Monomer, polymer, chemically amplified resist composition, and pattern forming method

Abstract

The present invention relates to a monomer, a polymer, a chemical amplification resist composition, and a pattern forming method. The present invention provides a monomer which is a raw material of a polymer used for a chemical amplification resist composition which is excellent in solvent solubility, high in sensitivity, high in contrast, excellent in lithography properties such as LWR, CDU, EL, DOF, and pattern shape, in optical lithography using a high-energy ray, a polymer obtained using the monomer, a chemical amplification resist composition containing the polymer, and a pattern forming method using the chemical amplification resist composition. A monomer represented by the following formula (A).

Description

Technical Field

[0001] This invention relates to monomers, polymers, chemically amplified resist compositions, and methods for patterning. Background Technology

[0002] With the increasing integration and speed of LSI (Lithium-ion Sensor), the miniaturization of patterning is progressing rapidly. Due to the widespread adoption of 5G high-speed communication and artificial intelligence (AI), high-performance devices are essential to handle these technologies. As the most advanced miniaturization technology, mass production of 5nm node devices using 13.5nm extreme ultraviolet (EUV) lithography is already underway. Furthermore, research on using EUV lithography in next-generation 3nm node devices and the next-next-generation 2nm node devices is ongoing.

[0003] As miniaturization progresses, image blurring due to acid diffusion becomes a problem. To ensure the resolution of fine patterns with a processing size of 45 nm and above, it has been proposed that not only is improving dissolution contrast as previously proposed, but also controlling acid diffusion is important (Non-Patent Literature 1). However, chemically amplified resist compositions can increase sensitivity and contrast due to acid diffusion. If the post-exposure baking (PEB) temperature is lowered or the time is shortened to suppress acid diffusion to the limit, the sensitivity and contrast will be significantly reduced.

[0004] Sensitivity, resolution, and edge roughness (LER, LWR) exhibit a triangular trade-off. To improve resolution, acid diffusion must be suppressed, but if the acid diffusion distance is shortened, sensitivity will decrease.

[0005] Adding an acid-generating agent that produces a large volume of acid is effective in suppressing acid diffusion. A scheme has been proposed that the polymer contain repeating units from onium salts with polymerizable unsaturated bonds. In this case, the polymer also acts as an acid-generating agent (polymer-bonded acid-generating agent). Patent Document 1 proposes sulfonium salts and sulfonium salts with polymerizable unsaturated bonds that produce specific sulfonic acids. Patent Document 2 provides that the sulfonic acid is a sulfonium salt directly bonded to the main chain.

[0006] As a component contributing to the performance of positive resist compositions, the structure of the acid-indestructible group in the base polymer is important. Here, it has been proposed that the acid-indestructible group be a tertiary ester type bonded to an aromatic group substituted with a fluorine atom (Patent Documents 3, 4). The acid-indestructible group of the tertiary ester type bonded to the aromatic group has very high acid-induced de-reactivity, making acid diffusion control difficult. However, the de-reactivity can be moderately suppressed by introducing a fluorine atom into the aromatic group.

[0007] Furthermore, to improve etching resistance in EUV lithography, acid-instable monomers with styrene structures are also suitable in terms of the structure of the polymerizable groups of the monomers. Patent Document 5 proposes an acid-instable monomer obtained from styrene carboxylic acid and a cyclic tertiary alcohol. Patent Document 6 proposes a styrene-type acid-instable monomer with an aromatic linking group containing iodine atoms that have high absorption capacity for EUV light. Iodine atoms have very high absorption for EUV at a wavelength of 13.5 nm, so it has been confirmed that there will be an effect of generating secondary electrons from iodine atoms during exposure, which has attracted attention in EUV lithography.

[0008] Patent document 7 proposes an acid-instable monomer having methacrylamide and iodine-containing aromatic linkage groups as polymerizable groups. This confirms an improvement in resolution and sensitivity, but it is not yet satisfactory. To meet the demands for finer details, there is a need to develop an acid-instable monomer that exhibits better acid de-reactivity and, after de-reactivity, suppresses swelling in alkaline developers.

[0009] Existing technical documents

[0010] Patent documents

[0011] [Patent Document 1] Japanese Patent Application Publication No. 2006-045311

[0012] [Patent Document 2] Japanese Patent Application Publication No. 2006-178317

[0013] [Patent Document 3] Japanese Patent No. 3832564

[0014] [Patent Document 4] Japanese Patent No. 5655754

[0015] [Patent Document 5] Japanese Patent No. 7055070

[0016] [Patent Document 6] Japanese Patent Application Publication No. 2025-005802

[0017] [Patent Document 7] Japanese Patent Application Publication No. 2025-004966

[0018] Non-patent literature

[0019] [Non-Patent Literature 1] SPIE Vol. 6520 65203L-1 (2007) Summary of the Invention

[0020] (The problem the invention aims to solve)

[0021] In view of the foregoing, the present invention aims to provide a monomer of a polymer used in a chemically amplified resist composition that exhibits excellent solvent solubility, high sensitivity, high contrast, and excellent lithographic performance such as LWR, dimensional uniformity (CDU), exposure margin (EL), and depth of focus (DOF), as well as excellent pattern shape, particularly in optical lithography using high-energy rays such as KrF excimer lasers, ArF excimer lasers, electron beams (EB), and EUV. The invention also includes a polymer obtained using the monomer, a chemically amplified resist composition comprising the polymer, and a method for patterning using the chemically amplified resist composition.

[0022] (Methods for solving problems)

[0023] In order to achieve the aforementioned objectives, the inventors of this application have made efforts to explore and have discovered that the monomers of a specific structure have excellent solvent solubility, and the chemically amplified resist composition containing polymers obtained therefrom as the base polymer has high sensitivity and high contrast, excellent photolithography performance such as LWR, CDU, EL, and DOF, and is still extremely effective in suppressing pattern collapse during the formation of fine patterns, thus completing this invention.

[0024] Therefore, the present invention provides the following monomers, polymers, chemically amplified resist compositions and patterning methods.

[0025] 1. A monomer, represented by the following formula (A),

[0026] [Chemistry 1]

[0027]

[0028] In the formula, n1 is 0 or 1, n2 is 0, 1, 2, 3 or 4, n3 is 0 or 1, n4 is 0, 1, 2, 3 or 4, and n5 is 0 or 1.

[0029] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0030] X A For single bonds, -C(=O)-O- 、or -C(=O)-N(H)- , This represents the atomic bond between the carbon atom and the aromatic ring.

[0031] R 1 The radical can be a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms, and when n2 is 2, 3 or 4, each R 1 They can be the same or different, 2 Rs 1They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0032] R 2 The group can be a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. When n4 is 2, 3, or 4, each R... 2 They can be the same or different, 2 Rs 2 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0033] X 1 It is -O- or -N(H)-.

[0034] R AL It is an acid-labile group.

[0035] 2. The monomer of 1. is represented by the following formula (A1).

[0036] [Chemistry 2]

[0037]

[0038] In the formula, n1~n5, R A X 1 R 1 R 2 and R AL As mentioned above.

[0039] 3. The monomers of 2. are represented by the following formula (A2).

[0040] [Chemistry 3]

[0041]

[0042] In the formula, n2, n4, n5, R A X 1 R 1 R 2 and R AL As mentioned above.

[0043] 4. For any of the monomers in 1.~3, where R AL The group represented by formula (AL-1) or (AL-2) is...

[0044] [Chemistry 4]

[0045]

[0046] In the formula, k1 is 0 or 1, and k2 is 0 or 1.

[0047] RL1 and R L2 Each is an independent hydrocarbon group having 1 to 12 carbon atoms, R L3 R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. L1 R L2 and R L3 The -CH2- group of the hydrocarbon group may also be partially replaced by -O- or -S-. When the hydrocarbon group contains an aromatic ring, some or all of the hydrogen atoms in the aromatic ring may be replaced by a halogen atom, a cyano group, a nitro group, an alkyl group containing 1 to 4 carbon atoms, or an alkoxy group containing 1 to 4 carbon atoms. Furthermore, R... L1 and R L2 They can also bond to each other and form a ring together with the carbon atoms they are bonded to. A portion of the -CH2- in this ring can be replaced by -O- or -S-, but R... L3 When R is a hydrogen atom L1 and R L2 They bond to each other and together with the carbon atoms they are bonded to, form alicyclic rings containing multiple bonds.

[0048] R L4 and R L5 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R L6 It is a hydrocarbon group with 1 to 20 carbon atoms. A portion of the -CH2- group of this hydrocarbon group may also be replaced by -O- or -S-. Also, R... L5 and R L6 They can also bond to each other and to the carbon atoms and L atoms they are bonded to. A Together they form a heterocyclic group with 3 to 20 carbon atoms, and part of the -CH2- of this heterocyclic group can also be replaced by -O- or -S-.

[0049] L A For -O- or -S-,

[0050] This represents the atomic bond between the -O- and the adjacent -O-.

[0051] 5. A polymer comprising repeating units from any one of monomers as described in 1 to 4.

[0052] 6. The polymer as described in 5. further contains at least one repeating unit selected from the repeating units represented by formula (a1), formula (a2), and formula (a3).

[0053] [Chemistry 5]

[0054]

[0055] In the formula, a1 is 0 or 1, and a2 is 0, 1, 2, 3, or 4.

[0056] b1 is 0 or 1, and b2 is 0, 1, 2 or 3 when b1 is 0, and 0, 1, 2, 3, 4 or 5 when b1 is 1.

[0057] R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0058] X 1 It is a single bond, phenylene, naphthylene or -C(=O)-OX 11 - The phenylene or naphthylene group may also be replaced by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, a saturated hydroxyl group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom. X 11 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms. This saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring.

[0059] X 2 For single bond, -C(=O)-O- or -C(=O)-N(H)-,

[0060] X 3 For single bond, -C(=O)-O- or -C(=O)-N(H)-,

[0061] This represents the atomic bonds between the carbon atoms in the main chain and the carbon atoms in the main chain.

[0062] X 4 A group obtained by means of a single bond, an aliphatic alkylene group, a carbonyl group, a sulfonyl group, or a combination thereof, having 1 to 4 carbon atoms.

[0063] X 5 and X 6 Each can be independently an oxygen atom or a sulfur atom, but X 4 and X 6 Bonded to adjacent carbon atoms on the aromatic ring,

[0064] R 11 The radical can be a halogen atom, cyano group, hydroxyl group, nitro group, pentafluorosulfur group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When a2 is 2, 3, or 4, each R... 11 They can be the same or different.

[0065] R 12 and R 13Each is an independent hydrocarbon group consisting of hydrogen atoms, or may contain heteroatoms, and has 1 to 20 carbon atoms. Also, R 12 and R 13 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0066] R 14 It can be a halogen atom, hydroxyl group, cyano group, nitro group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxygen group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms or -N(R) group. 14A (R) 14B ), R 14A and R 14B Each is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; when b2 is 2 or more, each R 14 They can be the same or different, multiple Rs 14 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0067] AL 1 and AL 2 Each is an acid-labile group.

[0068] 7. Polymers such as those in 5 or 6 also contain repeating units represented by the following formula (b1),

[0069] [Chemistry 6]

[0070]

[0071] In the formula, R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0072] Y 1 For single bond, -C(=O)-O- or -C(=O)-N(H)-, This represents the atomic bonds between the carbon atoms in the main chain and the carbon atoms in the main chain.

[0073] R 21 The group can be a halogen atom, carboxyl group, nitro group, cyano group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; or it can be a hydrocarbon oxygen carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When c3 is 2, 3, or 4, each R... 21 They can be the same or different.

[0074] c1 is 0 or 1, c2 is 1, 2, 3 or 4, c3 is 0, 1, 2, 3 or 4, but 1≤c2+c3≤5.

[0075] 8. The polymer of any one of 5.~7. further contains a repeating unit represented by the following formula (b2),

[0076] [Chemistry 7]

[0077]

[0078] In the formula, R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0079] Y 2 For single bonds, phenylene, naphthylene, -C(=O)-OY 21 -or -C(=O)-N(H)-Y 21 - The phenylene or naphthylene group may also be replaced by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, a saturated hydrocarbon oxygen group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom. Y represents the atomic bond between the carbon atoms in the main chain and the main chain. 21 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms. This saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring.

[0080] R 22 It is a hydrogen atom, or a group containing at least one of the following structures with 1 to 20 carbon atoms: hydroxyl group (other than phenolic hydroxyl group), cyano group, nitro group, carbonyl group, carboxyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulopentalide ring, lactam ring, sulopentalide ring, and carboxylic anhydride (-C(=O)-OC(=O)-).

[0081] 9. The polymer of any one of 5. to 8. further comprises at least one repeating unit selected from the following formula (c1), the following formula (c2), the following formula (c3), the following formula (c4), and the following formula (c5).

[0082] [Chemistry 8]

[0083]

[0084] In the formula, d1 and d2 are each independently 0, 1, 2 or 3.

[0085] e1 can be 0 or 1, e2 can be 0, 1, 2, 3 or 4, and e3 can be 0, 1, 2, 3 or 4. However, when e1 is 0, the condition is 0 ≤ e2 + e3 ≤ 4, and when e1 is 1, the condition is 0 ≤ e2 + e3 ≤ 6.

[0086] R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0087] Z 1 It can be a single bond or may have substituents, phenylene

[0088] Z 2 For single bond, -C(=O)-OZ 21 -、 -C(=O)-N(H)-Z 21 -or -OZ 21 -, Z 21 It is a divalent group obtained by aliphatic hydrocarbon groups, phenylene groups, or combinations thereof with 1 to 6 carbon atoms, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups.

[0089] Z 3 The bonds can be single bonds, ether bonds, ester bonds, sulfonate bonds, amide bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds.

[0090] Z 4 It is a divalent group obtained by a single bond, or an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, or a combination thereof, and may also contain a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group.

[0091] Z 5 Each can be a single bond independently, or may have substituents such as phenylene, naphthylene, or... -C(=O)-OZ 51 -, Z 51 It is an aliphatic hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms. This aliphatic hydrocarbon group may also contain a halogen atom, hydroxyl group, ether bond, ester bond, or lactone ring.

[0092] Z 6 The bonds can be single bonds, ether bonds, ester bonds, sulfonate bonds, amide bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds.

[0093] Z 7 Each is an independent single bond. -Z 71 -C(=O)-O-、 -C(=O)-N(H)-Z 71 -or -OZ 71 -, Z 71 It can also contain a hydrocarbon group with 1 to 20 carbon atoms, which is a heteroatom.

[0094] Z 8 Each is an independent single bond. -Z 81 -C(=O)-O-、 -C(=O)-N(H)-Z 81 -or -OZ 81 -, Z 81 It can also contain a hydrocarbon group with 1 to 20 carbon atoms, which is a heteroatom.

[0095] Z 9 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene -C(=O)-OZ 91 -、 -C(=O)-N(H)-Z 91 -or -OZ 91 -, Z 91 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms. It may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group.

[0096] This represents the atomic bonds between the carbon atoms in the main chain and the carbon atoms in the main chain. Indicates and Z 1 atomic bonds, Indicates and Z 6 atomic bonds, Indicates and Z 7 atomic bonds,

[0097] L 1The bonds can be single bonds, ether bonds, ester bonds, carbonyl groups, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds.

[0098] Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms.

[0099] Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms.

[0100] Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, but all Rf 5 and Rf 6 They are not both hydrogen atoms.

[0101] Rf 7 It is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl thio group having 1 to 6 carbon atoms, or a pentafluorothio group.

[0102] R 31 and R 32 Each can independently be a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms. Also, R 31 and R 32 They can also bond to each other and form rings together with the sulfur atoms they are bonded to.

[0103] R 33 The R group can be a halogen atom other than fluorine, or a hydrocarbon group containing heteroatoms with 1 to 20 carbon atoms. When e3 is 2, 3, or 4, each R... 33 They can be the same or different, multiple Rs 33 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0104] M - It is a non-nucleophilic relative ion.

[0105] A + It is a ium cation.

[0106] 10. A chemically amplified resist composition comprising a base polymer containing a polymer of any one of 5 to 9, and an organic solvent.

[0107] 11. As in 10, chemically amplified resist compositions also contain quenching agents.

[0108] 12. Chemically amplified resist compositions such as 10 or 11 also contain photoacid generators other than polymerically bonded photoacid generators.

[0109] 13. A chemically amplified resist composition, such as any one of 10. to 12, further comprises a surfactant.

[0110] 14. A method for forming a pattern, comprising the following steps:

[0111] A resist film is formed on the substrate using a chemically amplified resist composition such as any one of 10.~13.

[0112] The resist film was exposed to high-energy rays, and

[0113] The exposed resist film was developed using a developer.

[0114] 15. The pattern forming method of 14, wherein the high-energy ray is a KrF excimer laser, an ArF excimer laser, an electron beam, or extreme ultraviolet light with a wavelength of 3 to 15 nm.

[0115] (The effect of the invention)

[0116] When patterning is performed using a chemically amplified resist composition containing a polymer obtained using the monomers of the present invention as the base polymer, the contrast is high and the sensitivity is good, and resist patterns with excellent photolithography performance and suppressed pattern collapse, such as LWR, CDU, EL, and DOF, can be formed. Detailed Implementation

[0117] [monomer]

[0118] The monomer of the present invention is represented by the following formula (A).

[0119] [Chemistry 9]

[0120]

[0121] In formula (A), n1 is 0 or 1. When n1 is 0, it is a benzene ring; when n1 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with n1 of 0 is preferred. n2 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, n2 of 0, 1, or 2 is preferred. n3 is 0 or 1. When n3 is 0, it is a benzene ring; when n3 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with n3 of 0 is preferred. n4 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, n4 of 0, 1, or 2 is preferred. n5 is 0 or 1.

[0122] In formula (A), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Among these, hydrogen atoms and methyl groups are preferred.

[0123] In formula (A), X A For single bonds, -C(=O)-O- 、or -C(=O)-N(H)- . This represents the atomic bonds between carbon atoms on the aromatic ring. Among these, single bonds, -C(=O)-O- Better, single key is better.

