Resin, resist composition, and method for manufacturing resist pattern

Abstract

The present invention relates to providing a resist composition capable of producing resist patterns with good shape and good crack resistance. The solution is a resist composition comprising: a resin having acid-labile groups, a resin containing structural units of formula (I), an acid-generating agent, and a solvent. [Where R...] i41 It is a hydrogen atom or a methyl group; R i42 An acyl group or hydrogen atom having 2 to 7 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms that can be replaced by a hydroxyl group; R i43 alkyl or alkoxy groups having 1 to 6 carbon atoms; p is an integer from 0 to 4; Z represents a divalent hydrocarbon group having 3 to 20 carbon atoms containing the group shown in formula (Ia), wherein the methylene group can be replaced by an oxygen atom, a sulfur atom, or a carbonyl group. * represents the bonding site with an oxygen atom; w and r each independently represent integers from 1 to 10, where when w is 1, R... i42 It is an acyl group with 2 to 7 carbon atoms.

Description

[0001] This application is a divisional application of the following application.

[0002] Application date for the parent case: March 31, 2016

[0003] Parent application number: 201610200067.9

[0004] Parent application title: Method for manufacturing resin, resist composition and resist pattern Technical Field

[0005] This invention relates to a method for manufacturing resins, resist compositions, and resist patterns. Background Technology

[0006] In multi-pin thin-film packages of semiconductor chips, raised electrodes with a height of approximately 4 to 150 μm, serving as terminals (bumps), are formed on a substrate using photolithography. Patent document 1 describes a method for forming such terminals using a photoresist composition containing a resin with structural units derived from p-hydroxystyrene.

[0007] Existing technical documents

[0008] Patent documents

[0009] [Patent Document 1] Japanese Patent Application Publication No. 2011-75864 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] The object of this invention is to provide a resin and resist composition that can produce well-shaped and crack-resistant etch-resistant patterns.

[0012] Methods for solving problems

[0013] This invention includes the following inventions.

[0014] [1] An anti-corrosion composition comprising: a resin having acid-insensitive groups, a resin containing structural units of formula (I), an acid-generating agent, and a solvent.

[0015]

[0016] In formula (I),

[0017] R i41 It represents a hydrogen atom or a methyl group.

[0018] R i42 It represents an acyl group or hydrogen atom with 2 to 7 carbon atoms, or a hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a hydroxyl group.

[0019] R i43 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0020] p represents an integer from 0 to 4. When p is 2 or higher, multiple R... i43 They may be the same as or different from each other.

[0021] Z represents a divalent hydrocarbon group with 3 to 20 carbon atoms containing the group shown in formula (Ia). The methylene group in this hydrocarbon group can be replaced by an oxygen atom, a sulfur atom, or a carbonyl group. * indicates a bonding site with an oxygen atom.

[0022] *-〔(CH2) w -O] r — (Ia)

[0023] In equation (Ia), w and r each independently represent integers from 1 to 10.

[0024] Where w is 1, R i42 It is an acyl group with 2 to 7 carbon atoms.

[0025] [2] According to the resist composition of [1], wherein the resin of the structural unit shown in formula (I) is a structural unit shown in formula (I-1) or formula (I-2).

[0026]

[0027] In equations (I-1) and (I-2),

[0028] R i41 It represents a hydrogen atom or a methyl group.

[0029] R i42 It represents a hydrocarbon group with 1 to 10 carbon atoms, an acyl group with 2 to 7 carbon atoms, or a hydrogen atom that can be replaced by a hydroxyl group.

[0030] R i43 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0031] p represents an integer from 0 to 4. When p is 2 or higher, multiple R... i43 They may be the same as or different from each other.

[0032] R i44 Represents hydrocarbon groups with 1 to 10 carbon atoms.

[0033] r represents an integer from 1 to 10.

[0034] R i45 It represents a hydrocarbon group with 1 to 10 carbon atoms, an acyl group with 2 to 7 carbon atoms, or a hydrogen atom that can be replaced by a hydroxyl group.

[0035] [3] The resist composition according to [1] or [2], wherein the resin containing a resin having an acid-labile group is a resin containing a structural unit shown in formula (a1-2).

[0036]

[0037] In formula (a1-2),

[0038] R a1’ and R a2’ Each group independently represents a hydrocarbon group having 1 to 12 hydrogen atoms or carbon atoms, R a33’ It represents an aliphatic hydrocarbon group with 1 to 20 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms, or R a1’ It represents a hydrocarbon group with 1 to 12 hydrogen atoms or carbon atoms, or R a2’ and R a33’ The carbon and oxygen atoms bonded to it together represent a divalent heterocycle with 2 to 20 carbon atoms. The hydrocarbon groups with 1 to 20 carbon atoms, the hydrocarbon groups with 1 to 12 carbon atoms, and the methylene groups contained in the divalent heterocycle can be replaced with oxygen or sulfur atoms.

[0039] R a5 It represents a hydrogen atom or a methyl group.

[0040] R a6 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0041] mz represents an integer from 0 to 4. When mz is 2 or higher, multiple R... a6 They may be the same as or different from each other.

[0042] [4] The resist composition according to any one of [1] to [3], wherein the acid-generating agent is a compound having a group shown in formula (B1).

[0043]

[0044] In formula (B1),

[0045] R b1 This refers to a hydrocarbon group with 1 to 18 carbon atoms that may contain fluorine atoms, wherein the methylene group may be replaced by an oxygen atom or a carbonyl group.

[0046] [5] A method for manufacturing a resist pattern, comprising:

[0047] (1) The process of coating the resist composition described in any one of [1] to [4] onto a substrate.

[0048] (2) The process of drying and coating the resist composition to form a composition layer.

[0049] (3) The process of exposing the composite layer.

[0050] (4) The process of developing the exposed composite layer.

[0051] [6] A resin containing the structural unit shown in formula (I-2).

[0052]

[0053] In formula (I-2),

[0054] R i41 It represents a hydrogen atom or a methyl group.

[0055] R i43 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0056] p represents an integer from 0 to 4. When p is 2 or higher, multiple R... i43 They may be the same as or different from each other.

[0057] R i44 Represents hydrocarbon groups with 1 to 10 carbon atoms.

[0058] r represents an integer from 1 to 10.

[0059] R i45 This indicates a hydrocarbon group with 1 to 10 carbon atoms, an acyl group with 2 to 7 carbon atoms, or a hydrogen atom that can be replaced by a hydroxyl group.

[0060] The effects of the invention

[0061] The resist composition according to the present invention can produce resist patterns with good shape and excellent crack resistance. Attached Figure Description

[0062] 【 Figure 1 [A diagram showing the cross-sectional shape of a line and spacing pattern.] Figure 1 (a) represents a cross section where the top and bottom corners are nearly rectangular. Figure 1 (b) indicates a cross section with a circular shape at the lower turning point. Detailed Implementation

[0063] In this specification, "(meth)acrylate" means "at least one of acrylate and methacrylate". The terms "(meth)acrylic acid" and others convey the same meaning.

[0064] Furthermore, the functional groups described in this specification may exhibit both straight-chain and branched-chain structures, and can be either one. In the case of stereoisomers, all stereoisomers are included.

[0065] <Resistant Composition>

[0066] The resist composition of the present invention contains:

[0067] Resins containing acid-labile groups (hereinafter also referred to as "resin (Al)")

[0068] A resin containing the structural unit shown in formula (I) (hereinafter also referred to as "resin (A3)")

[0069] Acid-producing agent (hereinafter also referred to as "acid-producing agent (B)") and

[0070] Solvent (hereinafter also referred to as "solvent (D)").

[0071] The resist composition of the present invention may further contain: a resin different from resin (A1) (hereinafter also referred to as resin (A2)), a quencher (C), an adhesion promoter (E), etc.

[0072] <Resin (A1)>

[0073] The resin (A1) contains structural units with acid-labile groups (hereinafter also referred to as "structural units (a1)").

[0074] An acid-instable group refers to a group that, upon contact with an acid, undergoes elimination to form a hydrophilic group (such as a hydroxyl or carboxyl group). In other words, it refers to a group that, under the influence of an acid, increases the solubility of the structural unit containing the acid-instable group in an alkaline aqueous solution. Therefore, the resin (Al) exhibits increased solubility in an alkaline aqueous solution under the influence of an acid.

[0075] "Increased solubility in alkaline aqueous solution under the action of acid" means that the solubility in alkaline aqueous solution increases upon contact with acid. Preferably, the substance is insoluble or sparingly soluble in alkaline aqueous solution before contact with acid, but becomes soluble in alkaline aqueous solution after contact with acid.

[0076] In addition to structural units having acid-labile groups, the resin (A1) may further contain structural units without acid-labile groups (hereinafter also referred to as "structural units (a2)") and other structural units known in the art.

[0077] Examples of acid-labile groups include the group shown in formula (1) and the group shown in formula (2).

[0078]

[0079] In equation (1), R a1 R a2 and R a3Each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R a1 and R a2 Mutual bonding represents divalent hydrocarbon groups with 2 to 20 carbon atoms, R a3 Indicates an alkyl group with 1 to 8 carbon atoms or an alicyclic hydrocarbon group with 3 to 20 carbon atoms. * indicates a bonding site.

[0080]

[0081] In equation (2), R a1’ and R a2’ Each can independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a3’ Represents a hydrocarbon group with 1 to 20 carbon atoms, or R a1’ R represents a hydrocarbon group containing 1 to 12 hydrogen atoms or carbon atoms. a2’ and R a3’ Mutually bonded groups represent divalent heterocyclic groups with 2 to 20 carbon atoms. The methylene group in this hydrocarbon group and the divalent heterocyclic group can be replaced by an oxygen or sulfur atom. * indicates a bonding site.

[0082] As R a1 ~R a3 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc.

[0083] R a1 ~R a3 The alicyclic hydrocarbon group can be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bonding site).

[0084]

[0085] R a1 ~R a3 The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms.

[0086] As R a1 and R a2 -C(R) when they bond together to form divalent hydrocarbon groups a1 (R) a2 (R) a3 Examples of such groups include the following. The divalent hydrocarbon group preferably has 3 to 12 carbon atoms. * indicates the bonding site with -O-.

[0087]

[0088] As a group represented by formula (1), examples include alkoxycarbonyl (R in formula (1)). a1 R a2 and R a3 Any one of them is an alkyl group, preferably tert-butoxycarbonyl), 1-alkylcyclopentane-1-yloxycarbonyl, 1-alkylcyclohexane-1-yloxycarbonyl (in formula (1), R a1 and R a2 Bonding to form cyclopentyl or cyclohexyl, R a3 (where R is an alkyl group), 1-(cyclopentan-1-yl)-1-alkylalkoxycarbonyl and 1-(cyclohexan-1-yl)-1-alkylalkoxycarbonyl (in formula (1), R a1 and R a2 alkyl, R a3 (e.g., groups that are cyclopentyl or cyclohexyl).

[0089] R, as the basis shown in equation (2) a1’ ~R a3’ Hydrocarbon groups can include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combinations of these groups.

[0090] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, and dodecyl.

[0091] Examples of alicyclic hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and other cycloalkyl groups; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornyl.

[0092] Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthracene, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenel, mesitylene, biphenyl, phenanthrene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, and other aryl groups.

[0093] Examples of groups composed of alkyl groups and alicyclic hydrocarbon groups include methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, isobornyl, 2-alkyladamantane-2-yl and 1-(adamantane-1-yl)alkyl-1-yl.

[0094] As a group composed of alkyl and aromatic hydrocarbon groups, it can be, for example, aralkyl, specifically benzyl, phenethyl, phenylpropyl, triphenylmethyl, naphthylmethyl, naphthylethyl, etc.

[0095] As R a2’ and R a3’ The following are examples of divalent heterocyclic groups formed by mutual bonding between carbon and oxygen atoms. * indicates a bonding site.

[0096]

[0097] R a1 Hydrogen atoms are preferred.

[0098] As specific examples of the groups shown in formula (2), the following groups can be cited.

[0099]

[0100] <Structural Unit (a1)>

[0101] Monomers that derive structural unit (a1) are preferably monomers having acid-insecure groups and olefinic unsaturated bonds, and more preferably monomers having groups shown in formula (1) and / or groups shown in formula (2) and olefinic unsaturated bonds.

[0102] The resin (A1) may have only one structural unit (a1) or it may have multiple structural units.

[0103] As structural unit (a1), the structural unit represented by the preferred formula (a1-1) (hereinafter also referred to as "structural unit (a1-1)") and the structural unit represented by formula (a1-2) (hereinafter also referred to as "structural unit (a1-2)") are structural units.

