesized using the method described in Japanese Patent Application Publication No. 2001-42529.

[0335]

[0336] Weight-average molecular weight: 3700

[0337] The ratio of hydroxyl groups to ethoxy groups in poly(p-hydroxystyrene) is 27.0%.

[0338] (A1)-3: Resin (A1)-3

[0339] A resin containing the following structural units. Synthesized using the method described in Japanese Patent Application Publication No. 2001-42529.

[0340]

[0341] Weight-average molecular weight: 2800

[0342] The ratio of hydroxyl groups to ethoxy groups in poly(p-hydroxystyrene) is 21.0%.

[0343] <Acid-producing agent (B)>

[0344] (B1)-1: The compound shown in the following formula (synthesized using the method described in WO2014 / 084269).

[0345] (B2)-1: The compound shown in the following formula (manufactured by BASF)

[0346] <Crosslinking agent (E)>

[0347] (E)-1: The compound shown in the following formula (manufactured by Heraeus)

[0348] <Quencher (C)>

[0349] (C)-1: 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0350] <Compound (I)>

[0351] (I)-1: The compound shown in the following formula (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 246

[0352] (I)-2: The compound shown in the following formula (molecular weight: 380)

[0353] Based on Japanese Patent Application Publication No. 3-185447.

[0354]

[0355] (IX)-1: The compound shown in the following formula (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 273.

[0356] Solvent (D)

[0357] (D)-1: Propylene glycol monomethyl ether acetate

[0358] Examples 1-8, Comparative Examples 1 and 2

[0359] (i-line exposure evaluation of negative resist compositions)

[0360] The negative resist composition was spin-coated onto a 4-inch silicon wafer substrate treated with hexamethyldisilazane (HMDS) to a pre-baked film thickness of 550 nm.

[0361] Then, it is pre-baked at 110°C for 60 seconds on a direct hot plate to form the composite layer.

[0362] Next, using an i-line stepper lithography machine (NSR-2005i9C; manufactured by Nikon Corporation, NA=0.5), the exposure amount was varied in stages, and the composite layer formed on the wafer was exposed through a mask used to form 1:1 line and space patterns (linewidths of 800nm, 700nm, 600nm, and 500nm).

[0363] After exposure, the resist pattern was baked at 110°C for 60 seconds on a hot plate, followed by immersion development for 60 seconds using a 2.38% by mass tetramethylammonium hydroxide aqueous solution, thus obtaining the resist pattern.

[0364] The resist pattern obtained after development was observed using a scanning electron microscope, and the exposure of the line and spacing with a width of 500 nm was taken as the effective sensitivity.

[0365] <Residue Evaluation>

[0366] The spacing pattern of the line and spacing pattern with a linewidth of 800 nm obtained at effective sensitivity was observed using a scanning electron microscope. Cases with residue were evaluated as "×", and cases without residue were evaluated as "〇".

[0367] Roughness evaluation caused by standing wave effect

[0368] The cross-sectional shape of the line and spacing with a linewidth of 500 nm obtained at effective sensitivity was observed using a scanning electron microscope, and measurements were taken. Figure 1 The line widths 'a' and 'b' shown are rated "B" if the calculated value derived from b / a is less than 0.95, and rated "A" if the calculated value derived from b / a is greater than 0.95 and less than 1.00. 'a' is the line width of the longest segment of the specified line (the maximum line width), and 'b' is the line width of the shortest segment of the specified line (the minimum line width).

[0369] <Mask Linear Evaluation>

[0370] To study mask fidelity, the value of MEF (mask error factor) is calculated using the following formula.

[0371] MEF=(CD800-CD500) / (MD800-MD500)

[0372] CD800: Size (nm) of a spacing pattern with a linewidth of 800 nm obtained at the effective sensitivity.

[0373] CD500: Size (nm) of a spacing pattern with a linewidth of 500 nm obtained at the effective sensitivity.

[0374] MD800: 800nm ​​(the size of the mask for each pattern)

[0375] MD500: 500nm (the size of the mask for each pattern)

[0376] Cases with a MEF value of 1.11 or higher and cases with a MEF value less than 0.89 are rated as "C", cases with a MEF value of 1.06 or higher and cases with a MEF value of 1.11 or higher and cases with a MEF value of 0.89 or higher and cases with a MEF value less than 0.94 are rated as "B", and cases with a MEF value of 0.94 or higher and cases with a MEF value less than 1.06 are rated as "A".

[0377] The closer the MEF value is to 1, the better the mask linearity.

