Sulfonium salt type monomer, polymer, chemically amplified resist composition, and pattern forming method

Abstract

The present invention relates to a sulfonium salt type monomer, a polymer, a chemically amplified resist composition, and a pattern forming method. The present invention provides a sulfonium salt type monomer, a polymer containing a repeating unit derived from the sulfonium salt type monomer, a chemically amplified resist composition containing the polymer, and a pattern forming method using the chemically amplified resist composition, which are used in an optical lithography using a high-energy ray, have excellent solvent solubility, are high in sensitivity and high in contrast, and are excellent in lithography properties such as LWR, CDU, EL, DOF, and the like. The means for solving the problem is a sulfonium salt type monomer represented by the following formula (A). In the formula, Z ‑ is a fluoralkanesulfonic acid anion having a polymerizable group.

Description

Technical Field

[0001] This invention relates to sulfonium salt monomers, polymers, chemically amplified resist compositions, and methods for pattern formation. Existing technology

[0002] With the increasing integration and speed of LSI (Light Detector System), the miniaturization of patterning is also progressing rapidly. In particular, the expansion of the flash memory market and the increase in memory capacity are driving this miniaturization. Regarding the most advanced miniaturization technologies, mass production of 65nm node devices using ArF lithography is already underway, and preparations are underway for mass production of 45nm node devices using next-generation ArF immersion lithography. For next-generation 32nm node devices, options such as immersion lithography using ultra-high nanometer (NA) lenses (combining liquids with higher refractive indices than water with high-refractive-index lenses and high-refractive-index resist films), extreme ultraviolet (EUV) lithography with a wavelength of 13.5nm, and double exposure (dual patterning lithography) using ArF lithography are being explored.

[0003] As miniaturization progresses and the light diffraction limit approaches, the contrast of light gradually decreases. This decrease in contrast leads to a reduction in the resolution of hole patterns, groove patterns, or focal length latitude in positive resist films.

[0004] As patterns become more refined, the linewidth roughness (LWR) of the line pattern and the dimensional uniformity (CDU) of the hole pattern are considered problems. Issues cited include uneven distribution of the base polymer and acid generator, the effects of aggregation, and the influence of acid diffusion. Furthermore, the thinning of the resist film tends to increase the LWR, and the deterioration of LWR caused by thinning during refinement becomes a serious problem.

[0005] In EUV lithography resist compositions, high sensitivity, high resolution, and low light-to-weight ratio (LWR) must be achieved simultaneously. Shortening the acid diffusion distance will reduce LWR, but it will also lower sensitivity. For example, lowering the post-exposure baking (PEB) temperature will reduce LWR, but it will also lower sensitivity. Increasing the amount of quencher will also reduce LWR, but it will also lower sensitivity. Therefore, a trade-off between sensitivity and LWR needs to be struck.

[0006] To suppress acid diffusion, resist compounds containing repeating units from onium salts of sulfonic acids with polymerizable unsaturated bonds have been proposed (Patent Document 1). Such so-called polymer-bonded acid generators, due to the generation of polymeric sulfonic acids upon exposure, exhibit a very short acid diffusion distance. Furthermore, sensitivity can be improved by increasing the ratio of the acid generator. Additive acid generators, while increasing the amount added, also increase sensitivity, but this also increases the acid diffusion distance. Since acid diffuses unevenly, increased acid diffusion degrades LWR and CDU. In terms of balancing sensitivity, LWR, and CDU, polymeric acid generators offer superior performance.

[0007] Iodine atoms exhibit very high absorption at EUV wavelengths of 13.5 nm, leading to the observed generation of secondary electrons during exposure, thus attracting attention in EUV lithography. Patent Document 2 describes a photoacid generator incorporating iodine atoms into anion atoms, while Patent Documents 3 and 4 describe photoacid generators containing polymerizable groups of iodine atoms incorporating iodine atoms into anion atoms. While this results in some improvement in lithography performance, the low solubility of iodine atoms in organic solvents raises concerns about precipitation in solvents.

[0008] Patent documents 5 and 6 describe photoacid generators in which a pentafluorosulfide (-SF5) group is introduced into the cation. Patent document 7 describes a photoacid generator in which a trifluoromethoxy (-OCF3) group is introduced. Patent document 8 describes a photoacid generator containing a sulfonium cation having a fluorine atom, a trifluoromethoxy group, and an acid-instable group. Patent document 9 describes a photoacid generator containing an iodine atom and an acid-instable group introduced into the sulfonium cation. While these technologies have led to some progress in improving photolithography performance, there is still room for improvement, with the development of more effective resist materials for forming fine patterns being anticipated.