[0104]

[0105] In equations (a1-1) and (a1-2),

[0106] R a1 R a2 R a3 R a1’ and R a2’ Each of these represents the same meaning as described above. R a33’ It represents an aliphatic hydrocarbon group with 1 to 20 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms, or R a2’ and R a33’ Together with the carbon and oxygen atoms it bonds to, it represents a divalent heterocycle with 2 to 20 carbon atoms.

[0107] R a4 and R a5 Each can be used independently to represent a hydrogen atom or a methyl group.

[0108] R a6 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0109] mz represents an integer from 0 to 4. When mz is 2 or higher, multiple R... a6 They may be the same as or different from each other.

[0110] As Ra33’ Examples of R can be cited. a3’ Same group.

[0111] In equation (a1-1), R a4 Methyl is preferred.

[0112] In equation (a1-2), R a1’ Hydrogen atoms are preferred.

[0113] R a2’ Preferably, it is a hydrocarbon group with 1 to 12 carbon atoms, more preferably methyl and ethyl.

[0114] R a33’ The hydrocarbon group is preferably an alkyl group with 1 to 18 carbon atoms, an alicyclic hydrocarbon group with 3 to 18 carbon atoms, an aromatic hydrocarbon group with 6 to 18 carbon atoms, or a combination of these groups, more preferably an alkyl group with 1 to 18 carbon atoms, an alicyclic hydrocarbon group with 3 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. When the aromatic hydrocarbon group has a substituent, the substituent is preferably an aryloxy group with 6 to 10 carbon atoms.

[0115] R a5 Hydrogen atoms are preferred.

[0116] R a6 Preferably, it is an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group.

[0117] mz is preferably 0 or 1, more preferably 0.

[0118] As a structural unit (a1-1), for example, any one of the structural units shown in equations (a1-1-1) to (a1-1-17) can be cited.

[0119]

[0120]

[0121] As a single entity that derives structural unit (a1-2), for example, any one of the entities shown in equations (a1-2-1) to (a1-2-14) can be cited.

[0122]

[0123] Among the monomers mentioned above, methyl substitution and R can also be cited as examples. a4 and R a5 A monomer obtained with a corresponding number of hydrogen atoms is a specific example of the monomers mentioned above.

[0124] Preferably, the structural units are derived from the monomers shown in formulas (a1-2-2), (a1-2-3), (a1-2-4), (a1-2-9), and (a1-2-14), and more preferably, the structural units are derived from the monomers shown in formulas (a1-2-2), (a1-2-3), (a1-2-4), and (a1-2-9).

[0125] The resin (A1) having acid-labile groups is preferably a resin having structural units (a1-2).

[0126] When the resin (A1) has structural units (a1-1) and / or structural units (a1-2), their total content relative to all structural units of the resin (A1) is preferably 5 to 60 mol%, more preferably 10 to 55 mol%, even more preferably 15 to 50 mol%, and particularly preferably 20 to 45 mol%.

[0127] <Structural units lacking acid-labile groups>

[0128] In resin (A1), the structural unit (a2) can be only one type or multiple types.

[0129] As a structural unit (a2), for example, any one of the terms in equations (a2-1) to (a2-3) can be used to illustrate the structural unit (hereinafter, according to the equation number, it can also be called "structural unit (a2-1)" etc.).

[0130]

[0131] In equations (a2-1), (a2-2), and (a2-3),

[0132] R a7 R a8 and R a9 Each can be used independently to represent a hydrogen atom or a methyl group.

[0133] R a10 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0134] m' represents an integer from 0 to 4. When m' is 2 or higher, multiple R... a10 They may be the same as or different from each other.

[0135] R a11 Primary or secondary hydrocarbon groups representing 1 to 10 hydrogen or carbon atoms.

[0136] R a12 It refers to primary or secondary alkyl groups with 1 to 6 carbon atoms.

[0137] L a1This refers to alkylene groups with 2 to 6 carbon atoms. The carbon atoms bonded to oxygen atoms are either primary or secondary carbon atoms.

[0138] n represents an integer from 1 to 30. When n is 2 or more, multiple L a1 They may be the same as or different from each other.

[0139] As R a10 Or R a12 Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0140] As R a10 Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy.

[0141] As R a11 Examples of hydrocarbon groups shown include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these groups.

[0142] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.

[0143] Alicyclic hydrocarbon groups can be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bonding site).

[0144]

[0145] Examples of groups composed of alkyl groups and alicyclic hydrocarbon groups include methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, cyclohexylmethyl, adamantylmethyl, and norbornylethyl.

[0146] Examples of aromatic hydrocarbon groups include phenyl and naphthyl.

[0147] Aryl groups, such as benzyl, are examples of groups formed by combining alkyl and aromatic hydrocarbon groups.

[0148] As L a1 Examples of alkylene compounds include ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,5-pentaneene, 1,6-hexaneene, 1,1-ethylene, 1,1-propylene, and 2,2-propylene; branched alkylene compounds such as 1,2-propylene, 2,4-pentaneene, 2-methyl-1,3-propylene, 1,4-pentaneene, and 2-methyl-1,4-butylene; etc.

[0149] R a7Hydrogen atoms are preferred.

[0150] R a8 and R a9 Each of them is preferably methyl.

[0151] R a10 Preferably, it is an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy or ethoxy group, and even more preferably a methoxy group.

[0152] m' is preferably 0 or 1, more preferably 0.

[0153] R a11 Preferably, it is a primary or secondary alkyl group having 1 to 6 carbon atoms.

[0154] L a1 Preferably, it is an alkylene group having 2 to 4 carbon atoms, more preferably 1,2-ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, and even more preferably 1,2-ethylene.

[0155] n is preferably an integer from 1 to 10.

[0156] R a12 Preferably, it is a primary or secondary alkyl group having 1 to 3 carbon atoms.

[0157] As the structural unit (a2-1), it is preferably a structural unit represented by formula (a2-1-1), formula (a2-1-2), formula (a2-1-3), or formula (a2-1-4). Furthermore, the individual units from which the structural unit (a2-1) is derived may be as described in Japanese Patent Application Publication No. 2010-204634.

[0158]

[0159] Examples of monomers that can be derived from structural unit (a2-2) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, and other alkyl methacrylates.

[0160] Cyclopentyl methacrylate, cyclohexyl methacrylate, and other cycloalkyl methacrylates;

[0161] Polycyclic (meth)acrylates such as adamantyl methacrylate;

[0162] (Meth)phenyl acrylate, (meth)benzyl acrylate, etc. (meth)aryl acrylates; etc.

[0163] Examples of monomers that can be derived from structural units (a2-3) include ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monopropyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, 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, nonaethylene glycol monomethyl ether (meth)acrylate, octaethylene glycol monomethyl ether (meth)acrylate, and other (meth)acrylates.

[0164] Furthermore, examples of monomers that can be derived from structural unit (a2) include acrylic acid, methacrylic acid, crotonic acid, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, and 4-isopropoxystyrene.

[0165] As a structural unit (a2), for example, it can be a structural unit represented by equation (a2-4).

[0166]

[0167] In formula (a2-4),

[0168] R a13 It represents a hydrogen atom or a methyl group.

[0169] R a14 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0170] R a15 This refers to a primary or secondary hydrocarbon group with 1 to 12 carbon atoms, in which the methylene group can be replaced by an oxygen atom or a carbonyl group. However, the methylene group bonded to an oxygen atom cannot be replaced by an oxygen atom.

[0171] "m" represents an integer from 0 to 4. When "m" is 2 or higher, multiple R... a14 They may be the same as or different from each other.

[0172] m”' represents an integer from 0 to 4. When m”' is 2 or higher, multiple R a15 They may be the same as or different from each other.

[0173] Where the sum of m” and m”' is less than 5.

[0174] In other words, R a15 The hydrocarbon group in the text is a group whose bonding site with the oxygen atom is not a tertiary carbon atom. In other words, it can be a group that has one or more hydrogen atoms or other atoms other than carbon atoms bonded to the bonding carbon atom.

[0175] Therefore, the structural unit represented by equation (a2-4) does not contain structural unit (I) and structural unit (a1-2).

[0176] As R a14 Alkyl and alkoxy groups, for example, those related to R a10 Same group.

[0177] As R a15 Hydrocarbon groups, for example, are related to R. a11 Same group.

[0178] R a15 Preferably, the groups are straight-chain or branched alkyl groups with 1 to 5 carbon atoms, alicyclic hydrocarbon groups with 5 to 10 carbon atoms, phenyl groups, or groups formed by combining these groups, or groups in which the carbon atom adjacent to the oxygen atom of these groups is replaced with a carbonyl group.

[0179] As a structural unit (a2-4), for example, structural units represented by equations (a2-4-1) to (a2-4-10) can be cited.

[0180]

[0181] Among the structural units represented by formulas (a2-4-1) to (a2-4-10), examples can also be found that methyl substitution and R... a13 The structural unit obtained with equivalent hydrogen atoms is a specific example of the structural unit (a2-4).

[0182] When the resin (A1) has structural units (a2-1), (a2-2), (a2-3), and (a2-4), the total content of these groups relative to all structural units of the resin (A1) is preferably 1 to 30 mol%, more preferably 1 to 25 mol%, even more preferably 5 to 25 mol%, and particularly preferably 5 to 20 mol%.

[0183] When the resin (A1) has structural unit (a2), the content ratio of structural unit (a1) to structural unit (a2) [structural unit (a1): structural unit (a2)] based on molar ratio is preferably 10:90 to 80:20, more preferably 15:85 to 60:40, and even more preferably 15:85 to 45:55.

[0184] Examples of combinations of structural units contained in resin (A1) include those shown in formulas (A1-1) to (A1-46).

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192] In the above structural formula, examples can also be given of those involving R. a5 Monomers obtained by replacing methyl groups with equivalent hydrogen atoms, or by replacing methyl groups with hydrogen atoms, are specific examples of the aforementioned monomers. Furthermore, monomers having both hydrogen atoms and methyl groups may coexist in a resin.

[0193] The resin (A1) is preferably a resin having structural unit (a1) and structural unit (a2), and more preferably a resin having structural unit (a1-1) and / or structural unit (a1-2) and structural unit (a2).

[0194] Resin (A1) can also be a resin obtained by reacting a resin containing at least one of carboxyl and phenolic hydroxyl groups in its branched chain with a compound containing at least two vinyloxy groups in one molecule (hereinafter also referred to as "resin (A1b)").

[0195] The resin (A1b) is preferably a resin obtained by reacting a resin containing phenolic hydroxyl groups with a compound containing two or more vinyloxy groups per molecule. For example, such a resin can be obtained by reacting a resin having a structural unit (a2-1) with a compound containing two or more vinyloxy groups per molecule. Furthermore, as a resin containing phenolic hydroxyl groups, a resin obtained by reacting a phenolic varnish resin (described later) with the aforementioned compound containing vinyloxy groups can be used. Further, a resin can be obtained by mixing a resin having a structural unit (a2-1) with a phenolic varnish resin and reacting the resulting resin mixture with the aforementioned compound containing vinyloxy groups. Alternatively, a resin obtained by reacting a resin containing a structural unit (a2-1) with the aforementioned compound containing vinyloxy groups and a resin obtained by reacting a phenolic varnish resin with the aforementioned compound containing vinyloxy groups can be used simultaneously.

[0196] In the synthesis of resin (A1b), the compound containing at least two vinyloxy groups per molecule has a molar ratio of carboxyl groups to phenolic hydroxyl groups [carboxyl groups and phenolic hydroxyl groups: vinyloxy groups] of 60 to 99: 40 to 1, more preferably 70 to 95: 30 to 5.

[0197] Examples of resins (A1b) include those described in Japanese Patent Application Publication No. 2008-134515 and Japanese Patent Application Publication No. 2008-46594.

[0198] Examples of compounds containing at least two vinyl groups in one molecule include 1,4-cyclohexanediethanol divinyl ether and ethylene glycol divinyl ether.

[0199] When resin (A1b) is used as a raw material containing phenolic varnish resin, its content is 30-70% by mass relative to the total amount of resin (A1b).

[0200] The resin (A1) can be manufactured by polymerizing the above-mentioned monomers using a known polymerization method (e.g., free radical polymerization).

[0201] The weight-average molecular weight of the resin (A1) is preferably 8,000 or more, more preferably 10,000 or more, more preferably 600,000 or less, and even more preferably 500,000 or less. Furthermore, the weight-average molecular weight is obtained based on gel permeation chromatography analysis, using a conversion value as a standard polystyrene reference. Detailed analytical conditions for this analysis are described in the examples of this application.

[0202] The content of resin (A1) relative to the total amount of resin contained in the resist composition is preferably 10% by mass or more, more preferably 15% by mass or more, preferably 95% by mass or less, and more preferably 85% by mass or less.

[0203] <Resin (A3)>

[0204] Resin (A3) is a resin containing the structural unit shown in formula (I).

[0205]

[0206] In formula (I),

[0207] R i41 It represents a hydrogen atom or a methyl group.

