Photosensitive composition, method for forming resin film, method for producing substrate, and resin

Abstract

To provide a photosensitive composition that enables formation of a patterned resin film with low roughness through extreme ultraviolet (EUV) exposure, a method for forming a resin film using the photosensitive composition, a method for producing a substrate using the method for forming a resin film, and a resin.SOLUTION: A photosensitive composition contains a resin (A), a photoacid generator (B), a quencher (C), and a crosslinker (D). For the resin (A), a resin (A1) featuring a polyorganosiloxane structure with phenolic hydroxyl groups is utilized, and the molecular weight dispersity of the resin (A) is adjusted to 1.00 or more and 1.50 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive composition, a method for forming a resin film using the photosensitive composition, a method for manufacturing a substrate using the method for forming a resin film, and a resin. [Background technology]

[0002] In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, the advancement of lithography technology has led to rapid progress in miniaturization of patterns. A common method for miniaturizing patterns is to shorten the wavelength (higher energy) of the exposure light source. Extreme ultraviolet (EUV) is widely known as a short-wavelength exposure light source used to form fine patterns.

[0003] In order to form fine patterns by EUV exposure, resist materials are required to have excellent lithography properties, such as good sensitivity to EUV and the resolution required to accurately reproduce patterns with fine dimensions.

[0004] In addition, resist materials are often required to have etching resistance in order to function as a mask for substrate processing. As a material having etching resistance, silicon-containing polymers are often used as base components. For example, Patent Document 1 discloses a negative resist composition that contains a silsesquioxane resin having two specific structural units, an acid generator component, and a crosslinker component for the purpose of achieving finer patterns, and that is applicable to electron beam lithography and EUV exposure. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2005 / 091073 Summary of the Invention [Problem to be solved by the invention]

[0006] In the future, resist films will become thinner as patterns become finer, which will require improved etching resistance of the resist film. Furthermore, as the pattern becomes finer, the resist material is required to have high resolution when EUV exposure is performed. When forming a line pattern, the photosensitive composition is required to be able to form a line pattern with reduced LWR (line width roughness: non-uniformity of line width). When forming a hole pattern including holes with circular openings, the photosensitive composition is required to be able to form a hole pattern with improved circularity of the hole openings. Thus, the photosensitive composition is required to have improved lithography properties when EUV exposure is performed. However, when a photosensitive composition containing a silicon-containing polymer as a base component is used, a resist film having high etching resistance can be easily formed, but there is room for improvement in the lithography properties when the photosensitive composition is exposed to EUV.

[0007] The present invention has been made in consideration of the above-mentioned problems, and has an object to provide a photosensitive composition capable of forming a patterned resin film with small roughness by exposure to extreme ultraviolet (EUV) rays, a method for forming a resin film using the above-mentioned photosensitive composition, a method for manufacturing a substrate using the above-mentioned method for forming a resin film, and a resin.

[0008] The present inventors have discovered that the above-mentioned problems can be solved by using a resin (A1) having a polyorganosiloxane structure having a phenolic hydroxyl group as the resin (A) in a photosensitive composition containing a resin (A), a photoacid generator (B), a quencher (C), and a crosslinking agent (D), and by setting the molecular weight dispersity of the resin (A) to be 1.00 or more and 1.50 or less, thereby completing the present invention.

[0009] A first aspect of the present invention includes a resin (A), a photoacid generator (B), a quencher (C), and a crosslinking agent (D), The resin (A) contains a resin (A1) having a polyorganosiloxane structure having a phenolic hydroxyl group, the crosslinking agent (D) is a compound that crosslinks the resin (A) by the action of an acid generated by the photoacid generator (B) upon exposure to light; In the photosensitive composition, the molecular weight dispersity of the resin (A) is 1.00 or more and 1.50 or less.

[0010] A second aspect of the present invention includes a method for producing a coating film by applying the photosensitive composition according to the first aspect onto a substrate; exposing the coating film to extreme ultraviolet light in a position-selective manner; and developing the exposed coating film with a developer. A method for forming a patterned resin film.

[0011] A third aspect of the present invention provides a method for forming a patterned resin film on a substrate by the method for forming a resin film according to the second aspect; and performing dry etching on the substrate using the patterned resin film as an etching mask. A method for producing an etched substrate.

[0012] A fourth aspect of the present invention is a compound represented by the following formula (a1): [ka] It is a resin containing a structural unit represented by the following formula: (In formula (a1), R a1 is an organic group having 6 to 20 carbon atoms and a phenolic hydroxyl group; L a is an organic group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms; R a2 is a hydrogen atom or an organic group having 1 to 20 carbon atoms. Effect of the Invention

[0013] According to the present invention, it is possible to provide a photosensitive composition capable of forming a patterned resin film with small roughness by exposure to extreme ultraviolet (EUV) rays, a method for forming a resin film using the above-mentioned photosensitive composition, a method for manufacturing a substrate using the above-mentioned method for forming a resin film, and a resin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] ≪Photosensitive composition≫ The photosensitive composition will now be described.

[0015] The photosensitive composition contains a resin (A), a photoacid generator (B), a quencher (C), and a crosslinking agent (D). The resin (A) contains a resin (A1) having a polyorganosiloxane structure having a phenolic hydroxyl group. The crosslinking agent (D) is a compound that crosslinks the resin (A) by the action of an acid generated by the photoacid generator (B) upon exposure to light. The molecular weight dispersity of the resin (A) is 1.00 or more and 1.50 or less. By using the above-mentioned photosensitive composition, it is possible to form a patterned resin film with small roughness by exposure to extreme ultraviolet (EUV) rays.

[0016] <Resin (A)> Resin (A) is a resin that is crosslinked by a crosslinking agent (D) described later due to the action of an acid generated by a photoacid generator (B) described later upon exposure. Resin (A) includes a resin (A1) having a polyorganosiloxane structure having a phenolic hydroxyl group. Resin (A) may also include a resin having a polyorganosiloxane structure not having a phenolic hydroxyl group. The molecular weight dispersity of the resin (A) is preferably 1.00 to 1.50, more preferably 1.10 to 1.30. If the molecular weight dispersity of the resin (A) is within the above range, a resist pattern with low roughness can be formed. The molecular weight dispersity of the resin (A) can be measured by gel permeation chromatography (GPC). The resin (A1) may contain, together with the resin (A1), a resin (A2) that does not fall under the category of the resin (A1), so long as the desired effects are not impaired. The resin (A1) and the resin (A2) will be described below.

[0017] [Resin (A1)] The resin (A1) contains a structural unit represented by the following formula (a1). [ka]

[0018] In formula (a1), R a1 is an organic group having 6 to 20 carbon atoms and a phenolic hydroxyl group. a R is an organic group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms. a2 is a hydrogen atom or an organic group having 1 to 20 carbon atoms.

[0019] R a1 Examples of the organic group having 6 to 20 carbon atoms and having a phenolic hydroxyl group as the aryl group include groups represented by -Ph-OH, -CH2-Ph-OH, -CH2CH2-Ph-OH, -Np-OH, -CH2-Np-OH, and -CH2CH2-Np-OH. Ph is an o-phenylene group, an m-phenylene group, or a p-phenylene group, and is preferably a p-phenylene group. These phenylene groups may have a substituent. The substituent is not particularly limited as long as the desired effect is not impaired, and examples of the substituent include an aliphatic hydrocarbon group, an aryl group (aromatic hydrocarbon group), and an organic group having 1 to 10 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom. Np is naphthalene-1,2-diyl group, naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl group, naphthalene-1,8-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, or naphthalene-2,7-diyl group, and is preferably naphthalene-1,2-diyl group, naphthalene-1,4-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, and naphthalene-2,7-diyl group. These naphthalene diyl groups may have a substituent. The substituent is not particularly limited as long as the desired effect is not impaired, and examples of the substituent include an aliphatic hydrocarbon group, an aryl group, and an organic group having 1 to 10 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom.

[0020] L a is an organic group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms. Such an organic group is preferably a divalent group represented by the following formulae (AI) to (AV). -R A1 -X-···(AI) -R A2 -XR A3 - (A-II) -R A4 -XR A5 -X-···(A-III) -R A6 -XR A7 -XR A8 - (A-VI) -R A9 -XR A10 -XR A11 -X-···(AV) (In formulae (AI) to (AV), R A1 ~R A11is a divalent hydrocarbon group. X is a group selected from the group consisting of -O-, -CO-, -S-, -SO-, -SO2-, -SS-, -CS-, -NH-, -NCH3-, -N=N-, -Si(CH3)2-, -CO-O-, -CO-S-, and -CS-S-. The number of carbon atoms in the divalent groups represented by the following formulae (AI) to (AV) is 1 or more and 20 or less.

[0021] R A1 ~R A11 Examples of the hydrocarbon group as the radical include an alkylene group, an arylene group, and an aralkyl group in which one hydrogen atom has been removed from an aryl group.

[0022] L a The divalent organic group as is preferably a group containing an oxygen atom or a sulfur atom as a heteroatom.

[0023] L aSpecific examples of the alkylene group containing an oxygen atom include oxyalkylene groups such as *-CH2-O-**, *-CH2CH2-O-**, *-CH(CH3)-O-**, *-CH2CH2CH2-O-**, *-CH2CH(CH3)-O-**, *-CH2CH2CH2CH2-O-**, *-CH2CH(CH2CH3)-O-**, *-CH2CH2CH(CH3)-O-**, and *-CH(CH3)CH(CH3)-O-**. ;*-CH2-O-CH2-**, *-CH2CH2-O-CH2-**, *-CH2-O-CH2CH2-**, *-CH2CH2-O-CH2CH2-**, *-CH2CH2CH2-O-CH2-**, *- CH2CH2CH2-O-CH2CH2-**, *-CH2CH2CH2-O-CH2CH2CH2-**, *-CH2-O-CH2CH2CH2-**, and *-CH2CH2-O-CH2CH2CH2-**, etc. Alkylene groups interrupted by oxygen atoms; oxyarylene groups such as -Ph-O- and -Np-O-; oxyarylene groups such as *-Ph-O-** and *-Np-O-**; divalent groups in which an oxygen atom is bonded to an aryl group in an aralkyl group such as *-CH2-Ph-O-**, *-CH2CH2-Ph-O-**, *-CH2-Np-O-**, and *-CH2CH2-Np-O-**; *-CH2-O-CO-**, *-CH2CH2- Examples of alkylene groups having an ester bond bonded to the end include O-CO-**, *-CH(CH3)-O-CO-**, *-CH2CH2CH2-O-CO-**, *-CH2CH(CH3)-O-CO-**, *-CH2CH2CH2CH2-O-CO-**, *-CH2CH(CH2CH3)-O-CO-**, *-CH2CH2CH(CH3)-O-CO-**, *-CH2CH2CH(CH3)-O-CO-**, and *-CH(CH3)CH(CH3)-O-CO-**. In the above examples, Ph and Np are as defined above. In the above-mentioned divalent groups, the bond marked with "*" is bonded to the silicon atom in formula (a1). The bond marked with "**" is bonded to R a1 Bind to.

[0024] L aSpecific examples of the alkylene groups containing a sulfur atom include thioalkylene groups such as *-CH2-S-**, *-CH2CH2-S-**, *-CH(CH3)-S-**, *-CH2CH2CH2-S-**, *-CH2CH(CH3)-S-**, *-CH2CH2CH2CH2-S-**, *-CH2CH(CH2CH3)-S-**, *-CH2CH2CH(CH3)-S-**, and *-CH(CH3)CH(CH3)-S-**; alkylene groups interrupted by a sulfur atom, such as CH2-**, *-CH2CH2CH2-S-CH2-**, *-CH2CH2CH2-S-CH2CH2-**, *-CH2CH2CH2-S-CH2CH2CH2-**, *-CH2CH2CH2-S-CH2CH2CH2-**, and *-CH2CH2-S-CH2CH2CH2-**; thioarylene groups, such as -Ph-S- and -Np-S-; and divalent groups in which a sulfur atom is bonded to an aryl group in an aralkyl group, such as -CH2-Ph-S-, -CH2CH2-Ph-S-, -CH2-Np-S-, and -CH2CH2-Np-S-. In the above examples, Ph and Np are as defined above. In the above-mentioned divalent groups, the bond marked with "*" is bonded to the silicon atom in formula (a1). The bond marked with "**" is bonded to R a1 Bind to.