[0009] Existing technical documents

[0010] Patent documents

[0011] [Patent Document 1] Japanese Patent No. 4425776

[0012] [Patent Document 2] Japanese Patent No. 6720926

[0013] [Patent Document 3] Japanese Patent No. 6973274

[0014] [Patent Document 4] Japanese Patent Application Publication No. 2024-43941

[0015] [Patent Document 5] International Publication No. 2023 / 223624

[0016] [Patent Document 6] International Publication No. 2024 / 128017

[0017] [Patent Document 7] Japanese Patent Application Publication No. 2022-59112

[0018] [Patent Document 8] Japanese Patent Application Publication No. 2023-169812

[0019] [Patent Document 9] Japanese Patent No. 7367185 Summary of the Invention

[0020] [The problem that the invention aims to solve]

[0021] The goal is to develop resist compositions with higher sensitivity and improved photolithography properties such as LWR, CDU, exposure latitude (EL), and depth of focus (DOF) in chemically amplified resist compositions using acid as a catalyst.

[0022] The present invention was made in view of the foregoing circumstances, and aims to provide a sulfonium salt monomer used in a chemically amplified resist composition, particularly in optical lithography using high-energy rays such as KrF excimer lasers, ArF excimer lasers, electron beams (EB), and EUV, which exhibits excellent solvent solubility, high sensitivity, high contrast, and excellent lithographic performance such as LWR, CDU, EL, and DOF; a polymer containing repeating units from the sulfonium salt monomer; a chemically amplified resist composition containing the polymer; and a patterning method using the chemically amplified resist composition.

[0023] [Methods for solving the problem]

[0024] After repeated and in-depth investigations to achieve the aforementioned objectives, the inventors of this application discovered that by using a polymer containing the following repeating unit as a polymer-bonded acid generator, wherein the repeating unit is derived from a triarylsulfonium cation having a cyano group and an acid-unstable group having a tertiary / secondary ether structure, a tertiary / secondary ester structure, a tertiary / secondary carbonate structure, or an acetal structure on the same aromatic ring, and a sulfonate anion having a polymerizable group, a sulfonate-type monomer can be obtained. This results in high sensitivity, controlled acid diffusion of the generated acid, improved photolithography properties such as LWR, CDU, EL, and DOF, high contrast, and a high-resolution chemical amplification resist composition, thus completing this invention.

[0025] That is, the present invention provides the following composition of sulfonium salt monomer, polymer, chemically amplified resist and patterning method.

[0026] 1. A sulfonium salt type monomer, represented by the following formula (A).

[0027] [Chemistry 1]

[0028]

[0029] In the formula, n1 is 0 or 1. n2 is 0, 1, or 2. n3 is 0, 1, or 2. n4 is 0, 1, or 2. However, when n1 is 0, 0 ≤ n2 + n3 + n4 ≤ 5; when n1 is 1, 0 ≤ n2 + n3 + n4 ≤ 7. n5 is 0 or 1. n6 is 0, 1, or 2. n7 is 0, 1, or 2. n8 is 0, 1, or 2. However, when n5 is 0, 0 ≤ n6 + n7 + n8 ≤ 5; when n5 is 1, 0 ≤ n6 + n7 + n8 ≤ 7. n9 is 0 or 1. n10 is 0, 1, or 2. n11 is 0, 1, or 2. n12 is 0, 1, or 2. However, when n9 is 0, 0 ≤ n10 + n11 + n12 ≤ 5; when n9 is 1, 0 ≤ n10 + n11 + n12 ≤ 7. Also, 1≤n2+n6+n10≤6, 1≤n3+n7+n11≤6.

[0030] R 1 R 2 and R 3 Each R can be independently a halogen atom, nitro group, hydroxyl group, carboxyl 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, each R 1 They can be the same or different, and there are 2 Rs. 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When n8 is 2, each R 2 They can be the same or different, and there are 2 Rs. 2 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When n12 is 2, each R 3 They can be the same or different, and there are 2 Rs. 3 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0031] L 1 L 2 and L 3 Each bond is independently an ether bond, ester bond, or carbonate bond. When n3 is 2, each L 1 They can be the same or different. When n7 is 2, each L 2 They can be the same or different. When n11 is 2, each L 3 They can be the same or different.

[0032] R AL1 R AL2 and R AL3 Each is an acid-labile group independently. When n3 is 2, each R AL1 They can be the same or different. When n7 is 2, each R... AL2 They can be the same or different. When n11 is 2, each R... AL3 They can be the same or different.