[0208] R i42 It represents an acyl group or hydrogen atom with 2 to 7 carbon atoms, or a hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a hydroxyl group.

[0209] R i43 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0210] p represents an integer from 0 to 4. When p is 2 or higher, multiple R... i43 They may be the same as or different from each other.

[0211] Z represents a divalent hydrocarbon group containing 3 to 20 carbon atoms, as shown in formula (Ia). The methylene group in this hydrocarbon group can be replaced by an oxygen atom, a sulfur atom, or a carbonyl group. * indicates the bonding site with an oxygen atom.

[0212] *-〔(CH2) w -O] r — (Ia)

[0213] In equation (Ia), w and r each independently represent integers from 1 to 10.

[0214] Where w is 1, R i42 This indicates an acyl group with 2 to 7 carbon atoms.

[0215] Examples of hydrocarbon groups include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these groups.

[0216] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0217] Alicyclic hydrocarbon groups can be either monocyclic or polycyclic. Examples of alicyclic hydrocarbon groups include monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, as well as polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl and norbornyl.

[0218] Examples of groups composed of alkyl groups and alicyclic hydrocarbon groups include methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, cyclohexylmethyl, methylcyclohexylmethyl, and norbornylmethyl.

[0219] Examples of aromatic hydrocarbon groups include phenyl, naphthyl, p-methylphenyl, p-tert-butylphenyl, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, and other aryl groups.

[0220] Examples of acyl groups include acetyl, propionyl, and butyryl.

[0221] Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy.

[0222] As a divalent hydrocarbon group, it can be any group including *-[(CH2)] w -O] r The - group may further contain alkyl, alicyclic hydrocarbon, aromatic hydrocarbon, and groups formed by combinations of these groups. Furthermore, the methylene group contained in these groups may be replaced by an oxygen atom, a sulfur atom, or a carbonyl group. Here, * indicates a bonding site with an oxygen atom. w is 1–10, and r is 1–10.

[0223] Among them, as *-〔(CH2) w -O]r -, preferably - [(CH2)2-O] r -、-〔(CH2)3-O〕 r - etc., more preferably - [(CH2)2-O] r -. r is preferably 2 to 10, more preferably 2 to 5. w is preferably 2 to 10, more preferably 2 to 5.

[0224] Examples of Z groups include the following: * represents the bonding site with the oxygen atom, ** represents the bonding site with R. i42 The bonding sites.

[0225]

[0226] As the structural unit shown in equation (I), the structural units shown in equations (I-1) and (I-2) are preferred.

[0227]

[0228] In equations (I-1) and (I-2),

[0229] R i41 R i42 R i43 p and r have the same meaning as described above.

[0230] R i44 Represents hydrocarbon groups with 1 to 10 carbon atoms.

[0231] R i45 Each can independently represent a hydrocarbon group with 1 to 10 carbon atoms, an acyl group with 2 to 7 carbon atoms, or a hydrogen atom that can be substituted by a hydroxyl group.

[0232] R i44 Examples of hydrocarbon groups that are related to R i42 The groups that are the same as the hydrocarbon groups shown are grouped together.

[0233] R i45 Examples of R can be cited. i42 Groups that are the same as the groups shown.

[0234] The following structural units can be cited as structural units of equation (I), equation (I-1) or equation (I-2).

[0235]

[0236] Among the above structural units, examples related to R can be cited. i41 The structural unit obtained by replacing a number of hydrogen atoms with methyl groups is a specific example of the above structural unit.

[0237] The structural units of formulas (I), (I-1) and (I-2) and the resins containing these structural units can be manufactured by methods known in the art.

[0238] For example, monomers of the structural unit of formula (I-2) can be obtained by reacting the compound shown in formula (I-2a) with the compound shown in formula (I-2b) in a solvent such as ethyl acetate in the presence of a catalyst.

[0239] Examples of solvents include ethyl acetate and methyl isopropyl ketone.

[0240] Examples of catalysts include acid catalysts, such as p-toluenesulfonic acid and oxalic acid.

[0241]

[0242] [In the formula, R] i41 R i43 p, R i44 r and R i45 Same meaning as above.

[0243] Compounds of formula (I-2b), such as those of formula (I-2b'), can be obtained by protecting the hydroxyl group of formula (I-2c).

[0244]

[0245] Formulas (I-2c) and (I-2d) can be readily purchased from the market.

[0246] The resin (A3) may also have structural units other than those shown in formula (I). For example, it may also contain structural units known in the art, such as the structural unit (a1) with an acid-labile group and the structural unit (a2) without an acid-labile group.

[0247] When the resin (A3) contains structural unit (a1), the content of structural unit (a1) relative to all structural units of the resin (A3) is preferably 1 to 50 mol%, more preferably 5 to 45 mol%, and even more preferably 5 to 40 mol%.

[0248] When the resin (A3) contains structural unit (a2), the content of structural unit (a2) relative to all structural units of the resin (A3) is preferably 1 to 50 mol%, more preferably 5 to 45 mol%, even more preferably 5 to 40 mol%, and particularly preferably 5 to 35 mol%.

[0249] The content of resin (A3) relative to the total amount of resin contained in the resist composition is preferably 3% by mass or more, more preferably 5% by mass or more, more preferably 50% by mass or less, and more preferably 40% by mass or less.

[0250] <Resin (A2)>

[0251] The resin (A2) is preferably an alkali-soluble resin. An alkali-soluble resin is a resin containing acidic groups that is soluble in an alkaline developing solution. Examples of acidic groups include carboxyl groups, sulfonyl groups, and phenolic hydroxyl groups.

[0252] Examples of alkali-soluble resins include those known in the field of photoresists, such as phenolic varnish resins, resins having structural units (a2-1) but not structural units (a1), in other words, resins having polymeric units derived from hydroxystyrene, resins having polymeric units derived from (meth)acrylates, and polyalkylene glycols. Phenolic varnish resins are preferred. Alkali-soluble resins can be used alone or in combination of two or more.

[0253] Phenolic varnish resin is, for example, a resin obtained by condensing phenolic compounds with aldehydes in the presence of a catalyst. Examples of phenolic compounds include phenol; o-, m-, or p-cresol; 2,3-, 2,5-, 3,4-, or 3,5-xylenol; 2,3,5-trimethylphenol; 2,3-, or 4-tert-butylphenol; 2-tert-butyl-4-, or 5-methylphenol; 2,4-, or 5-methylresorcinol; 2,3-, or 4-methoxyphenol; 2,3-, 2,5-, or 3,5-dimethoxyphenol; 2-methoxyresorcinol; 4-tert-butylcatechol; 2,3-, or 4-ethylphenol; 2,5-, or 3,5-diethylphenol; 2,3,5-triethylphenol; 2-naphthol; 1,3-, 1,5-, or 1,7-dihydroxynaphthalene; and polyhydroxytriphenylmethane compounds obtained by the condensation of xylenol and hydroxybenzaldehyde. These phenolic compounds can be used alone or in combination of two or more. Among them, the preferred phenolic compounds are o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol, and 2-tert-butyl-5-methylphenol.

[0254] Examples of aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, acrolein, and butenaldehyde; alicyclic aldehydes such as cyclohexanal, cyclopentanal, or furanopropenaldehyde; aromatic aldehydes such as furanaldehyde, benzaldehyde, o-, m-, or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4-, or 3,5-dimethylbenzaldehyde, and o-, m-, or p-hydroxybenzaldehyde; and aromatic aliphatic aldehydes such as phenylacetaldehyde or cinnamaldehyde. These aldehydes can be used alone or in combination of two or more. Among these aldehydes, formaldehyde is preferred from an industrial ease of use perspective.

[0255] Examples of catalysts used for the condensation of phenolic compounds with aldehydes include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid, or phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid, and p-toluenesulfonic acid; and divalent metal salts such as zinc acetate, zinc chloride, and magnesium acetate. These catalysts can be used individually or in combination of two or more. The amount of the catalyst used is typically 0.01 to 1 mole relative to 1 mole of aldehyde.

[0256] The condensation reaction of phenolic compounds with aldehydes can be carried out using conventional methods. For example, this condensation reaction can be achieved by mixing the phenolic compound and the aldehyde and reacting them at a temperature of 60–120°C for approximately 2–30 hours. The condensation reaction can also be carried out in the presence of a solvent. Examples of solvents used in this condensation reaction include methyl ethyl ketone, methyl isobutyl ketone, and acetone. After the reaction is complete, the phenolic varnish resin can be obtained, for example, by adding a water-insoluble solvent to the reaction mixture as needed, washing the reaction mixture with water, and then concentrating it.

[0257] The phenolic varnish resin has a weight-average molecular weight of 3,000 to 10,000, preferably 6,000 to 9,000, and more preferably 7,000 to 8,000. By placing it within this range, film formation and residue after development can be effectively prevented.

[0258] Resins having polymeric units derived from hydroxystyrene are typically polyvinylphenol, preferably poly(p-vinylphenol). Specifically, resins formed from structural units represented by formula (a2-1) can be cited as examples. Such polyvinylphenol can be obtained, for example, by overlapping the monomers described in Japanese Patent Application Publication No. 2010-204634.

[0259] As a resin having polymer units derived from (meth)acrylate, examples include resins obtained by polymerizing one or more of the following monomers using conventional methods.

[0260] Compounds containing carboxyl groups, such as (meth)acrylic acid;

[0261] Compounds containing hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

[0262] Compounds 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, and nonaethylene glycol monomethyl ether (meth)acrylate.

[0263] The above monomers can also be used in combination with the following compounds: alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and tert-butyl methacrylate; cyclopentyl methacrylate and cyclohexyl methacrylate; polycyclic methacrylates such as adamantyl methacrylate; and 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, etc.

[0264] The content of resin (A2) relative to the total amount of resin contained in the resist composition is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 70% by mass or less, and more preferably 65% ​​by mass or less.

[0265] <Acid-producing agent (B)>

[0266] The resist composition of the present invention contains an acid-generating agent (B). The acid-generating agent generates acid upon exposure, and the generated acid acts as a catalyst, causing the elimination of groups in the resin (A) that would otherwise be eliminated under acid. Acid-generating agents are classified as nonionic or ionic, and both types can be used in the acid-generating agent (B) of the resist composition of the present invention.

[0267] Examples of nonionic acid-generating agents include organohalides, sulfonates (e.g., 2-nitrobenzene esters, 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 onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodide salts). Examples of onium salt anions include sulfonic acid anions, sulfonylimide anions, and sulfonylmethyl anions.

[0268] The acid-producing agent (B) can be a compound that generates acid through radiation, as described in, for example, Japanese Patent Application 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. 3,914,407, and European Patent No. 126,712. Furthermore, the acid-producing agent (B) can be synthesized by known methods or be a commercially available product.

[0269] Nonionic acid-generating agents are preferably compounds having the group shown in formula (B1).

[0270]

[0271] In formula (B1),

[0272] R b1 This refers to a hydrocarbon group with 1 to 18 carbon atoms that can contain fluorine atoms, wherein the methylene group may be replaced by an oxygen atom or a carbonyl group.

[0273] In addition, nitrogen atoms can also have double bonds.

[0274] Examples of hydrocarbon groups with 1 to 18 carbon atoms include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combinations of these groups.

[0275] As an aliphatic hydrocarbon group, alkyl groups are preferred, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.

[0276] Examples of alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl.

[0277] Aryl groups with 6 to 18 carbon atoms are preferred as aromatic hydrocarbon groups, such as phenyl, naphthyl, anthraceneyl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenel, mesitylene, biphenyl, phenanthrene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.

[0278] The preferred hydrocarbon group is an alkyl group with 1 to 10 carbon atoms or an aromatic hydrocarbon group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 8 carbon atoms, and even more preferably an alkyl group with 1 to 4 carbon atoms.

[0279] Examples of groups in which the methylene group contained in a hydrocarbon group is replaced by an oxygen atom or a carbonyl group include those represented by formulas (Y1) to (Y12). Groups represented by formulas (Y7) to (Y9) are preferred, and those represented by formula (Y9) are more preferred.

[0280]

[0281] Examples of hydrocarbon groups containing fluorine atoms 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, fluorocyclooctyl, and fluoroadamantyl; and fluoroaryl groups such as fluorophenyl, fluoronaphthyl, and fluoroanthrayl.

[0282] The preferred hydrocarbon group having fluorine atoms is an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon 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.

[0283] Examples of compounds having the group shown in formula (B1) include compounds shown in any one of formulas (b1) to (b3). Compounds shown in formulas (b1) and (b2) are preferred, and compounds shown in formula (b1) are more preferred.

[0284]

[0285] In equations (b1) to (b3),

[0286] R b1 Same meaning as above.