[0124] In formula (A), R 1 The halogen atom can be a nitro group, cyano group, hydroxyl group, carboxyl group, pentafluorosulfur group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon sulfur group with 1 to 20 carbon atoms containing heteroatoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with fluorine and iodine atoms being preferred. The hydrocarbon group, hydrocarbon oxy group, and hydrocarbon sulfur group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, decadecyl, heptadecyl, octadecyl, nonadecanyl, and icosyl; cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, and adamantyl; alkenyl groups with 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclohexenyl; aryl groups with 6 to 20 carbon atoms, such as phenyl and naphthyl; aralkyl groups with 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these. Among these, aryl groups are preferred. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0125] In formula (A), R 2 The halogen atom can be a nitro group, cyano group, hydroxyl group, carboxyl group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine and iodine atoms being preferred. The hydrocarbon group, hydrocarbon oxy group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples and R can be cited. 1 The examples of hydrocarbon groups are similar, but not limited to these.

[0126] When n2 is 2, 3, or 4, each R 1 They can be the same or different. Also, when n² is 2, 3, or 4, there are 2 R... 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to. Five- to eight-membered rings are preferred. When n4 is 2, 3, or 4, each R... 2 They can be the same or different. Also, when n₄ is 2, 3, or 4, there are 2 R₁ and 2 R₂. 2 They can also bond to each other and form rings together with the carbon atoms they are bonded to. Five- to eight-membered rings are preferred.

[0127] In formula (A), X 1 It is -O- or -N(H)-.

[0128] In formula (A), R AL It is an acid-indestructible group. It is preferred that the aforementioned acid-indestructible group is represented by the following formula (AL-1) or (AL-2).

[0129] [Chemistry 10]

[0130]

[0131] In the formula, This represents the atomic bond between the -O- and the adjacent -O-.

[0132] In equations (AL-1) and (AL-2), k1 is 0 or 1. k2 is 0 or 1.

[0133] In equation (AL-1), R L1 and R L2 Each is an independent hydrocarbon group having 1 to 12 carbon atoms. R L3 It consists of a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R L1 R L2 and R L3 The -CH2- group of the represented hydrocarbon group may also be partially replaced by -O- or -S-. When the hydrocarbon group contains an aromatic ring, some or all of the hydrogen atoms of the aromatic ring may be replaced by a halogen atom, a cyano group, a nitro group, an alkyl group containing 1 to 4 carbon atoms, or an alkoxy group containing 1 to 4 carbon atoms. R L1 R L2 and R L3 The hydrocarbon group representing 1 to 12 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given for R... 1 Examples of hydrocarbon groups are those with 1 to 12 carbon atoms. Also, R... L1 and R L2They can also bond to each other and form a ring with the carbon atoms they are bonded to, and a portion of the -CH2- in this ring can be replaced by -O- or -S-. But R L3 When R is a hydrogen atom L1 and R L2 They bond to each other and together with the carbon atoms they bond to, form alicyclic rings containing multiple bonds.

[0134] In equation (AL-2), R L4 and R L5 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R L4 and R L5 The hydrocarbon group representing 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given using R. 1 Examples of hydrocarbon groups with 1 to 10 carbon atoms are the same. R L6 It is a hydrocarbon group with 1 to 20 carbon atoms, and part of the -CH2- group can also be replaced by -O- or -S-. Also, R L5 and R L6 They can also bond to each other and to the carbon atoms and L atoms they are bonded to. A Together they form a heterocyclic group with 3 to 20 carbon atoms, and part of the -CH2- of this heterocyclic group can also be replaced by -O- or -S-. R L6 The hydrocarbon group representing 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given using R. 1 The hydrocarbon group shown is an example of the same.

[0135] In equation (AL-2), L A It can be either -O- or -S-.

[0136] Specific examples of acid-instable groups represented by formula (AL-1) are listed below, but are not limited to these. Furthermore, in the following formula, This represents the atomic bond between the -O- and the adjacent -O-.

[0137] [Chemistry 11]

[0138]

[0139] [Chemistry 12]

[0140]

[0141] [Chemistry 13]

[0142]

[0143] [Chemistry 14]

[0144]

[0145] [Chemistry 15]

[0146]

[0147] [Chemistry 16]

[0148]

[0149] [Chemistry 17]

[0150]

[0151] [Chemistry 18]

[0152]

[0153] [Chemistry 19]

[0154]

[0155] [Chemistry 20]

[0156]

[0157] [Chemistry 21]

[0158]

[0159] [Chemistry 22]

[0160]

[0161] [Chemistry 23]

[0162]

[0163] [Chemistry 24]

[0164]

[0165] [Chemistry 25]

[0166]

[0167] [Chemistry 26]

[0168]

[0169] [Chemistry 27]

[0170]

[0171] [Chemistry 28]

[0172]

[0173] [Chemistry 29]

[0174]

[0175] [Chemistry 30]

[0176]

[0177] [Chemistry 31]

[0178]

[0179] [Chemistry 32]

[0180]

[0181] [Chemistry 33]

[0182]

[0183] Specific examples of acid-instable groups represented by formula (AL-2) are listed below, but are not limited to these. Furthermore, in the following formula, This represents the atomic bond between the -O- and the adjacent -O-.

[0184] [Chemistry 34]

[0185]

[0186] [Chemistry 35]

[0187]

[0188] [Chemistry 36]

[0189]

[0190] The monomer represented by formula (A) is preferably represented by formula (A1).

[0191] [Chemistry 37]

[0192]

[0193] In the formula, n1~n5, R A X 1 R 1 R 2 and R AL As mentioned above.

[0194] The monomer represented by formula (A1) is preferably represented by formula (A2).

[0195] [Chemistry 38]

[0196]

[0197] In the formula, n2, n4, n5, R A X 1 R 1 R 2 and R AL As mentioned above.

[0198] Specific examples of monomers represented by formula (A) are listed below, but are not limited to these. Furthermore, the substitution positions of the substituents on the aromatic ring are not limited to these.

[0199] [Chemistry 39]

[0200]

[0201] [Chemistry 40]

[0202]

[0203] [Chemistry 41]

[0204]

[0205] [Chemistry 42]

[0206]

[0207] [Chemistry 43]

[0208]

[0209] [Chemistry 44]

[0210]

[0211] [Chemistry 45]

[0212]

[0213] [Chemistry 46]

[0214]

[0215] [Chemistry 47]

[0216]

[0217] [Chemistry 48]

[0218]

[0219] [Chemistry 49]

[0220]

[0221] [Transformation 50]

[0222]

[0223] [Chemistry 51]

[0224]

[0225] [Chemistry 52]

[0226]

[0227] [Chemistry 53]

[0228]

[0229] [Chemistry 54]

[0230]

[0231] [Chemistry 55]

[0232]

[0233] [Chemistry 56]

[0234]

[0235] [Chemistry 57]

[0236]

[0237] [Chem.58]

[0238]

[0239] [Chemistry 59]

[0240]

[0241] [Transformation 60]

[0242]

[0243] [Chemistry 61]

[0244]

[0245] [Chemistry 62]

[0246]

[0247] [Chemistry 63]

[0248]

[0249] [Chemistry 64]

[0250]

[0251] [Chemistry 65]

[0252]

[0253] [Chemistry 66]

[0254]

[0255] [Chemistry 67]

[0256]

[0257] [Chemistry 68]

[0258]

[0259] [Chemistry 69]

[0260]

[0261] [Chemistry 70]

[0262]

[0263] [Chemistry 71]

[0264]

[0265] [Chemistry 72]

[0266]

[0267] [Chemistry 73]

[0268]

[0269] [Chemistry 74]

[0270]

[0271] [Chemistry 75]

[0272]

[0273] [Chemistry 76]

[0274]

[0275] [Chemistry 77]

[0276]

[0277] [Chemistry 78]

[0278]

[0279] [Chemistry 79]

[0280]

[0281] [Chemistry 80]

[0282]

[0283] [Chemistry 81]

[0284]

[0285] [Chemistry 82]

[0286]

[0287] [Chemistry 83]

[0288]

[0289] [Chemistry 84]

[0290]

[0291] [Chemistry 85]

[0292]

[0293] [Chemistry 86]

[0294]

[0295] [Chemistry 87]

[0296]

[0297] [Chemistry 88]

[0298]

[0299] [Chemistry 89]

[0300]

[0301] [Chemistry 90]

[0302]

[0303] [Chemistry 91]

[0304]

[0305] [Chemistry 92]

[0306]

[0307] [Chemistry 93]

[0308]

[0309] [Chemistry 94]

[0310]

[0311] [Chemistry 95]

[0312]

[0313] [Chemistry 96]

[0314]

[0315] [Chemistry 97]

[0316]

[0317] [Chem. 98]

[0318]

[0319] [Chemistry 99]

[0320]

[0321] [Chemistry 100]

[0322]

[0323] [Chemistry 101]

[0324]

[0325] [Chemistry 102]

[0326]

[0327] [Chemistry 103]

[0328]

[0329] [Chemistry 104]

[0330]

[0331] [Chemistry 105]

[0332]

[0333] [Chemistry 106]

[0334]

[0335] [Chemistry 107]

[0336]

[0337] [Chemistry 108]

[0338]

[0339] [Chemistry 109]

[0340]

[0341] [Chemical 110]

[0342]

[0343] [Chemistry 111]

[0344]

[0345] [Chemistry 112]

[0346]

[0347] [Chemistry 113]

[0348]

[0349] [Chemistry 114]

[0350]

[0351] [Chemistry 115]

[0352]

[0353] [Chemistry 116]

[0354]

[0355] [Chemistry 117]

[0356]

[0357] [Chemistry 118]

[0358]

[0359] [Chemistry 119]

[0360]

[0361] [Chemistry 120]

[0362]

[0363] [Chemistry 121]

[0364]

[0365] The monomers of this invention can be synthesized using known methods. For example, regarding formula (A), X... 1 A description of the method for manufacturing a monomer (A') containing an oxygen atom.

[0366] [Chemistry 122]

[0367]

[0368] In the formula, n1~n5, R A X A R 1 R 2 and R AL As mentioned before. X Hal It can be any one of fluorine, chlorine, bromine, or iodine atoms.

[0369] The reaction involves reacting the hydroxyl group of the starting material (Pre-A') with a sulfonyl halide to obtain a monomer (A') of the target product having a sulfonate bond.

[0370] The starting materials (Pre-A') and (SM-A') can be synthesized using known methods or obtained commercially available products. The reaction can be carried out using known organic synthesis methods. Specifically, the starting material (Pre-A') is dissolved in solvents such as toluene, hexane, THF, acetonitrile, or dichloromethane in the presence of organic bases such as triethylamine or pyridine, and the starting material (SM-A') is added dropwise directly, or if it is a solid, it is diluted with the same solvent as the reaction solvent and added dropwise. To accelerate the reaction, 4-dimethylaminopyridine may also be added. The reaction temperature is preferably around 5°C to the boiling point of the solvent used. The reaction time is better in terms of yield if the reaction is monitored to completion by GC or TLC, but it is usually about 1 to 24 hours. The monomer (A') can be obtained from the reaction mixture using a conventional aqueous work-up. The obtained monomer (A') can be purified by conventional methods such as distillation, chromatography, and recrystallization, if necessary.

[0371] Furthermore, the aforementioned manufacturing method is only one example, and the manufacturing method of the monomer of the present invention is not limited thereto.

[0372] The structural features of the monomer of the present invention can be exemplified by acid-indestructible groups having hydroxyl or carboxyl bonds on the aromatic ring and polymerizable groups introduced by sulfonate or sulfonamide bonds. The acid-indestructible groups in the exposed portion undergo deprotection reactions due to acid, generating aromatic hydroxyl or aromatic carboxyl groups. For iodine atoms, especially in EUV lithography at a wavelength of 13.5 nm, the EUV absorption of iodine atoms is very large, so secondary electrons are generated from iodine atoms during exposure. Therefore, it is preferable that the aromatic ring in formula (A) has at least one iodine atom. That is, in formula (A), R... 1 It is an iodine atom and n2 is 1, 2, 3 or 4, and / or R. 2 It is preferable that the iodine atom is present and n3 is 1, 2, 3, or 4. Furthermore, polymerizable groups introduced by sulfonate or sulfonamide bonds, preferably having a styrene or vinylnaphthalene structure, are ideal. These polymerizable groups are more rigid than those of methacrylates, resulting in a higher glass transition temperature (Tg) for the polymer. Through the interaction of aromatic rings within or between polymers (π-π stacking effect), the polymer will arrange itself in a correct and regular manner, which is believed to provide resistance to pattern collapse during the formation of fine patterns. Sulfonate and sulfonamide bonds have high resistance to alkaline hydrolysis. In the case of positive resists using alkaline developers, the decomposition of unexposed areas is suppressed during development with an alkaline developer after pattern formation, thereby also suppressing pattern collapse. Patent Document 6 describes a monomer with an aromatic ester bond in a similar structure; however, aromatic esters are less resistant to hydrolysis than alkyl esters, and therefore are believed to cause partial hydrolysis and pattern collapse during alkaline development. Furthermore, in the etching step following the formation of the fine pattern, the aromatic rings directly bonded to the main chain exhibit excellent etching resistance. Due to these synergistic effects, when using the monomer of the present invention, it exhibits high dissolution contrast, excellent LWR for line patterns, CDU for hole patterns, resistance to pattern collapse, and strong etching resistance, making the monomer of the present invention suitable as a material for positive resist composition.

[0373] [polymer]

[0374] The polymer of the present invention contains repeating units (hereinafter also referred to as repeating unit A) derived from the monomer represented by formula (A). Repeating unit A is represented by the following formula (Aa).

[0375] [Chemistry 123]

[0376]

[0377] In the formula, n1~n5, R A X A X 1 R 1 R 2 and R AL As mentioned above.

[0378] In repeating unit A, the polymer may contain only one type of constituent unit or more than two types.

[0379] The aforementioned polymer may also contain repeating units represented by formula (a1) (hereinafter also referred to as repeating unit a1.), repeating units represented by formula (a2) (hereinafter also referred to as repeating unit a2.), or repeating units represented by formula (a3) ​​(hereinafter also referred to as repeating unit a3.).

[0380] [Chemistry 124]

[0381]

[0382] In equations (a1) and (a2), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0383] In equation (a1), X 1 It is a single bond, phenylene, naphthylene or -C(=O)-OX 11 - The phenylene or naphthylene group may also be replaced by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, a saturated hydrocarbon oxygen group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom. X 11 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms. The saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. It represents the atomic bonds between carbon atoms in the main chain and the main chain.

[0384] In equation (a2), X 2 For single bond, -C(=O)-O- or -C(=O)-N(H)-. Represents the atomic bonds between the carbon atoms in the main chain and the carbon atoms in the chain. R 11 The atom can be a halogen, cyano, hydroxyl, nitro, pentafluorothio, or a hydrocarbon group with 1-20 carbon atoms containing heteroatoms; a hydrocarbon oxygen group with 1-20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl group with 2-20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl oxygen group with 2-20 carbon atoms containing heteroatoms; or a hydrocarbon oxy carbonyl group with 2-20 carbon atoms containing heteroatoms. a2 can be 0, 1, 2, 3, or 4, preferably 0 or 1. a1 can be 0 or 1. When a1 is 0, it is a benzene ring; when a1 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with a1 of 0 is preferred. When a2 is 2, 3, or 4, each R... 11 They can be the same or different.

[0385] In equations (a1) and (a2), AL 1 and AL 2Each of these groups is an acid-indestructible group independently. Specific examples of the aforementioned acid-indestructible groups are, for example, those described in Japanese Patent Application Publication No. 2013-80033 and Japanese Patent Application Publication No. 2013-83821.

[0386] Generally speaking, specific examples of the aforementioned unstable acid groups can be represented by the formulas (AL-3) to (AL-5).

[0387] [Chemistry 125]

[0388]

[0389] In the formula, These are atomic bonds.

[0390] In equations (AL-3) and (AL-4), R L11 and R L12 Each hydrocarbon group is an independent hydrocarbon group with 1 to 40 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Hydrocarbon groups with 1 to 20 carbon atoms are preferred.

[0391] In formula (AL-3), a3 is an integer from 0 to 10, with 1, 2, 3, 4 or 5 being preferred.

[0392] In equation (AL-4), R L13 and R L14 Each group is independently composed of a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Furthermore, R... L12 R L13 and R L14 Any two of them can bond to each other and together with the carbon atoms they are bonded to, or carbon atoms and oxygen atoms, form a ring with 3 to 20 carbon atoms. The aforementioned rings with 4 to 16 carbon atoms are more ideal, especially alicyclic rings.

[0393] In equation (AL-5), R L15 R L16 and R L17 Each group is an independent hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Furthermore, R... L15 R L16 and R L17 Any two of them can bond to each other and together with the carbon atoms they are bonded to form a ring with 3 to 20 carbon atoms. The aforementioned rings with 4 to 16 carbon atoms are more ideal, especially alicyclic rings.

[0394] Other specific examples of the aforementioned acid-unstable groups can be found in paragraphs

[0064] to

[0068] of Japanese Patent Application Publication No. 2023-123222 and paragraphs

[0013] to

[0014] of Japanese Patent Publication No. 7492842. These methods use the formation of conjugated olefins or acrylate derivatives after acid desorption as the driving force for the reaction.

[0395] Specific examples of repeated unit a1 can be listed below, but are not limited to these. Also, in the following formula, R... A and AL 1 As mentioned above.

[0396] [Chemistry 126]

[0397]

[0398] [Chemistry 127]

[0399]

[0400] [Chemistry 128]

[0401]

[0402] [Chemistry 129]

[0403]

[0404] Specific examples of repeated unit a2 can be listed below, but are not limited to these. Also, in the following formula, R... A and AL 2 As mentioned above.

[0405] [Chemistry 130]

[0406]

[0407] [Chemistry 131]

[0408]

[0409] [Chemistry 132]

[0410]

[0411] [Chemistry 133]

[0412]

[0413] In formula (a3), b1 is 0 or 1. When b1 is 0, it is a benzene ring; when b1 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with b1 of 0 is preferred. b2 is 0, 1, 2, or 3 when b1 is 0, and 0, 1, 2, 3, 4, or 5 when b1 is 1. Considering the availability of raw materials, b2 of 0, 1, 2, or 3 is preferred, with 0, 1, or 2 being even better.