[0025] Specific preferred examples of the structural unit represented by formula (a1) include the following structural units. [ka] [ka]

[0026] The proportion of the structural unit represented by formula (a1) relative to the amount of all structural units of the polyorganosiloxane as resin (A1) is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 70 mol% or more and 100 mol% or less.

[0027] As described above, the resin (A1) may contain a structural unit other than the structural unit represented by formula (a1). The structural unit other than the structural unit represented by formula (a1) is not particularly limited as long as the desired effect is not impaired. A suitable example of a constitutional unit other than the constitutional unit represented by formula (a1) is a constitutional unit represented by the following formula (a2). [ka]

[0028] In formula (a2), R a3 , and R a4 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms which may contain a heteroatom. The structure of the organic group may be linear, branched, cyclic, or a combination of these. Examples of heteroatoms which the organic group may have include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms. However, the organic group is not limited to -L in formula (a1). a -R a1 This does not fall under the group represented by the following formula:

[0029] R a3 , and R a4Specific examples of the organic group represented by the formula (I) are alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-hexane-2-yl, n-hexane-3-yl, n-heptyl, n-heptan-2-yl, n-heptan-3-yl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octadecyl.

[0030] R a3 , and R a4 Specific examples of the organic group as an alkenyl group include a vinyl group, a 2-propenyl group (allyl group), a 3-butenyl group, a 4-pentenyl group, a 5-hexenyl group, a 6-heptenyl group, a 7-octenyl group, an 8-nonenyl group, a 9-decenyl group, a 10-undecenyl group, an 11-dodecenyl group, a 12-tridecenyl group, a 13-tetradecenyl group, a 14-pentadecenyl group, a 15-hexadecenyl group, a 16-heptadecenyl group, and a 17-octadecenyl group.

[0031] R a3 , and R a4 Specific examples of the organic group as an aliphatic hydrocarbon group include groups in which one hydrogen atom has been removed from a cyclic aliphatic hydrocarbon such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane, and adamantane.

[0032] R a3 , and R a4Specific examples of the organic group as the halogen atom-substituted aliphatic hydrocarbon group include a trifluoromethyl group, a pentafluoroethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a pentafluoro-n-propyl group, a 3-bromopropyl group, a nonafluoro-n-butyl group, a tridecafluoro-n-hexyl group, a heptadecafluoro-n-octyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 1,1-difluoro-n-propyl group, a 1,1,2,2-tetrafluoro-n-propyl group, a 3,3,3-trifluoro-n-propyl group, a 2,2,3,3,3-pentafluoro-n-propyl group, a 2-norbornyl-1,1-difluoroethyl group, a 2-norbornyltetrafluoroethyl group, and a 3-adamantyl-1,1,2,2-tetrafluoropropyl group.

[0033] R a3 , and R a4 Specific examples of the organic group as an optionally substituted aryl group include a phenyl group, a naphthalene-1-yl group, a naphthalene-2-yl group, a 4-phenylphenyl group, a 3-phenylphenyl group, a 2-phenylphenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 4-hydroxyphenyl group, a 3-hydroxyphenyl group, a 2-hydroxyphenyl group, a 4-chlorophenyl group, a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 3-bromophenyl group, a 2-bromophenyl group, a 4-cyanophenyl group, a 3-cyanophenyl group, and a 2-cyanophenyl group.

[0034] R a3 , and R a4Specific examples of the organic group as an optionally substituted aralkyl group include a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, a 4-methylphenylmethyl group, a 3-methylphenylmethyl group, a 2-methylphenylmethyl group, a 4-chlorophenylmethyl group, a 3-chlorophenylmethyl group, a 2-chlorophenylmethyl group, a 4-bromophenylmethyl group, a 3-bromophenylmethyl group, a 2-bromophenylmethyl group, a 4-hydroxyphenylmethyl group, a 3-hydroxyphenylmethyl group, and a 2-hydroxyphenylmethyl group.

[0035] R a3 , and R a4 Specific examples of the organic group containing an oxygen atom as the organic group include -CH2-O-CH3, -CH2-O-CH2CH3, -CH2CH2-O-CH2CH3, -CH2-O-Ph, -CH2-O-Np, -CH2-O-CH2-Ph, -CH2-O-CH2-Np, etc. Ph and Np are as described above.

[0036] R a3 , and R a4 Specific examples of the organic group containing a sulfur atom as the organic group include -CH2-S-CH2CH3, -CH2CH2-S-CH2CH3, -CH2-S-Ph, -CH2-S-Np, -CH2-S-CH2-Ph, -CH2-S-CH2-Np, etc.

[0037] Specific preferred examples of the structural unit represented by formula (a2) include the following: [ka]

[0038] [Resin (A2)] Resin (A) may contain resin (A2) that does not fall under the category of resin (A1) in addition to resin (A1), so long as the desired effect is not impaired. Resin (A2) is typically a silicon-containing resin. Resin (A2) is preferably a resin having a siloxane bond. Examples of resins having a siloxane bond include polyorganosiloxane and polyorganosilsesquioxane.

[0039] The polyorganosiloxane is preferably a polyorganosiloxane composed of one or more constituent units represented by the above formula (a2). The polyorganosiloxane is preferably a polyorganosiloxane that is composed of one or more structural units represented by the above formula (a2), and that contains one or more of the structural units described above as specific examples of the structural units represented by formula (a2).

[0040] Polyorganosilsesquioxane is typically obtained by hydrolysis and condensation of organosilane having three hydrolysis-condensable groups that generate silanol groups by hydrolysis. The structure of polyorganosilsesquioxane may be cage-type or ladder-type. As the organosilane having three hydrolysis-condensable groups, organotrialkoxysilane is preferred, organotrimethoxysilane and organotriethoxysilane are more preferred, and organotrimethoxysilane is even more preferred.

[0041] Specific examples of suitable organotrialkoxysilanes include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-butenyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, 3-butenyltriethoxysilane, phenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 3-hydroxyphenyltrimethoxysilane, cyclopentyltrimethoxysilane, and cyclophenyltrimethoxysilane. Examples of suitable silanes include hexyltrimethoxysilane, cycloheptyltrimethoxysilane, phenyltriethoxysilane, 4-hydroxyphenyltriethoxysilane, 3-hydroxyphenyltriethoxysilane, cyclopentyltriethoxysilane, cyclohexyltriethoxysilane, cycloheptyltriethoxysilane, benzyltrimethoxysilane, 4-hydroxyphenylmethyltrimethoxysilane, 3-hydroxyphenylmethyltrimethoxysilane, benzyltriethoxysilane, 4-hydroxyphenylmethyltriethoxysilane, and 3-hydroxyphenylmethyltriethoxysilane.

[0042] The polyorganosilsesquioxane is preferably a hydrolysis condensation product of one or more selected from trifunctional 4-hydroxyphenylsilane, trifunctional 3-hydroxyphenylsilane, trifunctional 4-hydroxyphenylmethylsilane, and trifunctional 3-hydroxyphenylmethylsilane, each of which has three hydrolysis condensable groups, and one or more selected from trifunctional methylsilane, trifunctional ethylsilane, and trifunctional phenylsilane, each of which has three hydrolysis condensable groups. Among the above hydrolysis condensates, a hydrolysis condensate of a trifunctional 4-hydroxyphenylmethylsilane and a trifunctional methylsilane is more preferred, and a hydrolysis condensate of 1 mol of a trifunctional 4-hydroxyphenylmethylsilane and 0.5 mol or more and 2 mol or less of a trifunctional methylsilane is even more preferred.

[0043] The ratio of the mass of resin (A2) to the mass of resin (A) is preferably 70 mass% or less, more preferably 50 mass% or less, even more preferably 30 mass% or less, particularly preferably 10 mass% or less, and most preferably 0 mass%.

[0044] <Photoacid generator (B)> The photosensitive composition contains a photoacid generator (B). The photoacid generator (B) generates an acid upon exposure to light, and the resin (A) is crosslinked by the crosslinking agent (D) described below.

[0045] The photoacid generator (B) is not particularly limited, and any photoacid generator that has conventionally been blended in a photosensitive composition can be used without any particular limitation. As the photoacid generator (B), it is preferable to use a compound represented by the following formula (b1). [ka]

[0046] In formula (b1), R b1 is an organic group having 1 to 40 carbon atoms. b1 The organic group represented by M is bonded to the sulfur atom in formula (b1) by a C-S bond. The carbon atom in the C-S bond is bonded to the fluorine atom. b1 is a sulfonium cation or an iodonium cation. The anion moiety and the cation moiety that constitute the compound represented by formula (B1) will be described below.

[0047] (anion part) In formula (b1), R b1 As the organic group as , an organic group represented by the following formula (b1-1-an1) is preferable. [ka]

[0048] In formula (b1-1-an1), R 101R is a cyclic group-containing group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. 102 is a fluorine atom or a fluorine-containing alkyl group having 1 to 5 carbon atoms. 101 is a divalent linking group containing an oxygen atom or a single bond. 101 represents a single bond, an alkylene group, or a fluorinated alkylene group. 101 is a bond that bonds to

[0049] R 101 The cyclic group-containing group, which may have a substituent as a substituent, preferably contains a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aryl group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is preferably saturated. The number of carbon atoms in the aryl group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 18. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.

[0050] R 101 Specific examples of the aromatic hydrocarbon ring contained in the cyclic group-containing group include a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a biphenyl ring.

[0051] R 101Specific examples of the cyclic group-containing group having an aryl group as the aryl group include an aryl group, an aralkyl group, a condensed cyclic group in which an aliphatic hydrocarbon ring is condensed to an aryl group, and a condensed cyclic group in which an aromatic hydrocarbon ring is condensed to an alicyclic hydrocarbon group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, and a biphenylyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthalene-1-ylmethyl group, a naphthalene-2-ylmethyl group, a naphthalene-1-ylethyl group, and a 2-naphthalene-2-ylethyl group. The number of carbon atoms in the alkyl chain in the aralkyl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0052] R 101 When the cyclic group-containing group as the substituent is an aliphatic hydrocarbon group containing a ring in its structure, examples of the aliphatic hydrocarbon group include alicyclic hydrocarbon groups, groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group.

[0053] The alicyclic hydrocarbon group preferably has 3 or more and 20 or less, and more preferably has 3 or more and 12 or less, carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane. The number of carbon atoms in the monocycloalkane is preferably 3 or more and 6 or less. Specific examples of the alicyclic hydrocarbon group include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane. The number of carbon atoms in the polycycloalkane is preferably 7 or more and 30 or less. Specific examples of the polycycloalkane include polycycloalkanes having a bridged ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a condensed polycyclic skeleton such as a ring group having a steroid skeleton.

[0054] As the aliphatic hydrocarbon group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane is preferable, a group in which one hydrogen atom has been removed from a polycycloalkane is more preferable, and an adamantyl group and a norbornyl group are particularly preferable.

[0055] The number of carbon atoms of the linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specific examples of the linear alkylene group include a methylene group [-CH2-], an ethylene group [-(CH2)2-], and a pentamethylene group [-(CH2)5-].