[0033] Furthermore, the bond is to S + Two of the three aromatic rings can also bond to each other and form a ring together with the sulfur atoms they are bonded to.

[0034] Z - It is a fluoroalkyl sulfonic acid anion with polymerizable groups.

[0035] 2. Such as the sulfonium salt type monomer in 1, which is represented by the following formula (A1).

[0036] [Chemistry 2]

[0037]

[0038] In the formula, n2~n4, n6~n8, n10~n12, R 1 ~R 3 L 1 ~L 3 R AL1 ~R AL3 and Z - Same as above.

[0039] 3. Sulfonium salt type monomers such as 1. or 2, wherein the aforementioned acid-unstable group is represented by the following formula (AL-1) or (AL-2).

[0040] [Chemistry 3]

[0041]

[0042] In the formula, p1 and p2 are independently 0 or 1, respectively. q1 and q2 are independently 0, 1, 2, 3 or 4, respectively.

[0043] 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-, and 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. Also, R L1 and R L2 They can also bond to each other and form a ring with the carbon atoms they are bonded to, and part of the -CH2- in this ring can be replaced by -O- or -S-. However, R L3 When R is a hydrogen atom, L1 and R L2They bond to each other and together with the carbon atoms they bond to, form alicyclic rings containing multiple bonds. Furthermore, some of the hydrogen atoms in the aforementioned alicyclic rings can be replaced by halogen atoms.

[0044] R L4 and R L5 Each can be 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, and part of the -CH2- group can 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. 4 Together they form a heterocyclic group with 3 to 20 carbon atoms, and part of the -CH2- of the heterocyclic group can also be replaced by -O- or -S-.

[0045] L 4 It can be either -O- or -S-.

[0046] R La ~R Ld Each group consists of a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms.

[0047] Indicates and L 1 L 2 and L 3 Atomic bonds.

[0048] 4. Sulfonate type monomers such as any one of 1.~3, wherein Z - Z1 represents the anion.

[0049] [Chemistry 4]

[0050]

[0051] In the formula, k is 0, 1, 2 or 3.

[0052] R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0053] Z 1 Each can be a single bond independently, or may have substituents such as phenylene, naphthylene, or... -C(=O)-OZ 11 -. Z 11 It is an aliphatic alkylene group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the aliphatic alkylene group may also contain halogen atoms, hydroxyl groups, ether bonds, ester bonds, or lactone rings.

[0054] Z 2 It can be a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0055] Z 3 Each independently constitutes a single bond, -Z 31 -C(=O)-O-、 -C(=O)-N(H)-Z 31 -or -OZ 31 -. Z 31 It can also contain alkylene groups with 1 to 20 carbon atoms and heteroatoms.

[0056] Z 4 Each independently constitutes a single bond, -Z 41 -C(=O)-O-、 -C(=O)-N(H)-Z 41 -or -OZ 41 -. Z 41 It can also contain alkylene groups with 1 to 20 carbon atoms and heteroatoms.

[0057] It represents the atomic bonds between carbon atoms in the main chain and the main chain. Indicates and Z 2 Atomic bonds. Indicates and Z 3 Atomic bonds.

[0058] L 5 It can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, sulfonamide bond, carbonate bond or carbamate bond.

[0059] Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms.

[0060] Rf 3 and Rf 4Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms.

[0061] 5. A sulfonium salt type monomer as described in any of 1.~3, wherein Z - Z2 represents the anion.

[0062] [Chemistry 5]

[0063]

[0064] In the formula, m1 is 0 or 1. m2 is 0, 1, 2, 3, or 4. m3 is 0, 1, 2, or 3. m4 is 0 or 1. m5 is 0, 1, 2, 3, or 4. m6 is 0, 1, 2, or 3. m7 is 0 or 1. m8 is 1, 2, 3, or 4. m9 is 0, 1, 2, or 3. m10 is 0, 1, 2, 3, or 4. m11 is 0 or 1. m12 is 0 or 1. However, when m1 is 0, 0 ≤ m2 + m3 + m12 ≤ 4; when m1 is 1, 0 ≤ m2 + m3 + m12 ≤ 6. When m4 is 0, 0 ≤ m5 + m6 ≤ 4; when m4 is 1, 0 ≤ m5 + m6 ≤ 6. When m7 is 0, 0 ≤ m8 + m9 ≤ 5; when m7 is 1, 0 ≤ m8 + m9 ≤ 7. Also, 1 ≤ m2 + m5 + m8 ≤ 4.