[0414] In equation (a3), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R A It is preferable to have a hydrogen atom or a methyl group, with a hydrogen atom being even better.

[0415] In equation (a3), X 3 For single bond, -C(=O)-O- or -C(=O)-N(H)-. This represents the atomic bonds between the carbon atoms in the main chain and the carbon atoms in the chain. Among these, single bonds, -C(=O)-O- is better, and a single bond is even more ideal.

[0416] In equation (a3), X 4 The group can be a single bond, an aliphatic alkylene group with 1 to 4 carbon atoms, a carbonyl group, a sulfonyl group, or a combination thereof. Among these, considering the raw materials, a single bond, a carbonyl group, or a sulfonyl group is preferred; considering the polar group formed after the reaction, a single bond or a carbonyl group is even better.

[0417] In equation (a3), X 5 and X 6 Each can be an oxygen atom or a sulfur atom independently. But X 4 and X 6 Bonded to adjacent carbon atoms on the aromatic ring. X 5 and X 6 They can be the same or different, taking into account the perspective of reactivity, X 5 and X 6 Both are better if they contain oxygen atoms.

[0418] In equation (a3), R 12 and R 13Each group consists of a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, decadecyl, heptadecyl, octadecyl, nonadecanyl, and icosyl; cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl; alkenyl groups with 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclohexenyl; aryl groups with 6 to 20 carbon atoms, such as phenyl and naphthyl; aralkyl groups with 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0419] Also, R 12 and R 13 They can also bond with each other and form rings together with the carbon atoms they are bonded to. Specific examples of rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0420] In equation (a3), R 14 It can be a halogen atom, hydroxyl group, cyano group, nitro group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxygen group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms or -N(R) group. 14A (R) 14B R 14A and R14B Each group is independently composed of a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. The aforementioned halogen atom is preferably a fluorine, chlorine, bromine, or iodine atom, with fluorine or iodine being more preferred. The hydrocarbon group, hydroxyl group, hydroxyl carbonyl group, and thiol group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given regarding R. 12 and R 13 The alkyl group represented is an example of the same. Furthermore, some or all of the hydrogen atoms in the aforementioned alkyl group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned alkyl group can be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, it may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. When b2 is 2 or more, each R... 14 They can be the same or different.

[0421] Furthermore, when b2 is 2 or more, multiple R 14 They can also bond with each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. Specific examples of rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, adamantane rings, etc. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc., and part of the -CH2- in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, etc. As a result, they may also contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0422] Specific examples of repeated unit a3 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned earlier, Me is methyl. Furthermore, the bonding positions of various substituents on the aromatic ring can also be interchanged.

[0423] [Chemistry 134]

[0424]

[0425] [Chemistry 135]

[0426]

[0427] [Chemistry 136]

[0428]

[0429] [Chemistry 137]

[0430]

[0431] [Chemistry 138]

[0432]

[0433] [Chemistry 139]

[0434]

[0435] [Chemistry 140]

[0436]

[0437] [Chemistry 141]

[0438]

[0439] [Chemistry 142]

[0440]

[0441] [Chemistry 143]

[0442]

[0443] [Chemistry 144]

[0444]

[0445] [Chemistry 145]

[0446]

[0447] [Chemistry 146]

[0448]

[0449] [Chemistry 147]

[0450]

[0451] [Chemistry 148]

[0452]

[0453] [Chemistry 149]

[0454]

[0455] [Chemistry 150]

[0456]

[0457] [Chemistry 151]

[0458]

[0459] [Chemistry 152]

[0460]

[0461] [Chemistry 153]

[0462]

[0463] [Chemistry 154]

[0464]

[0465] [Chemistry 155]

[0466]

[0467] [Chemistry 156]

[0468]

[0469] [Chemistry 157]

[0470]

[0471] [Chemistry 158]

[0472]

[0473] [Chemistry 159]

[0474]

[0475] [Chemistry 160]

[0476]

[0477] [Chemistry 161]

[0478]

[0479] [Chemistry 162]

[0480]

[0481] [Chemistry 163]

[0482]

[0483] [Chemistry 164]

[0484]

[0485] [Chemistry 165]

[0486]

[0487] [Chemistry 166]

[0488]

[0489] [Chemistry 167]

[0490]

[0491] [Chemistry 168]

[0492]

[0493] [Chemistry 169]

[0494]

[0495] [Chemistry 170]

[0496]

[0497] [Chemistry 171]

[0498]

[0499] [Chemistry 172]

[0500]

[0501] [Chemistry 173]

[0502]

[0503] [Chemistry 174]

[0504]

[0505] [Chemistry 175]

[0506]

[0507] [Chemistry 176]

[0508]

[0509] [Chemistry 177]

[0510]

[0511] [Chemistry 178]

[0512]

[0513] [Chemistry 179]

[0514]

[0515] [Chemistry 180]

[0516]

[0517] [Chemistry 181]

[0518]

[0519] [Chemistry 182]

[0520]

[0521] [Chemistry 183]

[0522]

[0523] The aforementioned polymer may also contain repeating units represented by the following formula (b1) (hereinafter also referred to as repeating unit b1).

[0524] [Chemistry 184]

[0525]

[0526] In equation (b1), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 For single bond, -C(=O)-O- or -C(=O)-N(H)-. Represents the atomic bonds between the carbon atoms in the main chain and the carbon atoms in the main chain. R 21 It can be a halogen atom, carboxyl group, nitro group, cyano group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; or it can be a hydrocarbon oxycarbonyl group with 2 to 20 carbon atoms containing heteroatoms. When c3 is 2, 3, or 4, each R 21 The elements can be the same or different. c1 can be 0, 1, or 2. When c1 is 0, it is a benzene ring; when c1 is 1, it is a naphthalene ring; and when c1 is 2, it is an anthracene ring. Considering solvent solubility, a benzene ring with c1 of 0 is preferred. c2 can be 1, 2, 3, or 4. c3 can be 0, 1, 2, 3, or 4. However, 1 ≤ c2 + c3 ≤ 5.

[0527] Specific examples of repeated unit b1 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above.

[0528] [Chemistry 185]

[0529]

[0530] [Chemistry 186]

[0531]

[0532] [Chemistry 187]

[0533]

[0534] [Chemistry 188]

[0535]

[0536] [Chemistry 189]

[0537]

[0538] Other specific examples of repeating unit b1 may be found in

[0180] to

[0182] of Patent Document 6, but are not limited to these.

[0539] The aforementioned base polymer may also contain repeating units represented by the following formula (b2) (hereinafter also referred to as repeating unit b2).

[0540] [Chemistry 190]

[0541]

[0542] In equation (b2), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 2 For single bonds, phenylene, naphthylene, -C(=O)-OY 21 -or -C(=O)-N(H)-Y 21 - The phenylene or naphthylene group may also be replaced by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group with 1 to 10 carbon atoms containing fluorine atoms, a saturated hydrocarbon oxygen group with 1 to 10 carbon atoms containing fluorine atoms, or a halogen atom. Y represents the atomic bond between the carbon atoms in the main chain and the main carbon atom. 21 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms. This saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. R 22 It is a hydrogen atom, or a group containing at least one of the following structures with 1 to 20 carbon atoms: hydroxyl group (other than phenolic hydroxyl group), cyano group, nitro group, carbonyl group, carboxyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulopentalide ring, lactam ring, sulopentalide ring, and carboxylic anhydride (-C(=O)-OC(=O)-).

[0543] Specific examples of repeated unit b2 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above.

[0544] [Chemistry 191]

[0545]

[0546] [Chemistry 192]

[0547]

[0548] [Chemistry 193]

[0549]

[0550] [Chemistry 194]

[0551]

[0552] [Chemistry 195]

[0553]

[0554] [Chemistry 196]

[0555]

[0556] [Chemistry 197]

[0557]

[0558] [Chemistry 198]

[0559]

[0560] [Chemistry 199]

[0561]

[0562] [Chem.200]

[0563]

[0564] [Chemical Engineering 201]

[0565]

[0566] [Chemical Engineering 202]

[0567]

[0568] [Chemical Engineering 203]

[0569]

[0570] [Chemical 204]

[0571]

[0572] [Chemical Engineering 205]

[0573]

[0574] [Chemical Engineering 206]

[0575]

[0576] [Chemical 207]

[0577]

[0578] [Chemical Engineering 208]

[0579]

[0580] [Chemical Engineering 209]

[0581]

[0582] [Chemical 210]

[0583]

[0584] The aforementioned polymer may also contain at least one repeating unit selected from the following formula (c1) (hereinafter also referred to as repeating unit c1.), repeating unit represented by the following formula (c2) (hereinafter also referred to as repeating unit c2.), repeating unit represented by the following formula (c3) (hereinafter also referred to as repeating unit c3.), repeating unit represented by the following formula (c4) (hereinafter also referred to as repeating unit c4.), and repeating unit represented by the following formula (c5) (hereinafter also referred to as repeating unit c5.).

[0585] [Chemistry 211]

[0586]

[0587] In equations (c1) to (c5), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It is a single bond or may have substituents. Z 2 For single bond, -C(=O)-OZ 21 -、 -C(=O)-N(H)-Z 21 -or -OZ 21 -. Z21 It is a divalent group obtained by aliphatic hydrocarbon groups, phenylene groups, or combinations thereof having 1 to 6 carbon atoms, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups. 3 It can be a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. 4 It is a single bond, or a divalent group obtained by aliphatic hydrocarbon groups, phenylene groups, or combinations thereof with 1 to 6 carbon atoms, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups. 5 Each can be a single bond, or a phenylene group with substituents, or a naphthylene group with substituents. -C(=O)-OZ 51 -or -C(=O)-N(R)-Z 51 -. Z 51 It is an aliphatic hydrocarbon group, phenylene, or naphthylene with 1 to 10 carbon atoms. The aliphatic hydrocarbon group may also contain a halogen atom, a hydroxyl group, an ether bond, an ester bond, or an lactone ring. R is a hydrogen atom, or may be a hydrocarbon group with 1 to 10 carbon atoms containing heteroatoms.

[0588] Z 6 It can be a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. 7 Each is an independent single bond. -Z 71 -C(=O)-O-、 -C(=O)-N(R)-Z 71 -or -OZ 71 -. Z 71 It can also contain a hydrocarbon group with 1 to 20 carbon atoms and a heteroatom. R is as described above. Z 8 Each is an independent single bond. -Z 81 -C(=O)-O-、 -C(=O)-N(R)-Z 81 -or -OZ 81 -. Z 81It can also contain a hydrocarbon group with 1 to 20 carbon atoms and a heteroatom. R is as described above. Z 9 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene -C(=O)-OZ 91 -、 -C(=O)-N(R)-Z 91 -or -OZ 91 -. Z 91 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group. R is as described above. It represents the atomic bonds between carbon atoms in the main chain and the main chain. Indicates and Z 1 Atomic bonds. Indicates and Z 6 Atomic bonds. Indicates and Z 7 Atomic bonds.

[0589] Z 21 Z 51 and Z 91 The aliphatic alkyl sub-groups can be linear, branched, or cyclic. Specific examples include alkyl diyl groups such as methane-diyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl, 1,1-dimethylethane-1,2-diyl, pentane-1,5-diyl, 2-methylbutane-1,2-diyl, and hexane-1,6-diyl; cycloalkyl diyl groups such as cyclopropane-diyl, cyclobutane-diyl, cyclopentane-diyl, and cyclohexane-diyl; and groups obtained by combining them.

[0590] Z 71 and Z 81 The subhydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples are listed below, but are not limited to these.

[0591] [Chemistry 212]

[0592]

[0593] In the formula, the dashed lines represent atomic bonds.

[0594] In equation (c1), R 31 and R 32 Each group can be an independent hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl; alkenyl groups with 2 to 20 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclohexenyl; aryl groups with 6 to 20 carbon atoms such as phenyl, naphthyl, and thiophene; aralkyl groups with 7 to 20 carbon atoms such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these, with aryl groups being preferred. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0595] Also, R 31 and R 32 They can also bond to each other and form rings together with the sulfur atoms they are bonded to. Specific examples of the aforementioned rings can be shown in the following formulas, etc.

[0596] [Chemistry 213]

[0597]

[0598] In the formula, the dashed line represents Z. 4 Atomic bonds.

[0599] Specific examples of the cations in repeating unit c1 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above.

[0600] [Chemistry 214]

[0601]

[0602] [Chemical 215]

[0603]

[0604] [Chemistry 216]

[0605]

[0606] [Chemistry 217]

[0607]

[0608] [Chemistry 218]

[0609]

[0610] [Chemistry 219]

[0611]

[0612] [Chem.220]

[0613]

[0614] [Chemistry 221]

[0615]

[0616] [Chemistry 222]

[0617]

[0618] [Chemistry 223]

[0619]

[0620] In equation (c1), M - These are non-nucleophilic relative ions. Preferred non-nucleophilic relative ions are halide ions, sulfonic acid anions, imide acid anions, and methylated acid anions. Specific examples of halide ions include chloride ions and bromide ions. Specific examples of sulfonic acid anions (sulfonate ions) include trifluoromethanesulfonate ions, 1,1,1-trifluoroethanesulfonate ions, nonafluorobutanesulfonate ions, and other fluoroalkyl sulfonate ions; toluenesulfonate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, 1,2,3,4,5-pentafluorobenzenesulfonate ions, and other aryl sulfonate ions; methanesulfonate ions, butanesulfonate ions, and other alkyl sulfonate ions. Specific examples of imide acid anions (imide ions) include bis(trifluoromethylsulfonyl)imide ions, bis(perfluoroethylsulfonyl)imide ions, and bis(perfluorobutylsulfonyl)imide ions. Specific examples of the aforementioned methylated acid anions (methylated ions) include tris(trifluoromethylsulfonyl) methylated ions and tris(perfluoroethylsulfonyl) methylated ions.

[0621] Other examples of the aforementioned non-nucleophilic relative ions can be exemplified by anions represented by any of the following formulas (c1-1) to (c1-4).

[0622] [Chemistry 224]

[0623]

[0624] In equation (c1-1), R fa It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain fluorine atoms or heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given by R in the following formula (c1-1-1). fa1 The alkyl group represented is an example of the same. Furthermore, some or all of the hydrogen atoms in the aforementioned alkyl group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned alkyl group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentatone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0625] The anion represented by formula (c1-1) is preferably represented by the following formula (c1-1-1).

[0626] [Chemistry 225]

[0627]

[0628] In equation (c1-1-1), Q 1 and Q 2 Each atom is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. To improve solvent solubility, at least one atom is preferably trifluoromethyl. m can be 0, 1, 2, 3, or 4, with 1 being particularly preferred. R fa1 Hydrocarbon groups with 1 to 40 carbon atoms that can also contain heteroatoms are preferred. Ideal heteroatoms include oxygen, nitrogen, sulfur, and halogen atoms, with oxygen atoms being even more desirable. From the viewpoint of achieving high resolution in the formation of fine patterns, hydrocarbon groups with 6 to 30 carbon atoms are particularly advantageous.

[0629] In formula (Xa-1-1), R fa1The hydrocarbon groups representing 1 to 40 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 40 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecanyl, and icosyl; and cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms such as cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornel, norbornelmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl. Hydrocarbon groups; unsaturated aliphatic hydrocarbon groups with 2 to 40 carbons such as 2-propenyl and 3-cyclohexenyl; aryl groups with 6 to 40 carbons such as phenyl, 1-naphthyl, 2-naphthyl, and 9-fluorenyl; aralkyl groups with 7 to 40 carbons such as benzyl and diphenylmethyl; polycyclic hydrocarbon groups containing aromatic rings with 7 to 40 carbons such as 9,10-ethbridged-9,10-dihydroanthrayl and 6,13-ethbridged-6,13-dihydropentacycloenyl; hydrocarbon groups with 17 to 40 carbons having a steroid skeleton; and groups obtained by combining them.

[0630] Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, it may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Specific examples of hydrocarbon groups containing heteroatoms include tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidemethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, 3-oxocyclohexyl, etc.

[0631] In equation (c1-1-1), L a1 The bonds can be single bonds, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, or carbamate bonds. From a synthetic point of view, ether bonds or ester bonds are preferred, with ester bonds being more ideal.

[0632] Specific examples of anions represented by equation (c1-1) can be listed below, but are not limited to these. Furthermore, in the following equation, Q... 1 As mentioned above, Ac represents the acetyl group.

[0633] [Chemistry 226]

[0634]

[0635] [Chemistry 227]

[0636]

[0637] [Chemistry 228]

[0638]

[0639] [Chemistry 229]

[0640]

[0641] [Chemistry 230]

[0642]

[0643] [Chemistry 231]

[0644]

[0645] [Chemistry 232]

[0646]

[0647] [Chemistry 233]

[0648]

[0649] [Chemistry 234]

[0650]

[0651] [Chemistry 235]

[0652]

[0653] [Chemistry 236]

[0654]

[0655] [Chemistry 237]

[0656]

[0657] [Chemistry 238]

[0658]

[0659] Other specific examples of anions represented by formula (c1-1) can be found in paragraphs

[0042] to

[0049] of Japanese Patent Application Publication No. 2025-23601, paragraphs

[0015] to

[0017] of Japanese Patent Application Publication No. 2021-70692, paragraphs

[0145] and

[0148] of Japanese Patent Publication No. 7091762, paragraphs

[0022] to

[0023] of Japanese Patent Publication No. 7628783, and paragraph

[0224] of Japanese Patent Publication No. 7109178.

[0660] In equation (c1-2), R fb1 and R fb2 Each group consists of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given by R in formula (c1-1-1). fa1 The hydrocarbon group represented is an example of the same. R fb1 and R fb2 Preferably, it is a straight-chain fluorinated alkyl group having fluorine atoms or 1 to 4 carbon atoms. Also, R fb1 and R fb2 They can also bond to each other and to the groups they are bonded to (-CF2-SO2-N). - -SO2-CF2-) together form a ring, in which case R fb1 and R fb2 The groups obtained by mutual bonding are preferably fluorinated ethylidene or fluorinated propylene.