[0287] R b2’ R b3 and R b4 Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

[0288] Ring W b1 It represents an aromatic hydrocarbon ring with 6 to 14 carbon atoms or an aromatic heterocycle with 6 to 14 carbon atoms.

[0289] x represents an integer from 0 to 2. When x is 2, multiple R b2’ They can be the same or different.

[0290] Examples of alkyl groups include methyl, ethyl, propyl, butyl, and pentyl, with methyl being preferred.

[0291] Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy, with methoxy being preferred.

[0292] Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, and anthracene rings.

[0293] Examples of aromatic heterocycles include rings with 6 to 14 atoms constituting the ring, with the following rings being preferred.

[0294]

[0295] As a ring W b1 Examples of substituents that can be present on the surface include alkyl groups having 1 to 5 carbon atoms.

[0296] Ring W b1 Naphthalene ring is preferred.

[0297] As the compound represented by formula (b1), the compound represented by any one of formulas (b4) to (b7) is preferred, and the compound represented by formula (b4) is more preferred.

[0298]

[0299] In equations (b4) to (b7),

[0300] R b1 Same meaning as above.

[0301] R b2 R b5 R b6 and R b7 Each can independently represent an alkyl group having 1 to 8 hydrogen atoms or carbon atoms.

[0302] As a compound represented by formula (b1), any compound represented by any one of formulas (b1-1) to (b1-14) can be cited.

[0303] Preferably, it is a compound represented by formula (b1-6) or formula (b1-7).

[0304]

[0305] As a compound represented by formula (b2), compounds represented by the following formula can be cited.

[0306]

[0307] As a compound represented by formula (b3), compounds represented by the following formula can be cited.

[0308]

[0309] As an ionic acid-producing agent, the compound shown in formula (b8) or formula (b9) is preferred.

[0310]

[0311] In equations (b8) and (b9),

[0312] A b1 and A b2 Each can be used to represent an oxygen atom or a sulfur atom independently.

[0313] R b8 R b9 R b10 and R b11 Each can be independently represented as an alkyl group with 1 to 10 carbon atoms or an aromatic hydrocarbon group with 6 to 12 carbon atoms.

[0314] X1 - and X2 - This indicates an organic anion.

[0315] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0316] Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthracene, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenel, mesitylene, biphenyl, phenanthrene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, and other aryl groups.

[0317] R b8 R b9 R b10 and R b11 Each of the aromatic compounds having 6 to 12 carbon atoms is preferred, with phenyl being more preferred.

[0318] As X1 - and X2 - Examples of organic anions shown include sulfonic acid anions, di(alkylsulfonyl)amide anions, and tri(alkylsulfonyl)methyl anions, with sulfonic acid anions being preferred, and sulfonic acid anions being more preferred, as shown in formula (b10).

[0319]

[0320] In formula (b10),

[0321] R b12 This refers to a hydrocarbon group with 1 to 18 carbon atoms that may contain fluorine atoms, wherein the methylene group may be replaced by an oxygen atom or a carbonyl group.

[0322] As R b12 Examples of R in equation (B1) can be cited. b1 Same group.

[0323] The following compounds can be cited as examples of compounds represented by formula (b9).

[0324]

[0325] The following compounds can be cited as examples of compounds represented by formula (b10).

[0326]

[0327] In the resist composition, acid-generating agent (B) can be used alone or in combination of two or more.

[0328] The content of acid-producing agent (B) relative to 100 parts by weight of resin (A) is preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight or more, even more preferably 1 part by weight or more, preferably 30 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less.

[0329] <Solvent (D)>

[0330] The solvent (D) is not particularly limited to any solvent capable of dissolving the components contained in the resist composition of the present invention. Examples include glycol ether esters such as ethylene glycol ethyl ether acetate, ethylene glycol methyl ether 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; lactones such as γ-butyrolactone, and mixed solvents thereof.

[0331] The content of solvent (D) relative to the total amount of the resist composition of the present invention is generally 40% by mass or more and 75% by mass or less, preferably 45% by mass or more and 70% by mass or less, and more preferably 50% by mass or more and 68% by mass or less.

[0332] If the content of solvent (D) is within this range, it is easy to form a resist composition layer with a thickness of 3 to 150 μm when manufacturing resist patterns.

[0333] <Quencher (C)>

[0334] The quencher (C) contained in the resist composition of the present invention is a compound that has the function of capturing acid generated by acid-producing agents caused by exposure. Examples of quenchers (C) are basic nitrogen-containing organic compounds.

[0335] Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines; primary amines, secondary amines, and tertiary amines.

[0336] Examples of amines include compounds represented by formula (C1) or formula (C2).

[0337]

[0338] In formula (C1), R c1 R c2 and R c3 Each of the following groups independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom in the alkyl group or the alicyclic hydrocarbon group may be replaced by a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. The hydrogen atom in the aromatic hydrocarbon group may be replaced by an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon group having 5 to 10 carbon atoms.

[0339] The alkyl, alicyclic hydrocarbon, aromatic hydrocarbon, alkoxy, and alkylene groups in formula (C1) can be the same groups as those mentioned above.

[0340] Examples of compounds represented by formula (C1) include 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, methyldipentylamine, dihexylmethylamine, dicyclohexylmethylamine, diheptylmethylamine, and methyldioctylamine. Amines, 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., preferably diisopropylaniline, more preferably 2,6-diisopropylaniline.

[0341]

[0342] In formula (C2),

[0343] Ring W 1 This refers to a heterocycle containing nitrogen atoms in the atoms constituting the ring, or a benzene ring having substituted or unsubstituted amino groups, wherein the heterocycle and the benzene ring may have at least one group selected from the group consisting of hydroxyl groups and alkyl groups having 1 to 4 carbon atoms.

[0344] A 1 It indicates phenyl or naphthyl.

[0345] nc represents 2 or 3.

[0346] The substituted or unsubstituted amino group is composed of -N(R) 4 (R) 5 ) indicates that R 4 and R 5 Each can independently represent a hydrogen atom, an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 10 carbon atoms, or an aromatic hydrocarbon group with 6 to 14 carbon atoms.

[0347] Examples of aliphatic hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0348] Examples of alicyclic hydrocarbon groups include R in formula (1). a1 ~R a3 The same group. Examples of aromatic hydrocarbon groups include R in formula (2). a1’ ~R a3’ Same group.

[0349] A heterocycle containing nitrogen atoms in its ring can be an aromatic or non-aromatic ring, and may also contain other heteroatoms (e.g., oxygen or sulfur atoms). The number of nitrogen atoms in this heterocycle is, for example, 1 to 3. Examples of such heterocycles include any one of formulas (Y13) to (Y28). Removing one hydrogen atom from the ring results in a ring with A... 1 The bonding sites.

[0350]

[0351] Ring W 1 Preferably, the atoms constituting the ring are heterocycles containing nitrogen atoms, more preferably, they are 5- or 6-membered aromatic heterocycles containing nitrogen atoms, and even more preferably, they are rings represented by any one of formulas (Y20) to (Y25).

[0352] As a compound represented by formula (C2), any compound represented by any one of formulas (C2-1) to (C2-11) can be cited.

[0353] Among them, compounds represented by any one of formulas (C2-2) to (C2-8) are preferred.

[0354]

[0355] The content of quencher (C) in the solid component of the resist composition 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, particularly preferably 0.01 to 1.0% by mass, and especially preferably 0.1 to 0.7% by mass.

[0356] <Adhesion Promoter (E)>

[0357] There are no particular limitations on adhesion promoters (E) as long as they can prevent corrosion of the metal used in the substrate or wiring and / or improve adhesion. By preventing corrosion of the metal, they can act as rust inhibitors. In addition, while performing these functions, they can also improve the adhesion of the substrate or metal to the resist composition.

[0358] Adhesion promoters (E) include, for example, sulfur-containing compounds, aromatic hydroxyl compounds, benzotriazole compounds, triazine compounds, and silicon-containing compounds. These can be used alone or in combination of two or more.

[0359] As a sulfur-containing compound, it can be any compound containing a thioether bond and / or a thiol group. Sulfur-containing compounds can be chain compounds or compounds with a cyclic structure.

[0360] Examples of chain compounds include dithiodiglycerol [S(CH2CH(OH)CH2(OH))2], di(2,3-dihydroxypropylthio)ethylene [CH2CH2(SCH2CH(OH)CH2(OH))2], sodium 3-(2,3-dihydroxypropylthio)-2-methyl-propylsulfonate [CH2(OH)CH(OH)CH2SCH2CH(CH3)CH2SO3Na], 1-thioglycerol [HSCH2CH(OH)CH2(OH)], sodium 3-mercapto-1-propanesulfonate [HSCH2CH2CH2SO3Na], 2-mercaptoethanol [HSCH2CH2(OH)], mercaptoacetic acid [HSCH2CO2H], and 3-mercapto-1-propanol [HSCH2CH2CH2].

[0361] The sulfur-containing compound is preferably a compound having a thioether bond and a thiol group, and more preferably a heterocyclic compound having both a thioether bond and a thiol group. The number of thioether bonds and thiol groups in the sulfur-containing compound is not particularly limited, as long as each is one or more.

[0362] The heterocycle can be any type of monocyclic or polycyclic ring, and can be either saturated or unsaturated. The heterocycle is further preferably composed of heteroatoms other than sulfur atoms. Examples of heteroatoms include oxygen atoms and nitrogen atoms, with nitrogen atoms being preferred.

[0363] The heterocycle is preferably a heterocycle with 2 to 12 carbon atoms, more preferably a heterocycle with 2 to 6 carbon atoms. The heterocycle is preferably a monocyclic ring. The heterocycle is preferably unsaturated. The heterocycle is preferably an unsaturated monocyclic ring.

[0364] Examples of heterocycles include the following heterocycles.

[0365]

[0366] The sulfur-containing compound can be a polymer. The polymer preferably contains structural units with thioether bonds and thiol groups on the side chain. The structure with thioether bonds and thiol groups (hereinafter also referred to as unit (1)) is preferably bonded to the main chain by linking groups such as amide bonds, ether bonds, thioether bonds, and ester bonds.

[0367] The polymer can be a homopolymer or a copolymer.

[0368] When the polymer is a copolymer, it may contain structural units (a1) with acid-labile groups as described above, or it may contain structural units (a2) without acid-labile groups.

[0369] The weight-average molecular weight of the polymer is typically above 3,000, preferably above 5,000, typically below 100,000, preferably below 50,000.

[0370] When the sulfur-containing compound is a polymer, the content of structural units having thioether bonds and thiol groups is typically 0.1 to 50 mol% relative to all structural units of the sulfur-containing compound polymer, preferably 0.5 to 30 mol%, and more preferably 1 to 20 mol%.

[0371] The sulfur-containing compounds are preferably, for example, compounds represented by formula (IA) or polymers having structural units represented by formula (IB).

[0372]

[0373] In formula (IA),

[0374] R i1 Represents hydrogen atoms, aliphatic hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 14 carbon atoms, alicyclic hydrocarbon groups with 3 to 18 carbon atoms, and -SR. 11 The indicated group or -NR 12 R 13 The group shown.

[0375] R 11 R 12 and R 13 Each group independently represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, or an acyl group with 1 to 12 carbon atoms. The hydrogen atoms of these aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and acyl groups can be replaced by hydroxyl groups.

[0376] R i2 and R i3 Each can independently represent a hydrogen atom, an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, or an alicyclic hydrocarbon group with 3 to 18 carbon atoms.

[0377] A and B each independently represent a nitrogen atom or a carbon atom.

[0378] n and m each independently represent 0 or 1. Where A is a nitrogen atom, n represents 0; A is a carbon atom, n represents 1; B is a nitrogen atom, m represents 0; B is a carbon atom, m represents 1.

[0379] Examples of aliphatic hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0380] Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthracene, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenel, mesitylene, biphenyl, phenanthrene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, and other aryl groups.

[0381] Examples of alicyclic hydrocarbon groups include monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, as well as polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornyl.

[0382] R 11 Preferably, aliphatic hydrocarbon groups or acyl groups, R 12 and R 13 Each group independently selects hydrogen atoms, aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and acyl groups.

[0383] Examples of acyl groups include acetyl, propionyl, butyryl, valeryl, hexylcarbonyl, heptylcarbonyl, octylcarbonyl, decylcarbonyl, dodecylcarbonyl, and benzoyl.

[0384] R i1 More preferably, hydrogen atoms or thiol groups.

[0385] R i2 and R i3 Each is preferably composed of hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, with hydrogen atoms being more preferred.

[0386] Preferably, at least one of A and B is a nitrogen atom, and more preferably, both are nitrogen atoms.

[0387]

[0388] In formula (IB),

[0389] R i21 and R i31 Each can independently represent a hydrogen atom, an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, or an alicyclic hydrocarbon group with 3 to 18 carbon atoms.

[0390] A 1 and B 1Each can be used to represent either a nitrogen atom or a carbon atom independently.