[0065] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0066] R 11 R 12 and R 13 Each R can be an independent halogen atom other than iodine, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxycarbonyl group with 2 to 20 carbon atoms containing heteroatoms. When m3 is 2 or 3, each R 11 They can be the same or different, and there are 2 Rs. 11 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m6 is 2 or 3, each R 12 They can be the same or different, and there are 2 Rs. 12 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m9 is 2 or 3, each R 13 They can be the same or different, and there are 2 Rs. 13 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0067] L A L B L C L D and L EEach bond can be independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0068] X L1 and X L2 Each is an independent single bond or may contain a heteroatom and a hydrocarbon group with 1 to 40 carbon atoms.

[0069] Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms.

[0070] 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.

[0071] However, m11 and m12 cannot both be 0, and L A L B L C L D X L1 and X L2 It cannot be a single key at the same time.

[0072] 6. A monomeric photoacid generator, which is composed of a sulfonium salt type monomer as described in any one of 1. to 5.

[0073] 7. A polymer comprising repeating units from a monomeric photoacid generator, such as 6.

[0074] 8. The polymer of 7, further comprising at least one repeating unit selected from the repeating unit represented by formula (a1), the repeating unit represented by formula (a2) and the repeating unit represented by formula (a3).

[0075] [Chemistry 6]

[0076]

[0077] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0078] X 1 For single bonds, phenylene, naphthylene, -C(=O)-OX 11 -or -C(=O)-N(H)-X 11 - and 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 11It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring.

[0079] X 2 For single key or -C(=O)-O- or -C(=O)-N(H)-.

[0080] It represents the atomic bonds between carbon atoms in the main chain and the main chain.

[0081] R 21 It can be a halogen atom, cyano group, hydroxyl group, nitro group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyloxy group with 2 to 20 carbon atoms containing heteroatoms; or it can be a hydrocarbon carbonyloxy group with 2 to 20 carbon atoms containing heteroatoms. When a1 is 2, 3, or 4, each R 21 They can be the same or different.

[0082] AL 1 and AL 2 Each is an acid-labile group.

[0083] a1 can be 0, 1, 2, 3 or 4.

[0084] [Chemistry 7]

[0085]

[0086] In the formula, b1 is 0 or 1. b2 is 0, 1, 2 or 3 when b1 is 0, and 0, 1, 2, 3, 4 or 5 when b1 is 1.

[0087] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0088] X 3 For single bond, -C(=O)-O- or -C(=O)-N(H)-. It represents the atomic bonds between carbon atoms in the main chain and the main chain.

[0089] X 4 It is a single bond, an aliphatic alkylene group, carbonyl group, sulfonyl group, or a combination thereof, having 1 to 4 carbon atoms.

[0090] X 5 and X 6 Each can be independently an oxygen atom or a sulfur atom. However, X 4 and X 6Adjacent carbon atoms bonded to an aromatic ring.

[0091] R 22 and R 23 Each group consists independently of a hydrogen atom or may contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. Also, R 22 and R 23 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0092] R 24 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 oxy group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms or -N(R) group. 24A (R) 24B R 24A and R 24B Each is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. When b2 is 2 or more, each R 24 They can be the same or different, and there are multiple Rs. 24 They can also bond to each other and form rings together with the carbon atoms on the aromatic rings they are bonded to.

[0093] 9. The polymer of 7 or 8, further comprising at least one repeating unit selected from repeating units represented by formula (b1) and repeating units represented by formula (b2).

[0094] [Chemistry 8]

[0095]

[0096] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0097] Y 1 For single bonds, phenylene, naphthylene, -C(=O)-OY 11 -or -C(=O)-N(H)-Y 11 - and 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 11 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring.

[0098] Y 2 For single key or -C(=O)-O-. It represents the atomic bonds between carbon atoms in the main chain and the main chain.

[0099] R 31 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, sulcinolone ring, and carboxylic anhydride (-C(=O)-OC(=O)-).

[0100] R 32 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 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 oxygen group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxygen carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When c2 is 2, 3, or 4, each R 32 They can be the same or different.

[0101] c1 can be 1, 2, 3, or 4. c2 can be 0, 1, 2, 3, or 4. However, 1 ≤ c1 + c2 ≤ 5.

[0102] 10. A chemically amplified resist composition comprising (A) a base polymer comprising any one of the polymers described in 7 to 9.

[0103] 11. As in 10, the chemically amplified resist composition also contains (B) organic solvents.