[0661] In equation (c1-3), R fc1 R fc2 and R fc3 Each group consists of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given by R in formula (c1-1-1). fa1 The hydrocarbon group represented is an example of the same. R fc1 R fc2 and R fc3 Preferably, it is a straight-chain fluorinated alkyl group having fluorine atoms or 1 to 4 carbon atoms. Also, R fc1 and R fc2 They can also bond to each other and to the groups they are bonded to (-CF2-SO2-C). - -SO2-CF2-) together form a ring, in which case R fc1 and R fc2 The groups obtained by mutual bonding are preferably fluorinated ethylidene or fluorinated propylene.

[0662] In equation (c1-4), R fdIt can also be a hydrocarbon group with 1 to 40 carbon atoms containing heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given by R in formula (c1-1-1). fa1 The alkyl group represented is an example of the same. Furthermore, some or all of the hydrogen atoms in the aforementioned alkyl group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned alkyl group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentatone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0663] Specific examples of anions represented by formula (c1-4) are listed below, but are not limited to these.

[0664] [Chemistry 239]

[0665]

[0666] [Chemistry 240]

[0667]

[0668] [Chemistry 241]

[0669]

[0670] Other specific examples of anions represented by formula (c1-4) can be found in paragraphs

[0050] to

[0058] of Japanese Patent Application Publication No. 2025-23601.

[0671] The aforementioned examples of non-nucleophilic relative ions can be further illustrated by anions having aromatic rings substituted with iodine or bromine atoms. Specific examples of such anions can be exemplified by those represented by the following formula (c1-5).

[0672] [Chemistry 242]

[0673]

[0674] In equation (c1-5), x is 1, 2, or 3. y is 1, 2, 3, 4, or 5. z is 0, 1, 2, or 3. However, 1 ≤ y + z ≤ 5. y being 1, 2, or 3 is ideal, with 2 or 3 being even more ideal. z being 0, 1, or 2 is preferable.

[0675] In equation (c1-5), X BI It is an iodine atom or a bromine atom. When x and / or y are 2 or more, each X BI They can be the same or different.

[0676] In equation (c1-5), L 11 It can be a single bond, ether bond, ester bond, sulfonate bond, carbonate bond, carbamate bond, or a saturated hydrocarbon group with 1 to 6 carbon atoms. Part of the -CH2- of the hydrocarbon group may also be replaced by an ether bond or ester bond. The aforementioned saturated hydrocarbon group can be linear, branched, or cyclic.

[0677] In equation (c1-5), L 12 When x is 1, it is a single bond or a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms. When x is 2 or 3, it is a (x+1) valence hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms.

[0678] L 12 The alkylene groups representing 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl diyl groups with 1 to 20 carbon atoms, such as methane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl; cyclopentane diyl, cyclohexane diyl, norcamphene diyl, adamantane diyl, and tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3-20 carbon atoms, such as decanediyl; unsaturated aliphatic hydrocarbon groups with 2-20 carbon atoms, such as vinylene and propene-1,3-diyl; aryl groups with 6-20 carbon atoms, such as phenylene, naphthylene, and anthracenediyl; aromatic rings with 7-20 carbon atoms containing polycyclic hydrocarbon groups, such as 9,10-ethbridged-9,10-dihydroanthracenediyl and 6,13-ethbridged-6,13-dihydropentaphenyl; and groups obtained by combining these.] 12 The (x+1) valence hydrocarbon group representing 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be obtained by removing one or two hydrogen atoms from the aforementioned hydrocarbon groups representing 1 to 20 carbon atoms.

[0679] Furthermore, some or all of the hydrogen atoms of the aforementioned alkylene group and (x+1) valence hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group of the aforementioned alkylene group and (x+1) valence hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0680] In equation (c1-5), L 13 It can be a single bond, ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond.

[0681] In equation (c1-5), R fe It can be a hydroxyl group, carboxyl group, fluorine atom, chlorine atom, bromine atom, amino group, hydrocarbon group with 1 to 20 carbon atoms, hydrocarbon oxygen group with 1 to 20 carbon atoms, hydrocarbon thioyl group with 1 to 20 carbon atoms, hydrocarbon carbonyl group with 2 to 20 carbon atoms, hydrocarbon carbonyl group with 2 to 20 carbon atoms, or hydrocarbon sulfonyl group with 1 to 20 carbon atoms, -N(R feA (R) feB ), -N(R feC )-C(=O)-R feD or -N(R) feC )-C(=O)-OR feD The hydrocarbon group, hydrocarbon oxy group, hydrocarbon thio group, hydrocarbon carbonyl group, hydrocarbon oxycarbonyl group, hydrocarbon carbonyloxy group, and hydrocarbon sulfonyloxy group may also contain at least one selected from fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, amino group, ester bond, and ether bond. feA and R feB Each is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. R feC It is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms. R feD It can be an aliphatic hydrocarbon group with 1-16 carbon atoms, an aryl group with 6-12 carbon atoms, or an aralkyl group with 7-15 carbon atoms. It may also contain a halogen atom, a hydroxyl group, a saturated alkyloxy group with 1-6 carbon atoms, a saturated alkylcarbonyl group with 2-6 carbon atoms, or a saturated alkylcarbonyloxy group with 2-6 carbon atoms. The aforementioned aliphatic hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned hydrocarbon group, alkyloxy group, alkylcarbonyl group, alkyloxycarbonyl group, alkylcarbonyloxy group, and alkylsulfonyloxy group can be any of linear, branched, or cyclic. When x and / or z are 2 or more, each R... fe They can be the same or different.

[0682] Among these, R fe Hydroxyl group, -N(R) feC )-C(=O)-R feD -N(R) feC )-C(=O)-OR feD Fluorine atoms, chlorine atoms, bromine atoms, methyl groups, and methoxy groups are preferred.

[0683] In equation (c1-5), Rf 11 ~Rf 14 Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of these must be a fluorine atom or a trifluoromethyl group. Also, Rf 11With Rf 12 They can also combine to form carbonyl groups. Especially Rf 13 and Rf 14 Both are preferred if they contain fluorine atoms.

[0684] Specific examples of anions represented by equation (c1-5) are listed below, but are not limited to these. Furthermore, in the following equation, X... BI As mentioned above.

[0685] [Chemistry 243]

[0686]

[0687] [Chemistry 244]

[0688]

[0689] [Chemistry 245]

[0690]

[0691] [Chemistry 246]

[0692]

[0693] [Chemistry 247]

[0694]

[0695] [Chemistry 248]

[0696]

[0697] [Chemistry 249]

[0698]

[0699] [Chemistry 250]

[0700]

[0701] [Chemistry 251]

[0702]

[0703] [Chemistry 252]

[0704]

[0705] [Chemistry 253]

[0706]

[0707] [Chemistry 254]

[0708]

[0709] [Chemistry 255]

[0710]

[0711] [Chemistry 256]

[0712]

[0713] [Chemistry 257]

[0714]

[0715] [Chemistry 258]

[0716]

[0717] [Chemistry 259]

[0718]

[0719] [Chemistry 260]

[0720]

[0721] [Chemistry 261]

[0722]

[0723] [Chemistry 262]

[0724]

[0725] [Chemistry 263]

[0726]

[0727] [Chemistry 264]

[0728]

[0729] [Chemistry 265]

[0730]

[0731] [Chemistry 266]

[0732]

[0733] M -Other examples of anions represented include paragraphs

[0076] and

[0106] of International Publication No. 2023 / 157455, paragraphs

[0111] of International Publication No. 2024 / 24801, paragraphs

[0253] to

[0256] of International Publication No. 2024 / 43121, paragraphs

[0044] to

[0045] of International Publication No. 2024 / 57751, paragraphs

[0205] to

[0220] of International Publication No. 2024 / 122423, paragraphs

[0170] to

[0178] of Japanese Patent Application Publication No. 2023-123183, paragraphs

[0026] to

[0028] of Japanese Patent Application Publication No. 2024-62406, and Japanese Patent Application Publication No. 2 Paragraphs

[0022] to

[0025] of Japanese Patent Application Publication No. 024-62407,

[0026] to

[0028] of Japanese Patent Application Publication No. 2024-62408,

[0028] to

[0030] of Japanese Patent Application Publication No. 2024-68156,

[0026] to

[0028] of Japanese Patent Application Publication No. 2024-68157,

[0028] to

[0030] of Japanese Patent Application Publication No. 2024-68158,

[0028] to

[0030] of Japanese Patent Application Publication No. 2024-68159,

[0031] to

[0033] of Japanese Patent Application Publication No. 2024-72280, and

[0034] of Japanese Patent Application Publication No. 2024-72281. Paragraphs

[0023] ~

[0025] , paragraphs

[0026] ~

[0029] of Japanese Patent Application Publication No. 2024-77618, paragraphs

[0020] ~

[0021] of Japanese Patent Application Publication No. 2024-77619, paragraphs

[0140] ~

[0143] of Japanese Patent Application Publication No. 2024-80672, paragraphs

[0023] ~

[0025] of Japanese Patent Application Publication No. 2024-83304, paragraphs

[0028] ~

[0031] of Japanese Patent Application Publication No. 2024-99500, paragraphs

[0030] ~

[0033] of Japanese Patent Application Publication No. 2024-99502, paragraphs

[0028] ~

[0029] of Japanese Patent Application Publication No. 2024-99502.

[030] , Paragraphs from Japanese Patent Application Publication No. 2024-101557

[0030] ~

[0032] , Paragraphs from Japanese Patent Application Publication No. 2024-102842

[0025] ~

[0027] , Paragraphs from Japanese Patent Application Publication No. 2024-102843

[0033] ~

[0035] , Paragraphs from Japanese Patent Application Publication No. 2024-127832

[0021] ~

[0022] , Paragraphs from Japanese Patent Application Publication No. 2024-144354

[0169] ~

[0172] , Paragraphs from Japanese Patent Application Publication No. 2024-144356

[0178] ~

[0181] , Paragraphs from Japanese Patent Application Publication No. 2024-160436

[0040] ~

[0143] ,The authors of paragraphs

[0030] to

[0031] of Japanese Patent Application Publication No. 2025-705, paragraphs

[0157] to

[0158] of Japanese Patent Publication No. 7247732, paragraphs

[0227] to

[0238] of Japanese Patent Publication No. 7446352, paragraphs

[0253] to

[0256] of Japanese Patent Publication No. 7466597, and paragraphs

[0309] to

[0312] of Japanese Patent Publication No. 7466782, etc.

[0734] Other examples of the aforementioned non-nucleophilic relative ions include paragraphs

[0186] to

[0188] of Japanese Patent No. 7398551, paragraphs

[0028] to

[0029] of Japanese Patent No. 7067271, paragraphs

[0220] to

[0225] of Japanese Patent No. 7032549, paragraphs

[0040] to

[0045] of Japanese Patent No. 6645464, paragraphs

[0027] to

[0029] of Japanese Patent No. 6248882, and Japanese Patent No. 60 The fluorine-free aromatic sulfonic acid anions and alkyl sulfonic acid anions described in paragraphs

[0034] to

[0037] of Japanese Patent Application Publication No. 90585, paragraphs

[0037] to

[0060] of Japanese Patent Application Publication No. 2024-104830, paragraphs

[0033] to

[0093] of Japanese Patent Application Publication No. 2024-140135, paragraphs

[0039] to

[0066] of Japanese Patent Application Publication No. 2023-177038, and paragraphs

[0100] to

[0102] of Japanese Patent Application Publication No. 2006-276759. Alternatively, examples can be found in paragraphs

[0029] to

[0034] of Japanese Patent No. 6648726, paragraphs

[0264] to

[0267] of Japanese Patent Application Publication No. 2024-077330, and paragraphs

[0040] to

[0071] of Japanese Patent Application Publication No. 2025-000201.

[0735] The aforementioned non-nucleophilic relative ions may further include the anions of disulfonic acid as described in Japanese Patent Application Publication No. 2015-206932, the anions of sulfonamides and sulfonamides as described in International Publication No. 2020 / 158366, which are sulfonic acid on one side and different from sulfonamides or sulfonamides on the other side, and the anions of sulfonic acid and carboxylic acid as described in Japanese Patent Application Publication No. 2015-24989.

[0736] In equations (c2) and (c3), d1 and d2 are each independently 0, 1, 2 or 3, with 1 being preferred.

[0737] In equation (c4), e1 is 0 or 1. e2 is 0, 1, 2, 3 or 4. e3 is 0, 1, 2, 3 or 4. However, when e1 is 0, it is 0 ≤ e2 + e3 ≤ 4, and when e1 is 1, it is 0 ≤ e2 + e3 ≤ 6.

[0738] In equations (c2), (c3) and (c4), L 1 The bonds can be single bonds, ether bonds, ester bonds, carbonyl groups, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. Among these, from a synthetic point of view, ether bonds, ester bonds, and carbonyl groups are more ideal, with ester bonds and carbonyl groups being even more ideal.

[0739] In equation (c2), Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among these, Rf... 1 and Rf 2 In order to increase the acid strength, fluorine atoms are preferred. Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among these, Rf is used to improve solvent solubility. 3 and Rf 4 At least one of them is preferably trifluoromethyl.

[0740] In equation (c3), Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. However, all Rf... 5 and Rf 6 They are not all hydrogen atoms at the same time. Among these, in order to improve solvent solubility, Rf... 5 and Rf 6 At least one of them is preferably trifluoromethyl.

[0741] In equation (c4), Rf 7 It is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated alkyl thio group having 1 to 6 carbon atoms. Rf 7 The most desirable components are fluorine atoms, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, or difluoromethylthio, with fluorine atoms, trifluoromethyl, or trifluoromethoxy being even more desirable. When e2 is 2, 3, or 4, each Rf... 7 They can be the same or different.

[0742] In equation (c4), R 33 It can be a halogen atom other than fluorine, or a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given and described in the explanation of formula (A) regarding R. 1and R 2 The examples representing hydrocarbon groups are the same, but not limited to these. Also, when e3 is 2, 3, or 4, each R... 33 They can be the same or different.

[0743] Furthermore, when e3 is 2, 3, or 4, multiple R... 33 They can also bond with each other and form rings together with the carbon atoms they are bonded to. Specific examples of rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0744] Specific examples of the anion in repeating unit c2 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above, Me is a methyl group.

[0745] [Chemistry 267]

[0746]

[0747] [Chemistry 268]

[0748]

[0749] [Chemistry 269]

[0750]

[0751] [Chemistry 270]

[0752]

[0753] [Chemistry 271]

[0754]

[0755] [Chemistry 272]

[0756]

[0757] [Chemistry 273]

[0758]

[0759] [Chemistry 274]

[0760]

[0761] [Chemistry 275]

[0762]

[0763] [Chemistry 276]

[0764]

[0765] [Chemistry 277]

[0766]

[0767] [Chemistry 278]

[0768]

[0769] [Chemistry 279]

[0770]

[0771] Other specific examples of the repeating unit c2 include paragraphs

[0043] ~

[0044] of International Publication No. 2024 / 176672, paragraphs

[0067] ~

[0070] of International Publication No. 2024 / 176701, paragraphs

[0057] ~

[0058] of International Publication No. 2024 / 190386, paragraphs

[0020] ~

[0023] of Japanese Patent Application Publication No. 2024-103465, and Japanese Patent Application Publication No. 2024-12 Paragraphs

[0067] to

[0070] of Japanese Patent No. 0703, paragraphs

[0075] to

[0084] of Japanese Patent No. 7520258, paragraphs

[0032] to

[0047] of Japanese Unexamined Patent Application No. 2024-043941, paragraphs

[0385] to

[0390] of Japanese Unexamined Patent Application No. 2025-013053, and paragraphs

[0062] to

[0064] of International Publication No. 2025 / 018169, etc.

[0772] Specific examples of the anion of repeating unit c3 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above.

[0773] [Chemistry 280]

[0774]

[0775] [Chemistry 281]

[0776]

[0777] [Chemistry 282]

[0778]

[0779] [Chemistry 283]

[0780]

[0781] [Chemistry 284]

[0782]

[0783] [Chemistry 285]

[0784]

[0785] [Chemistry 286]

[0786]

[0787] [Chemistry 287]

[0788]

[0789] [Chemistry 288]

[0790]

[0791] [Chemistry 289]

[0792]

[0793] [Chemistry 290]

[0794]

[0795] Specific examples of the anion in repeating unit c4 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above.

[0796] [Chemistry 291]

[0797]

[0798] [Chemistry 292]

[0799]

[0800] [Chemistry 293]

[0801]

[0802] [Chemistry 294]

[0803]

[0804] [Chemistry 295]

[0805]

[0806] [Chemistry 296]

[0807]

[0808] [Chemistry 297]

[0809]

[0810] [Chemistry 298]

[0811]

[0812] [Chemistry 299]

[0813]

[0814] [Chemical 300]

[0815]

[0816] [Chemical Engineering 301]

[0817]

[0818] [Chemical 302]

[0819]

[0820] [Chemical 303]

[0821]

[0822] [Chemical 304]

[0823]

[0824] [Chemical 305]

[0825]

[0826] [Chemical 306]

[0827]

[0828] [Chemical 307]

[0829]

[0830] Other specific examples of the anion of repeating unit c4 can be found in paragraphs

[0023] to

[0026] of Japanese Patent Application Publication No. 2024-103464 and paragraphs

[0419] to

[0420] of Japanese Patent Application Publication No. 2024-120702.

[0831] Specific examples of the anion in repeating unit c5 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above.

[0832] [Chemical 308]

[0833]

[0834] In equations (c2) to (c5), A + The cation is a sulfonium cation. Examples of sulfonium cations include sulfonium cations, monium cations, and ammonium cations, with sulfonium cations and monium cations being preferred. Specific examples of the sulfonium cations mentioned above include paragraphs

[0102] to

[0125] of Japanese Patent Application Publication No. 2024-3744, paragraphs

[0044] to

[0049] of International Publication No. 2024 / 128017, and paragraphs

[0035] to

[0046] of Japanese Patent Publication No. 7491173, but are not limited to these.