[0391] n i and m i Each can independently represent either 0 or 1. Among them, A 1 When n is a nitrogen atom i Represents 0, A 1 When n is a carbon atom, i Indicates 1, B 1 When it is a nitrogen atom, m i Represents 0, B 1 When m is a carbon atom i Indicates 1.

[0392] R i4 It represents a hydrogen atom or a methyl group.

[0393] X i1 It represents a sulfur atom and an NH group.

[0394] L i1 This represents a divalent hydrocarbon group with 1 to 20 carbon atoms. The methylene group within this hydrocarbon group can be replaced by an oxygen atom or a carbonyl group.

[0395] As R i21 and R i31 The aliphatic hydrocarbon group can be exemplified by alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, with alkyl groups having 1 to 4 carbon atoms being preferred.

[0396] As R i21 and R i31 Aromatic hydrocarbon groups include phenyl, naphthyl, anthracene, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenel, mesitylene, biphenyl, phenanthrene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc., with aryl groups having 6 to 10 carbon atoms being preferred.

[0397] As R i21 and R i31 Alicyclic hydrocarbons include monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornel, with alicyclic hydrocarbon groups having 5 to 10 carbon atoms being preferred.

[0398] R i21 and R i31 Each is independently preferred to have alkyl groups having 1 to 4 hydrogen atoms or carbon atoms.

[0399] L i1Examples of divalent hydrocarbon groups shown include methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentaneene, 1,6-hexaneene, 1,7-heptaneene, 1,8-octaneene, 1,9-nonaneene, 1,10-decaneene, 1,11-undecaneene, 1,12-dodecaneene, 1,13-tridecaneene, 1,14-tetradecaneene, 1,15-pentadecaneene, 1,16-hexadecaneene, and 1,17-heptadecaneene, 1,1-ethylene, 1,1-propylene, 1,2-propylene, 2,2-propylene, 2,4-pentaneene, 2-methyl-1,3-propylene, 2-methyl-1,2-propylene, 1,4-pentaneene, and 2-methyl-1,4-butylene, etc.

[0400] 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,5-cyclooctylene, and other cycloalkylene monocyclic divalent alicyclic saturated hydrocarbon groups;

[0401] Polycyclic divalent alicyclic saturated hydrocarbon groups such as 1,4-norbornyl, 2,5-norbornyl, 1,5-adamantyl, and 2,6-adamantyl;

[0402] Aryl groups such as phenylene, methylphenylene, and naphthylene.

[0403] L i1 Preferably, it is a group composed of an alkylene group containing 2 to 14 carbon atoms or an aryl group containing 6 to 10 carbon atoms, combined with an alkylene group containing 1 to 11 carbon atoms.

[0404] The structural unit shown in formula (IB) is preferably the structural unit shown in formula (IB-1) or the structural unit shown in formula (IB-2).

[0405]

[0406] In formula (IB-1),

[0407] R i22 and R i32 Each can independently represent a hydrogen atom, an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, or an alicyclic hydrocarbon group with 3 to 18 carbon atoms.

[0408] A 2 and B 3 Each can be used to represent either a nitrogen atom or a carbon atom independently.

[0409] n3 and m3 each independently represent 0 or 1. Where A 2 When it is a nitrogen atom, n3 represents 0, A 2 When the atom is carbon, n3 represents 1, B 2When it is a nitrogen atom, m3 represents 0, B 2 When the atom is carbon, m3 represents 1.

[0410] X i11 It represents a sulfur atom and an NH group.

[0411] L i2 This indicates a divalent hydrocarbon group with 1 to 18 carbon atoms. The methylene group contained in this hydrocarbon group can be replaced with an oxygen atom or a carbonyl group.

[0412] R i5 It represents a hydrogen atom or a methyl group.

[0413] In equation (IB-2),

[0414] R i23 and R i33 Each can independently represent a hydrogen atom, an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, or an alicyclic hydrocarbon group with 3 to 18 carbon atoms.

[0415] A 3 and B 3 Each can be used to represent either a nitrogen atom or a carbon atom independently.

[0416] n4 and m4 each independently represent 0 or 1. Where A 3 When it is a nitrogen atom, n4 represents 0, A 3 When it is a carbon atom, n4 represents 1, B 3 When it is a nitrogen atom, m4 represents 0, B 3 When the atom is carbon, m4 represents 1.

[0417] X i12 It represents a sulfur atom and an NH group.

[0418] L i3 This indicates a divalent hydrocarbon group with 1 to 14 carbon atoms. The methylene group contained in this hydrocarbon group can be replaced with an oxygen atom or a carbonyl group.

[0419] R i7 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0420] R i6 It represents a hydrogen atom or a methyl group.

[0421] mx represents an integer from 0 to 4.

[0422] As R i22 R i32 R i23 and R i33 The aliphatic hydrocarbon groups with 1 to 10 carbon atoms shown can be exemplified by those related to R. i21 and R i31The groups shown are the same as the aliphatic hydrocarbon groups with 1 to 10 carbon atoms.

[0423] As R i22 R i32 R i23 and R i33 The aromatic hydrocarbon groups with 6 to 14 carbon atoms shown can be exemplified by those related to R. i21 and R i31 The groups shown are the same as aromatic hydrocarbon groups with 6 to 14 carbon atoms.

[0424] As R i22 R i32 R i23 and R i33 Examples of alicyclic hydrocarbon groups with 3 to 18 carbon atoms shown are related to R. i21 and R i31 The groups shown are the same as the alicyclic hydrocarbon groups with 3 to 18 carbon atoms.

[0425] L i2 Examples of divalent hydrocarbon groups with 1 to 18 carbon atoms include methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentaneene, 1,6-hexaneene, 1,7-heptaneene, 1,8-octaneene, 1,9-nonaneene, 1,10-decaneene, 1,11-undecaneene, 1,12-dodecaneene, 1,13-tridecaneene, 1,14-tetradecaneene, 1,15-pentadecaneene, 1,16-hexadecaneene, and 1,17-heptadecaneene, 1,1-ethylene, 1,1-propylene, 1,2-propylene, 2,2-propylene, 2,4-pentaneene, 2-methyl-1,3-propylene, 2-methyl-1,2-propylene, 1,4-pentaneene, and 2-methyl-1,4-butylene.

[0426] 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,5-cyclooctylene, etc., are monocyclic divalent alicyclic saturated hydrocarbon groups of cycloalkylene compounds;

[0427] Polycyclic divalent alicyclic saturated hydrocarbon groups such as 1,4-norbornyl, 2,5-norbornyl, 1,5-adamantyl, and 2,6-adamantyl.

[0428] L i2 Preferably, the alkylene group has 1 to 14 carbon atoms, and more preferably, it has 1 to 11 carbon atoms.

[0429] As L i3Examples of divalent hydrocarbon groups with 1 to 14 carbon atoms include methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentane, 1,6-hexane, 1,7-heptane, 1,8-octane, 1,9-nonane, 1,10-decane, 1,11-undecane, 1,12-dodecane, 1,1-ethylene, 1,1-propylene, 1,2-propylene, 2,2-propylene, 2,4-pentane, 2-methyl-1,3-propylene, 2-methyl-1,2-propylene, 1,4-pentane, and 2-methyl-1,4-butylene.

[0430] 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,5-cyclooctylene, etc., are monocyclic divalent alicyclic saturated hydrocarbon groups of cycloalkylene compounds;

[0431] Polycyclic divalent alicyclic saturated hydrocarbon groups such as 1,4-norbornyl, 2,5-norbornyl, 1,5-adamantyl, and 2,6-adamantyl.

[0432] L i3 Preferably, the alkylene group has 1 to 14 carbon atoms, and more preferably, it has 1 to 11 carbon atoms.

[0433] Based on the position of the phenyl group bonded to the main chain, L i3 Preferred bonding is performed at the alignment point.

[0434] Examples of sulfur-containing compounds include any one of the compounds shown in formula (I-1) to formula (I-26). Among these, compounds shown in formula (I-1) to formula (I-13) are preferred, and compounds shown in formula (I-1), formula (I-4), and formula (I-11) are more preferred.

[0435]

[0436] Examples of sulfur-containing compounds include homopolymers composed of any one of the structural units shown in formulas (I-27) to (I-38) or copolymers containing one or more of these structural units.

[0437] Preferably, it is a copolymer containing one or more structural units of formula (I-27) to formula (I-36), and more preferably a copolymer containing structural units of formula (I-33).

[0438]

[0439] Examples of such copolymers include copolymers composed of structural units shown in formulas (I-39) to (I-48). Among these, polymers having structural units shown in formulas (I-39) to (I-44) are preferred.

[0440]

[0441]

[0442] The sulfur-containing compound can be a compound synthesized by a known method (e.g., Japanese Patent Application Publication No. 2010-79081) or a commercially available product. The polymer containing the sulfur-containing compound can be a commercially available product (e.g., 2,5-dimercaptothiadiazole (manufactured by Tokyo Chemical Industry Co., Ltd., etc.) or a compound synthesized by a known method (e.g., Japanese Patent Application Publication No. 2001-75277).

[0443] Examples of aromatic hydroxyl compounds include phenol, cresol, xylenol, catechol (=1,2-dihydroxybenzene), tert-butylcatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicylol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenylethanol, p-aminophenol, m-aminophenol, diaminophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, etc.

[0444] Examples of benzotriazole compounds include those represented by formula (IX).

[0445]

[0446] In formula (IX),

[0447] R 1 and R 2 Each group independently represents a hydrogen atom, and may have 1 to 10 carbon atoms of a hydrocarbon group, carboxyl group, amino group, hydroxyl group, cyano group, formyl group, sulfonylalkyl group or sulfonyl group.

[0448] Q represents a hydrogen atom, a hydroxyl group, a hydrocarbon group with 1 to 10 carbon atoms that may have substituents, an aryl group, or **-R. 3 -N(R 4 (R) 5 The structure of the above hydrocarbon group can contain amide bonds and ester bonds.

[0449] R 3 Indicates an alkylene group having 1 to 6 carbon atoms. ** indicates a bonding site with a nitrogen atom contained in the ring.

[0450] R4 and R 5 Each of the following can be independently represented: hydrogen atom, hydroxyl group, alkyl group with 1 to 6 carbon atoms, hydroxyalkyl group with 1 to 6 carbon atoms, or alkoxyalkyl group with 1 to 6 carbon atoms.

[0451] R 1 R 2 The hydrocarbon group of Q can be any of aliphatic hydrocarbon groups or aromatic hydrocarbon groups, and can also have saturated and / or unsaturated bonds.

[0452] Alkyl groups are preferred as aliphatic hydrocarbon groups, and examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, methylpentyl, n-hexyl, and n-heptyl.

[0453] Aryl groups are preferred as aromatic hydrocarbon groups, and examples of such aryl groups include phenyl, naphthyl, anthraceneyl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenel, mesitylene, biphenyl, phenanthrene, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl.

[0454] R 3 Examples of alkylene groups are as described above.

[0455] Examples of substituents that can be present in a hydrocarbon group include hydroxyalkyl and alkoxyalkyl groups.

[0456] Examples of hydroxyalkyl groups include hydroxymethyl, hydroxyethyl, and dihydroxyethyl.

[0457] Examples of alkoxyalkyl groups include methoxymethyl, methoxyethyl, and dimethoxyethyl.

[0458] When the resist composition of the present invention is applied to a copper-formed substrate, in formula (IX), Q is preferably **-R. 3 -N(R 4 (R) 5 The compound shown is R. 4 and R 5 When at least one of the components is an alkyl group having 1 to 6 carbon atoms, although benzotriazole compounds lack water solubility, they are preferred if other components that can dissolve the compound are present.

[0459] Furthermore, when the resist composition of the present invention is applied to a substrate having an inorganic material layer (e.g., a polysilicon film, an amorphous silicon film, etc.), in formula (IX), the group Q preferably exhibits water solubility. Specifically, hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, hydroxyalkyl groups having 1 to 3 carbon atoms, hydroxyl groups, etc., are preferred. Accordingly, the corrosion resistance of the substrate can be more effectively utilized.

[0460] Examples of benzotriazole compounds include benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxymethylbenzotriazole, methyl 1-benzotriazole carboxylate, 5-benzotriazole carboxylic acid, 1-methoxybenzotriazole, 1-(2,2-dihydroxyethyl)benzotriazole, 1-(2,3-dihydroxypropyl)benzotriazole, or as "Irgamet (registered trademark) The “label” series includes 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol, 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}diethane, or 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}dipropane, etc., sold by BASF.

[0461] Examples of triazine compounds include those represented by formula (II).