[0104] 12. Chemically amplified resist compositions such as 10 or 11, which also contain (C) quencher.

[0105] 13. A chemically amplified resist composition, such as any one of 10. to 12, further contains (D) a photoacid generator.

[0106] 14. A chemically amplified resist composition, such as any one of 10. to 13, further contains (E) a surfactant.

[0107] 15. A method for forming a pattern, comprising the following steps:

[0108] A resist film is formed on a substrate using a chemically amplified resist composition such as any one of 10.~14.

[0109] The aforementioned resist film was exposed to high-energy rays, and

[0110] The previously exposed resist film was developed using a developer.

[0111] 16. The pattern forming method of 15, wherein the aforementioned high-energy rays are KrF excimer lasers, ArF excimer lasers, EB, or EUV with a wavelength of 3 to 15 nm.

[0112] [The effects of the invention]

[0113] When patterning is performed using a chemically amplified resist composition containing a polymer that functions as a photoacid generator and includes repeating units of a polymer containing sulfonium salt-type monomers from the present invention, resist patterns with high contrast, good sensitivity, and excellent photolithographic properties such as LWR, CDU, EL, and DOF can be formed. Detailed Implementation

[0114] The present invention will now be described in detail. Furthermore, in the following description, the structure represented by the chemical formula may contain asymmetric carbons, and enantiomers and diastereomers may exist; in such cases, each is represented by a single formula. These isomers may be used individually or in mixtures of two or more.

[0115] [Sulfonate type monomer]

[0116] The sulfonium salt type monomer of the present invention is represented by the following formula (A).

[0117] [Chemistry 9]

[0118]

[0119] 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 more ideal. n2 is 0, 1, or 2. n3 is 0, 1, or 2. n4 is 0, 1, or 2. Considering the availability of raw materials, n4 with n4 of 0 or 1 is more ideal. However, when n1 is 0, 0 ≤ n2 + n3 + n4 ≤ 5; when n1 is 1, 0 ≤ n2 + n3 + n4 ≤ 7.

[0120] In formula (A), n5 is 0 or 1. When n5 is 0, it is a benzene ring; when n5 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with n5 of 0 is more ideal. n6 is 0, 1, or 2. n7 is 0, 1, or 2. n8 is 0, 1, or 2. Considering the availability of raw materials, n8 being 0 or 1 is more ideal. However, when n5 is 0, 0 ≤ n6 + n7 + n8 ≤ 5; when n5 is 1, 0 ≤ n6 + n7 + n8 ≤ 7.

[0121] In formula (A), n9 is 0 or 1. When n9 is 0, it is a benzene ring; when n9 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with n9 of 0 is more ideal. n10 is 0, 1, or 2. n11 is 0, 1, or 2. n12 is 0, 1, or 2. Considering the availability of raw materials, n12 being 0 or 1 is more ideal. However, when n9 is 0, 0 ≤ n10 + n11 + n12 ≤ 5; when n9 is 1, 0 ≤ n10 + n11 + n12 ≤ 7.

[0122] In equation (A), 1≤n²+n⁶+n¹⁰≤6 is preferably 1≤n²+n⁶+n¹⁰≤3, and 1≤n²+n⁶+n¹⁰≤2 is even better. Also, 1≤n³+n⁷+n¹¹≤6 is preferably 1≤n³+n⁷+n¹¹≤3, and 1≤n³+n⁷+n¹¹≤2 is even better.

[0123] In formula (A), R 1 R 2 and R 3 Each group can be independently composed of a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms; or a hydrocarbon thio group with 1 to 20 carbon atoms that may contain heteroatoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. The hydrocarbon group, as well as the hydrocarbon oxy and thio 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, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; 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, and some of the -CH2- 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.

[0124] When n4 is 2, each R1 They can be the same or different. Also, when n4 is 2, there are 2 R... 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to. The aforementioned rings are preferably 5- to 8-membered rings. When n8 is 2, each R... 2 They can be the same or different. Also, when n8 is 2, there are 2 R... 2 They can also bond to each other and form rings together with the carbon atoms they are bonded to. The aforementioned rings are preferably 5- to 8-membered rings. When n12 is 2, each R... 3 They can be the same or different. Also, when n12 is 2, there are 2 R... 3 They can also bond to each other and form rings together with the carbon atoms they are bonded to. The aforementioned rings are preferably 5- to 8-membered rings.

[0125] In formula (A), L 1 L 2 and L 3 Each bond can be independently formed by an ether bond, an ester bond, or a carbonate bond. Among these, an ether bond or an ester bond is preferable. When n3 is 2, each L... 1 They can be the same or different. When n7 is 2, each L 2 They can be the same or different. When n11 is 2, each L 3 They can be the same or different.