[0835] Furthermore, the aforementioned sulfonium cation represented by the formula (sulfo-1) is also ideal.

[0836] [Chemical 309]

[0837]

[0838] In formula (sulfo-1), f1 is 0 or 1. When f1 is 0, it is a benzene ring; when f1 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with f1 of 0 is preferred. f2 is 0 or 1. When f2 is 0, it is a benzene ring; when f2 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with f1 of 0 is preferred. f3 is 0 or 1. When f3 is 0, it is a benzene ring; when f3 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with f3 of 0 is preferred.

[0839] In formula (sulfo-1), f4 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the better the absorption, especially for EUV, but the less solvent-soluble it becomes, raising concerns about precipitation in the resist composition. Therefore, f4 is preferred to be 0, 1, 2, or 3, with 0, 1, or 2 being even better.

[0840] In formula (sulfo-1), f5 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, f5 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred. f6 is 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, f6 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred. f7 is 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, f7 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred.

[0841] In formula (sulfo-1), f8 is 0, 1, or 2. Considering the availability of raw materials, f8 being 0 or 1 is preferred. f9 is 0, 1, or 2. Considering the availability of raw materials, f9 being 0 or 1 is preferred. f10 is 0, 1, or 2. Considering the availability of raw materials, f10 being 0 or 1 is preferred.

[0842] In formula (sulfo-1), f11 is 0 or 1. When f11 is 0, it is a benzene ring; when f11 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with f11 of 0 is preferred.

[0843] In formula (sulfo-1), f12 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the better the absorption, especially for EUV, but the less solvent-soluble it becomes, raising concerns about precipitation in the resist composition. F12 of 0, 1, 2, or 3 is preferred, with 0, 1, or 2 being even better.

[0844] In formula (sulfo-1), f13 is 0, 1, or 2. From the perspective of raw material availability, f13 being 0 or 1 is preferred. f14 is 0, 1, or 2. From a synthetic perspective, f14 being 0 or 1 is preferred.

[0845] However, when f1 is 0, 0 ≤ f6 + f9 ≤ 4; when f1 is 1, 0 ≤ f6 + f9 ≤ 6. When f2 is 0, 0 ≤ f7 + f10 ≤ 4; when f2 is 1, 0 ≤ f7 + f10 ≤ 6. When f3 is 0, 1 ≤ f4 + f5 + f8 + f14 ≤ 4; when f3 is 1, 1 ≤ f4 + f5 + f8 + f14 ≤ 6. When f11 is 0, 0 ≤ f12 + f13 ≤ 4; when f11 is 1, 0 ≤ f12 + f13 ≤ 6. Also, f4 + f12 ≥ 1.

[0846] In formula (sulfo-1), R F1 ~R F3 Each of these can be independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms. Among these, trifluoromethyl, trifluoromethoxy, and trifluorothiomethoxy are preferred. When f5 is 2, 3, or 4, each R... F1 They can be the same or different. When f6 is 2, 3, 4, 5 or 6, each R F2 They can be the same or different. When f7 is 2, 3, 4, 5 or 6, each R F3 They can be the same or different.

[0847] In formula (sulfo-1), R ct1 ~R ct4The radical can be a halogen atom other than iodine or fluorine, a nitro group, a cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. The hydrocarbon group, hydrocarbon oxy group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given and explained in the description of formula (A) regarding R. 1 and R 2 The examples of the hydrocarbon groups are the same. Furthermore, some or all of the hydrogen atoms in the hydrocarbon group, hydrocarbon oxygen group, and hydrocarbon sulfide group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0848] Also, when f8 is 2, there are 2 Rs. ct1 They can be the same or different, 2 Rs ct1 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When f9 is 2, there are 2 R atoms. ct2 They can be the same or different, 2 Rs ct2 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When f10 is 2, there are 2 R atoms. ct3 They can be the same or different, 2 Rs ct3 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When f13 is 2, there are 2 R atoms. ct4 They can be the same or different, 2 Rs ct4 They can also bond with each other and form rings together with the carbon atoms they are bonded to. Specific examples of rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0849] Furthermore, the sum of S in the sulfonium cation represented by formula (sulfo-1) + Directly bonded aromatic rings can also bond to each other and with S +Together they form a ring. Specific examples of the aforementioned ring structure can be represented by the following formulas, etc.

[0850] [Chemical 310]

[0851]

[0852] In the formula, the dashed lines represent atomic bonds.

[0853] In formula (sulfo-1), L B and L C Each bond can be independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. Among these, L... B Single bonds, ether bonds, ester bonds, or sulfonate bonds are preferred, with ester bonds or sulfonate bonds being even more preferred. L C Single bonds, ether bonds, or ester bonds are preferred, with single bonds being even better.

[0854] In formula (sulfo-1), X L It is a single bond, or may contain heteroatoms, of 1 to 40 carbon atoms. The aforementioned alkylene groups can be linear, branched, or cyclic; specific examples include alkyldiyl, cyclic saturated alkylene groups, and arylene groups. Specific examples of the aforementioned heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0855] X L Examples of hydrocarbon groups containing 1 to 40 carbon atoms that can also represent heteroatoms are listed below, but are not limited to these. Furthermore, in the following formula, Each for L B and L C Atomic bonds.

[0856] [Chemistry 311]

[0857]

[0858] [Chemistry 312]

[0859]

[0860] [Chemistry 313]

[0861]

[0862] [Chemical 314]

[0863]

[0864] Among these, X L -0~X L -22, X L -29~X L -34 and X L-47~X L -61 is better.

[0865] The sulfonium cation represented by formula (sulfo-1) is preferably represented by formula (sulfo-1-1).

[0866] [Chemical 315]

[0867]

[0868] In the formula, f4~f10, f12~f14, R F1 ~R F3 R ct1 ~R ct4 L B L C and X L As mentioned above.

[0869] The sulfonium cation represented by formula (sulfo-1-1) is preferably represented by formula (sulfo-1-2).

[0870] [Chemistry 316]

[0871]

[0872] In the formula, f4~f10, R F1 ~R F3 and R ct1 ~R ct3 As mentioned above.

[0873] Specific examples of sulfonium cations represented by formula (sulfo-1) are listed below, but are not limited to these. Also, in the following formula, Me is a methyl group.

[0874] [Chemistry 317]

[0875]

[0876] [Chemistry 318]

[0877]

[0878] [Chemistry 319]

[0879]

[0880] [Chem.320]

[0881]

[0882] [Chemistry 321]

[0883]

[0884] [Chemistry 322]

[0885]

[0886] [Chemistry 323]

[0887]

[0888] [Chemistry 324]

[0889]

[0890] [Chemistry 325]

[0891]

[0892] [Chemistry 326]

[0893]

[0894] [Chemistry 327]

[0895]

[0896] [Chemistry 328]

[0897]

[0898] [Chemistry 329]

[0899]

[0900] [Chemistry 330]

[0901]

[0902] [Chemistry 331]

[0903]

[0904] [Chemistry 332]

[0905]

[0906] [Chemistry 333]

[0907]

[0908] [Chemistry 334]

[0909]

[0910] [Chemistry 335]

[0911]

[0912] [Chemistry 336]

[0913]

[0914] [Chemistry 337]

[0915]

[0916] [Chemistry 338]

[0917]

[0918] [Chemistry 339]

[0919]

[0920] [Transformation 340]

[0921]

[0922] [Chemistry 341]

[0923]

[0924] [Chemistry 342]

[0925]

[0926] [Chemistry 343]

[0927]

[0928] [Chemistry 344]

[0929]

[0930] Specific examples of the aforementioned citric acid can be found in paragraph

[0181] of Japanese Patent Application Publication No. 2024-259, but are not limited to these.

[0931] Specific examples of the aforementioned ammonium cations can be represented by the following formula (am-1).

[0932] [Chemistry 345]

[0933]

[0934] In equation (am-1), R ct5 ~R ct8 Each can independently be a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R ct5 and R ct6 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to. Specific examples of the aforementioned hydrocarbon groups can be given and explained in the description of formula (A) regarding R. 1 and R 2The hydrocarbon group shown is an example of the same.

[0935] Specific examples of ammonium cations represented by formula (am-1) are listed below, but are not limited to these.

[0936] [Chemistry 346]

[0937]

[0938] The specific structures of repeating units c1 to c5 can be any combination of the aforementioned anions and cations.

[0939] Among the repeating units c1 to c5, considering the acid diffusion control, repeating units c2 to c5 are more ideal; considering the acid strength of the produced acid, repeating units c2, c4, and c5 are better; and considering the solvent solubility, repeating unit c2 is more ideal.

[0940] The aforementioned polymer may also contain repeating units (hereinafter also referred to as repeating units d) with hydroxyl groups protected by acid-indestructible groups. Repeating units d are not particularly limited as long as they have one or more hydroxyl groups protected and the protecting groups decompose and generate hydroxyl groups due to acid action, but those represented by the following formula (d1) are preferred.

[0941] [Chemistry 347]

[0942]

[0943] In equation (d1), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 41 It can also contain a (g+1) valence hydrocarbon group with 1 to 30 carbon atoms and a heteroatom. R 42 It is an acid-labile group. g can be 1, 2, 3, or 4.

[0944] In equation (d1), R 42 The acid-unstable group can be any group that deprotects and forms a hydroxyl group due to acid action. R 42 The structure is not particularly limited, but acetal, ketal, hydrocarbon carbonyl, or hydrocarbon oxymethyl represented by formula (d2) are preferred, especially hydrocarbon oxymethyl represented by formula (d2).

[0945] [Chemistry 348]

[0946]

[0947] In the formula, Represents an atomic bond. R 43 It is a hydrocarbon group with 1 to 15 carbon atoms.

[0948] R 42Specific examples of the acid-labile group represented by , the hydrocarbonoxymethyl group represented by formula (d2), and the repeating unit d include the same examples as those exemplified in the description of the repeating unit d described in Japanese Patent Laid-Open No. 2020-111564.

[0949] The aforementioned polymer may further contain a repeating unit e derived from indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, norbornadiene, or derivatives thereof. Specific examples of the monomer that provides the repeating unit e include, but are not limited to, the following.

[0950] [Chem. 349]

[0951]

[0952] The aforementioned polymer may further contain a repeating unit f derived from indane, vinylpyridine or vinylcarbazole.

[0953] In the aforementioned polymer, the content ratios of the repeating units A, a1, a2, a3, b1, b2, c1 to c5, d, e and f are preferably 0 < A ≤ 0.8, 0 ≤ a1 ≤ 0.5, 0 ≤ a2 ≤ 0.5, 0 ≤ a3 ≤ 0.5, 0 ≤ b1 ≤ 0.6, 0 ≤ b2 ≤ 0.6, 0 ≤ c1 ≤ 0.4, 0 ≤ c2 ≤ 0.4, 0 ≤ c3 ≤ 0.4, 0 ≤ c4 ≤ 0.4, 0 ≤ c5 ≤ 0.4, 0 ≤ d ≤ 0.5, 0 ≤ e ≤ 0.3 and 0 ≤ f ≤ 0.3, more preferably 0 < A ≤ 0.7, 0 ≤ a1 ≤ 0.4, 0 ≤ a2 ≤ 0.4, 0 ≤ a3 ≤ 0.4, 0 ≤ b1 ≤ 0.5, 0 ≤ b2 ≤ 0.5, 0 ≤ c1 ≤ 0.3, 0 ≤ c2 ≤ 0.3, 0 ≤ c3 ≤ 0.3, 0 ≤ c4 ≤ 0.3, 0 ≤ c5 ≤ 0.3, 0 ≤ d ≤ 0.3, 0 ≤ e ≤ 0.3 and 0 ≤ f ≤ 0.3, provided that A + a1 + a2 + a3 + b1 + b2 + c1 + c2 + c3 + c4 + d + e + f ≤ 1.0.

[0954] The weight average molecular weight (Mw) of the aforementioned polymer is desirably 1,000 to 500,000, more desirably 3,000 to 100,000. When Mw is within this range, sufficient etching resistance can be obtained, and there is no risk of resolution degradation due to failure to secure the difference in dissolution rate before and after exposure. In the present invention, Mw is a polystyrene-equivalent measured value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as a solvent.

[0955] The molecular weight distribution (Mw / Mn) of the aforementioned polymers tends to increase with the refinement of the pattern. Therefore, to obtain a resist composition suitable for fine pattern sizes, a narrow dispersion of Mw / Mn of 1.0 to 2.0 is preferable. Within this range, there are fewer low- and high-molecular-weight polymers, eliminating the risk of foreign matter appearing on the pattern after exposure or deterioration of the pattern shape.

[0956] The aforementioned polymer synthesis method, for example, involves placing the monomer providing the aforementioned repeating unit in an organic solvent, adding a free radical polymerization initiator, and heating to polymerize it.

[0957] Specific examples of organic solvents used in polymerization include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). Specific examples of polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2-azobis(2-methylpropionic acid), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The optimal amount of these initiators relative to the monomers to be polymerized is 0.01–25 mol%. A reaction temperature of 50–150 °C is ideal, with 60–100 °C being more ideal. A reaction time of 2–24 hours is ideal; considering production efficiency, 2–12 hours is more ideal.

[0958] The aforementioned polymerization initiator can be added to the monomer solution and supplied to the reactor, or an initiator solution can be prepared separately from the monomer solution and supplied to the reactor independently. During the waiting period, free radicals generated from the initiator may cause the polymerization reaction to proceed and generate ultrapolymers. Therefore, from a quality control point of view, it is preferable to prepare the monomer solution and initiator solution independently and add them dropwise. Acid-labile groups can be used directly from those already introduced into the monomer, or they can be protected or partially protected after polymerization. Furthermore, to adjust the molecular weight, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol can be used in conjunction. In this case, the amount of these chain transfer agents added relative to the total amount of monomers to be polymerized is preferably 0.01 to 20 mol%.

[0959] When the monomer contains hydroxyl groups, the hydroxyl groups can be replaced by acetal groups such as ethoxy-ethoxy, which are easily deprotected by acid, during polymerization. After polymerization, the protection can be removed by weak acid and water. Alternatively, acetyl, formyl, neopentyl, etc., can be replaced first, and alkaline hydrolysis can be performed after polymerization.

[0960] When copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, hydroxystyrene or hydroxyvinylnaphthalene and other monomers can be added to an organic solvent, a free radical polymerization initiator can be added, and the mixture can be heated to polymerize. Alternatively, acetoxystyrene or acetoxyvinylnaphthalene can be used, and after polymerization, the acetoxy groups can be deprotected by alkaline hydrolysis to produce polyhydroxystyrene or hydroxyvinylnaphthalene.

[0961] Specific examples of alkali used in alkaline hydrolysis include ammonia and triethylamine. The preferred reaction temperature is -20 to 100°C, more preferably 0 to 60°C. The preferred reaction time is 0.2 to 100 hours, more preferably 0.5 to 20 hours.

[0962] Furthermore, the amount of each monomer in the aforementioned monomer solution can be appropriately set to the ideal content ratio of the aforementioned repeating units.

[0963] The polymer obtained by the aforementioned manufacturing method can be used as the final product by using the reaction solution obtained from the polymerization reaction, or it can be used as the final product by using a refining step such as adding the polymer liquid to a poor solvent and obtaining powder through reprecipitation. Considering the perspectives of work efficiency and quality stabilization, it is better to use the polymer solution obtained by using the refining step or dissolving the powder in the solvent as the final product.

[0964] Specific examples of solvents used at this time can be found in paragraphs

[0144] to

[0145] of Japanese Patent Application Publication No. 2008-111103, including ketones such as cyclohexanone and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; and propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, and propylene glycol dimethyl ether. Ethers such as diethylene glycol dimethyl ether; esters such as PGMEA, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactones such as GBL; alcohols such as diacetone alcohol (DAA); high-boiling-point alcohol solvents such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, and 1,3-butanediol; and mixed solvents of these.

[0965] In the aforementioned polymer solution, a polymer concentration of 0.01–30% by mass is ideal, and 0.1–20% by mass is even more ideal.

[0966] The aforementioned reaction solutions and polymer solutions are preferably filtered. Filtering removes foreign matter and gel that could cause defects, effectively stabilizing the quality.

[0967] Regarding the materials used in the aforementioned filters, examples include fluorocarbon, cellulose, nylon, polyester, and hydrocarbon-based materials. For the filtration step involving the resist composition, filters made of fluorocarbon (such as Teflon, a registered trademark), polyethylene, polypropylene, or nylon are preferred. The filter pore size can be appropriately selected to match the target cleanliness level, preferably below 100 nm, and more preferably below 20 nm. Furthermore, these filters can be used individually or in combination. The filtration method can either pass the solution through only once or circulate the solution and perform multiple filtrations, which is preferable. The filtration steps in the polymer manufacturing process can be performed in any order and number of times, but filtering the reaction solution after polymerization, the polymer solution, or both is preferred.

[0968] [Chemical amplification resist composition]

[0969] [(A) Basic Polymer]

[0970] The chemically amplified resist composition of the present invention comprises a base polymer containing the aforementioned polymer as component (A).

[0971] (A) The base polymer of the composition may be used alone or in combination of two or more polymers with different composition ratios, Mw and / or Mw / Mn. Furthermore, (A) the base polymer may contain, in addition to the aforementioned polymers, hydrides of ring-opening metathesis polymers; in this regard, the polymer disclosed in Japanese Patent Application Publication No. 2003-66612 may be used.

[0972] [(B) Organic solvents]

[0973] The chemically amplified resist composition of the present invention may include an organic solvent as component (B). The organic solvent (B) may be any solvent capable of dissolving the foregoing components and the components described below, and there are no particular limitations. Specific examples of such organic solvents include ketones such as cyclopentanone, cyclohexanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ketols such as DAA; ethers such as PGME, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as PGMEA, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactones such as GBL; and mixed solvents of these.

[0974] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, cyclohexanone, GBL, ethyl lactate, DAA, and their mixtures are particularly good solvents for the base polymer of component (A).