[0462]

[0463] In formula (II),

[0464] R 6 R 7 and R 8 Each of these can independently represent a halogen, hydrogen atom, hydroxyl group, amino group, mercapto group, substituted hydrocarbon group with 1 to 10 carbon atoms, substituted alkoxy group with 1 to 10 carbon atoms, or amino group substituted with a hydrocarbon group with 1 to 10 carbon atoms.

[0465] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0466] Hydrocarbon groups and alkoxy groups can be the same as those mentioned above.

[0467] Examples of triazine compounds include 1,3,5-triazine-2,4,6-trithiol.

[0468] Examples of silicon-containing compounds include compounds represented by formula (IIA).

[0469]

[0470] In formula (IIA),

[0471] R j1 It represents an aliphatic hydrocarbon group with 1 to 5 carbon atoms or a mercaptoalkyl group with 1 to 5 carbon atoms.

[0472] R j2 ~R j4Each of the following groups independently represents an aliphatic hydrocarbon group, an alkoxy group, a mercapto group, or a mercaptoalkyl group with 1 to 5 carbon atoms, R. j2 ~R j4 At least one of them is a mercapto group or a mercaptoalkyl group having 1 to 5 carbon atoms.

[0473] t i Represents integers from 1 to 10.

[0474] Examples of aliphatic hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, and pentyl.

[0475] Examples of alkoxy groups include methoxy and ethoxy.

[0476] Examples of mercaptoalkyl groups include methyl mercapto, ethyl mercapto, and propyl mercapto.

[0477] R j1 Preferably, the aliphatic hydrocarbon group with 1 or 2 carbon atoms, or the mercaptoalkyl group with 1 to 3 carbon atoms, is preferred; more preferably, methyl or mercaptopropyl is preferred.

[0478] R j2 ~R j4 Each of the groups is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms, an alkoxy group with 1 or 2 carbon atoms, and more preferably methyl or methoxy. Preferably, at least one of them is a mercapto group or a mercaptoalkyl group with 1 to 3 carbon atoms, and more preferably a mercapto group or a mercaptopropyl group.

[0479] R j2 and R j3 They can be the same or different from each other; from a productivity point of view, they are preferably the same.

[0480] Examples of compounds of formula (IIA) include the compounds shown in formulas (II-1) to (II-7).

[0481]

[0482] Among them, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane are preferred.

[0483] The content of adhesion promoter (E), relative to the total amount of solid components in the resist composition, is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, even more preferably 0.005% by mass or more, particularly preferably 0.008% by mass or more, and further preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 4% by mass or less, even more preferably 3% by mass or less, particularly preferably 1% by mass or less, and especially preferably 0.1% by mass or less. By placing it within this range, it can become a resist composition capable of forming high-precision resist patterns, thus ensuring the adhesion of the resist pattern to the substrate.

[0484] <Other ingredients (hereinafter also referred to as "Other ingredients (F)")>

[0485] The resist composition of the present invention may contain other components (F) as needed. These other components (F) are not particularly limited and include additives known in the field of resists, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes.

[0486] When using this other ingredient (F), its content can be appropriately selected according to the type of other ingredient (F).

[0487] <Method for manufacturing the resist composition of the present invention>

[0488] The resist composition of the present invention can be prepared by mixing resin (A1), resin (A3), acid-generating agent (B), and solvent (D), as well as resin (A2), quencher (C), adhesion promoter (E), and other components (F) as needed. The mixing order is not particularly limited and can be arbitrary. The mixing temperature can be appropriately selected in the range of 10 to 40°C, depending on the type of resin and its solubility in the solvent (D). The mixing time can be appropriately selected in the range of 0.5 to 24 hours, depending on the mixing temperature. The mixing method is also not limited and can be stirring or the like. After mixing the components, it is preferable to filter the mixture using a filter with a pore size of 0.11 to 50 μm.

[0489] <Method for Manufacturing Anti-corrosion Patterns>

[0490] The method for manufacturing the resist pattern of the present invention includes the following steps:

[0491] (1) The process of coating the resist composition of the present invention onto a substrate.

[0492] (2) The process of drying and coating the resist composition to form a composition layer.

[0493] (3) The process of exposing the composite layer, and

[0494] (4) The process of developing the exposed composite layer.

[0495] The coating of the resist composition of the present invention onto the substrate in step (1) can be performed using a coating apparatus commonly used in the art, such as a spin coater. Examples of substrates include silicon wafers, on which semiconductor devices such as transistors and diodes can be pre-formed. When the resist composition of the present invention is used to form bumps, a substrate further having a conductive material deposited on it is preferable. Examples of conductive materials include one or more metals selected from the group consisting of gold, copper, nickel, tin, palladium, and silver, or alloys containing one or more metals selected from this group, preferably copper or copper-containing alloys.

[0496] These substrates can be pre-cleaned, and anti-reflective films can be formed. To form an anti-reflective film, commercially available organic anti-reflective film compositions can be used.

[0497] In step (2), by drying the coated composition, the solvent can be removed, and a composition layer can be formed on the substrate. Drying can be performed by heating (so-called pre-drying) using a heating device such as a heating plate, depressurization drying using a depressurization device, or a combination of these methods. In this case, the temperature is preferably around 50 to 200°C. The pressure is preferably 1 to 1.0 × 10⁻⁶. 5 Approximately Pa.

[0498] The thickness of the composite layer obtained in step (2) is preferably 3 to 150 μm, more preferably 4 to 100 μm.

[0499] In step (3), it is preferable to use an exposure machine to expose the composition layer. At this time, exposure is usually performed through a mask corresponding to the desired pattern. The exposure light source of the exposure machine can be selected according to the resolution of the resist pattern to be manufactured, but it is preferable to have a light source that can illuminate light with a wavelength of 345 to 436 nm, and more preferably g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), or i-line (wavelength: 365 nm).

[0500] After step (3), a step of heating the exposed composite layer (so-called post-exposure baking) can be performed. A development step using a heating device is preferred. Examples of heating devices include heating plates. The heating temperature is typically 50–200°C, preferably 60–120°C. The heating time is typically 40–400 seconds, preferably 50–350 seconds.

[0501] In step (4), the exposed composition layer is preferably developed using a developing apparatus. During the heating step, the heated composition layer is developed. An alkaline developing solution is typically used for development. Examples of alkaline developing solutions include aqueous solutions of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline).

[0502] After development, the substrate and resist pattern are cleaned with ultrapure water to further remove residual moisture.

[0503] <Uses>

[0504] The resist composition containing the above-mentioned resin (A1), resin (A3), acid-generating agent (B), and solvent (D) can be used in the manufacture of thick resist films.

[0505] This photoresist composition, which can be used to manufacture photoresist films with a thickness of 3 to 150 μm, constitutes one aspect of the present invention.

[0506] Furthermore, the resist composition of the present invention can be used in the manufacture of bumps.

[0507] When using a resist composition to create bumps, they can typically be formed in the following order.

[0508] First, a conductive layer is formed on a wafer on which semiconductor elements are formed, by laminating a conductive material (seed metal) and forming a resist pattern on the conductive layer using the resist composition of the present invention. Next, using the resist pattern as a mold, electrode materials (e.g., copper, nickel, solder, etc.) are deposited by electroplating. The resist pattern and the remaining conductive layer beneath it are then removed by etching or the like, thereby forming bumps. Alternatively, after removing the conductive layer, electrode materials that have been melted by heat treatment can be used as bumps, if necessary.

[0509] The resist composition of the present invention can produce resist patterns with extremely excellent shapes, and therefore can be used in the manufacture of raised dots.

[0510] Example

[0511] The invention will be further illustrated by examples. In these examples, unless otherwise specified, "%" and "parts" indicating content or dosage are used as quality standards.

[0512] The weight-average molecular weight of the resin was obtained by gel permeation chromatography under the following analytical conditions.

[0513] Device: HLC-8120GPC type (manufactured by Tosoh Corporation)

[0514] Column: TSKgel Multipore H XL -M x 3+guardcolumn (manufactured by Tosoh Corporation)

[0515] Eluent: Tetrahydrofuran

[0516] Flow rate: 1.0 mL / min

[0517] Detector: RI detector

[0518] Column temperature: 40℃

[0519] Injection volume: 100μL

[0520] Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

[0521] Synthesis Example 1 [Synthesis of Resin A1-1]

[0522] 20 parts of polyvinylphenol (VP-15000; manufactured by Nippon Soda Co., Ltd.) were dissolved in 240 parts of methyl isobutyl ketone and concentrated in an evaporator. In a four-necked flask equipped with a reflux condenser, stirrer, and thermometer, 0.003 parts of p-toluenesulfonic acid monohydrate were added. While maintaining a temperature of 20–25°C, 5.05 parts of vinyl ether were added dropwise over 10 minutes. While maintaining the mixture at the same temperature, stirring was continued for 2 hours. The mixture was then diluted with 200 parts of methyl isobutyl ketone and washed five times with deionized water. The organic layer after washing was concentrated to 45 parts using an evaporator. 150 parts of propylene glycol monomethyl ether acetate were added, and the mixture was concentrated again to obtain 78 parts of a propylene glycol monomethyl ether acetate solution of resin A1-1 (29% solids). The weight-average molecular weight of resin A1-1 was 2.21 × 10⁻⁶. 4 The ethoxyethyl content is 38.5%. Resin A1-1 has the following structural units.

[0523]

[0524] Synthesis Example 2 [Synthesis of Resin A1-2]

[0525] 120g of phenolic varnish resin (PSM-4326 manufactured by Gunei Chemicals) was added to a flask and dissolved in 960g of methyl isobutyl ketone. The phenolic varnish resin solution was washed five times with deionized water. The resulting resin solution was concentrated to 327.3g. The resin concentration in this solution was 35.2%.

[0526] 56.8 g (molecular weight: 189 mmol) of the resin solution obtained above, 76.52 g of methyl isobutyl ketone, and 3.6 mg (0.0189 mmol) of p-toluenesulfonic acid monohydrate were added to a flask. 6.54 g (0.0907 mmol) of vinyl ethyl ether was added dropwise to the resin solution, and the mixture was reacted at room temperature for 3 hours. Ion-exchanged water was added to the reaction solution, and after stirring, the mixture was allowed to stand. The organic layer was then separated. This was repeated 4 times with the ion-exchanged water, for a total of 5 times. The organic layer was then concentrated. Subsequently, to remove water through an azeotropic reaction with methyl isobutyl ketone, propylene glycol monomethyl ether acetate was added, and the mixture was further concentrated to obtain a resin solution with a viscosity of 59.77 g. The obtained liquid is a solution of phenolic varnish resin with some hydroxyl groups 1-ethoxyethylated. 1 ¹H-NMR analysis of the resin revealed that 36.3% of the hydroxyl groups were etherified with 1-ethoxyethyl groups. Furthermore, the concentration of the resin solution was determined using the dry weight reduction method, yielding a result of 38.8%. This resin was designated as Resin A1-2. The weight-average molecular weight of Resin A1-2 is 5.1 × 10⁻⁶. 3 .

[0527]

[0528] Synthesis Example 3 [Synthesis of Phenolic Varnish Resin A2-1]

[0529] In a four-necked flask equipped with a stirrer, reflux condenser, and thermometer, 413.5 parts of 2,5-xylenol, 103.4 parts of salicylaldehyde, 20.1 parts of p-toluenesulfonic acid, and 826.9 parts of methanol were added. The mixture was heated to reflux and held at this temperature for 4 hours. After cooling, 1320 parts of methyl isobutyl ketone were added, and 1075 parts were distilled off under normal pressure. 762.7 parts of m-cresol and 29.0 parts of 2-tert-butyl-5-methylphenol were added, and the mixture was heated to 65°C. 678 parts of a 37% formaldehyde aqueous solution were added dropwise over 1.5 hours, while adjusting the temperature to 87°C at the end of the addition. After holding at 87°C for 10 hours, 1115 parts of methyl isobutyl ketone were added, and the mixture was washed three times with deionized water. 500 parts of methyl isobutyl ketone were added to the obtained resin solution, and the mixture was concentrated under reduced pressure to a total volume of 3435 parts. 3796 parts of methyl isobutyl ketone and 4990 parts of n-heptane were added to the obtained resin solution, and the mixture was heated to 60°C and stirred for 1 hour. Then, the mixture was separated, and the lower resin solution was diluted with 3500 parts of propylene glycol monomethyl ether acetate and concentrated to obtain 1690 parts of a propylene glycol monomethyl ether acetate solution of phenolic varnish resin A2-1 (solid content 43%). The weight-average molecular weight of resin A2-1 is 7 × 10⁻⁶. 3 .