[0126] In formula (A), R AL1 R AL2 and R AL3 Each is an acid-labile group independently. When n3 is 2, each R... AL1 They can be the same or different. When n7 is 2, each R... AL2 They can be the same or different. When n11 is 2, each R... AL3 They can be the same or different.

[0127] The aforementioned acid-unstable groups should preferably be represented by the following formula (AL-1) or (AL-2).

[0128] [Chemistry 10]

[0129]

[0130] In the formula, Indicates and L 1 L 2 and L 3 Atomic bonds.

[0131] In equations (AL-1) and (AL-2), p1 and p2 are independently 0 or 1. q1 and q2 are independently 0, 1, 2, 3, or 4. When p1 is 1, q1 should preferably be 1 or 2; when p1 is 0, q1 is 0. When p2 is 1, q2 should preferably be 1 or 2; when p2 is 0, q2 is 0.

[0132] 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 hydrocarbon group may also be replaced by -O- or -S-, and when the hydrocarbon group contains an aromatic ring, part 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.

[0133] R L1 R L2 and R L3 The hydrocarbon groups representing 1 to 12 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, etc., alkyl groups with 1 to 12 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornel, norbornelmethyl, adamantyl, adamantylmethyl, tricyclic [5.2.1.0] 2,6 ] decyl, tetracyclic [6.2.1.1 3,6 .0 2,7 Cyclic saturated hydrocarbon groups with 3 to 12 carbon atoms, such as dodecyl; alkenyl groups with 2 to 12 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, butenyl, pentenyl, and hexenyl; alkynyl groups with 2 to 12 carbon atoms, such as ethynyl, propynyl, butynyl, pentynyl, and hexynyl; cyclic unsaturated aliphatic hydrocarbon groups with 3 to 12 carbon atoms, such as cyclopentenyl and cyclohexenyl; aryl groups with 6 to 12 carbon atoms, such as phenyl, naphthyl, and dihydroindenyl; aralkyl groups with 7 to 12 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these groups.

[0134] Also, 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, and part of the -CH2- in this ring can be replaced by -O- or -S-. Specific examples of the rings formed in this case include: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, norcamphene ring, adamantane ring, tricyclic ring [5.2.1.0] 2,6 Decane ring, tetracyclic ring [6.2.1.1] 3,6 .0 2,7Dodecane ring, etc. Furthermore, a portion of the -CH2- group in the aforementioned rings can also be replaced by -O- or -S-. However, 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. Furthermore, some of the hydrogen atoms in the aforementioned alicyclic rings can be replaced by halogen atoms.

[0135] In equation (AL-2), R L4 and R L5 Each can be 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 listed and illustrated as R. L1 R L2 and R L3 The same applies to those hydrocarbon groups that have 1 to 10 carbon atoms.

[0136] In equation (AL-2), R L6 It is a hydrocarbon group with 1 to 20 carbon atoms, and part of the -CH2- of this hydrocarbon group may be replaced by -O- or -S-. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: 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, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, etc., alkyl groups with 1 to 20 carbon atoms; cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, norbornelmethyl, adamantyl, adamantylmethyl, tricyclic [5.2.1.0] 2,6 ] decyl, tetracyclic [6.2.1.1 3,6 .0 2,7 [Dodecyl and other cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms; vinyl, propenyl, butenyl, pentenyl, hexenyl and other alkenyl groups with 2 to 20 carbon atoms; ethynyl, propynyl, butynyl, pentynyl, hexynyl and other alkynyl groups with 2 to 20 carbon atoms; cyclopentenyl, cyclohexenyl, norcamphenyl and other cyclic unsaturated aliphatic hydrocarbon groups with 3 to 20 carbon atoms; phenyl, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butenaphthyl, isobutenaphthyl, sec-butenaphthyl, tert-butenaphthyl and other aryl groups with 6 to 20 carbon atoms; benzyl, phenethyl and other aralkyl groups with 7 to 20 carbon atoms; and groups formed by combining these. Also, R] L5 and R L6They can also bond to each other and to the carbon atoms and L atoms they are bonded to. 4 Together they form a heterocyclic group with 3 to 20 carbon atoms, and part of the -CH2- of the heterocyclic group can also be replaced by -O- or -S-.

[0137] In equation (AL-2), L 4 It can be either -O- or -S-.