[0975] In the chemically amplified resist composition of the present invention, the content of (B) organic solvent is ideally 200-5000 parts by mass relative to 80 parts by mass of (A) base polymer, and more ideally 400-3500 parts by mass. (B) Organic solvent can be used alone or in combination of two or more.

[0976] [(C) Quenching agent]

[0977] The chemically amplified resist composition of the present invention may also include a quencher as component (C). Furthermore, in the present invention, the quencher refers to a material used to form the desired pattern by preventing diffusion to unexposed areas by capturing strong acids generated from photoacid generators in the chemically amplified resist composition. Also, the strong acid refers to an acid with sufficient acidity to induce a deprotection reaction of unstable acid groups.

[0978] (C) Specific examples of quenchers can be exemplified by onium salts represented by formula (1) or (2).

[0979] [Chemical 350]

[0980]

[0981] In equation (1), R q1 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain heteroatoms, but excludes the α-position carbon atom bonded by the sulfonic acid group where the hydrogen atom is replaced by a fluorine atom or a fluoroalkyl group. In formula (2), R q2 It consists of a hydrogen atom, or may contain a hydrocarbon group with 1 to 40 carbon atoms and heteroatoms.

[0982] R q1 The hydrocarbon groups represented are alkyl groups with 1 to 40 carbon atoms, specifically including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., which are alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl and adamantyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the hydrocarbon groups may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc.]

[0983] R q2 The hydrocarbon group represented, specifically, except for R q1 In addition to the specific examples of substituents shown, examples include fluorinated saturated hydrocarbon groups such as trifluoromethyl and trifluoroethyl, and fluorinated aryl groups such as pentafluorophenyl and 4-trifluoromethylphenyl.

[0984] Specific examples of onium salt anions represented by equation (1) are listed below, but are not limited to these.

[0985] [Chemistry 351]

[0986]

[0987] [Chemistry 352]

[0988]

[0989] [Chemistry 353]

[0990]

[0991] [Chemistry 354]

[0992]

[0993] [Chemistry 355]

[0994]

[0995] Other specific examples of the onium salt anion represented by formula (1) can be found in paragraphs

[0027] to

[0029] of Japanese Patent No. 6248882, paragraphs

[0029] to

[0034] of Japanese Patent No. 6648726, paragraphs

[0220] to

[0225] of Japanese Patent No. 7032549, and paragraphs

[0028] to

[0029] of Japanese Patent No. 7067271. The authors include: paragraphs

[0037] to

[0060] of Japanese Patent Application Publication No. 2024-104830; paragraphs

[0039] to

[0066] of Japanese Patent Application Publication No. 2023-177038; paragraphs

[0033] to

[0093] of Japanese Patent Application Publication No. 2024-140135; and paragraphs

[0056] to

[0059] of International Publication No. 2024 / 241820.

[0996] Specific examples of onion salt anions represented by equation (2) are listed below, but are not limited to these.

[0997] [Chemistry 356]

[0998]

[0999] [Chemistry 357]

[1000]

[1001] [Chemistry 358]

[1002]

[1003] [Chemistry 359]

[1004]

[1005] [Hua360]

[1006]

[1007] Other specific examples of onium salt anions represented by formula (2) include paragraphs

[0097] of International Publication No. 2023 / 189502, paragraphs

[0231] to

[0233] and

[0236] of International Publication No. 2023 / 199907, paragraphs

[0240] to

[0242] of International Publication No. 2023 / 223865, paragraphs

[0203] to

[0211] of International Publication No. 2024 / 122425, paragraphs

[0282] to

[0294] of International Publication No. 2024 / 166822, paragraphs

[0013] to

[0015] of Japanese Patent Application Publication No. 2022-077505, and Japanese Patent Application Publication No. 2022-091720. Paragraphs

[0022] ~

[0024] , paragraphs

[0026] ~

[0031] of Japanese Patent Application Publication No. 2023-018671, paragraphs

[0017] ~

[0018] of Japanese Patent Application Publication No. 2023-062898, paragraphs

[0157] of Japanese Patent Application Publication No. 2023-108593, paragraphs

[0147] of Japanese Patent Application Publication No. 2024-040793, paragraphs

[0181] ~

[0194] of Japanese Patent Application Publication No. 2024-067732, paragraphs

[0171] of Japanese Patent Application Publication No. 2024-074267, paragraphs

[0029] ~

[0030] of Japanese Patent Application Publication No. 202 Paragraphs from Japanese Patent Application Publication No. 4-074268

[0022] , Japanese Patent Application Publication No. 2024-079160

[0233] ~

[0237] , Japanese Patent Application Publication No. 2024-083302

[0025] ~

[0026] , Japanese Patent Application Publication No. 2024-083305

[0030] ~

[0031] , Japanese Patent Application Publication No. 2024-084141

[0032] ~

[0034] , Japanese Patent Application Publication No. 2024-099498

[0030] ~

[0031] , Japanese Patent Application Publication No. 2024-099503

[0032] ~

[0033] , Japanese Patent Application Publication No. 2024-101558 Paragraphs

[0032] ~

[0033] of the Japanese Patent Application Publication No. 2024-102839

[0027] ~

[0028] , Paragraphs

[0035] ~

[0036] of the Japanese Patent Application Publication No. 2024-102841, Paragraphs

[0256] ~

[0261] of the Japanese Patent Application Publication No. 2024-131484

[0266] , Paragraphs

[0022] ~

[0024] of the Japanese Patent Application Publication No. 2025-010082, Paragraphs

[0299] of the Japanese Patent Application Publication No. 2025-027484, and Paragraphs

[0190] ~

[0198] of the Japanese Patent Application Publication No. 7611887.The authors of paragraphs

[0285] to

[0290] of Japanese Patent No. 7614747 and paragraphs

[0201] to

[0209] of Japanese Patent No. 7621323, etc.

[1008] In equations (1) and (2), Mq + The aforementioned onium cations include sulfonium cations, monium cations, and ammonium cations. Specific examples of the aforementioned sulfonium cations include cations of sulfonium salts represented by formula (1), paragraphs

[0102] to

[0125] of Japanese Patent Application Publication No. 2024-3744, paragraphs

[0044] to

[0049] of International Publication No. 2024 / 128017, paragraphs

[0035] to

[0046] of Japanese Patent Application Publication No. 7491173, and sulfonium cations represented by formula (sulfo-1), but are not limited to these. Specific examples of monium cations include paragraph

[0181] of Japanese Patent Application Publication No. 2024-259, but are not limited to these. Specific examples of the aforementioned ammonium cations include those represented by the formula (am-1).

[1009] Specific examples of onium salts represented by formula (1) or (2) can be any combination of the aforementioned anions and cations. Furthermore, these onium salts can be easily prepared using ion exchange reactions employing known organic chemical methods. For example, Japanese Patent Application Publication No. 2007-145797 can be consulted regarding ion exchange reactions.

[1010] The onium salts represented by formula (1) or (2) act as quenchers in the chemically amplified resist composition of the present invention. This is because the relative anions of the aforementioned onium salts are conjugate bases of weak acids. The weak acid referred to here is an acid that exhibits an acidity that cannot deprotect the acid unstable groups of units containing acid unstable groups used in the base polymer. The onium salts represented by formula (1) or (2) act as quenchers when used in combination with the conjugate base of a strong acid such as α-fluorinated sulfonic acid as an onium salt-type photoacid generator with a relative anion. That is, when an onium salt that generates a strong acid such as α-fluorinated sulfonic acid is mixed with an onium salt that generates a weak acid such as unfluorinated sulfonic acid or carboxylic acid, if the strong acid generated from the photoacid generator due to high-energy radiation irradiation collides with the onium salt having unreacted weak acid anions, weak acid will be released due to salt exchange, producing an onium salt with strong acid anions. In this process, the strong acid is exchanged for a weak acid with lower catalytic ability, thus the acid appears to be deactivated and the diffusion of acid can be controlled.

[1011] Furthermore, (C) the quenching agent may also be an onium salt having a sulfonium cation and a benzene oxide anion site in the same molecule as described in Japanese Patent No. 6848776, and furthermore, an onium salt having a sulfonium cation and a carboxylate anion site in the same molecule as described in Japanese Patent No. 6583136, Japanese Patent Application Publication No. 2020-200311, and an onium salt having a monazine cation and a carboxylate anion site in the same molecule as described in Japanese Patent No. 6274755.

[1012] Here, when the photoacid generator producing a strong acid is an onium salt, as mentioned above, the strong acid produced by high-energy ray irradiation can be exchanged into a weak acid. However, on the other hand, the weak acid produced by high-energy ray irradiation is considered unlikely to collide with the unreacted onium salt that produces the strong acid and undergo salt exchange. This is because onium cations readily form ion pairs with the anions of stronger acids.

[1013] In the chemically amplified resist composition of the present invention, when the onium salt represented by formula (1) or (2) is used as the quencher in (C), its content is ideally 0.1 to 20 parts by mass relative to 80 parts by mass of the base polymer in (A), and even more ideally 0.1 to 10 parts by mass. If the content of the aforementioned onium salt-type quencher is within the aforementioned range, the resolution is good and the sensitivity will not decrease significantly, thus it is ideal. The onium salt represented by formula (1) or (2) can be used alone or in combination of two or more.

[1014] The chemically amplified resist composition of the present invention may also include a nitrogen-containing compound as a (C) quencher. Specific examples of the aforementioned nitrogen-containing compounds include the first, second, or third-order amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Publication No. 2008-111103, and in particular, amine compounds having hydroxyl groups, ether bonds, ester bonds, lactone rings, cyano groups, or sulfonate bonds. Furthermore, compounds in which a first or second-order amine is protected with a carbamate group, as described in Japanese Patent Publication No. 3790649, may also be cited. Moreover, amine compounds in which any of the lactone ring, sulfonyl lactone ring, lactam ring, or sulfonyl lactam ring coexists with an acid-instable group, as described in Japanese Patent Publication No. 7615989, may also be cited.

[1015] Furthermore, nitrogen-containing compounds can also be sulfonate sulfonates with nitrogen-containing substituents. Such compounds act as quenchers in the unexposed areas, but lose their quenching ability in the exposed areas due to neutralization with their own generated acid, thus acting as so-called photodegrading bases. By using photodegrading bases, the contrast between the exposed and unexposed areas can be enhanced. For example, Japanese Patent Application Publication Nos. 2009-109595 and 2012-46501 can be found on photodegrading bases.

[1016] When the chemically amplified resist composition of the present invention contains a nitrogen-containing compound as a quencher (C), its content is preferably 0.001 to 12 parts by mass relative to 80 parts by mass of the base polymer (A), and more preferably 0.01 to 8 parts by mass. The aforementioned nitrogen-containing compound may be used alone or in combination of two or more.

[1017] [(D) Photoacid generator]

[1018] The chemically amplified resist composition of the present invention may also contain a photoacid generator as component (D). There are no particular limitations on the aforementioned photoacid generator, as long as it is a compound that generates a strong acid upon irradiation by high-energy rays. Ideal photoacid generators can be represented by formulas (3) or (4).

[1019] [Chemistry 361]

[1020]

[1021] In equations (3) and (4), R 101 ~R 105 Each group is an independent halogen atom, or may contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. Also, R 101 R 102 and R 103 Any two of them can also bond to each other and form a ring together with the sulfur atoms they are bonded to. Specific examples of the aforementioned hydrocarbon groups can be given and explained in the description of formula (A) regarding R. 1 and R 2 The hydrocarbon group shown is an example of the same.

[1022] Specific examples of sulfonium salt cations represented by formula (3) can be found in paragraphs

[0102] to

[0125] of Japanese Patent Application Publication No. 2024-3744, paragraphs

[0044] to

[0049] of International Publication No. 2024 / 128017, paragraphs

[0035] to

[0046] of Japanese Patent Application Publication No. 7491173, and specific examples of sulfonium cations represented by formula (sulfo-1), but are not limited to these. Specific examples of ferrous salt cations represented by formula (4) can be found in paragraph

[0181] of Japanese Patent Application Publication No. 2024-259, but are not limited to these.

[1023] In equations (3) and (4), Xa -It is an anion of a strong acid. Preferably, the anion of the aforementioned strong acid is the anion represented by formula (c1-1), formula (c1-4), or formula (c1-5). Furthermore, the aromatic sulfonic acid anions containing fluorine atoms described in paragraphs

[0029] to

[0034] of Japanese Patent No. 6648726, paragraphs

[0264] to

[0267] of Japanese Patent Application Publication No. 2024-077330, and paragraphs

[0040] to

[0071] of Japanese Patent Application Publication No. 2025-000201 can also be used as anions of strong acids.

[1024] Furthermore, it is also ideal for the photoacid generator of component (D) to be represented by the following formula (5).

[1025] [Chemistry 362]

[1026]

[1027] In equation (5), R 201 and R 202 Each can be an independent hydrocarbon group containing 1 to 30 carbon atoms, which may also contain heteroatoms. R 203 It can also contain a hydrocarbon group with 1 to 30 carbon atoms and a heteroatom. Also, R 201 R 202 and R 203 Any two of them can also bond to each other and form a ring together with the sulfur atoms they are bonded to.

[1028] R 201 and R 202 The hydrocarbon groups representing 1 to 30 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornel, oxanorbornel, and tricyclic [5.2.1.0]. 2,6] Decyl, adamantyl, and other cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms; phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, tert-butylnaphthyl, anthracene, and other aryl groups with 6 to 30 carbon atoms; groups obtained by combining them, etc. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1029] R 203 The alkylene groups representing carbon atoms from 1 to 30 can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, and hexadecane-1,16-diyl. Alkyl groups with 1 to 30 carbon atoms, such as heptadecanyl-1,17-diyl; cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norcamphenediyl, and adamantanediyl; and aryl groups such as phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, isobutylphenylene, sec-butylphenylene, tert-butylphenylene, naphthylene, methylnaphthylene, ethylnaphthylene, n-propylnaphthylene, isopropylnaphthylene, n-butylnaphthylene, isobutylnaphthylene, sec-butylnaphthylene, and tert-butylnaphthylene. Furthermore, some or all of the hydrogen atoms in the aforementioned alkylene group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned alkylene group can be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, it may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. Oxygen atoms are preferred as the aforementioned heteroatoms.

[1030] In equation (5), L 21It is a hydrocarbon group with 1 to 20 carbon atoms, which can be a single bond, an ether bond, or may contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given in R. 203 The examples representing the alkylene groups are the same.

[1031] In equation (5), X a X b X c and X d Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group. But X a X b X c and X d At least one of them is a fluorine atom or a trifluoromethyl group.

[1032] The photoacid generator represented by formula (5) is preferably represented by formula (5').

[1033] [Chem.363]

[1034]

[1035] In equation (5'), L 21 As mentioned before. X e It can be a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. R 301 R 302 and R 303 Each hydrocarbon group consists independently of a hydrogen atom, or may contain heteroatoms, and has 1 to 20 carbon atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given by R in formula (c1-1-1). fa1 The hydrocarbon groups represented are examples of the same. p and q are each independently 0, 1, 2, 3, 4 or 5, and r is 0, 1, 2, 3 or 4.

[1036] Specific examples of photoacid generators represented by formula (5) are the same as those represented by formula (2) in Japanese Patent Application Publication No. 2017-26980.

[1037] Among the aforementioned photoacid generators, those containing anions represented by formulas (c1-1-1), (c1-4), or (c1-5) exhibit low acid diffusion and excellent solubility in solvents, making them particularly ideal. Furthermore, those represented by formula (5') exhibit extremely low acid diffusion, making them particularly ideal.

[1038] When the chemically amplified resist composition of the present invention contains a photoacid generator (D), its content is ideally 0.1 to 40 parts by mass relative to 80 parts by mass of the base polymer (A), and more ideally 0.5 to 20 parts by mass. If the amount of photoacid generator (D) added is within the aforementioned range, the resolution is good, and there is no risk of foreign matter generation during resist film development or peeling, thus it is ideal. The photoacid generator (D) can be used alone or in combination of two or more.

[1039] [(E) Surfactant]

[1040] The chemically amplified resist composition of the present invention may also further include a surfactant as component (E). The surfactant (E) is preferably a surfactant that is insoluble or poorly soluble in water but soluble in alkaline developer, or a surfactant that is insoluble or poorly soluble in both water and alkaline developer. Such surfactants can be referred to in Japanese Patent Application Publication Nos. 2010-215608 and 2011-16746.

[1041] Among the surfactants described in the aforementioned announcement that are insoluble or poorly soluble in water and alkaline developing solutions, FC-4430 (manufactured by 3M Corporation), surflon (registered trademark) S-381 (manufactured by AGC Seimichemical Co., Ltd.), OLFINE (registered trademark) E1004 (manufactured by Nissin Chemical Industry Co., Ltd.), KH-20, KH-30 (manufactured by AGC Seimichemical Co., Ltd.), and oxocyclic butane ring-opening polymers represented by the following formula (surf-1) are preferred.

[1042] [Chem.364]

[1043]

[1044] Here, R, Rf, A, B, C, m, and n are irrelevant to the foregoing description and only apply to formula (surf-1). R is an aliphatic group with 2 to 5 carbon atoms in a 2 to 4-valent configuration. Examples of the aforementioned aliphatic groups, for those with a 2-valent configuration, include ethylene, 1,4-butylene, 1,2-propylene, 2,2-dimethyl-1,3-propylene, and 1,5-pentanediol; examples of those with a 3- or 4-valent configuration include the following.

[1045] [Chem365]

[1046]

[1047] In the formula, the dashed lines represent atomic bonds, each of which is a partial structure derived from glycerol, trimethylolethane, trimethylolpropane, and neopentyl tertrol.

[1048] Among these, 1,4-butylene and 2,2-dimethyl-1,3-propylene are preferred.