[0530] Synthesis Example 4 [Synthesis of the compound shown in formula (aa)]

[0531]

[0532] In a four-necked flask equipped with a reflux condenser, stirrer, and thermometer, 100 parts of triethylene glycol monomethyl ether, 100 parts of triethylamine, and 600 parts of chloroform were added and stirred at room temperature until dissolved. In an ice bath, a solution obtained by dissolving 143 parts of p-toluenesulfonyl chloride in 360 parts of chloroform was added dropwise to the reaction solution. The mixture was stirred at room temperature for one day. 288 parts of deionized water were added to the resulting reaction solution, and the mixture was washed twice. 288 parts of a 1% oxalic acid aqueous solution were added to the resulting organic layer, and the mixture was washed twice. 288 parts of deionized water were added to the further obtained organic layer, and the mixture was washed twice. 9.6 parts of activated carbon were added to the resulting organic layer, and the mixture was stirred and then filtered. The filtrate was concentrated to 214 parts. The obtained concentrate was purified by column chromatography using an elution solvent (n-heptane / ethyl acetate = 4 / 1). The solution containing the target product was concentrated and dried under reduced pressure to obtain 169 parts (97% purity) of the compound represented by formula (aa).

[0533] Synthesis Example 5 [Synthesis of Resin A3-1]

[0534] In a four-necked flask equipped with a reflux condenser, stirrer, and thermometer, 26 parts of polyvinylphenol (VP-8000; manufactured by Nippon Soda Co., Ltd.), 25 parts of isopropanol, 3.3 parts of sodium hydroxide, and 100 parts of deionized water were added and stirred. After complete dissolution, 17 parts of the compound shown in formula (aa) were added, the temperature was raised to 80°C, and the mixture was stirred for 5 hours. After cooling to room temperature, 100 parts of methyl isobutyl ketone were added, followed by 50 parts of a 10% oxalic acid aqueous solution for separation and washing. 50 parts of a 2% oxalic acid aqueous solution were added to the resulting organic layer for separation and washing. 100 parts of methyl isobutyl ketone were added to the resulting organic layer, followed by 50 parts of deionized water and 2.5 parts of methanol, for 8 separation and washing cycles. The washed organic layer was concentrated to 45 parts using an evaporator. Then, 156 parts of propylene glycol monomethyl ether acetate were added, and the mixture was concentrated again to obtain 70 parts of a propylene glycol monomethyl ether acetate solution of resin A3-1 (solid content 39%). The weight-average molecular weight of resin A3-1 is 1.50 × 10⁻⁶. 4 hydroxyl protection rate (-ZR in formula (I)) i42 The incorporation rate is 21.2%. Resin A3-1 has the following structural units.

[0535]

[0536] Synthesis Example 6 [Synthesis of Resin A3-2]

[0537] In a four-necked flask equipped with a reflux condenser, stirrer, and thermometer, 26 parts of polyvinylphenol (VP-8000; manufactured by Nippon Soda Co., Ltd.), 25 parts of isopropanol, 3.3 parts of sodium hydroxide, and 100 parts of deionized water were added and stirred. After complete dissolution, 10.18 parts of the compound shown in formula (aa) were added, the temperature was raised to 80°C, and the mixture was stirred for 5 hours. After cooling to room temperature, 100 parts of methyl isobutyl ketone were added, followed by 50 parts of a 10% oxalic acid aqueous solution for separation and washing. 50 parts of a 2% oxalic acid aqueous solution were added to the resulting organic layer for separation and washing. 100 parts of methyl isobutyl ketone were added to the resulting organic layer, followed by 50 parts of deionized water and 2.5 parts of methanol, for 8 separate washings. The washed organic layer was concentrated to 82 parts using an evaporator. Then, 156 parts of propylene glycol monomethyl ether acetate were added, and the mixture was concentrated again to obtain 67 parts of a propylene glycol monomethyl ether acetate solution of resin A3-2 (solid content 41%). The weight-average molecular weight of resin A3-2 was 1.43 × 10⁻⁶. 4 hydroxyl protection rate (-ZR in formula (I)) i42 The incorporation rate is 13.2%. Resin A3-2 has the following structural units.

[0538]

[0539] Synthesis Example 7 [Synthesis of the compound shown in formula (ab)]

[0540]

[0541] In a four-necked flask equipped with a reflux condenser, stirrer, and thermometer, 50 parts of diethylene glycol monovinyl ether, 2.3 parts of N,N-dimethylaminopyridine, and 250 parts of pyridine were added and stirred at room temperature until dissolved. 77 parts of anhydrous acetic acid were added dropwise to the reaction solution. The mixture was stirred at room temperature for 5 hours, and 250 parts of a saturated sodium bicarbonate aqueous solution were added to the resulting reaction solution. 250 parts of ethyl acetate were further added, and the target product was extracted. 250 parts of ethyl acetate were added to the aqueous layer after separation, and the target product was further extracted. 250 parts of a 10% copper sulfate aqueous solution were added to the resulting organic layer, and the mixture was washed separately. 250 parts of deionized water were added to the further obtained organic layer, and the mixture was washed four times separately. Toluene was added to the resulting organic layer, and the mixture was concentrated until pyridine was no longer present, yielding 56 parts (100% purity) of the compound shown in formula (ab).

[0542] Synthesis Example 8 [Synthesis of Resin A3-3]

[0543] 128 parts of polyvinylphenol (VP-8000; manufactured by Nippon Soda Co., Ltd.) and 0.08 parts of p-toluenesulfonic acid monohydrate were dissolved in 403 parts of methyl isobutyl ketone and concentrated in an evaporator. The concentrated resin solution was added to a four-necked flask equipped with a reflux condenser, stirrer, and thermometer. While maintaining a temperature of 20–25°C, 18.4 parts of the compound shown in formula (ab) were added dropwise. After stirring for 3 hours while keeping the mixture at the same temperature, it was diluted with 10 parts of methyl isobutyl ketone, and 60 parts of deionized water and 0.1 parts of triethylamine were added for two separate washings. 60 parts of deionized water were added to the resulting organic layer for separate washing. The washed organic layer was concentrated to 111 parts using an evaporator. Then, 311 parts of propylene glycol monomethyl ether acetate were added, and the mixture was concentrated again to obtain 107 parts of a propylene glycol monomethyl ether acetate solution of resin A3-3 (49% solids). The weight-average molecular weight of resin A3-3 is 1.66 × 10⁻⁶. 4 , hydroxyl protection rate (-ZR in formula (I) i42 The incorporation rate is 23.0%. Resin A3-3 has the following structural units.

[0544]

[0545] Examples 1-6, Comparative Example 1

[0546] (Preparation of the resist composition)

[0547] The components shown in Table 1 were mixed according to the mass parts shown in the table, dissolved in a solvent, and then filtered through a fluoropolymer filter with a pore size of 5 μm to prepare the resist composition.

[0548] Table 1

[0549]

[0550] The resist compositions of the examples and comparative examples further contain 0.002 parts of polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) as a surfactant.

[0551] The symbols shown in the table represent the following materials.

[0552] <Resin>

[0553] A1-1: Resin A1-1

[0554] A1-2: Resin A1-2

[0555] A2-1: Phenolic varnish resin A2-1

[0556] A3-1: Resin A3-1

[0557] A3-2: Resin A3-2

[0558] A3-3: Resin A3-3

[0559] <Acid-producing agent>

[0560] B1: N-hydroxynaphthalenedicarboximide trifluoromethanesulfonate; (NAI-105; manufactured by Green Chemical Co., Ltd.)

[0561]

[0562] B2: Structural formula below; (PAI-101; manufactured by Green Chemical Co., Ltd.)

[0563]

[0564] B3: The following is the structural formula; (PAG-103; BASF standard)

[0565]

[0566] <Quencher>

[0567] C1: 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0568] <Adhesion Promoter>

[0569] E1: 2,5-Dimercaptothiadiazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0570] <Solvent>

[0571] 21 parts of propylene glycol monomethyl ether acetate

[0572] (Manufacturing of anti-corrosion patterns)

[0573] The above-mentioned resist composition was spin-coated onto a substrate on a 4-inch silicon wafer that had been deposited with copper, so that the pre-baked film thickness was 10 μm.

[0574] Then, pre-baking is performed for 180 seconds using a direct-heating hot plate at the temperature shown in column "PB" of Table 1 to form the composite layer.

[0575] Next, the composite layer was exposed using an i-line stepper (NSR 1755i7A; Nikon Corporation, NA=0.5) with the exposure amount changed in stages through a mask used to form a 1:1 line and spacing pattern (5 μm line width).

[0576] After exposure, the resist pattern was obtained by paddle development for 180 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0577] The resist pattern obtained by observation using a scanning electron microscope was used to determine the effective photosensitivity based on the exposure of the line and spacing pattern with a line width of 5 μm.

[0578] Shape evaluation: A 5μm wide line pattern obtained from the effective photosensitivity was observed using a scanning electron microscope at 2000x magnification. A good pattern, where the top and bottom transition shapes are close to rectangles, was selected. Figure 1 (a)] is judged as ○, and the pattern with a circular shape at the lower turning point is [ Figure 1 (b)] is judged as ×. The results are shown in Table 2.

[0579] Crack resistance evaluation: The above-mentioned photoresist composition was spin-coated onto a 4-inch silicon wafer, resulting in a pre-baked film thickness of 10 μm.

[0580] Then, pre-baking is performed for 180 seconds using a direct-heating hot plate at the temperature shown in column "PB" of Table 1 to form the composite layer.

[0581] The obtained substrate was baked on a hot plate at 130°C for 5 minutes, then rapidly cooled to 23°C, and the presence of cracks was observed. Samples without cracks were marked with ◎, samples with 1 to 10 cracks were marked with ○, and samples with more than 10 cracks were marked with ×.

[0582] Table 2

[0583] shape Crack resistance Example 1 ○(a) ○ Example 2 ○(a) ○ Example 3 ○(a) ◎ Example 4 ○(a) ○ Example 5 ○(a) ○ Example 6 ○(a) ◎ Comparative Example 1 ○(a) ×

[0584] The above results indicate that the resist composition according to the present invention can produce a resist pattern with excellent shape and good crack resistance.

[0585] Industrial availability

[0586] The resist composition of the present invention can produce resist patterns with good shape and excellent crack resistance.

Claims

1. A resist composition comprising: a resin having an acid-labile group, a resin having a structural unit represented by formula (I) and a structural unit represented by formula (a2-1), an alkali-soluble resin, an acid generator, an adhesion promoter, and a solvent; the acid-labile group being a group represented by formula (1) or a group represented by formula (2), ###0001### formula (1) ###0002### formula (2) in formula (I), p represents 0; Z represents a divalent hydrocarbon group having 3 to 20 carbon atoms containing a group represented by formula (la); the methylene group contained in the hydrocarbon group can be replaced with an oxygen atom, a sulfur atom, a carbonyl group; * represents a bonding site with an oxygen atom; in formula (la), w and r each independently represent an integer of 2 to 10, ###0003### formula (la) in formula (a2-1), m' represents 0. In formula (1), R a1 , R a2 , and R a3 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R a1 and R a2 are mutually bonded to represent a divalent hydrocarbon group having 2 to 20 carbon atoms, R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and * represents a bonding site. In formula (2), R a1’ and R a2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a2’ and R a3’ bonded to each other represent a 2-valent heterocyclic group having 2 to 20 carbon atoms, a methylene group contained in the hydrocarbon group and the 2-valent heterocyclic group can be replaced with an oxygen atom or a sulfur atom, and * represents a bonding site, 2. A resist composition comprising: a resin having an acid-labile group, a resin having a structural unit represented by formula (I-2) and a structural unit represented by formula (a2-1), an alkali-soluble resin, an acid generator, and a solvent; the acid-labile group being a group represented by formula (1) or a group represented by formula (2), ###0004### formula (1) ###0005### formula (2) in formula (I-2), p represents 0; r represents an integer of 1 to 10; in formula (a2-1), m' represents 0. R i41 represents a hydrogen atom or a methyl group; R i42 represents a hydrocarbon group having 1 to 10 carbon atoms which can be substituted with a hydroxyl group, an acyl group having 2 to 7 carbon atoms, or a hydrogen atom; R i43 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; 3. A resist composition comprising: a resin having an acid-labile group, a resin composed of a structural unit represented by formula (I-2) and a structural unit selected from at least one of structural units represented by formulae (a2-1) to (a2-4), an alkali-soluble resin, an acid generator, and a solvent; the acid-labile group being a group represented by formula (1) or a group represented by formula (2), ###0006### formula (1) ###0007### formula (2) in formula (I-2), p represents 0; r represents an integer of 1 to 10; in formulae (a2-1), (a2-2), and (a2-3), m' represents 0; the carbon atom bonded to the oxygen atom is a primary carbon atom or a secondary carbon atom; in formula (a2-4), the methylene group bonded to the oxygen atom cannot be replaced with an oxygen atom; wherein m" and m'" in total are 5 or less.