[0056] The number of carbon atoms in the branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group is preferably from 2 to 10, more preferably from 3 to 6, preferably 3 or 4, and most preferably 3. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable. Specific examples of branched alkylene groups include alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -CH(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkyl ethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0057] R 101The cyclic group-containing group as may be a fused ring group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused. The fused ring may be, for example, a fused ring in which one or more aromatic rings are fused to a polycycloalkane having a polycyclic skeleton of a bridged ring system. Specific examples of bridged ring polycycloalkanes include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring group is preferably a fused ring in which two or three aromatic hydrocarbon rings are fused to a group in which one hydrogen atom is removed from a bicycloalkane, and more preferably a fused ring in which two or more aromatic hydrocarbon rings are fused to a group in which one hydrogen atom is removed from a bicyclo[2.2.2]octane. 101 Specific examples of the fused ring group when the cyclic group-containing group as is the above-mentioned fused ring group include groups represented by the following formulae (r-br-1) and (r-br-2). In the formulae, * represents Y in formula (b1-1-an1). b11 Represents a bond that bonds to .

[0058] [ka]

[0059] R 101 The cyclic group contained in the cyclic group-containing group as may contain a heteroatom. Examples of the cyclic group containing a heteroatom include lactone-containing cyclic groups, -SO2--containing cyclic groups represented by formulas (b-r2-1) to (b-r2-4) described later, and other heterocyclic groups.

[0060] The "-SO2-containing cyclic group" is a cyclic group containing an -SO2- bond in its ring skeleton. The -SO2-containing cyclic group may be a monocyclic group or a polycyclic group. When the -SO2-containing cyclic group consists of only an -SO2-containing ring, the -SO2-containing cyclic group is a monocyclic group. When the -SO2-containing cyclic group consists of two or more -SO2- rings or has a ring of a structure other than the -SO2- ring structure in addition to the -SO2- ring, the -SO2-containing cyclic group is a polycyclic group. As the -SO2- containing cyclic group, a cyclic group containing an -O-SO2- bond in its ring skeleton is particularly preferred. Such a cyclic group contains a sultone ring. More specific examples of the -SO2- containing cyclic group include groups represented by the following formulae (b-r2-1) to (b-r2-4).

[0061] [ka]

[0062] In formulas (b-r2-1) to (b-r2-4), R b21 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO2- containing cyclic group; B" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom, an alkylene group having 1 to 5 carbon atoms which may contain a sulfur atom, an oxygen atom, or a sulfur atom; and n' is 0, 1, or 2.

[0063] In formulas (b-r2-1) to (b-r2-4), R b21 The alkyl group as the aryl group is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group. Among these, a methyl group and an ethyl group are preferred, and a methyl group is particularly preferred.

[0064] R b21The alkoxy group as is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group may be linear or branched. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Among these, a methoxy group and an ethoxy group are preferred, and a methoxy group is particularly preferred.

[0065] R b21 Examples of the halogen atom as the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferred.

[0066] R b21 As the halogenated alkyl group, R b21 As the halogenated alkyl group, a part or all of the hydrogen atoms of the alkyl group are substituted with the above-mentioned halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

[0067] R b21 In -COOR" and -OC(=O)R" as the groups, R" is a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO2- containing cyclic group. The alicyclic hydrocarbon group as R" may be substituted with a fluorine atom or a fluorinated alkyl group.

[0068] In formulae (b-r2-1) to (b-r2-4), the alkylene group having 1 to 5 carbon atoms as B" may be linear or branched. Specific examples of the alkylene group include a methylene group, an ethylene group, a propane-1,3-diyl group, and a propane-1,2-diyl group. When the alkylene group contains an oxygen atom or a sulfur atom, examples of the alkylene group include groups in which -O- or -S- is present at the terminal or between the carbon atoms of the alkylene group. Specific examples of such groups include -O-CH2-, -CH2-O-CH2-, -S-CH2-, and -CH2-S-CH2-. B" is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group. Specific examples of groups represented by formulae (b-r2-1) to (b-r2-4) are shown below, in which Ac represents an acetyl group.

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] In formula (b1-1-an1), R 101 Examples of the substituent that the cyclic group-containing group may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a tert-butoxy group, and still more preferably a methoxy group or an ethoxy group. As the halogen atom as a substituent, a bromine atom, an iodine atom, and a fluorine atom are preferred, and a bromine atom and an iodine atom are more preferred. Examples of halogenated alkyl groups as substituents include methyl, ethyl, propyl, n-butyl, and tert-butyl groups, and other groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. The carbonyl group as a substituent is a group that replaces a methylene group (—CH2—) that constitutes a cyclic hydrocarbon group.

[0073] R 101 As the substituent that the cyclic group-containing group as may have, among the above, a hydroxyl group, an alkoxy group, a bromine atom, and an iodine atom are preferable, and a hydroxyl group, a bromine atom, and an iodine atom are more preferable.

[0074] R 101 The chain alkyl group as may be either linear or branched. The linear alkyl group preferably has 1 or more and 20 or less carbon atoms, more preferably has 1 or more and 15 or less carbon atoms, and most preferably has 1 or more and 10 or less carbon atoms. Specific preferred examples of the straight-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group.

[0075] The number of carbon atoms in the branched alkyl group is preferably from 3 to 20, more preferably from 3 to 15, and most preferably from 3 to 10. Specific examples of suitable branched alkyl groups include a 1-methylethyl group (isopropyl group), a 1-methylpropyl group (sec-butyl group), a 2-methylpropyl group (isobutyl group), a 1-methylbutyl group (sec-pentyl group), a 2-methylbutyl group, a 3-methylbutyl group (isobutyl group), a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0076] R 101 The chain alkenyl group as may be linear or branched. The number of carbon atoms in the chain alkenyl group is preferably 2 to 10, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 2. Suitable specific examples of the linear alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), and a butenyl group. Suitable specific examples of the branched alkenyl group include a 1-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Among the above alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0077] R 101 Examples of the substituent that the chain alkyl group or the chain alkenyl group may have include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the above-mentioned R 101 Examples of the cyclic group-containing group include a cyclic group-containing group as the above.

[0078] Among the above, R 101 is preferably a cyclic group which may have a substituent. 101From the viewpoint of roughness prevention, R is more preferably a polycyclic hydrocarbon group which may have a substituent, and further preferably a cross-linked ring polycyclic hydrocarbon group which may have a substituent. 101 From the viewpoint of improving sensitivity, is preferably a cyclic group having an iodine atom or a bromine atom, and more preferably an aryl group having an iodine atom or a bromine atom.

[0079] Examples of the polycyclic hydrocarbon group include a group in which one hydrogen atom is removed from a polycycloalkane having a polycyclic skeleton, and a group in which one hydrogen atom is removed from a condensed ring in which an aromatic ring is condensed to a polycycloalkane having a polycyclic skeleton. Examples of the polycycloalkane include polycycloalkanes having a bridged ring system such as adamantane, norbornane (bicycloheptane), and bicyclooctane; and polycycloalkanes having a condensed ring system such as a ring group having a steroid skeleton. Among them, polycycloalkanes having a bridged ring system polycyclic skeleton are preferred. Specific examples of suitable polycyclic aliphatic hydrocarbon groups include an adamantyl group and a norbornyl group.

[0080] Examples of the group in which one hydrogen atom has been removed from a fused ring in which an aromatic ring is fused to a polycycloalkane having a polycyclic skeleton include groups in which one hydrogen atom has been removed from a fused ring in which the above-mentioned polycycloalkane is fused to a benzene ring.

[0081] As the polycyclic hydrocarbon having a heterocycle, a polycyclic hydrocarbon group having a bridged ring system and a heterocycle is preferable, and specific examples thereof include a polycyclic group having a -SO2-- containing bridged ring system represented by the above formula (b-r2-1).

[0082] In formula (b1-1-an1), Y 101 is a single bond or a divalent linking group containing an oxygen atom. Y 101 is a divalent linking group containing an oxygen atom, Y 101 may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms. Examples of the divalent linking group containing an oxygen atom include an oxygen atom (-O-), -C(=O)-, -OC(=O)-, -C(=O)-NH-, a carbonyl group, and an oxygen atom-containing linking group such as -OC(=O)-O-; and a combination of an oxygen atom-containing linking group and an alkylene group. A sulfonyl group (-SO2-) may be further linked to this combination. Examples of the divalent linking group containing an oxygen atom include linking groups represented by the following formulae (by-1) to (by-7).

[0083] [ka]

[0084] In formula (by-1) to formula (by-7), V' 101 V' is a single bond or an alkylene group having 1 to 5 carbon atoms. 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.

[0085] V' 102 The divalent saturated hydrocarbon group as V' may be a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, or a combination of a chain saturated hydrocarbon group and a cyclic saturated hydrocarbon group. 102 The divalent saturated hydrocarbon group as is preferably an alkylene group. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms.

[0086] V' 101 and V' 102 The alkylene group as may be linear or branched, and is preferably linear. V' 101 and V' 102Specific examples of the alkylene group as the alkylene group include a methylene group; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; an ethylene group (-CH2CH2-); -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, and -CH(CH2CH3)CH alkyl ethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; a trimethylene group (-CH2CH2CH2-); alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; a tetramethylene group (-CH2CH2CH2CH2-); alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; a pentamethylene group (-CH2CH2CH2CH2CH2-).

[0087] Also, V' 101 , or V' 102 In the alkylene group as the above, some of the methylene groups may be substituted with a divalent aliphatic cyclic group having from 5 to 10 carbon atoms. The aliphatic cyclic group may be a monocyclic group or a polycyclic group. The monocyclic aliphatic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane. The number of carbon atoms in the monocycloalkane is preferably 3 or more and 6 or less. Examples of the group in which two hydrogen atoms have been removed from a monocycloalkane include a cyclopentylene group and a cyclohexylene group. Of these, the cyclohexylene group is more preferred. The aliphatic hydrocarbon group, which is a polycyclic group, is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane. The number of carbon atoms in the polycycloalkane is preferably 7 or more and 12 or less. Examples of the group in which two hydrogen atoms have been removed from a polycycloalkane include an adamantanediyl group, a norbornanediyl group, an isobornanediyl group, a tricyclodecanediyl group, and a tetracyclododecanediyl group. Among these, an adamantane-1,5-diyl group and an adamantane-2,6-diyl group are more preferred.

[0088] The aliphatic cyclic group may have a substituent. Examples of the substituent include -R P1 , -R P2 -OR P1 , -R P2 -CO-R P1 , -R P2 -CO-OR P1 , -R P2 -O-CO-R P1 , -R P2 -OH, -R P2 -CN and -R P2 -COOH, etc. R P1 is an alkyl group having from 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having from 3 to 20 carbon atoms, or an aryl group having from 6 to 30 carbon atoms. R P2 is a single bond, a divalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aryl group having 6 to 30 carbon atoms. R P1 and R P2 may be a group in which some or all of the hydrogen atoms in the above-mentioned chain saturated hydrocarbon group, cyclic saturated hydrocarbon group, and aryl group have been substituted with fluorine atoms. The above cyclic hydrocarbon group may have one or more of one type of the above substituents, or may have one or more of each of two or more types of the above substituents.

[0089] Examples of the monovalent alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an octyl group, and a decyl group. Examples of the monovalent cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.0 ... 2,6 ]decanyl group, tricyclo[3.3.1.1 3,7]decanyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 ]Dodecanyl group, and adamantyl group. Examples of the monovalent aryl group having 6 to 30 carbon atoms include a phenyl group, a biphenylyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

[0090] Y 101 As the linking group, a divalent linking group containing an ester bond or a divalent linking group containing an ether bond is preferable, and the linking groups represented by the above formulas (by-1) to (by-5) are more preferable.

[0091] In formula (b1-1-an1), V 101 is a single bond, an alkylene group, or a fluorinated alkylene group. 101 The number of carbon atoms in the alkylene group and the fluorinated alkylene group represented by V is preferably 1 or more and 4 or less. 101 As the fluorinated alkylene group, V 101 In particular, the alkylene group represented by the formula (I) is substituted with fluorine atoms in part or in whole. 101 is preferably a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms.

[0092] In formula (b1-1-an1), R 102 R is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 102 As the group, a fluorine atom and a perfluoroalkyl group having 1 to 5 carbon atoms are preferable, and a fluorine atom is more preferable.