[0138] In equations (AL-1) and (AL-2), R La ~R Ld Each group consists independently of a hydrogen atom or may contain heteroatoms and has 1 to 20 carbon atoms as a hydrocarbon group. These 1 to 20 carbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. L6 Examples of hydrocarbon groups are similar, but not limited to these.

[0139] Specific examples of acid-instable groups represented by formula (AL-1) are shown below, but are not limited to these. Additionally, in the following formula, Indicates and L 1 L 2 and L 3 Atomic bonds.

[0140] [Chemistry 11]

[0141]

[0142] [Chemistry 12]

[0143]

[0144] [Chemistry 13]

[0145]

[0146] [Chemistry 14]

[0147]

[0148] [Chemistry 15]

[0149]

[0150] [Chemistry 16]

[0151]

[0152] [Chemistry 17]

[0153]

[0154] [Chemistry 18]

[0155]

[0156] [Chemistry 19]

[0157]

[0158] [Chemistry 20]

[0159]

[0160] [Chemistry 21]

[0161]

[0162] [Chemistry 22]

[0163]

[0164] [Chemistry 23]

[0165]

[0166] [Chemistry 24]

[0167]

[0168] [Chemistry 25]

[0169]

[0170] [Chemistry 26]

[0171]

[0172] [Chemistry 27]

[0173]

[0174] [Chemistry 28]

[0175]

[0176] [Chemistry 29]

[0177]

[0178] [Chemistry 30]

[0179]

[0180] [Chemistry 31]

[0181]

[0182] [Chemistry 32]

[0183]

[0184] Specific examples of acid-instable groups represented by formula (AL-2) are shown below, but are not limited to these. Additionally, in the following formula, Indicates and L 1 L 2 and L 3 Atomic bonds.

[0185] [Chemistry 33]

[0186]

[0187] [Chemistry 34]

[0188]

[0189] [Chemistry 35]

[0190]

[0191] In formula (A), the cyano group and -L 1 -R AL1 It is advisable to bond to adjacent carbon atoms. This proximity, combined with the electron-withdrawing property of the cyano group, improves the -R group. AL1 It reduces the acidity of phenols and carboxylic acids generated during deprotection and improves solubility contrast.

[0192] In formula (A), the cyano group and -L 2 -R AL2 It is advisable to bond to adjacent carbon atoms. This proximity, combined with the electron-withdrawing property of the cyano group, improves the -R group. AL2 It reduces the acidity of phenols and carboxylic acids generated during deprotection and improves solubility contrast.

[0193] In formula (A), the cyano group and -L 3 -R AL3 It is advisable to bond to adjacent carbon atoms. This proximity, combined with the electron-withdrawing property of the cyano group, improves the -R group. AL3 It reduces the acidity of phenols and carboxylic acids generated during deprotection and improves solubility contrast.

[0194] Furthermore, the bond is to S + Two of the three aromatic rings can also bond to each other and form a ring together with the sulfur atoms they are bonded to. Specific examples of the aforementioned ring structures can be shown in the following formulas, etc.

[0195] [Chemistry 36]

[0196]

[0197] In the formula, the dashed lines represent atomic bonds.

[0198] The sulfonium salt type monomer represented by formula (A) should preferably be represented by the following formula (A1).

[0199] [Chemistry 37]

[0200]

[0201] In the formula, n2~n4, n6~n8, n10~n12, R 1 ~R 3 L 1 ~L 3 and R AL1 ~R AL3 Same as above. Z - As will be described below.

[0202] Specific examples of cations of sulfonium salt type monomers represented by formula (A) are shown below, but are not limited thereto. Additionally, in the following formula, Me is a methyl group.

[0203] [Chemistry 38]

[0204]

[0205] [Chemistry 39]

[0206]

[0207] [Chemistry 40]

[0208]

[0209] [Chemistry 41]

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[0211] [Chemistry 42]

[0212]

[0213] [Chemistry 43]

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[0215] [Chemistry 44]

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[0217] [Chemistry 45]

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[0219] [Chemistry 46]

[0220]

[0221] [Chemistry 47]

[0222]

[0223] [Chemistry 48]

[0224]

[0225] [Chemistry 49]

[0226]

[0227] [Transformation 50]

[0228]

[0229] [Chemistry 51]

[0230]

[0231] [Chemistry 52]

[0232]

[0233] [Chemistry 53]

[0234]

[0235] [Chemistry 54]

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[0237] [Chemistry 55]

[0238]

[0239] [Chemistry 56]

[0240]

[0241] [Chemistry 57]

[0242]

[0243] [Chem.58]