4. The resist composition according to claim 1 or 2, wherein the structural unit represented by formula (I) is a structural unit represented by formula (I-1) or formula (I-2); ###0008### formula (I-1) ###0009### formula (I-2) in formulae (I-1) and (I-2), p represents 0; r represents an integer of 2 to 10; the resin having a structural unit represented by formula (I) or formula (I-2) is a resin composed of a structural unit represented by formula (I) or formula (I-2), or it is a resin composed of a structural unit represented by formula (I) or formula (I-2) and a structural unit represented by formula (a2-1), or it is a resin composed of a structural unit represented by formula (I) or formula (I-2), a structural unit represented by formula (a2-1), and at least one structural unit selected from structural units represented by formulae (a2-2) to (a2-4). * - (CH2) w - O r - (Ia) 5. The resist composition according to claim 1 or 2, wherein the resin having a structural unit represented by formula (I) or formula (I-2) and a structural unit represented by formula (a2-1) is a novolak resin.

6. The resist composition according to claim 1 or 2, wherein the adhesion promoter is contained. R a7 represents a hydrogen atom or a methyl group, R a10 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, 7. The resist composition according to claim 2 or 3, wherein r in the structural unit represented by formula (I-2) is 1.

8. The resist composition according to claim 2 or 3, wherein r in the structural unit represented by formula (I-2) is an integer of 2 to 10. In formula (1), R a1 , R a2 , and R a3 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R a1 and R a2 are mutually bonded to represent a divalent hydrocarbon group having 2 to 20 carbon atoms, R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and * represents a bonding site. In formula (2), R a1’ and R a2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a2’ and R a3’ bonded to each other represent a 2-valent heterocyclic group having 2 to 20 carbon atoms, a methylene group contained in the hydrocarbon group and the 2-valent heterocyclic group can be replaced with an oxygen atom or a sulfur atom, and * represents a bonding site, 9. The resist composition according to claim 1 or 2, wherein the resin having a structural unit represented by formula (I) or formula (I-2) and a structural unit represented by formula (a2-1) is a resin composed of a structural unit represented by formula (I) or formula (I-2) and a structural unit represented by formula (a2-1), or it is a resin composed of a structural unit represented by formula (I) or formula (I-2), a structural unit represented by formula (a2-1), and at least one structural unit selected from structural units represented by formulae (a2-2) to (a2-4), ###0010### formula (a2-2) ###0011### formula (a2-3) in formulae (a2-2) and (a2-3), the carbon atom bonded to the oxygen atom is a primary carbon atom or a secondary carbon atom; ###0012### formula (a2-4) in formula (a2-4), the methylene group bonded to the oxygen atom cannot be replaced with an oxygen atom; wherein m" and m'" in total are 5 or less. R i41 represents a hydrogen atom or a methyl group; R i43 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; ​ R i44 represents a hydrocarbon group having 1 to 10 carbon atoms; ​ R i45 represents an alicyclic hydrocarbon group having a carbon number of 3 to 10 or an acyl group having a carbon number of 2 to 7 which can be substituted with a hydroxyl group, ​ R a7 represents a hydrogen atom or a methyl group, R a10 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, ​ ​ ​ ​ ​ ​ ​ In formula (1), R a1 , R a2 , and R a3 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R a1 and R a2 bonded to each other represent a divalent hydrocarbon group having 2 to 20 carbon atoms, R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and * represents a bonding site. In formula (2), R a1’ and R a2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a2’ and R a3’ bonded to each other represent a 2-valent heterocyclic group having 2 to 20 carbon atoms, a methylene group contained in the hydrocarbon group and the 2-valent heterocyclic group can be replaced with an oxygen atom or a sulfur atom, and * represents a bonding site, ​ R i41 represents a hydrogen atom or a methyl group; R i43 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; ​ R i44 represents a hydrocarbon group having 1 to 10 carbon atoms; ​ R i45 represents a hydrocarbon group having 1 to 10 carbon atoms which can be substituted with a hydroxyl group, an acyl group having 2 to 7 carbon atoms, or a hydrogen atom, the hydrocarbon group being selected from the group consisting of an alkyl group, an alicyclic hydrocarbon group, and a group formed by combining these groups, ​ R a7 , R a8 , and R a9 each independently represent a hydrogen atom or a methyl group; R a10 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; ​ R a11 represents a hydrogen atom or a primary or secondary hydrocarbon group having 1 to 10 carbon atoms; R a12 represents a primary or secondary alkyl group having 1 to 6 carbon atoms; L a1 represents an alkylene group having a carbon number of 2 to 6, and wherein, ​ n represents an integer of 1 to 30, and when n is 2 or more, the plurality of L a1 are the same as or different from each other; ​ R a13 represents a hydrogen atom or a methyl group; R a14 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; R a15 represents a primary or secondary hydrocarbon group having 1 to 12 carbon atoms, in which a methylene group contained in the hydrocarbon group can be replaced with an oxygen atom or a carbonyl group, and in which, ​ m" represents an integer of 0 to 4, and when m" is 2 or more, the plurality of R a14 are the same or different from each other; m'" represents an integer of 0 to 4, and when m'" is 2 or more, the plurality of R a15 the same or different from each other, ​ 4. The resist composition according to claim 1, wherein, ​ ​ R i41 represents a hydrogen atom or a methyl group; R i42 represents a hydrocarbon group having 1 to 10 carbon atoms which can be substituted with a hydroxyl group, an acyl group having 2 to 7 carbon atoms, or a hydrogen atom; R i43 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; ​ R i44 represents a hydrocarbon group having 1 to 10 carbon atoms; ​ R i45 represents a hydrocarbon group having 1 to 10 carbon atoms which can be substituted with a hydroxyl group, an acyl group having 2 to 7 carbon atoms, or a hydrogen atom.

5. The resist composition according to any one of claims 1 to 3, wherein ​ 6. The resist composition according to claim 2 or 3, wherein, ​ ​ 8. The resist composition according to claim 2 or 3, wherein, ​ ​ ​ R a8 and R a9 each independently represents a hydrogen atom or a methyl group; R a11 represents a hydrogen atom or a primary or secondary hydrocarbon group having 1 to 10 carbon atoms; R a12 represents a primary or secondary alkyl group having 1 to 6 carbon atoms; L a1 represents an alkylene group having a carbon number of 2 to 6, and wherein, ​ n represents an integer of 1 to 30, and when n is 2 or more, the plurality of L a1 are the same or different from each other; ​ R a13 represents a hydrogen atom or a methyl group; R a14 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; R a15 represents a primary or secondary hydrocarbon group having 1 to 12 carbon atoms, in which a methylene group contained in the hydrocarbon group can be replaced with an oxygen atom or a carbonyl group, and in which, the methylene group bonded to the oxygen atom is not replaced with an oxygen atom; m" represents an integer of 0 to 4, and when m" is 2 or more, the plurality of R a14 are the same or different from each other; m'" represents an integer of 0 to 4, and when m'" is 2 or more, the plurality of R a15 the same or different from each other, wherein the sum of m" and m'" is 5 or less.

10. The resist composition according to any one of claims 1 to 3, wherein The resin having an acid-labile group is a resin containing a structural unit represented by formula (a1-2); in formula (a1-2), R a1’ and R a2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a33’ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, or R a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a2’ and R a33’ together with the carbon atom and the oxygen atom to which they are bonded represent a 2-valent heterocyclic ring having 2 to 20 carbon atoms; the methylene group contained in the aliphatic hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 1 to 12 carbon atoms and the 2-valent heterocyclic ring can be replaced with an oxygen atom or a sulfur atom; R a5 represents a hydrogen atom or a methyl group; R a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; mz represents an integer of 0 to 4; when mz is 2 or more, a plurality of R a6 are the same or different from each other.

11. The resist composition according to any one of claims 1 to 3, wherein the acid generator is a compound having a group represented by formula (B1); in formula (B1), R b1 represents a hydrocarbon group having 1 to 18 carbon atoms which can have a fluorine atom, the methylene group in the hydrocarbon group can be replaced with an oxygen atom or a carbonyl group.

12. A method for producing a resist pattern, comprising: (1) a step of applying the resist composition according to any one of claims 1 to 10 on a substrate, (2) a step of drying the applied resist composition to form a composition layer, (3) a step of exposing the composition layer, (4) a step of developing the exposed composition layer.

13. A resin containing a structural unit represented by formula (I-2) and a structural unit represented by formula (a2-1), in formula (I-2), R i41 represents a hydrogen atom or a methyl group; R i43 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; p represents 0; R i44 represents a hydrocarbon group having 1 to 10 carbon atoms; r represents an integer of 1 to 10; R i45 represents a hydrocarbon group having a carbon number of 3 to 10 which can be substituted with a hydroxyl group or an acyl group having a carbon number of 2 to 7, in formula (a2-1), R a7 represents a hydrogen atom or a methyl group, R a10 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, m' represents 0.

14. A resin composed of a structural unit represented by formula (I-2) and a structural unit selected from at least one of structural units represented by formula (a2-1) to formula (a2-4); in formula (I-2); R i41 represents a hydrogen atom or a methyl group; R i43 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; p represents 0; R i44 represents a hydrocarbon group having 1 to 10 carbon atoms; r represents an integer of 1 to 10; R i45 represents a hydrocarbon group having 1 to 10 carbon atoms which can be substituted with a hydroxyl group, an acyl group having 2 to 7 carbon atoms, or a hydrogen atom, the hydrocarbon group being selected from the group consisting of an alkyl group, an alicyclic hydrocarbon group, and a group formed by combining these groups, in formula (a2-1), formula (a2-2), and formula (a2-3), R a7 , R a8 , and R a9 each independently represent a hydrogen atom or a methyl group; R a10 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; m' represents 0. R a11 represents a hydrogen atom or a primary or secondary hydrocarbon group having 1 to 10 carbon atoms; R a12 represents a primary or secondary alkyl group having 1 to 6 carbon atoms; L a1 represents an alkylene group having a carbon number of 2 to 6, and wherein, the carbon atom bonded to the oxygen atom is a primary carbon atom or a secondary carbon atom; n represents an integer of 1 to 30, and when n is 2 or more, the plurality of L a1 are the same as or different from each other; in formula (a2-4), R a13 represents a hydrogen atom or a methyl group; R a14 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; R a15 represents a primary or secondary hydrocarbon group having 1 to 12 carbon atoms, in which a methylene group contained in the hydrocarbon group can be replaced with an oxygen atom or a carbonyl group, and in which, the methylene group bonded to the oxygen atom is not replaced with an oxygen atom; m" represents an integer of 0 to 4, and when m" is 2 or more, the plurality of R a14 are the same or different from each other; m'" represents an integer of 0 to 4, and when m'" is 2 or more, the plurality of R a15 are the same or different from each other; and wherein the sum of m" and m'" is 5 or less.

15. The resin according to claim 13, which is a resin containing a structural unit represented by formula (I-2) and a structural unit represented by formula (a2-1), which is a resin composed of a structural unit represented by formula (I-2) and a structural unit represented by formula (a2-1), or which is a resin composed of a structural unit represented by formula (I-2), a structural unit represented by formula (a2-1), and a structural unit selected from at least one of structural units represented by formula (a2-2) to formula (a2-4), in formula (a2-2) and formula (a2-3), R a8 and R a9 each independently represents a hydrogen atom or a methyl group; R a11 represents a hydrogen atom or a primary or secondary hydrocarbon group having 1 to 10 carbon atoms; R a12 represents a primary or secondary alkyl group having 1 to 6 carbon atoms; L a1 represents an alkylene group having a carbon number of 2 to 6, and wherein, the carbon atom bonded to the oxygen atom is a primary carbon atom or a secondary carbon atom; n represents an integer of 1 to 30, and when n is 2 or more, the plurality of L a1 are the same as or different from each other; in formula (a2-4), R a13 represents a hydrogen atom or a methyl group; R a14 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; R a15 represents a primary or secondary hydrocarbon group having 1 to 12 carbon atoms, in which a methylene group contained in the hydrocarbon group can be replaced with an oxygen atom or a carbonyl group, and in which, the methylene group bonded to the oxygen atom is not replaced with an oxygen atom; m" represents an integer of 0 to 4, and when m" is 2 or more, the plurality of R a14 are the same or different from each other; m'" represents an integer of 0 to 4, and when m'" is 2 or more, the plurality of R a15 the same or different from each other, and wherein the sum of m" and m'" is 5 or less.

16. The resin according to claim 13 or 14, wherein r in the structural unit represented by formula (I-2) is an integer of 1.

17. The resin according to claim 13 or 14, wherein r in the structural unit represented by formula (I-2) is an integer of 2 to 10.

18. The resin according to claim 13 or 14, R in the structural unit represented by formula (I-2) is a hydrocarbon group having 1 carbon atom. i44 a hydrocarbon group having 1 carbon atom.

19. A resist composition containing the resin according to claim 13 or 14, an acid generator, and a solvent.

Images