[0093] Y 101 When Y is a single bond, specific examples of the anion moiety represented by formula (b1-1-an1) include fluorinated alkylsulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion. 101When is a divalent linking group containing an oxygen atom, specific examples of the anion moiety represented by formula (b1-1-an1) include the anions represented by the following formulas (ba-1) to (ba-3).

[0094] [ka] (In formulas (ba-1) to (ba-3), R 101 R" is an aliphatic cyclic group which may have a substituent, a heterocyclic group which may have a substituent, or an alkyl group which may have a substituent. 102 R" is an alicyclic hydrocarbon group which may have a substituent, a lactone-containing cyclic group, or an -SO2- containing cyclic group represented by formula (b-r2-1) to formula (b-r2-4). 103 V" is an aromatic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or an alkenyl group which may have a substituent. 101 R is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Each v" is independently an integer of 0 to 3. Each q" is independently an integer of 0 to 20. Each n" is 0 or 1.

[0095] R” 101 , and R.” 103 The optionally substituted aliphatic cyclic group represented by R 101 Preferably, it is a group exemplified as the alicyclic hydrocarbon group as mentioned above. R” 102 The optionally substituted aliphatic hydrocarbon group represented by R 101 Preferably, it is a group exemplified as the alicyclic hydrocarbon group as mentioned above. As the substituent, R in formula (b1-1-an1) 101 Examples of the substituents include the same groups as those which the alicyclic hydrocarbon group may have as the substituent.

[0096] R” 103The aromatic group which may have a substituent as R in formula (b1-1-an1) is 101 The substituents are preferably the groups exemplified as the aryl group in formula (b1-1-an1). 101 Examples of the substituents which may be substituted on the aryl group in the above formula (I) include the same groups as those which may be substituted on the aryl group in the above formula (I).

[0097] R” 101 The chain alkyl group which may have a substituent as R in formula (b1-1-an1) is 101 Preferably, it is a group exemplified as the chain alkyl group as above. R” 103 The chain alkenyl group which may have a substituent as R in formula (b1-1-an1) is 101 Preferably, it is a group exemplified as the chain alkenyl group as mentioned above.

[0098] As the anion moiety explained above, the anions represented by the following formulae (ba1-1) to (ba1-6) are particularly preferable. [ka]

[0099] (cation part) In formula (b1), M b1 The organic cation represented by the formula (I) is not particularly limited, and any organic cation known as a cationic moiety constituting a conventional photoacid generator can be appropriately used. As such a cationic moiety, a sulfonium cation or an iodonium cation is preferable.

[0100] M b1 Specific examples of the sulfonium cation in the formula (bc-1) or (bc-2) include the sulfonium cations represented by the following formula (bc-1) or (bc-2). [ka]

[0101] In formulas (bc-1) and (bc-2), R bc1~R bc5 R each independently represents an aryl group which may have a substituent, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an alkenyl group which may have a substituent. bc1 ~R bc3 Two of R may be bonded to each other to form a ring together with the sulfur atom in the formula. bc4 , and R bc5 may be bonded to each other to form a ring together with the sulfur atom in the formula. bc6 ~R bc7 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. bc8 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted SO2-containing cyclic group. bc1 is -C(=O)- or -C(=O)-O-.

[0102] In formulas (bc-1) and (bc-2), R bc1 ~R bc5 The aryl group as the aryl group includes an unsubstituted aryl group having a carbon atom number of 6 to 20. As the unsubstituted aryl group, a phenyl group and a naphthyl group are preferable. R bc1 ~R bc5 The alkyl group preferably has 1 or more and 30 or less carbon atoms. R bc1 ~R bc5 The cycloalkyl group as the alkyl group preferably has 3 or more and 30 or less carbon atoms. R bc1 ~R bc5 The alkenyl group as the alkyl group preferably has 2 or more and 10 or less carbon atoms. R bc1 ~R bc5 , or R bc8Examples of the substituent that the aryl group, alkyl group, cycloalkyl group, alkenyl group, and SO-containing cyclic group as the substituent may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following formulas (bc-r-1) to (bc-r-7), respectively.

[0103] [ka]

[0104] In formulas (bc-r-1) to (bc-r-7), R' b11 each independently represents a hydrogen atom, an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group.

[0105] R' b11 The cyclic group as the cyclic group is preferably a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aryl group, an alicyclic hydrocarbon group, or a group containing an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. The alicyclic hydrocarbon group may be saturated or unsaturated. The alicyclic hydrocarbon group is preferably a saturated alicyclic hydrocarbon group.

[0106] R' b11 The number of carbon atoms in the aryl group as is preferably 3 or more and 30 or less, more preferably 5 or more and 30 or less, even more preferably 5 or more and 20 or less, particularly preferably 6 or more and 15 or less, and most preferably 6 or more and 10 or less, provided that the number of carbon atoms does not include the number of carbon atoms of the substituent.

[0107] R' b11 Specific examples of the aromatic hydrocarbon ring contained in the aryl group as the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a biphenyl ring, and a fluorene ring.

[0108] R' b11The cyclic group as may contain an aromatic heterocycle in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0109] R' b11 Specific examples of the aryl group as the aryl group include a phenyl group, a naphthalene-1-yl group, a naphthalene-2-yl group, a 4-phenylphenyl group, a 3-phenylphenyl group, and a 2-phenylphenyl group.

[0110] R' b11 The alicyclic hydrocarbon group as the alkyl group preferably has 3 or more and 20 or less, and more preferably has 3 or more and 12 or less, carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is a cycloalkyl group. The number of carbon atoms of the cycloalkyl group is preferably 3 or more and 6 or less. Suitable specific examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. The polycyclic alicyclic hydrocarbon group is preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane. The number of carbon atoms of the polycycloalkane is preferably 7 or more and 30 or less. Suitable specific examples of the polycycloalkane include polycycloalkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a polycyclic skeleton of a condensed ring system such as a ring group having a steroid skeleton.

[0111] Among them, R' b11 As the alicyclic hydrocarbon group as , an adamantyl group and a norbornyl group are preferred, and an adamantyl group is more preferred.

[0112] R' b11 The cyclic group as may be a heterocyclic group containing a hetero atom, specifically, lactone-containing cyclic groups, -SO2--containing cyclic groups represented by formulae (b-r2-1) to (b-r2-4), and other heterocyclic groups.

[0113] R' in formulas (bc-r-1) to (bc-r-7) b11 Examples of the substituent that the cyclic group as may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a tert-butoxy group, and still more preferably a methoxy group or an ethoxy group. As the halogen atom as a substituent, a fluorine atom is preferred. Examples of halogenated alkyl groups as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with halogen atoms. The carbonyl group as a substituent is a group that substitutes a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0114] R' b11 The alkyl group as may be either linear or branched. The linear alkyl group preferably has 1 or more and 20 or less carbon atoms, more preferably has 1 or more and 15 or less carbon atoms, and further preferably has 1 or more and 10 or less carbon atoms. Specific examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl groups. The branched alkyl has preferably 3 or more and 20 or less carbon atoms, more preferably 3 or more and 15 or less, and even more preferably 3 or more and 10 or less carbon atoms. Specific examples of branched alkyl groups include an isopropyl group, a sec-butyl group, an isobutyl group, a sec-pentyl group, a 2-methylbutyl group, an isopentyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0115] R' b11 The alkenyl group as may be either linear or branched. The linear alkenyl group preferably has 2 or more and 10 or less carbon atoms, more preferably has 2 or more and 5 or less carbon atoms, further preferably has 2 or more and 4 or less carbon atoms, and particularly preferably has 2 carbon atoms. Specific examples of linear alkenyl groups include vinyl, 1-propenyl, 2-propenyl (allyl), and butenyl groups. Specific examples of branched alkenyl groups include a 1-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. As the alkenyl group, a straight-chain alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.

[0116] R' b11 Examples of the substituent that the alkyl group and alkenyl group may have as R' include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the above-mentioned R' b11 Examples of the cyclic groups include the cyclic groups represented by the formula (I).

[0117] Among them, R' b11 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane, a lactone-containing cyclic group, an -SO2--containing cyclic group represented by formulae (b-r2-1) to (b-r2-4), and the like are preferred.

[0118] R in formula (bc-1) or (bc-2) bc1 ~R bc3 When two of the groups are bonded to each other to form a ring with the sulfur atom in the formula, R bc1 ~R bc3 Two of the groups may be bonded to each other via a heteroatom such as a sulfur atom, an oxygen atom, or a nitrogen atom, or a functional group such as a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(RN)- (RN is an alkyl group having 1 to 5 carbon atoms). R bc1 ~R bc3 The ring formed by combining two of them is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring. Specific examples of the ring include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0119] R bc6 ~R bc7 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. bc6 ~R bc7 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. bc6 , and R bc7 When both are alkyl groups, R bc6 , and R bc7 may be bonded to each other to form a ring.

[0120] R bc8 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R bc8 When is an aryl group, the aryl group is preferably an unsubstituted aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group, a naphthalene-1-yl group, or a naphthalene-2-yl group. R bc8 When is an alkyl group, the alkyl group may be a chain or cyclic alkyl group. The alkyl group preferably has 1 or more and 30 or less carbon atoms. R bc8 When is an alkenyl group, the alkenyl group preferably has 2 or more and 10 or less carbon atoms. R bc8 The -SO2-containing cyclic group which may have a substituent as the following is preferably a -SO2-containing polycyclic group.

[0121] Suitable examples of the cation represented by formula (bc-1) are shown below.

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] In formulas (bc-1-35) to (bc-1-37), g1, g2, and g3 represent the number of repetitions of the group in parentheses. g1 is an integer of 1 or more and 5. g2 is an integer of 0 or more and 20 or less. g3 is an integer of 0 or more and 20 or less.

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] In the formula, R” b11 is a hydrogen atom or a substituent. The substituent is R bc1 ~R bc5 , and R bc8 The substituents are the same as those that may be possessed by the group.

[0131] [ka]

[0132] Preferred specific examples of the cation represented by formula (bc-2) include the cations represented by the following formulas (bc-2-1) to (bc-2-6).

[0133] [ka]

[0134] The sulfonium cation as the cationic moiety of the photoacid generator (b1) is preferably the sulfonium cation represented by formula (bc-1) or (bc-2). Among them, the cations represented by formulas (bc-1-1) to (bc-1-6), (bc-1-52) to (bc-1-60), and (bc-1-76) to (bc-1-81) are preferred.

[0135] M b1 A specific example of the iodonium cation in the formula (bc-3) is an iodonium cation represented by the following formula (bc-3). [ka]

[0136] In formula (bc-3), R bc9 , and R bc10R each independently represents an aryl group which may have a substituent. bc9 , and R bc10 may be bonded to each other to form a ring together with the iodine atom in the formula.

[0137] In formula (bc-3), R bc9 , and R bc10 The aryl group in R is an unsubstituted aryl group having 6 to 20 carbon atoms. The unsubstituted aryl group is preferably a phenyl group or a naphthyl group. bc9 , and R bc10 The substituents which may be possessed by R in the above formula (bc-1) and formula (bc-2) are as follows: bc1 ~R bc5 , and R bc8 The substituents which may be contained in the xylene group include the same substituents as those which the xylene group may have.

[0138] Preferred specific examples of the cation represented by formula (bc-3) are shown below. [ka]

[0139] [ka]

[0140] [ka]

[0141] In formulae (bc-3-35) to (bc-3-37), g1, g2, and g3 represent the number of repetitions of the group in parentheses. g1 is an integer of 1 or more and 5. g2 is an integer of 0 or more and 20 or less. g3 is an integer of 0 or more and 20 or less.

[0142] [ka]

[0143] [ka]

[0144] The iodonium cation as the cationic moiety of the photoacid generator (b1) is preferably the iodonium cation represented by formula (bc-3). Among them, the cations represented by formulae (bc-3-1) to (bc-3-8) and (bc-3-60) to (bc-3-67) are preferred.