[1049] Rf is trifluoromethyl or pentafluoroethyl, preferably trifluoromethyl. m is an integer of 0 to 3, n is an integer of 1 to 4, and the sum of n and m is the valence of R, which is an integer of 2 to 4. A is 1. B is an integer of 2 to 25, preferably an integer of 4 to 20. C is an integer of 0 to 10, preferably 0 or 1. Further, the arrangement of the respective constituent units in formula (surf-1) is not specified, and they may be bonded in a block form or in a random form. For the production of the partially fluorinated oxetane ring-opened polymer-based surfactant, reference is made in detail to the specification of U.S. Patent No. 5650483 and the like.

[1050] A surfactant that is insoluble or sparingly soluble in water and soluble in an alkaline developer, when a resist protective film is not used in ArF immersion lithography, acts to reduce water penetration and leaching by aligning on the surface of the resist film. Therefore, it is useful because it suppresses the elution of water-soluble components from the resist film and reduces damage to the exposure apparatus, and it is also useful because it is solubilized during development with an aqueous alkaline solution after exposure or after post-exposure bake (PEB), and hardly becomes foreign matter that causes defects. Such a surfactant has the property of being insoluble or sparingly soluble in water and soluble in an alkaline developer, is a polymer-type surfactant, also referred to as a hydrophobic resin, and those having particularly high water repellency and improving slippage are preferred.

[1051] Specific examples of such polymer-type surfactants include those containing at least one selected from the repeating unit represented by the following formula (6A) (hereinafter also referred to as repeating unit 6A), the repeating unit represented by the following formula (6B) (hereinafter also referred to as repeating unit 6B), the repeating unit represented by the following formula (6C) (hereinafter also referred to as repeating unit 6C), the repeating unit represented by the following formula (6D) (hereinafter also referred to as repeating unit 6D), and the repeating unit represented by (6E) (hereinafter also referred to as repeating unit 6E).

[1052] [Chem. 366]

[1053]

[1054] In formulas (6A) to (6E), R B is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. W 1 is -CH2-, -CH2CH2-, -O-, or two separate -H groups. R s1 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R s2 is a single bond, or a linear or branched alkylene group having 1 to 5 carbon atoms. R s3 are each independently a hydrogen atom, a hydrocarbon group or fluorinated hydrocarbon group having 1 to 15 carbon atoms, or an acid-labile group. When R s3 is a hydrocarbon group or fluorinated hydrocarbon group, an ether bond or a carbonyl group may be inserted between carbon-carbon bonds. Rs4 It is a (u+1) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 20 carbon atoms. u can be 1, 2, or 3. R s5 Each is independently a hydrogen atom, or -C(=O)-OR sa The group indicated by R. sa It is a fluorinated hydrocarbon group with 1 to 20 carbon atoms. R s6 It is a hydrocarbon group or fluorinated hydrocarbon group with 1 to 15 carbon atoms, and an ether bond or carbonyl group may be inserted between the carbon-carbon bonds.

[1055] R s1 Ideally, the hydrocarbon group representing 1 to 10 carbon atoms should be a saturated hydrocarbon group, and it can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornel. Among these, those with 1 to 6 carbon atoms are preferred.

[1056] R s2 Ideally, the represented hydrocarbon group should be a saturated hydrocarbon group, which can be linear, branched, or cyclic. Specific examples include methylene, ethylene, propylene, butylene, and pentylene.

[1057] R s3 or R s6 The hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include saturated hydrocarbon groups, alkenyl groups, alkynyl groups, and other aliphatic unsaturated hydrocarbon groups, with saturated hydrocarbon groups being preferred. Specific examples of the aforementioned saturated hydrocarbon groups, besides R... s1 Besides the alkyl groups shown as examples, other examples include undecyl, dodecyl, thiol, tetradecyl, and decadecyl groups. s3 or R s6 The fluorinated hydrocarbon group can be exemplified by a group in which some or all of the hydrogen atoms bonded to the carbon atoms of the aforementioned hydrocarbon group are replaced by fluorine atoms. As mentioned earlier, ether bonds or carbonyl groups can also be inserted between these carbon-carbon bonds.

[1058] R s3 Specific examples of acid-instable groups include groups represented by the aforementioned formulas (AL-3) to (AL-5), trialkylsilyl groups where each alkyl group has 1 to 6 carbon atoms, and alkyl groups containing oxygen groups with 4 to 20 carbon atoms.

[1059] R s4 The (u+1) valence hydrocarbon group or fluorinated hydrocarbon group can be straight-chain, branched, or cyclic. Specific examples include groups obtained by removing more than u hydrogen atoms from the aforementioned hydrocarbon group or fluorinated hydrocarbon group.

[1060] R saIdeally, the fluorinated hydrocarbon group should be saturated, and can be linear, branched, or cyclic. Specific examples include hydrocarbon groups in which some or all of the hydrogen atoms are replaced by fluorine atoms, such as trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoro-1-propyl, 3,3,3-trifluoro-2-propyl, 2,2,3,3-tetrafluoropropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 2,2,3,3,4,4,4-heptafluorobutyl, 2,2,3,3,4,4,5,5-octafluoropentyl, 2,2,3,3,4,4,5,5,6,6,7,7-dodecylheptyl, 2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl, 2-(perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl, etc.

[1061] Specific examples of repeated units 6A~6E can be listed below, but are not limited to these. Also, in the following formula, R... B As mentioned above.

[1062] [Chemistry 367]

[1063]

[1064] [Chem.368]

[1065]

[1066] [Chemistry 369]

[1067]

[1068] [Transformation 370]

[1069]

[1070] [Chemistry 371]

[1071]

[1072] [Chemistry 372]

[1073]

[1074] The aforementioned polymeric surfactants may also contain other repeating units besides repeating units 6A to 6E. Specific examples of other repeating units include repeating units obtained from methacrylic acid, α-trifluoromethacrylic acid derivatives, etc. In polymeric surfactants, the content of repeating units 6A to 6E is ideally 20 mol% or more of all repeating units, more preferably 60 mol% or more, and even more preferably 100 mol%.

[1075] For the aforementioned polymeric surfactants, a Mw of 1,000 to 500,000 is ideal, and 3,000 to 100,000 is even more ideal. An Mw / Mn ratio of 1.0 to 2.0 is ideal, and 1.0 to 1.6 is even more ideal.

[1076] A method for synthesizing the aforementioned polymeric surfactants includes polymerizing a monomer containing unsaturated bonds, selected from at least one repeating unit 6A-6E and other repeating units as needed, in an organic solvent by adding a free radical initiator and heating. Examples of organic solvents used in polymerization include toluene, benzene, THF, diethyl ether, and dioxane. Examples of polymerization initiators include AIBN, 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2-azobis(2-methylpropionic acid), benzoyl peroxide, and lauroyl peroxide. A reaction temperature of 50-100°C is preferred. A reaction time of 4-24 hours is preferred. Acid-labile groups can be directly used from monomers, or they can be protected or partially protected after polymerization.

[1077] When synthesizing the aforementioned polymeric surfactants, known chain-transfer agents such as dodecyl mercaptan and 2-mercaptoethanol can be used to adjust the molecular weight. In this case, the amount of these chain-transfer agents added relative to the total molar percentage of the monomers to be polymerized is preferably 0.01 to 10 mol%.

[1078] When the chemically amplified resist composition of the present invention contains surfactant (E), its content is ideally 0.1 to 50 parts by mass relative to 80 parts by mass of the base polymer (A), and more ideally 0.5 to 10 parts by mass. If the content of surfactant (E) is 0.1 parts by mass or more, the receding contact angle between the resist film surface and water can be sufficiently increased; if it is 50 parts by mass or less, the dissolution rate of the resist film surface to the developer is low, and the height of the formed fine pattern can be sufficiently maintained. Surfactant (E) can be used alone or in combination of two or more.

[1079] [(F) Other ingredients]

[1080] The chemically amplified resist composition of the present invention may also contain compounds that decompose and produce acid due to acid (acid-increasing compounds), organic acid derivatives, fluorinated alcohols, and compounds whose Mw changes to solubility in developer due to acid action and is less than 3000 (dissolution inhibitors) as other components in (F). The aforementioned acid-increasing compounds can be referred to in Japanese Patent Application Publication No. 2009-269953 or Japanese Patent Application Publication No. 2010-215608. When containing the aforementioned acid-increasing compounds, an amount of 0 to 5 parts by mass relative to 80 parts by mass of the base polymer in (A) is ideal, and 0 to 3 parts by mass is more ideal. If the amount is too high, acid diffusion is difficult to control, and sometimes it can cause degradation of resolution and pattern shape. The aforementioned organic acid derivatives, fluorinated alcohols, and dissolution inhibitors can be referred to in Japanese Patent Application Publication No. 2009-269953 or Japanese Patent Application Publication No. 2010-215608.

[1081] [Pattern Formation Method]

[1082] The pattern forming method of the present invention includes the steps of forming a resist film on a substrate using the aforementioned chemically amplified resist composition, exposing the aforementioned resist film with high-energy rays, and developing the exposed resist film using a developing solution.

[1083] The aforementioned substrate can be, for example, a substrate used for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.) or a substrate used for mask circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.).

[1084] The resist film can be formed by coating the aforementioned chemically amplified resist composition onto a substrate by methods such as spin coating, with a film thickness preferably being 0.05~2μm, and then pre-baking it on a hot plate, preferably at 60~150°C for 1~10 minutes, more preferably at 80~140°C for 1~5 minutes.

[1085] High-energy rays used for photoresist film exposure include KrF excimer lasers, ArF excimer lasers, EB, and EUV with wavelengths of 3-15 nm. When using KrF excimer lasers, ArF excimer lasers, or EUV, a mask used to form the desired pattern can be used for irradiation to achieve an optimal exposure dose of 1-200 mJ / cm². 2 The optimal value is 10~100mJ / cm. 2 To perform this, when using EB, use a mask to form the desired pattern or irradiate directly, with the optimal exposure being 1~300 μC / cm. 2 It is better to achieve a temperature of 10~200μC / cm 2 .

[1086] Furthermore, in addition to the usual exposure method, an immersion method can be used, in which a liquid with a refractive index of 1.0 or higher is inserted between the resist film and the projection lens. In this case, a water-insoluble protective film can also be used.

[1087] The aforementioned water-insoluble protective film is used to prevent leaching from the resist film and improve the hydrophobicity of the film surface, and is generally of two types. One type is an organic solvent-stripping type, which must be peeled off before alkaline aqueous development using an organic solvent that does not dissolve the resist film. The other type is an alkaline aqueous solution-soluble type, which is soluble in alkaline developer and removes the protective film at the same time as the soluble portion of the resist film. The latter is particularly preferred as a material based on a polymer containing 1,1,1,3,3,3-hexafluoro-2-propanol residues that is water-insoluble but soluble in alkaline developer, and obtained by dissolving it in an alcohol solvent with 4 or more carbon atoms, an ether solvent with 8 to 12 carbon atoms, or a mixture thereof. Alternatively, a material obtained by dissolving the aforementioned water-insoluble but alkaline developer-soluble surfactant in an alcohol solvent with 4 or more carbon atoms, an ether solvent with 8 to 12 carbon atoms, or a mixture thereof may also be used.

[1088] After exposure, PEB can also be performed. PEB, for example, on a hot plate, preferably at 60~150°C for 1~5 minutes, more preferably at 80~140°C for 1~3 minutes.

[1089] Developing, for example, is preferably done using a developing solution of 0.1 to 5% by mass, more preferably 2 to 3% by mass, such as a tetramethylammonium hydroxide (TMAH) aqueous solution, for 0.1 to 3 minutes, more preferably 0.5 to 2 minutes, by conventional methods such as dip, immersion, or spray, to dissolve the exposed portion and form the desired pattern on the substrate.

[1090] Furthermore, after the resist film is formed, it can be rinsed with pure water to extract acid-generating agents from the film surface or to wash away particulate matter. It can also be rinsed to remove water remaining on the film after exposure.

[1091] Furthermore, patterns can also be formed using a double patterning method. Examples of double patterning methods include the trench method, which processes a substrate with a 1:3 trench pattern by first exposure and etching, then offsets the position and forms a 1:3 trench pattern with a second exposure to create a 1:1 pattern; and the line method, which processes a first substrate with a 1:3 isolated residual pattern by first exposure and etching, then offsets the position and processes a second substrate with the 1:3 isolated residual pattern already formed under the first substrate by a second exposure to create a 1:1 pattern with half the pitch.

[1092] In the pattern forming method of the present invention, an organic solvent can be used instead of the aforementioned alkaline aqueous solution to develop a negative tone that dissolves the unexposed portion.

[1093] In the aforementioned organic solvent development, the developer may include 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methyl acetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butyl acetate, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, methyl valerate, methyl valerate, methyl crotonate, croton... Ethyl propionate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenyl acetate, ethyl phenyl acetate, benzyl formate, phenyl ethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, etc. These organic solvents can be used alone or in combination.

[1094] [Example]

[1095] The following examples, embodiments, and comparative examples illustrate the present invention in detail, but the present invention is not limited to the following embodiments. Furthermore, the apparatus used is shown below.

[1096] MALDI TOF-MS: S3000 manufactured by Nippon Electronics Co., Ltd.

[1097] [1] Synthesis of monomers

[1098] [Example 1-1] Synthesis of monomer A-1

[1099] [Chemistry 373]

[1100]

[1101] (1) Synthesis of intermediate In-1

[1102] Under a nitrogen atmosphere, raw materials SM-1 (389.9 g) and DMF (0.7 g) were suspended in dichloromethane (1600 g), and the internal temperature was raised to 35°C. Then, oxalyl chloride (152.3 g) was added dropwise. After addition, the mixture was matured at 35°C for 4 hours. After maturation, the reaction system was cooled, and the reaction solution was concentrated to prepare a 30% by mass dichloromethane solution. Intermediate In-1 was not further purified and was used in subsequent steps.

[1103] (2) Synthesis of intermediate In-2

[1104] Under nitrogen atmosphere, starting materials SM-2 (110.2 g), triethylamine (131.5 g), and N,N-dimethylaminopyridine (12.2 g) were dissolved in dichloromethane (500 g) and cooled in an ice bath. Then, maintaining an internal temperature below 30°C, a 30% by mass solution of intermediate In-1 in dichloromethane was added dropwise. After the addition, the internal temperature was raised to 35°C, and maturation was carried out for 8 hours. The reaction solution was cooled in an ice bath, and the reaction was stopped with water (300 ml). Afterwards, a standard aqueous work-up was performed, the solvent was distilled off, and the solution was purified by silica gel column chromatography to obtain 358.8 g of the oily intermediate In-2 (76% yield).

[1105] (3) Synthesis of monomer A-1

[1106] Under nitrogen atmosphere, intermediate In-2 (94.4 g), triethylamine (24.3 g), and N,N-dimethylaminopyridine (2.4 g) were dissolved in THF (200 g) and cooled in an ice bath. The reaction mixture was then maintained at an internal temperature below 20°C, and starting material SM-3 was added dropwise under these conditions. After the addition, the internal temperature was raised to 25°C and matured for 8 hours. The reaction mixture was cooled in an ice bath, and the reaction was stopped with saturated sodium bicarbonate solution (100 ml). Following standard aqueous work-up, the solvent was distilled off, and the mixture was purified by silica gel column chromatography to obtain 118.7 g of an oily monomer A-1 (93% yield).

[1107] The results of the quality analysis of monomer A-1 are shown below.

[1108] MASS: 638.9 [M+H] +

[1109] [Examples 1-2~1-11] Synthesis of monomers A-2~A-11

[1110] Monomers A-2 to A-11 were synthesized using the corresponding raw materials and various organic synthesis reactions. The structures of monomers A-2 to A-11 are shown below.

[1111] [Chemistry 374]

[1112]

[1113] [2] Synthesis of basic polymers

[1114] The monomers used in the synthesis of the basic polymer, other than monomers A-1 to A-11, are shown below.

[1115] [Chemistry 375]

[1116]

[1117] [Chemistry 376]

[1118]

[1119] [Chemistry 377]

[1120]

[1121] [Chemistry 378]

[1122]

[1123] [Chemistry 379]

[1124]

[1125] [Example 2-1] Synthesis of Polymer P-1

[1126] Under nitrogen atmosphere, monomer A-1 (85.5g), monomer Pre-b2-1 (14.7g), V-601 (manufactured by Fujifilm and Koko Pure Chemical Industries, Ltd.) 2.57g, and MEK 139g were taken in a flask to prepare a monomer-polymerization initiator solution. In another flask under nitrogen atmosphere, MEK 46g was taken, and the mixture was heated to 80°C with stirring. The aforementioned monomer-polymerization initiator solution was then added dropwise over 4 hours. After the addition was complete, the polymerization solution was kept at 80°C and stirred for another 2 hours, followed by cooling to room temperature. The obtained polymerization solution was added dropwise to a vigorously stirred solution to obtain 2000g of hexane. The precipitated polymer was separated by filtration. The obtained polymer was then washed twice with 600g of hexane to obtain a coarse powder of polymer Pre-P-1. The coarse powder of polymer Pre-P-1 was dissolved in THF (200g), and ethanolamine (3.2g) was added. The mixture was matured at 50°C for 2 hours. The reaction solution was then cooled and added dropwise to 2,000 g of hexane after vigorous stirring. The precipitated polymer was separated by filtration. The obtained polymer was then washed twice with 600 g of hexane and dried under vacuum at 50°C for 20 hours to obtain a white powder, polymer P-1 (yield 98.1 g, 98% yield). The Mw of polymer P-1 was 6800, and the Mw / Mn ratio was 1.53. Mw is a polystyrene conversion value obtained by GPC using DMF as a solvent.

[1127] [Chemistry 380]

[1128]

[1129] [Example 2-2] Synthesis of Polymer P-46

[1130] In a nitrogen atmosphere, monomers A-1 (61.8 g), b1-2 (8.1 g), c-1 (30.1 g), V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 2.23 g, and MEK 139 g were prepared in a flask to form a monomer-polymerization initiator solution. In another flask under nitrogen atmosphere, MEK 46 g was added dropwise over 4 hours while stirring and heating to 80°C. After the addition was complete, the polymerization solution was maintained at 80°C and stirred for another 2 hours, then cooled to room temperature. The obtained polymerization solution was added dropwise to 2,000 g of hexane after vigorous stirring, and the precipitated polymer was separated by filtration. The obtained polymer was then washed twice with 600 g of hexane and dried under vacuum at 50°C for 20 hours to obtain a white powdered polymer P-46 (yield 97.3 g, 97% yield). The Mw of polymer P-46 is 9,700, and the Mw / Mn ratio is 1.54. Furthermore, Mw is a converted value of polystyrene obtained by GPC using DMF as a solvent.