[0378] [Table 2]

[0379] In Examples 1 to 8, compared with Comparative Examples 1 and 2, no residue was produced, the roughness caused by standing waves was small, and a resist pattern with a good shape could be formed.

[0380] Industrial practicality

[0381] The negative resist composition of the present invention leaves no residue, has a good shape, and can be used for the microfabrication of semiconductors.

Claims

1. A negative resist composition, wherein, The negative resist composition comprises: a resin (A1) containing structural units of formula (a2-1) and formula (a2-4), an acid-generating agent (B), a crosslinking agent (E), and an aromatic compound (I) with a molecular weight of less than 2000 and having more than three phenolic hydroxyl groups. In equations (a2-1) and (a2-4), R a7 and R a13 They can represent hydrogen atoms or methyl groups independently; R a10 and R a14 Alkyl groups having 1 to 6 carbon atoms can be represented independently of each other; R a15 Represents hydrocarbon groups with 1 to 12 carbon atoms; m 1 Represent any integer from 0 to 4, when m 1 When the value is 2 or higher, multiple R a10 They can be the same or different; m 2 Represents any integer from 1 to 4; Where, m 1 With m 2 The total is less than 5; m 3 Represent any integer from 0 to 4, when m 3 When the value is 2 or higher, multiple R a14 They can be the same or different; m 4 Represent any integer from 1 to 4, when m 4 When the value is 2 or higher, multiple R a15 They can be the same or different; Where, m 3 With m 4 The total is less than 5.

2. The negative resist composition according to claim 1, wherein, Aromatic compound (I) is the compound represented by formula (I0). In equation (I0), L 0 and L 1 Each can independently represent a hydrocarbon group having 1 to 20 carbon atoms that can have substituents, wherein the methylene group contained in the hydrocarbon group can be replaced by an oxygen atom or a carbonyl group; R h12 R h13 and R h14 Independently representing halogen atoms or hydrocarbon groups having 1 to 20 carbon atoms that may have substituents, or R h12 With R h13 R h12 With R h14 R h13 With R h14 Or R h12 R h13 or R h14 With L 0 or L 1 They can bond together to form rings that can have substituents; k0 represents any integer from 0 to 6. When k0 is 2 or higher, the groups within the parentheses can be the same or different from each other. k1 represents any integer from 1 to 6. When k1 is 2 or higher, the groups within the parentheses can be the same or different from each other. h1 and h2 represent any integer from 0 to 5 independently; h5 represents any integer from 0 to 4; h3 and h4 independently represent any integer from 0 to 5. When h3 is 2 or greater, multiple R... h12 They can be the same or different. When h4 is 2 or more, multiple Rs h13 They can be the same or different; h6 represents any integer from 0 to 4. When h6 is 2 or higher, multiple R... h14 They can be the same or different; Among them, the total of h1, h2 and h5 is 3 or more, the total of h1 and h3 is 5 or less, the total of h2 and h4 is 5 or less, and the total of h5 and h6 is 4 or less.

3. The negative resist composition according to claim 1, wherein, Aromatic compound (I) is the compound represented by formula (I1). In equation (I1), Xi represents a single bond or an oxygen atom; A represents an alkyldiyl group having 1 to 6 carbon atoms that can have substituents. The methylene group contained in the alkyldiyl group can be replaced by an oxygen atom or a carbonyl group. In the case that Xi is an oxygen atom, the methylene group bonded to Xi is not replaced by an oxygen atom. i1 and i2 represent any integer from 0 to 4 independently, where the sum of i1 and i2 is 3 or more; R i12 and R i13 The halogen atom or the alkyl group having 1 to 12 carbon atoms that may have substituents can be represented independently; i3 and i4 independently represent any integer from 0 to 4. When i3 is 2 or higher, multiple R... i12 They can be the same or different. When i4 is 2 or higher, multiple Rs... i13 They can be the same or different; R i1 R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms that may have substituents, or, in the case of A being an alkyldiyl group, R i1 It can bond with A to form a ring that can have substituents; Among them, the sum of i1 and i3 is less than 4, and the sum of i2 and i4 is less than 5.

4. The negative resist composition according to claim 1, wherein, The crosslinking agent (E) is a glycourea-based crosslinking agent.

5. A manufacturing method, which is a method for manufacturing a resist pattern, wherein, The manufacturing method includes the following steps: (1) The process of coating the negative resist composition according to any one of claims 1 to 4 onto a substrate; (2) A process of drying the coated composition to form a composition layer; (3) The process of exposing the composition layer; and (4) The process of heating and developing the exposed composite layer.

Images