[0145] In the photosensitive composition, the photoacid generator (B) may be used alone or in combination of two or more kinds. The content of the photoacid generator (B) in the photosensitive composition is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 40 parts by mass or less, and even more preferably 15 parts by mass or more and 35 parts by mass or less, relative to 100 parts by mass of the resin (A).

[0146] <Quencher (C)> The photosensitive composition contains a quencher (C). Examples of the quencher (C) include photodegradable bases (C-1) that decompose upon exposure to control acid diffusion, and nitrogen-containing organic compounds (C-2) that do not fall under the category of photodegradable bases (C-1). Among these, photodegradable bases (C-1) are preferred because they are likely to enhance all of the characteristics of high sensitivity, reduced roughness, and suppression of the occurrence of coating defects.

[0147] [Photodecomposable base (C-1)] The photodecomposable base (C-1) is not particularly limited as long as it decomposes upon exposure to light and loses its acid diffusion controllability, and is preferably one or more compounds selected from the group consisting of a compound represented by the following formula (c1) (hereinafter referred to as "component (c1)") and a compound represented by the following formula (c2) (hereinafter referred to as "component (c2)"). The components (c1) and (c2) do not act as quenchers in exposed areas of a coating film formed using the photosensitive composition because they decompose and lose their acid diffusion control property (basicity) in the exposed areas of the coating film, but act as quenchers in unexposed areas of the coating film.

[0148] [ka]

[0149] In formula (c1), R c1 is an organic group having 1 to 20 carbon atoms, R c1 The organic group represented by M is bonded to the sulfur atom in formula (c1) through a C-S bond, and no fluorine atom is bonded to the carbon atom in the C-S bond. c1 is a sulfonium cation or an iodonium cation. In formula (c2), R c2 is an organic group having 1 to 20 carbon atoms, M c2 is a sulfonium cation or an iodonium cation. Hereinafter, the compound represented by formula (c1) will also be referred to as "component (c1)", and the compound represented by formula (c2) will also be referred to as "component (c2)".

[0150] [(c1) component] (anion part) In formula (c1), R c1 R' in Formulae (bc-r-1) to (bc-r-7) is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. b11 The same groups as those shown below can be mentioned. However, R c1 In the above, the carbon atom adjacent to the sulfur atom is not bonded to a fluorine atom (is not substituted with a fluorine atom). This makes the anion of the compound represented by formula (c1) an appropriately weak acid anion, improving the quenching ability of the quencher (C).

[0151] R c1 is preferably a chain alkyl group which may have a substituent, or an aliphatic cyclic group which may have a substituent. The number of carbon atoms in the chain alkyl group is preferably 1 or more and 10 or less, and more preferably 3 or more and 10 or less. The aliphatic cyclic group is preferably a group in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc., or a group in which one or more hydrogen atoms have been removed from camphor, etc. These aliphatic cyclic groups may have a substituent. R c1 The hydrocarbon group as R may have a substituent. Examples of the substituent include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, an iodine atom, a bromine atom, a fluorinated alkyl group, a lactone-containing cyclic group, and combinations thereof. c1 When the hydrocarbon group as represented by formula (I) is a chain alkyl group or contains an alkylene group, the chain alkyl group and alkylene group may be interrupted by an ether bond or an ester bond, or may have an ether bond or an ester bond at a terminal.

[0152] Specific preferred examples of the anion moiety in the component (c1) are shown below. [ka]

[0153] (cation part) In formula (c1), M c1 is a sulfonium cation or an iodonium cation. As the sulfonium cation, the same cations as those represented by the above formulas (bc-1-1) to (bc-1-111) are preferred. Among these, the cations represented by the above formulas (bc-1-70) to (bc-1-81) are preferred. That is, cations having a fluorine atom are preferred as the cation moiety. As the iodonium cation, the same cations as those represented by the above formulae (bc-3-1) to (bc-1-75) are preferred. Among these, the cations represented by the above formulae (bc-3-60) to (bc-1-67) are preferred. That is, cations having a fluorine atom are preferred as the cation moiety.

[0154] [(c2) component] (anion part) In formula (c2), R c2 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and R' in Formulae (bc-r-1) to (bc-r-7) b11 The same groups as those shown below can be mentioned. Among these, R c2 As the alkyl group, an aryl group which may have a substituent, an aliphatic cyclic group which may have a substituent, and a chain alkyl group which may have a substituent are preferable. Examples of the substituents that these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, an iodine atom, a bromine atom, a fluorinated alkyl group, and combinations thereof. When an ether bond or an ester bond is contained as a substituent, it may be connected via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the above formulas (by-1) to (by-5). Also, R c2 is a chain alkyl group or contains an alkylene group, the chain alkyl group or alkylene group may be interrupted by an ether bond or an ester bond, or may have an ether bond or an ester bond at a terminal.

[0155] R c2 Suitable examples of the cyclic group as the alkyl group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton. R c2 When is an aliphatic cyclic group, the aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane, such as an adamantyl group, a norbornyl group, an isobornyl group, a tricyclodecanyl group, or a tetracyclododecanyl group. R c2When is a chain alkyl group, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 10 or less. Specific examples of the chain alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; and branched alkyl groups such as 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0156] When the chain alkyl group is a fluorinated alkyl group, the number of carbon atoms of the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain an atom other than a fluorine atom. Examples of the atom other than a fluorine atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0157] Specific preferred examples of the anion moiety in the component (c2) are shown below. [ka]

[0158] (cation part) In formula (c2), M c1 is a sulfonium cation or an iodonium cation. As the sulfonium cation, the same cations as those represented by the above formulae (bc-1-1) to (bc-1-111) are preferred. Among these, the cations represented by the above formulae (bc-1-70) to (bc-1-81) are preferred. That is, cations having a fluorine atom are preferred as the cation moiety. As the iodonium cation, the same cations as those represented by the above formulae (bc-3-1) to (bc-1-75) are preferred. Among these, the cations represented by the above formulae (bc-3-60) to (bc-1-67) are preferred. That is, cations having a fluorine atom are preferred as the cation moiety.

[0159] From the viewpoint of improving sensitivity, the component (c2) preferably contains, among the above, a compound represented by the following formula (c0) (hereinafter referred to as "component (c0)"):

[0160] [ka]

[0161] In formula (c0), X 0 is a bromine atom or an iodine atom. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nc1 is an integer of 1 to 5. nc2 is an integer of 0 to 4. nc1+nc2 is an integer of 1 to 5. Y c0 is a divalent linking group or a single bond. M c0 is a sulfonium cation or an iodonium cation.

[0162] [(c0) component] (anion part) In formula (c0), X 0 is a bromine atom or an iodine atom, and an iodine atom is more preferred.

[0163] In formula (c0), R m R is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. m As the alkyl group for , an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.

[0164] In formula (c0), nc1 is an integer of 1 or more and 5 or less. nc2 is an integer of 0 or more and 4 or less. nc1+nc2 is 1 or more and 5 or less. nc1 is preferably an integer of 1 or more and 3 or less, more preferably 2 or 3, and even more preferably 3, from the viewpoint of radiation absorbency. nc2 is preferably an integer of 0 or more and 3 or less, more preferably 0 or 1, and even more preferably 0.

[0165] In formula (c0), Y c0 Y is a divalent linking group or a single bond. c0 The divalent linking group in is preferably a divalent linking group containing an oxygen atom. Y c0 When Y is a divalent linking group containing an oxygen atom, c0 may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms. Examples of the divalent linking group containing an oxygen atom include an oxygen atom (-O-), -C(=O)-, -OC(=O)-, -C(=O)-NH-, a carbonyl group, an oxygen atom-containing linking group such as -OC(=O)-O-, etc.; a combination of an oxygen atom-containing linking group and an alkylene group, etc. A sulfonyl group (-SO2-) may be further linked to this combination. Y c0 is preferably a divalent linking group containing an oxygen atom or a single bond, and more preferably a single bond.

[0166] Specific examples of the anion portion of the component (c0) are shown below.

[0167] [ka]

[0168] (cation part) In formula (c0), M c0 is a sulfonium cation or an iodonium cation. As the sulfonium cation, the same cations as those represented by the above formulae (bc-1-1) to (bc-1-111) are preferred. Among these, the cations represented by the above formulae (bc-1-70) to (bc-1-81) are preferred. As the iodonium cation, the same cations as those represented by the above formulae (bc-3-1) to (bc-1-75) are preferred. Among these, the cations represented by the above formulae (bc-3-60) to (bc-1-67) are preferred.

[0169] [Nitrogen-containing organic compound (C-2)] As the nitrogen-containing organic compound (C-2), a low molecular weight compound (non-polymer) is usually used. As the nitrogen-containing organic compound (C-2), for example, amines such as aliphatic amines and aromatic amines can be mentioned. As the quencher (D), aliphatic amines are preferable, and secondary aliphatic amines and tertiary aliphatic amines are particularly preferable. Here, the aliphatic amine is an amine having one or more aliphatic groups. The number of carbon atoms of the aliphatic group of the aliphatic amine is preferably 1 or more and 20 or less.

[0170] Examples of aliphatic amines include alkylamines in which at least one hydrogen atom of ammonia (NH3) is substituted with an alkyl group having 20 or less carbon atoms, alkanolamines in which at least one hydrogen atom of ammonia (NH3) is substituted with a hydroxyalkyl group, and cyclic amines.

[0171] Specific examples of alkylamines and alkanolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkanolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, stearyldiethanolamine, and lauryldiethanolamine. Of these, trialkylamines and alkanolamines are preferred.

[0172] Examples of the cyclic amine include nitrogen-containing heterocyclic compounds. The nitrogen-containing heterocyclic compounds may be monocyclic aliphatic amines or polycyclic aliphatic amines.

[0173] Specific examples of the aliphatic monocyclic amine include piperidine and piperazine. The number of carbon atoms of the aliphatic polycyclic amine is preferably 6 or more and 10 or less. Specific examples of the aliphatic polycyclic amine include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0174] Specific examples of other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, and tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine.

[0175] Specific examples of aromatic amines include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole, or derivatives thereof, diphenylamine, triphenylamine, tribenzylamine, 2,6-diisopropylaniline, 2,2'-dipyridyl, and 4,4'-dipyridyl.

[0176] In the photosensitive composition, the quencher (C) may be used alone or in combination of two or more kinds. The content of the quencher (C) in the photosensitive composition is preferably 1 part by mass or more and 60 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, and even more preferably 20 parts by mass or more and 45 parts by mass or less, per 100 parts by mass of the resin (A1).

[0177] <Crosslinking agent (D)> The photosensitive composition contains a crosslinking agent (D). The crosslinking agent (D) is not particularly limited as long as it is a compound that crosslinks the resin (A) by the action of an acid generated by the photoacid generator (B) upon exposure to light. The crosslinking agent (D) is preferably a methylol-type crosslinking agent (D1) that is a compound having two or more groups selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group in the molecule. The alkoxy group in the alkoxymethyl group and the acyl group in the acyloxymethyl group may be substituted with a halogen atom.The crosslinking agent (D1) is preferably a compound having two or more groups selected from a methylol group and an alkoxymethyl group. When the photosensitive composition contains the crosslinking agent (D1), the resin (A) is crosslinked by the crosslinking agent (D1) by heating the photosensitive composition, and as a result, a cured product having excellent chemical resistance is formed. In addition, after the coating film made of the photosensitive composition is patterned by exposure and development, the patterned coating film is heated to crosslink the resin (A) with the crosslinking agent, thereby forming a patterned resin film (cured film) having excellent chemical resistance.

[0178] In terms of the chemical resistance of the cured product obtained by heating the photosensitive composition, the number of groups selected from methylol groups and alkoxymethyl groups in one molecule of the crosslinking agent (D1) is preferably 2 or more and 10 or less, more preferably 2 or more and 8 or less, and even more preferably 2 or more and 4 or less.