[1131] [Chemistry 381]

[1132]

[1133] [Examples 2-3~2~80, Comparative Examples 1-1~1-70] Synthesis of polymers P-2~P-45, P-47~P-80, CP-1~CP-70

[1134] By changing the type and blending ratio of each monomer, the basic polymers shown in Tables 1-4 below were synthesized using Examples 2-1, 2-2, and known formulations.

[1135] [Table 1]

[1136]

[1137] [Table 2]

[1138]

[1139] [Table 3]

[1140]

[1141] [Table 4]

[1142]

[1143] [3] Preparation of chemically amplified resist composition

[1144] [Examples 3-1 to 3-80, Comparative Examples 2-1 to 2-70]

[1145] The basic polymers (P-1 to P-80) of the present invention, the comparative basic polymers (CP-1 to CP-70), the photoacid generators (PAG-X to PAG-Z), and the quenchers (Q-1 to Q-4) were dissolved in a solvent containing 0.01% by mass of surfactant A (Omnova) to prepare a solution. The solution was filtered through a 0.2 μm Teflon (registered trademark) type filter to prepare chemically amplified resist compositions (R-1 to R-80, CR-1 to CR-70).

[1146] [Table 5]

[1147]

[1148] [Table 6]

[1149]

[1150] [Table 7]

[1151]

[1152] [Table 8]

[1153]

[1154] Tables 5-8 show the solvent, photoacid generators PAG-X, PAG-Y, PAG-Z, quenchers Q-1 to Q-4, and surfactant A.

[1155] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[1156] EL (ethyl lactate)

[1157] DAA (diacetone alcohol)

[1158] • Photoacid generators: PAG-X, PAG-Y, PAG-Z

[1159] [Chemistry 382]

[1160]

[1161] Quenching agents: Q-1~Q-4

[1162] [Chemistry 383]

[1163]

[1164] Surfactant A: 3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane / tetrahydrofuran / 2,2-dimethyl-1,3-propanediol copolymer (manufactured by Omnova).

[1165] [Chem. 384]

[1166]

[1167] a : (b + b') : (c + c') = 1 : 4~7 : 0.01~1 (molar ratio)

[1168] [4] Evaluation of EUV lithography (1)

[1169] [Examples 4-1 to 4-80, Comparative Examples 3-1 to 3-70]

[1170] Various chemically amplified resist compositions (R-1~R-80 and CR-1~CR-70) were spin-coated onto a Si substrate containing a silicon spin-coating hard mask (SHB-A940, 43% by mass) manufactured by Shin-Etsu Chemical Industry Co., Ltd., with a pre-formed film thickness of 20 nm. The substrate was pre-baked at 100°C for 60 seconds using a hot plate to create a 50 nm thick resist film. This film was then subjected to an EUV scanning exposure machine (ASML NXE3300, NA 0.33, σ 0.9 / 0.6, dipole illumination) while varying the exposure and focus (exposure pitch: 1 mJ / cm). 2 1. Exposure of an LS pattern with a size of 18nm and a pitch of 36nm on the wafer was performed at the focusing pitch of 0.020μm. After exposure, PEB was performed for 60 seconds at the temperatures shown in Tables 9-12. Then, immersion development was performed for 30 seconds with a 2.38% by mass TMAH aqueous solution, followed by rinsing with a surfactant-containing rinsing material and vortexing to obtain a positive pattern.

[1171] The obtained LS patterns were observed using a Hitachi Advanced Technology Co., Ltd. critical dimension SEM (CG6300), and the sensitivity, EL, LWR, DOF, and collapse limit were evaluated according to the following methods. The results are shown in Tables 9-12.

[1172] [Sensitivity Evaluation]

[1173] Find the optimal exposure E for obtaining an LS pattern with a linewidth of 18nm and a pitch of 36nm. op (mJ / cm 2 This value is defined as sensitivity. The smaller the value, the higher the sensitivity.

[1174] [EL Review]

[1175] The EL (in %) is calculated by taking the exposure within ±10% (16.2~19.8nm) of the 18nm spacing width in the aforementioned LS pattern. The larger this value, the better the performance.

[1176] EL(%)=(|E1-E2| / E op )×100

[1177] E1: Provides optimal exposure for LS patterns with a linewidth of 16.2nm and a pitch of 36nm.

[1178] E2: Provides optimal exposure for LS patterns with a linewidth of 19.8nm and a pitch of 36nm.

[1179] Eop: Provides optimal exposure for LS patterns with a linewidth of 18nm and a pitch of 36nm.

[1180] [LWR Evaluation]

[1181] For E op The dimensions of the LS pattern obtained by irradiation are measured at 10 points along the long side of the line. The standard deviation (σ) of the measured dimensions is calculated as three times the value of the standard deviation (3σ) as the LWR. The smaller this value is, the smaller the roughness and the more uniform the linewidth of the pattern can be obtained.

[1182] [DOF Rating]

[1183] As an evaluation of focal depth, the focal range formed within ±10% (16.2~19.8nm) of the 18nm size of the aforementioned LS pattern is determined. The larger this value, the wider the focal depth.

[1184] [Collapse Limit Assessment of Line Patterns]

[1185] For the aforementioned LS pattern, the line dimensions at various exposures for the optimal focal point were measured at 10 points along the long side. The dimension of the thinnest line obtained without collapse was defined as the collapse limit dimension. The smaller this value, the better the collapse limit.

[1186] [Table 9]

[1187]

[1188] [Table 10]

[1189]

[1190] [Table 11]

[1191]

[1192] [Table 12]

[1193]

[1194] As shown in Tables 9-12, the chemically amplified resist composition containing the polymer of the present invention exhibits good sensitivity and excellent EL, LWR, and DOF. Furthermore, a low collapse limit value was confirmed, demonstrating resistance to pattern collapse even when forming fine patterns. Therefore, the chemically amplified resist composition of the present invention is suitable as a material for EUV lithography.

[1195] [5] Evaluation of EUV lithography (2)

[1196] [Examples 5-1 to 5-80, Comparative Examples 4-1 to 4-70]

[1197] Each chemically amplified resist composition (R-1 to R-80 and CR-1 to CR-70) was spin-coated onto a Si substrate with a silicon-containing spin-coated hard mask SHB-A940 (silicon content 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., with a film thickness of 20 nm. The resist film was pre-baked at 105°C for 60 seconds using a hot plate to create a 50 nm thick resist film. The resist film was then exposed using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, quadruple illumination, 46 nm pitch, +20% deviation hole pattern mask on wafer). PEB was performed for 60 seconds at the temperatures listed in Tables 13-16 using a hot plate, followed by 30 seconds of development with a 2.38% by mass TMAH aqueous solution to form a 23 nm hole pattern.

[1198] The exposure was measured using a Hitachi Advanced Technology Co., Ltd. critical dimension SEM (CG6300) when the aperture size was 23 nm, and this was defined as the sensitivity. Furthermore, the size of 50 apertures at this time was measured, and the standard deviation (σ) was calculated as three times the value of the result (3σ), defined as the CDU. The results are shown in Tables 13-16.

[1199] [Table 13]

[1200]

[1201] [Table 14]

[1202]

[1203] [Table 15]

[1204]

[1205] [Table 16]

[1206]

[1207] The results shown in Tables 13 to 16 confirm that the chemically amplified resist composition of the present invention has good sensitivity and excellent CDU.

[1208] [6] Alkali decomposition test

[1209] [Examples 6-1 to 6-5, Comparative Example 5-1]

[1210] Dissolve 2g of each monomer (A-1~A-5 and cA-1) in 10g of THF. Add 1.0 equivalent of ethanolamine to each monomer while stirring at an internal temperature of 40°C. Samples of the reaction solution are taken at 2 hours and 8 hours of stirring time. 1 The decomposition rate was calculated using H-NMR. The results are shown in Table 17.

[1211] [Table 17]

[1212]

[1213] The results shown in Table 17 confirm that the monomers of the present invention exhibit decomposition resistance under alkaline conditions.

Claims

1. A monomer, represented by the following formula (A), In the formula, n1 is 0 or 1, n2 is 0, 1, 2, 3 or 4, n3 is 0 or 1, n4 is 0, 1, 2, 3 or 4, and n5 is 0 or 1. R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X A For single bonds, -C(=O)-O- 、or -C(=O)-N(H)- , This represents the atomic bond between the carbon atom and the aromatic ring. R 1 The radical can be a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms, and when n2 is 2, 3 or 4, each R 1 They can be the same or different, 2 Rs 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to. R 2 The group can be a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. When n4 is 2, 3, or 4, each R... 2 They can be the same or different, 2 Rs 2 They can also bond to each other and form rings together with the carbon atoms they are bonded to. X 1 It is -O- or -N(H)-. R AL It is an acid-labile group.

2. The monomer according to claim 1, represented by the following formula (A1), In the formula, n1~n5, R A X 1 R 1 R 2 and R AL As mentioned above.

3. The monomer according to claim 2, represented by the following formula (A2), In the formula, n2, n4, n5, R A X 1 R 1 R 2 and R AL As mentioned above.

4. The monomer according to claim 1, wherein, R AL The group represented by formula (AL-1) or (AL-2) is... In the formula, k1 is 0 or 1, and k2 is 0 or 1. R L1 and R L2 Each is an independent hydrocarbon group having 1 to 12 carbon atoms, R L3 R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. L1 R L2 and R L3 The -CH2- group of the hydrocarbon group may also be partially replaced by -O- or -S-. When the hydrocarbon group contains an aromatic ring, some or all of the hydrogen atoms in the aromatic ring may be replaced by a halogen atom, a cyano group, a nitro group, an alkyl group containing 1 to 4 carbon atoms, or an alkoxy group containing 1 to 4 carbon atoms. Furthermore, R... L1 and R L2 They can also bond to each other and form a ring together with the carbon atoms they are bonded to. A portion of the -CH2- in this ring can be replaced by -O- or -S-, but R... L3 When R is a hydrogen atom L1 and R L2 They bond to each other and together with the carbon atoms they are bonded to, form alicyclic rings containing multiple bonds. R L4 and R L5 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R L6 It is a hydrocarbon group with 1 to 20 carbon atoms. A portion of the -CH2- group of this hydrocarbon group may also be replaced by -O- or -S-. Also, R... L5 and R L6 They can also bond to each other and to the carbon atoms and L atoms they are bonded to. A Together they form a heterocyclic group with 3 to 20 carbon atoms, and part of the -CH2- of this heterocyclic group can also be replaced by -O- or -S-. L A For -O- or -S-, This represents the atomic bond between the -O- and the adjacent -O-.

5. A polymer comprising repeating units derived from the monomer according to claim 1.

6. The polymer according to claim 5, further comprising at least one repeating unit selected from the following formula (a1), the following formula (a2), and the following formula (a3). In the formula, a1 is 0 or 1, and a2 is 0, 1, 2, 3, or 4. b1 is 0 or 1, and b2 is 0, 1, 2 or 3 when b1 is 0, and 0, 1, 2, 3, 4 or 5 when b1 is 1. R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X 1 For single bonds, phenylene, naphthylene or -C(=O)-OX 11 - The phenylene or naphthylene group may also be replaced by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, a saturated hydroxyl group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom. X 11 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms. This saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. X 2 For single bond, -C(=O)-O- or -C(=O)-N(H)-, X 3 For single bond, -C(=O)-O- or -C(=O)-N(H)-, This represents the atomic bonds between the carbon atoms in the main chain and the carbon atoms in the main chain. X 4 A group obtained by means of a single bond, an aliphatic alkylene group, a carbonyl group, a sulfonyl group, or a combination thereof, having 1 to 4 carbon atoms. X 5 and X 6 Each can be independently an oxygen atom or a sulfur atom, but X 4 and X 6 Bonded to adjacent carbon atoms on the aromatic ring, R 11 The radical can be a halogen atom, cyano group, hydroxyl group, nitro group, pentafluorosulfur group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When a2 is 2, 3, or 4, each R... 11 They can be the same or different. R 12 and R 13 Each is an independent hydrocarbon group consisting of hydrogen atoms, or may contain heteroatoms, and has 1 to 20 carbon atoms. Also, R 12 and R 13 They can also bond to each other and form rings together with the carbon atoms they are bonded to. R 14 It can be a halogen atom, hydroxyl group, cyano group, nitro group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxygen group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms or -N(R) group. 14A (R) 14B ), R 14A and R 14B Each is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; when b2 is 2 or more, each R 14 They can be the same or different, multiple Rs 14 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. AL 1 and AL 2 Each is an acid-labile group.

7. The polymer according to claim 5, further comprising a repeating unit represented by formula (b1), In the formula, R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Y 1 For single bond, -C(=O)-O- or -C(=O)-N(H)-, This represents the atomic bonds between the carbon atoms in the main chain and the carbon atoms in the main chain. R 21 The group can be a halogen atom, carboxyl group, nitro group, cyano group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; or it can be a hydrocarbon oxygen carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When c3 is 2, 3, or 4, each R... 21 They can be the same or different. c1 is 0 or 1, c2 is 1, 2, 3 or 4, c3 is 0, 1, 2, 3 or 4, but 1≤c2+c3≤5.

8. The polymer according to claim 5, further comprising a repeating unit represented by formula (b2), In the formula, R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Y 2 For single bonds, phenylene, naphthylene, -C(=O)-OY 21 -or -C(=O)-N(H)-Y 21 - The phenylene or naphthylene group may also be replaced by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, a saturated hydrocarbon oxygen group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom. Y represents the atomic bond between the carbon atoms in the main chain and the main chain. 21 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms. This saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. R 22 It is a hydrogen atom, or a group containing at least one of the following structures with 1 to 20 carbon atoms: hydroxyl group (other than phenolic hydroxyl group), cyano group, nitro group, carbonyl group, carboxyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulopentalide ring, lactam ring, sulopentalide ring, and carboxylic anhydride (-C(=O)-OC(=O)-).

9. The polymer according to claim 5, further comprising at least one repeating unit selected from the following formula (c1), the following formula (c2), the following formula (c3), the following formula (c4), and the following formula (c5). In the formula, d1 and d2 are each independently 0, 1, 2 or 3. e1 can be 0 or 1, e2 can be 0, 1, 2, 3 or 4, and e3 can be 0, 1, 2, 3 or 4. However, when e1 is 0, the condition is 0 ≤ e2 + e3 ≤ 4, and when e1 is 1, the condition is 0 ≤ e2 + e3 ≤ 6. R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z 1 It can be a single bond or may have substituents, phenylene Z 2 For single bond, -C(=O)-OZ 21 -、 -C(=O)-N(H)-Z 21 -or -OZ 21 -, Z 21 It is a divalent group obtained by aliphatic hydrocarbon groups, phenylene groups, or combinations thereof with 1 to 6 carbon atoms, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups. Z 3 The bonds can be single bonds, ether bonds, ester bonds, sulfonate bonds, amide bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. Z 4 It is a divalent group obtained by a single bond, or an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, or a combination thereof, and may also contain a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 5 Each can be a single bond independently, or may have substituents such as phenylene, naphthylene, or... -C(=O)-OZ 51 -, Z 51 It is an aliphatic hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms. This aliphatic hydrocarbon group may also contain a halogen atom, hydroxyl group, ether bond, ester bond, or lactone ring. Z 6 The bonds can be single bonds, ether bonds, ester bonds, sulfonate bonds, amide bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. Z 7 Each is an independent single bond. -Z 71 -C(=O)-O-、 -C(=O)-N(H)-Z 71 -or -OZ 71 -, Z 71 It can also contain a hydrocarbon group with 1 to 20 carbon atoms, which is a heteroatom. Z 8 Each is an independent single bond. -Z 81 -C(=O)-O-、 -C(=O)-N(H)-Z 81 -or -OZ 81 -, Z 81 It can also contain a hydrocarbon group with 1 to 20 carbon atoms, which is a heteroatom. Z 9 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene -C(=O)-OZ 91 -、 -C(=O)-N(H)-Z 91 -or -OZ 91 -, Z 91 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms. It may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group. This represents the atomic bonds between the carbon atoms in the main chain and the carbon atoms in the main chain. Indicates and Z 1 atomic bonds, Indicates and Z 6 atomic bonds, Indicates and Z 7 atomic bonds, L 1 The bonds can be single bonds, ether bonds, ester bonds, carbonyl groups, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, but all Rf 5 and Rf 6 They are not both hydrogen atoms. Rf 7 It is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl thio group having 1 to 6 carbon atoms, or a pentafluorothio group. R 31 and R 32 Each can independently be a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms. Also, R 31 and R 32 They can also bond to each other and form rings together with the sulfur atoms they are bonded to. R 33 The R group can be a halogen atom other than fluorine, or a hydrocarbon group containing heteroatoms with 1 to 20 carbon atoms. When e3 is 2, 3, or 4, each R... 33 They can be the same or different, multiple Rs 33 They can also bond to each other and form rings together with the carbon atoms they are bonded to. M - It is a non-nucleophilic relative ion. A + It is a ium cation.

10. A chemically amplified resist composition comprising a base polymer containing the polymer according to any one of claims 5 to 9, and an organic solvent.

11. The chemically amplified resist composition according to claim 10, further comprising a quenching agent.

12. The chemically amplified resist composition according to claim 10 further comprises a photoacid generator other than a polymer-bonded photoacid generator.

13. The chemically amplified resist composition according to claim 10, further comprising a surfactant.

14. A method for forming a pattern, comprising the following steps: A resist film is formed on a substrate using the chemically amplified resist composition according to claim 10. The resist film was exposed to high-energy rays, and The exposed resist film was developed using a developer.

15. The pattern forming method according to claim 14, wherein, The high-energy rays are KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet rays with wavelengths of 3-15 nm.

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