[0179] The number of carbon atoms in the alkoxy group in the alkoxymethyl group is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1. In other words, the most preferable alkoxymethyl group is a methoxymethyl group. An alkoxy group in an alkoxymethyl group may be linear or branched, and is preferably linear.

[0180] The acyloxy group in the acyloxymethyl group is not particularly limited as long as it is a group represented by R-CO-O-. R is an organic group. R is bonded to a carbonyl group by a CC bond. The organic group represented by R is preferably an alkyl group or an aryl group, more preferably an alkyl group. The number of carbon source atoms in the organic group represented by R is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6.

[0181] Suitable examples of the crosslinking agent (D1) include melamine-based compounds, guanamine-based compounds, urea-based compounds, resol resins, and aromatic compounds having a methylol group or an alkoxymethyl group on the aromatic ring. Among these, one or more compounds selected from the group consisting of melamine-based compounds, guanamine-based compounds, and urea-based compounds are preferred.

[0182] Examples of aromatic compounds having a methylol group or an alkoxymethyl group on an aromatic ring include the compounds described in paragraphs

[0136] to

[0139] of JP2013-064829A and the compounds described in paragraphs

[0029] to

[0036] of JP10-0120940A.

[0183] As the crosslinking agent (D1), a compound having a methylol group bonded to a nitrogen atom or an alkoxymethyl group bonded to a nitrogen atom is particularly preferred. As the crosslinking agent (D1) having a methylol group bonded to a nitrogen atom or an alkoxymethyl group bonded to a nitrogen atom, a melamine-based compound, a guanamine-based compound, and a urea-based compound are preferred, a melamine-based compound and a methylol urea compound are more preferred, and a melamine-based compound is even more preferred.

[0184] As the melamine-based compound, a compound represented by the following formula (d1) is preferable. [ka]

[0185] In formula (d1), R d11 ~R d16 Each independently represents a hydrogen atom or -CH-OR d R is a group represented by the formula: d is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. d11 ~R d16 At least two of -CH2-OR d It is a group represented by the following formula:

[0186] R d The alkyl group as R may be linear or branched, and is preferably linear. dThe alkyl group as has 1 or more and 6 or less carbon atoms, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, further preferably 1 or 2, and particularly preferably 1.

[0187] In formula (d1), R d11 ~R d16 Of -CH2-OR d The number of groups represented by the following formula (I) is preferably 4 or more and 6, more preferably 5 or 6, and even more preferably 6.

[0188] The guanamine compound is preferably a compound represented by the following formula (d2). [ka]

[0189] In formula (d2), R d21 R is a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. d22 ~R d25 Each independently represents a hydrogen atom or -CH-OR d R is a group represented by the formula: d22 ~R d25 At least two of -CH2-OR d It is a group represented by the following formula:

[0190] R d21 The alkyl group as R may be linear or branched, and is preferably linear. d21 The number of carbon atoms in the alkyl group as is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, still more preferably 1 or 2, and particularly preferably 1. R d21 The cycloalkyl group as the alkyl group preferably has 3 or more and 10 or less, more preferably has 3 or more and 8 or less, further preferably has 4 or more and 7 or less, and particularly preferably has 5 or 6 carbon atoms. R d21 The number of carbon atoms in the aryl group as is preferably 6 or more and 14 or less, and more preferably 6 or more and 10 or less. The aryl group is preferably a phenyl group. R d21 As the alkyl group, a hydrogen atom, a methyl group, and a phenyl group are preferable, a hydrogen atom and a phenyl group are more preferable, and a phenyl group is further preferable.

[0191] In formula (d2), R d22 ~R d25 Of -CH2-OR d The number of groups represented by the following formula (I) is preferably 2 or more and 4 or less, more preferably 3 or 4, and even more preferably 4.

[0192] As the urea compound, a compound represented by the following formula (d3) is preferable. [ka]

[0193] In formula (d3), R d31 , and R d33 are each independently a hydrogen atom, an alkyl group, or a cycloalkyl group. d32 , and R d34 is -CH2-OR d R is a group represented by the formula: d31 , and R d33 may be bonded to each other to form a ring. d31 , and R d33 The ring formed by bonding may be condensed with another ring. d31 , and R d33 Compounds containing a ring formed by bonding may be condensed with each other.

[0194] R d31 , or R d33 The alkyl group as R may be linear or branched, and is preferably linear. d31 , or R d33 The number of carbon atoms in the alkyl group as the radical is preferably 1 or more and 8 or less, more preferably 1 or more and 6 or less, and even more preferably 1 or more and 4 or less. R d31 , or R d33The cycloalkyl group as the alkyl group preferably has 3 or more and 10 or less, more preferably has 3 or more and 8 or less, further preferably has 4 or more and 7 or less, and particularly preferably has 5 or 6 carbon atoms.

[0195] In formula (d3), R d31 , and R d33 R are preferably both hydrogen atoms or are bonded to each other to form a ring. d31 , and R d33 When the ring is formed, the compound represented by formula (d3) is preferably a compound represented by the following formula (d4) or the following formula (d5): The compound represented by the following formula (d5) is also called a methylol glycol uril compound. [ka]

[0196] In formula (d4), R d41 , and R d42 is -CH2-OR d R is a group represented by the formula: d43 , and R d44 is a hydrogen atom or a monovalent organic group. L is a single bond or a divalent linking group.

[0197] In formula (d4), R d41 , and R d42 are preferably both methoxymethyl groups.

[0198] In formula (d4), R d43 , and R d44 is preferably a monovalent organic group. The monovalent organic group is not particularly limited. As the monovalent organic group, an alkyl group and an alkoxy group are preferable, and an alkoxy group is more preferable. The number of carbon atoms of the alkyl group and the alkoxy group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, particularly preferably 1 or 2, and most preferably 1.

[0199] In formula (d4), L is preferably a single bond. The divalent linking group represented by L is preferably an alkylene group. The alkylene group may be interrupted by an oxygen atom, a carbonyl group, or a carboxylate bond.

[0200] In formula (d5), R d51 ~R d54 is a hydrogen atom or -CH2-OR d R is a group represented by the formula: d51 ~R d54 At least two of the are -CH2-OR d R is a group represented by the formula: d51 ~R d54 -CH2-OR as d The number of groups represented by the following formula (I) is preferably 3 or 4, and more preferably 4.

[0201] Specific preferred examples of the crosslinking agent (D1) described above include the following compounds. [ka]

[0202] [ka]

[0203] [ka]

[0204] As the crosslinking agent (D1), commercially available products can also be used. Specific examples of commercially available products include Nikalac MX-270, Nikalac MW-100LM, Nikalac MX-280, and Nikalac MX-290 (all manufactured by Sanwa Chemical Co., Ltd.).

[0205] The crosslinking agent (D1) may be used alone or in combination of two or more kinds.

[0206] The content of the crosslinking agent (D1) in the photosensitive composition is not particularly limited as long as the desired effect is not impaired. The content of the crosslinking agent (D1) in the photosensitive composition is preferably 1.0 part by mass or more and 20.0 parts by mass or less, more preferably 1.0 part by mass or more and 15.0 parts by mass or less, and particularly preferably 1.0 part by mass or more and 10.0 parts by mass or less, relative to 100 parts by mass of the resin (A).

[0207] <Solvent (S)> The photosensitive composition may contain a solvent for the purpose of adjusting the coating property, etc. The type of the solvent is not particularly limited, but is typically an organic solvent.

[0208] Examples of organic solvents that can be incorporated in the photosensitive composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ...ethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol (Poly)alkylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (Poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl esters of lactate such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;Other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more kinds.

[0209] Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (GPMEA), propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (MEDG), cyclohexanone, and 3-methoxybutyl acetate (MBA) are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred. In the photosensitive composition, the content of the solvent (S) is preferably 500 parts by mass or more and 30,000 parts by mass or less, and more preferably 1,000 parts by mass or more and 20,000 parts by mass or less, relative to 100 parts by mass of the resin (A). When the content is within the above range, the coatability of the photosensitive composition is likely to be improved, and the thickness of the coating film formed using the photosensitive composition is easily adjusted.

[0210] <Other ingredients (E)> The photosensitive composition may contain various additives in addition to the above components, as long as the desired effect is not impaired. The additives may be appropriately selected from various additives that have been conventionally incorporated into photosensitive compositions. Specific examples of other components include polyvinyl resins, surfactants, and acids or acid anhydrides.

[0211] The photosensitive composition may contain a polyvinyl resin to improve the plasticity of the coating film formed. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and copolymers thereof.

[0212] The photosensitive composition may contain an adhesion aid in order to improve adhesion to the support.

[0213] The photosensitive composition may contain a surfactant to improve coating properties, defoaming properties, leveling properties, etc. Specific examples of surfactants include BM-1000, BM-1100 (all manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all manufactured by DIC Corporation), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon Examples of commercially available fluorine-based surfactants include, but are not limited to, commercially available fluorine-based surfactants such as S-131, Surflon S-141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicones Co., Ltd.), Polyfox PF-136A, Polyfox PF-156A, Polyfox PF-151N, Polyfox PF-636, Polyfox PF-656, Polyfox PF-6520 (all manufactured by OMNOVA Solutions).

[0214] The photosensitive composition may contain an acid or an acid anhydride in order to finely adjust the solubility in the developer. The acid used is one that does not promote the crosslinking of the resin (A) by the crosslinking agent (D).

[0215] Specific examples of acids and acid anhydrides that can be incorporated in the photosensitive composition include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; hydroxymonocarboxylic acids such as lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, and syringic acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, and butanetetracarboxylic acid. polyvalent carboxylic acids such as tetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentane tetracarboxylic acid, butane tetracarboxylic acid, and 1,2,5,8-naphthalene tetracarboxylic acid; and acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, himic anhydride, 1,2,3,4-butane tetracarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate anhydride, and glycerin tristrimellitate anhydride.

[0216] <Method of preparing photosensitive composition> The photosensitive composition is prepared by mixing and stirring the above-mentioned components in a conventional manner. Examples of devices that can be used when mixing and stirring the above-mentioned components include a dissolver, a homogenizer, and a three-roll mill. After the above-mentioned components are mixed uniformly, the resulting mixture may be further filtered using a mesh, a membrane filter, or the like.

[0217] <Patterned resin film> Using the photosensitive composition described above, a patterned resin film can be formed by photolithography. Specifically, the method comprises coating the above-mentioned photosensitive composition on a substrate to form a coating film; exposing the coating film to extreme ultraviolet (EUV) radiation in a position-selective manner; and developing the exposed coating film with a developer. According to the above method, by using the above-mentioned photosensitive composition, a patterned resin film with small roughness can be formed by exposure to extreme ultraviolet (EUV) rays.

[0218] First, the above-mentioned photosensitive composition is applied onto a substrate using a spinner or the like. It is preferable to subject the applied photosensitive composition to a pre-bake (post-applied bake (PAB)) treatment. PAB is performed, for example, at a temperature condition of 80° C. to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds.

[0219] The coating film thus formed is subjected to position-selective exposure through a mask (mask pattern) on which a predetermined pattern is formed, using an EUV exposure device.

[0220] The exposed coating film is preferably subjected to a baking (post-exposure bake (PEB)) treatment. PEB is performed, for example, at a temperature of 80° C. to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds.

[0221] Next, the exposed coating film is developed with a developer, resulting in a patterned resin film. In the case of an alkaline development process, development is carried out using an alkaline developer, whereas in the case of a solvent development process, development is carried out using a developer containing an organic solvent (organic developer).

[0222] After development, a rinsing treatment is preferably performed. In the case of an alkaline development process, rinsing with pure water is preferable. In the case of a solvent development process, rinsing with a rinsing liquid containing an organic solvent is preferable.

[0223] After development or rinsing, the patterned resin film on the substrate is preferably dried. After development, the patterned resin film may be subjected to a baking treatment (post-bake). In this manner, a patterned resin film can be formed.

[0224] The substrate is not particularly limited, and a conventionally known substrate can be used, for example, a substrate for electronic components, a substrate on which a predetermined wiring pattern is formed, etc. More specifically, a substrate made of a metal such as a silicon wafer, copper, chromium, iron, or aluminum, a glass substrate, etc. Examples of materials that can be used for the wiring pattern include copper, aluminum, nickel, and gold. In addition, an inorganic and / or organic film may be provided on the substrate. Examples of inorganic films include inorganic anti-reflective coatings (inorganic BARCs). Examples of organic films include organic anti-reflective coatings (organic BARCs) and organic films such as lower organic films in multi-layer resist methods.

[0225] An example of an alkaline developer used in the alkaline development process is an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 0.1% by mass or more and 10% by mass or less.

[0226] The organic solvent contained in the organic developer used in the solvent development process may be any organic solvent capable of dissolving the resin (A) (the resin (A) before exposure). The organic solvent used as the organic developer may be appropriately selected from known organic solvents. Suitable examples of the organic solvent include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0227] Ketone-based solvents are organic solvents having a structure represented by CC(=O)-C. Ester-based solvents are organic solvents having a carboxylic acid ester group. Alcohol-based solvents are organic solvents having an alcoholic hydroxyl group. Nitrile-based solvents are organic solvents having a nitrile group. Amide-based solvents are organic solvents containing a carboxylic acid amide group. The nitrogen atom in the carboxylic acid amide group may be substituted with an organic group, preferably a hydrocarbon group. Ether-based solvents are organic solvents having an ether bond.

[0228] Some organic solvents contain multiple types of functional groups that characterize the above-mentioned solvents in their structures, and in such cases, the organic solvent is considered to fall under any of the solvent types that contain the functional groups possessed by the organic solvent. For example, diethylene glycol monomethyl ether is considered to fall under both the alcohol-based solvents and the ether-based solvents in the above classification. The hydrocarbon solvent is a hydrocarbon solvent that is composed of a hydrocarbon that may be halogenated and has no substituents other than halogen atoms. The halogen atom is preferably a fluorine atom. Of the above, the organic solvent contained in the organic developer is preferably a polar solvent, and more preferably a ketone solvent, an ester solvent, a nitrile solvent, or the like.

[0229] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, and methyl amyl ketone (2-heptanone). Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0230] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxy Butyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Examples of the ester-based solvent include ethyl acetate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. Of these, butyl acetate is preferred as the ester-based solvent.

[0231] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0232] The organic developer may contain known additives as necessary. Examples of additives include surfactants. The surfactants are not particularly limited, but may include, for example, ionic or nonionic fluorine-based surfactants and silicon-based surfactants. The surfactant is preferably a nonionic surfactant, and more preferably a nonionic fluorine-based surfactant and a nonionic silicon-based surfactant. When a surfactant is added, the amount of the surfactant added is usually preferably from 0.001% by mass to 5% by mass, more preferably from 0.005% by mass to 2% by mass, and even more preferably from 0.01% by mass to 0.5% by mass, based on the total amount of the organic developer.

[0233] Development can be performed by a known developing method, such as a method of immersing a substrate in a developing solution for a certain period of time (dip method), a method of piling up a developing solution on the substrate surface by surface tension and leaving it still for a certain period of time (paddle method), a method of spraying a developing solution on the substrate surface (spray method), and a method of continuously dispensing a developing solution while scanning a developing solution dispensing nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispense method).

[0234] In the solvent development process, the organic solvent contained in the rinse solution used for rinsing after development can be selected appropriately from the organic solvents listed above as organic solvents used in the organic developer, and can be used from those that do not easily dissolve the formed resin film.Usually, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used.Among these, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents and amide solvents is preferred, at least one solvent selected from alcohol solvents and ester solvents is more preferred, and alcohol solvents are particularly preferred. The alcohol-based solvent used as the rinse liquid is preferably a monohydric alcohol having 6 to 8 carbon atoms. The monohydric alcohol may be linear, branched, or cyclic. Specific examples of the monohydric alcohol include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferred, and 1-hexanol and 2-hexanol are more preferred. These organic solvents may be used alone or in combination of two or more. They may also be used in combination with other organic solvents or water. However, in consideration of development characteristics, the amount of water in the rinse solution is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, based on the total amount of the rinse solution. The rinse solution may contain known additives as necessary. Examples of the additives include surfactants. Examples of the surfactants include the same surfactants as described above. As the surfactant, nonionic surfactants are preferred, and nonionic fluorine-based surfactants and nonionic silicon-based surfactants are more preferred. When a surfactant is added, the amount of the surfactant added is usually from 0.001 to 5% by mass, preferably from 0.005 to 2% by mass, and more preferably from 0.01 to 0.5% by mass, based on the total amount of the rinse solution.

[0235] Rinsing (cleaning) using a rinse liquid can be performed by a known rinse method, such as a method of continuously applying the rinse liquid onto a support rotating at a constant speed (spin coating method), a method of immersing the support in the rinse liquid for a certain period of time (dip method), or a method of spraying the rinse liquid onto the surface of the support (spray method).

[0236] <Method for manufacturing an etched substrate> forming a patterned resin film on a substrate by the above-mentioned method; and performing dry etching on the substrate using the patterned resin film as an etching mask. The method allows for the production of etched substrates. As described above, by using the above photosensitive composition, a finely patterned resin film with low roughness can be formed by EUV exposure. Furthermore, the resin film in which the polyorganosiloxane-containing resin (A) is crosslinked has excellent resistance to various etchants. Therefore, by performing dry etching on a substrate using the patterned resin film formed by the above-mentioned method as an etching mask, the substrate can be processed finely and precisely. A preferable combination of the material to be etched and the etchant is, for example, a carbon hard mask and N2 / O2, or SiO2 and CF4. Dry etching is carried out according to a conventional method depending on the type of etchant and the type of substrate.

[0237] As described above, the present inventors provide the following (1) to (10). (1) A composition comprising a resin (A), a photoacid generator (B), a quencher (C), and a crosslinking agent (D), The resin (A) contains a resin (A1) having a polyorganosiloxane structure having a phenolic hydroxyl group, the crosslinking agent (D) is a compound that crosslinks the resin (A) by the action of an acid generated by the photoacid generator (B) upon exposure to light; A photosensitive composition, wherein the molecular weight dispersity of the resin (A) is 1.00 or more and 1.50 or less. (2) The resin (A1) is represented by the following formula (a1): [ka] The photosensitive composition according to (1), comprising a structural unit represented by the following formula: (In the above formula (a1), R a1is an organic group having 6 to 20 carbon atoms and a phenolic hydroxyl group; L a is an organic group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms; R a2 is a hydrogen atom or an organic group having 1 to 20 carbon atoms. (3) The resin (A1) is a polyorganosiloxane, The photosensitive composition according to (1) or (2), wherein the ratio of the amount of the structural unit represented by formula (a1) to the amount of all structural units of the polyorganosiloxane as the resin (A1) is 50 mol% or more and 100 mol% or less. (4) The photoacid generator (B) is represented by the following formula (b1): [ka] The photosensitive composition according to any one of (1) to (3), wherein the compound is represented by the following formula: (In formula (b1), R b1 is an organic group having 1 to 40 carbon atoms, R b1 The organic group represented by M is bonded to the sulfur atom in formula (b1) through a C-S bond, and the carbon atom in the C-S bond is bonded to a fluorine atom. b1 is a sulfonium cation or an iodonium cation. (5) The quencher (C) is represented by the following formula (c1) or (c2): [ka] The photosensitive composition according to any one of (1) to (4), wherein the compound is represented by the following formula: (In formula (c1), R c1 is an organic group having 1 to 20 carbon atoms, R c1 The organic group represented by M is bonded to the sulfur atom in formula (c1) through a C-S bond, and no fluorine atom is bonded to the carbon atom in the C-S bond. c1 In the formula (c2), R is a sulfonium cation or an iodonium cation. c2 is an organic group having 1 to 20 carbon atoms, M c2is a sulfonium cation or an iodonium cation. (6) The photosensitive composition according to any one of (1) to (5), wherein the crosslinking agent (D) comprises a methylol-type crosslinking agent (D1) having a methylol group bonded to a nitrogen atom or an alkoxymethyl group bonded to a nitrogen atom. (7) The photosensitive composition according to any one of (1) to (6), wherein the methylol-type crosslinking agent (D1) is at least one selected from the group consisting of melamine-based compounds, guanamine-based compounds, and urea-based compounds. (8) Coating a photosensitive composition according to any one of (1) to (7) on a substrate to form a coating film; exposing the coating film to extreme ultraviolet light in a position-selective manner; and developing the exposed coating film with a developer. A method for forming a patterned resin film. (9) Forming a patterned resin film on a substrate by the method according to (8); and performing dry etching on the substrate using the patterned resin film as an etching mask. A method for producing an etched substrate. (10) Formula (a1) below: [ka] A resin comprising a structural unit represented by the formula: (In formula (a1), R a1 is an organic group having 6 to 20 carbon atoms and a phenolic hydroxyl group; L a is an organic group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms; R a2 is a hydrogen atom or an organic group having 1 to 20 carbon atoms. EXAMPLES

[0238] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0239] <Preparation of Resin (A)> The resin (A) used in the examples was prepared by the following method.

[0240] [Preparation of Resin (A-0)] 60.0 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 0.42 g of water, 51 g of dehydrated tetrahydrofuran, and 77.0 g of dichloromethane were added to a reaction vessel and mixed. The resulting mixture was stirred at 30° C. for 60 minutes under a nitrogen atmosphere. Then, 32.3 mg of 1,5,7-triazabicyclo[4.4.0]dec-5-ene was added to the mixture and stirred at 30° C. for 72 minutes. Next, 9.28 g of pyridine and 11.9 g of chlorodimethylphenylsilane were added to the mixture. Then, the mixture was stirred at 30° C. for 90 minutes. After the stirring was completed, the mixture was cooled to room temperature. 200 g of heptane and 100 g of water were added to the cooled mixture and stirred. Then, the liquid in the reaction vessel was left to stand and separated into an aqueous layer and an organic layer. The organic layer recovered by removing the aqueous layer was further washed three times with 100 g of pure water. Next, the organic layer obtained after washing was concentrated using a rotary evaporator. Then, 20 g of heptane and 500 g of methanol were added to the residue after concentration. The diluted residue was left to stand and separated into an upper layer and a lower layer. The lower layer obtained by removing the upper layer was concentrated using a rotary evaporator. Then, the residue after concentration was dissolved in 90 g of toluene, and the obtained solution was concentrated using a rotary evaporator three times. Then, the obtained residue was dissolved in toluene so that the concentration was 40% by mass, and 158 g of a 40% by mass toluene solution of resin (A-0) consisting of a constitutional unit represented by the following formula was obtained. The weight average molecular weight of the resin (A-0) measured by GPC was 5,100, and the molecular weight dispersity was 1.15. [ka]

[0241] [Preparation of Resin (A-1)] 11.0 g of 4-hydroxybenzenethiol, 6.00 g of toluene, and 11.7 g of trimethylsilyl chloride were added to the reaction vessel and dissolved uniformly. Then, while stirring the solution in the reaction vessel, 10.3 g of pyridine was dropped into the reaction vessel over 5 minutes. Next, while stirring the solution in the reaction vessel for 90 minutes, 10.0 g of a toluene solution with a concentration of 40 mass% of resin (A-0) and 1.30 g of azobisisobutyronitrile were added to the reaction vessel. Then, the reaction solution in the reaction vessel was stirred at 70°C for 12 hours. After the stirring was completed, the reaction solution was cooled to room temperature. Then, toluene and hot water were added to the reaction solution and stirred. After stirring, the liquid in the reaction vessel was left to stand and separated. The organic layer obtained by removing the water layer was further washed three times with 60 g of hot water. The washed organic layer was concentrated using a rotary evaporator to obtain a residue. Then, 72 g of methanol and 72 g of 1M hydrochloric acid were added to the residue, and the resulting mixture was stirred at room temperature for 90 minutes. 30 g of propylene glycol monomethyl ether and 60 g of pure water were further added to the mixture. The mixture was left to stand, and separated into an aqueous layer and an organic layer. The organic layer obtained by removing the aqueous layer was further washed twice with 60 g of pure water. The washed organic layer was concentrated using a rotary evaporator. The residue obtained by concentration was diluted with 75 g of toluene and 50 g of heptane. The resulting diluted solution was stirred, and then the diluted solution was left to stand. The supernatant that was generated after standing was removed. Dilution of the residue after concentration or after removing the supernatant with 70 g of toluene and 50 g of heptane, standing, and removal of the supernatant were repeated three times in total. Next, 50 g of propylene glycol monomethyl ether was added to the residue after the final removal of the supernatant to dilute it. The resulting diluted solution was concentrated to dryness using a rotary evaporator. Dilution with 50 g of propylene glycol monomethyl ether and concentration to dryness were repeated three times in total. After that, the residue after the final concentration to dryness was dissolved in propylene glycol monomethyl ether to a concentration of 10 mass%, to obtain 56.3 g of a propylene glycol monomethyl ether solution having a concentration of 10 mass% of resin (A-1) composed of a structural unit represented by the following formula. The weight average molecular weight of resin (A-1) measured by GPC was 6,200, and the molecular weight dispersity was 1.23. [ka]

[0242] [Preparation of Resin (A-2)] A propylene glycol monomethyl ether solution with a concentration of 10% by mass of resin (A-2) consisting of a structural unit represented by the following formula was obtained in the same manner as in the preparation of resin (A-0) and resin (A-1), except that 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was replaced with 2,4,6-triphenyl-2,4,6-trivinylcyclotrisiloxane. The weight average molecular weight of resin (A-2) measured by GPC was 5,200, and the molecular weight dispersity was 1.18. [ka]

[0243] [Preparation of Resin (A-3)] 2.97g of benzenethiol and 6.00g of toluene were added to the reaction vessel and dissolved uniformly. Next, 10.0g of the toluene solution of resin (A-0) and 0.44g of azobisisobutyronitrile were added to the reaction vessel, and the reaction solution in the reaction vessel was stirred at 70°C for 12 hours. Then, 8.83g of hydroxybenzenethiol and 10.2g of trimethylsilyl chloride were added to the reaction vessel. Next, while stirring the reaction solution in the reaction vessel, 8.86g of pyridine was dropped into the reaction vessel over 5 minutes. Then, the reaction solution was stirred for 90 minutes. Next, 1.03g of azobisisobutyronitrile was added to the reaction vessel, and the reaction solution was stirred at 70°C for 12 hours. Then, the reaction solution was cooled to room temperature. The reaction solution cooled to room temperature was treated in the same manner as in the preparation of resin (A-1) to obtain a propylene glycol monomethyl ether solution having a concentration of 10% by mass of resin (A-3) consisting of a structural unit represented by the following formula. The weight average molecular weight of the resin (A-3) measured by GPC was 5,800, and the molecular weight dispersity was 1.29. [ka]

[0244] [Preparation of Resin (A-4)] The amount of benzenethiol was changed from 2.97g to 4.96g, the amount of 4-hydroxybenzenethiol was changed from 8.83g to 6.13g, the amount of trimethylsilyl chloride was changed from 10.2g to 7.30g, and the amount of pyridine was changed from 8.86g to 6.33g, but the same procedure was used to prepare resin (A-3), to obtain a propylene glycol monomethyl ether solution having a concentration of 10% by mass of resin (A-4) consisting of a structural unit represented by the following formula. The weight average molecular weight of resin (A-4) measured by GPC was 5,800, and the molecular weight dispersity was 1.25. [ka]

[0245] [Preparation of Resin (A-5)] The amount of 4-hydroxybenzenethiol was changed from 11.0g to 8.80g, the amount of trimethylsilyl chloride was changed from 11.7g to 10.2g, the amount of pyridine was changed from 10.3g to 8.9g, and the amount of azobisisobutyronitrile was changed from 1.30g to 5.17g, but the same procedure was used to prepare resin (A-1), except that a propylene glycol monomethyl ether solution with a concentration of 10% by mass of resin (A-5) consisting of a structural unit represented by the following formula was obtained. The weight average molecular weight of resin (A-5) measured by GPC was 4,800, and the molecular weight dispersity was 1.21. [ka]

[0246] <Preparation of Photosensitive Composition> In the examples, the above-mentioned resins (A-1) to (A-5) were used as the resin (A1). In the examples and comparative examples, the following resins (A-6) and (A-7) were used as the resin (A2). In Example 13, 75 parts by mass of the resin (A-1) and 25 parts by mass of the resin (A-6) were combined and used as the resin (A). The molecular weight dispersity of the resin (A) used in Example 13 is in the range of 1.00 to 1.50. [ka]

[0247] In the examples and comparative examples, the following compound (B-1) and compound (B-2) were used as the photoacid generator (B). [ka]

[0248] In the examples and comparative examples, the following compounds (C-1) and (C-2) were used as the quencher (C). [ka]

[0249] In the examples and comparative examples, the following compound (D-1) and compound (D-2) were used as the crosslinking agent (D). [ka]

[0250] In the examples and comparative examples, salicylic acid (E-1) was used as the additive (E).

[0251] In the examples and comparative examples, propylene glycol monomethyl ether (S-1) and propylene glycol monomethyl ether acetate (S-2) were used as the solvent (S).

[0252] The resin (A1) or resin (A2), the photoacid generator (B), the quencher (C), the crosslinking agent (D), and the additive (E) of the types and parts by mass shown in Table 1 were dissolved in the solvent (S) of the types and parts by mass shown in Table 1 to obtain photosensitive compositions of each of the Examples and Comparative Examples.

[0253] [Table 1]

[0254] <Evaluation> A resist organic underlayer film composition (product name: AL412, manufactured by Brewer Science) was applied onto a 12-inch silicon wafer using a spin coater, and baked on a hot plate at 205°C for 60 seconds to form an organic underlayer film with a thickness of 20 nm. The photosensitive composition of each Example and Comparative Example was applied onto the organic underlayer film using a spin coater, and a pre-baked (PAB) treatment was performed on a hot plate at 90°C for 60 seconds to form a coating film with a thickness of 22 nm. Next, the coating film was irradiated with EUV light (wavelength 13.5 nm) through a photomask for forming a line and space pattern using an EUV exposure device (product name: NXE3400, ASML, NA (numerical aperture) = 0.33, illumination conditions: annular σ-in = 0.60, σ-out = 0.82). Then, a post-exposure bake (PEB) treatment was performed at 90 ° C for 60 seconds. After that, alkaline development was performed for 10 seconds with a 2.38 mass % TMAH aqueous solution (product name: NMD-3, Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. Then, rinsing was performed for 30 seconds using pure water, shaking off and drying were performed, and a cured film with a line width of 14 nm and a line and space shape was formed.

[0255] [Evaluation of optimal exposure (Eop)] In each Example and Comparative Example, the optimum exposure dose Eop (mJ / cm) at which a cured film with a line width of 14 nm and a line-space shape was formed 2 ) was measured. The results of these measurements are shown in Table 2.

[0256] [Line width roughness (LWR) evaluation] For the cured films formed in each Example and Comparative Example and having a line width of 14 nm and a line-space shape, 3σ, which is a scale indicating LWR, was determined. 3σ indicates three times the standard deviation (σ) (unit: nm) obtained by measuring 400 line positions in the longitudinal direction of the line using a scanning electron microscope (product name: S-9380, Hitachi High-Technologies Corporation, accelerating voltage 800 V). The results of these measurements are shown in Table 2. A smaller 3σ value means that the line sidewall roughness is smaller and a LS pattern with a more uniform width is obtained. Each example and each comparative example was evaluated according to the following criteria. ◯: 3σ was 2.50 or less. ×: 3σ was more than 2.50.

[0257] [Table 2]

[0258] According to Table 2, a photosensitive composition capable of forming a resist pattern with small LWR can be obtained by containing a resin (A), a photoacid generator (B), a quencher (C), and a crosslinking agent (D), where the resin (A) contains a resin (A1) having a polyorganosiloxane structure having a phenolic hydroxyl group, and the molecular weight dispersity of the resin (A) is 1.00 or more and 1.50 or less.

Claims

1. A composition comprising a resin (A), a photoacid generator (B), a quencher (C), and a crosslinking agent (D), The resin (A) includes a resin (A1) having a polyorganosiloxane structure having a phenolic hydroxyl group, the crosslinking agent (D) is a compound that crosslinks the resin (A) by the action of an acid generated by the photoacid generator (B) upon exposure to light; The photosensitive composition, wherein the molecular weight dispersity of the resin (A) is 1.00 or more and 1.50 or less.

2. The resin (A1) is represented by the following formula (a1): [Case 1] The photosensitive composition according to claim 1 , comprising a structural unit represented by the following formula: (In the above formula (a1), R ａ１ is an organic group having 6 to 20 carbon atoms and a phenolic hydroxyl group; L ａ is an organic group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms; R ａ２ is a hydrogen atom or an organic group having 1 to 20 carbon atoms.

3. The resin (A1) is a polyorganosiloxane, 3. The photosensitive composition according to claim 1, wherein the ratio of the amount of the structural unit represented by the formula (a1) to the amount of all structural units of the polyorganosiloxane as the resin (A1) is 50 mol% or more and 100 mol% or less.

4. The photoacid generator (B) is represented by the following formula (b1): [Case 2] The photosensitive composition according to claim 1 or 2, wherein the compound is represented by the formula: (In the above formula (b1), R ｂ１ is an organic group having 1 to 40 carbon atoms; R ｂ１The organic group represented by M is bonded to the sulfur atom in formula (b1) through a C-S bond, and the carbon atom in the C-S bond is bonded to a fluorine atom. ｂ１ is a sulfonium cation or an iodonium cation.

5. The quencher (C) is represented by the following formula (c1) or formula (c2): [C3] The photosensitive composition according to claim 1 or 2, wherein the compound is represented by the formula: (In the formula (c1), R ｃ１ is an organic group having 1 to 20 carbon atoms; R ｃ１ The organic group represented by M is bonded to the sulfur atom in formula (c1) through a C-S bond, no fluorine atom is bonded to the carbon atom in the C-S bond, ｃ１ In the formula (c2), R ｃ２ is an organic group having 1 to 20 carbon atoms; M ｃ２ is a sulfonium cation or an iodonium cation.

6. 3. The photosensitive composition according to claim 1, wherein the crosslinking agent (D) comprises a methylol-type crosslinking agent (D1) having a methylol group bonded to a nitrogen atom or an alkoxymethyl group bonded to a nitrogen atom.

7. The photosensitive composition according to claim 6, wherein the methylol-type crosslinking agent (D1) is at least one selected from the group consisting of melamine-based compounds, guanamine-based compounds, and urea-based compounds.

8. Coating a substrate with the photosensitive composition according to claim 1 or 2 to form a coating film; exposing the coating film to extreme ultraviolet light in a position-selective manner; and developing the exposed coating film with a developer. A method for forming a patterned resin film.

9. forming the patterned resin film on the substrate by the method according to claim 8; and performing dry etching on the substrate using the patterned resin film as an etching mask. A method for producing an etched substrate.

10. The following formula (a1): [C4] A resin comprising a structural unit represented by the formula: (In the above formula (a1), R ａ１ is an organic group having 6 to 20 carbon atoms and a phenolic hydroxyl group; L ａ is an organic group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms; R ａ２ is a hydrogen atom or an organic group having 1 to 20 carbon atoms.

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