[0244]

[0245] [Chemistry 59]

[0246]

[0247] [Transformation 60]

[0248]

[0249] [Chemistry 61]

[0250]

[0251] [Chemistry 62]

[0252]

[0253] [Chemistry 63]

[0254]

[0255] [Chemistry 64]

[0256]

[0257] [Chemistry 65]

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[0259] [Chemistry 66]

[0260]

[0261] [Chemistry 67]

[0262]

[0263] [Chemistry 68]

[0264]

[0265] [Chemistry 69]

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[0267] [Chemistry 70]

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[0271] [Chemistry 72]

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[0273] [Chemistry 73]

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[0275] [Chemistry 74]

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[0277] [Chemistry 75]

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[0279] [Chemistry 76]

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[0281] [Chemistry 77]

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[0283] [Chemistry 78]

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[0285] [Chemistry 79]

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[0287] [Chemistry 80]

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[0289] [Chemistry 81]

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[0323] [Chem. 98]

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[0349] [Chemistry 111]

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[0351] [Chemistry 112]

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[0357] [Chemistry 115]

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[0359] [Chemistry 116]

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[0361] [Chemistry 117]

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[0363] [Chemistry 118]

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[0365] [Chemistry 119]

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[0367] [Chemistry 120]

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[0371] [Chemistry 122]

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[0375] [Chemistry 124]

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[0379] [Chemistry 126]

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[0381] [Chemistry 127]

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[0383] [Chemistry 128]

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[0385] [Chemistry 129]

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[0389] [Chemistry 131]

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[0391] [Chemistry 132]

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[0393] [Chemistry 133]

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[0397] [Chemistry 135]

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[0399] [Chemistry 136]

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[0401] [Chemistry 137]

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[0413] [Chemistry 143]

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[0415] [Chemistry 144]

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[0417] [Chemistry 145]

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[0419] [Chemistry 146]

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[0421] [Chemistry 147]

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[0423] [Chemistry 148]

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[0425] [Chemistry 149]

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[0427] [Chemistry 150]

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[0429] [Chemistry 151]

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[0435] [Chemistry 154]

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[0437] [Chemistry 155]

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[0439] [Chemistry 156]

[0440]

[0441] [Chemistry 157]

[0442]

[0443] [Chemistry 158]

[0444]

[0445] [Chemistry 159]

[0446]

[0447] [Chemistry 160]

[0448]

[0449] [Chemistry 161]

[0450]

[0451] [Chemistry 162]

[0452]

[0453] [Chemistry 163]

[0454]

[0455] [Chemistry 164]

[0456]

[0457] [Chemistry 165]

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[0459] [Chemistry 166]

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[0461] [Chemistry 167]

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[0465] [Chemistry 169]

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[0467] [Chemistry 170]

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[0469] [Chemistry 171]

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[0471] [Chemistry 172]

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[0475] [Chemistry 174]

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[0477] [Chemistry 175]

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[0481] [Chemistry 177]

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[0483] [Chemistry 178]

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[0485] [Chemistry 179]

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[0487] [Chemistry 180]

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[0489] [Chemistry 181]

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[0491] [Chemistry 182]

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[0493] [Chemistry 183]

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[0495] [Chemistry 184]

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[0497] [Chemistry 185]

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[0499] [Chemistry 186]

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[0501] [Chemistry 187]

[0502]

[0503] [Chemistry 188]

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[0505] [Chemistry 189]

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[0507] [Chemistry 190]

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[0509] [Chemistry 191]

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[0511] [Chemistry 192]

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[0513] [Chemistry 193]

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[0515] [Chemistry 194]

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[0517] [Chemistry 195]

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[0519] [Chemistry 196]

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[0521] [Chemistry 197]

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[0523] [Chemistry 198]

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[0525] [Chemistry 199]

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[0527] [Chem.200]

[0528]

[0529] [Chemical Engineering 201]

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[0531] [Chemical Engineering 202]

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[0533] [Chemical Engineering 203]

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[0535] [Chemical 204]

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[0537] [Chemical Engineering 205]

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[0539] [Chemical Engineering 206]

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[0541] [Chemical 207]

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[0543] [Chemical Engineering 208]

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[0545] [Chemical Engineering 209]

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[0547] [Chemical 210]

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[0549] [Chemistry 211]

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[0551] [Chemistry 212]

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[0553] [Chemistry 213]

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[0555] [Chemistry 214]

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[0557] [Chemical 215]

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[0559] [Chemistry 216]

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[0561] [Chemistry 217]

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[0563] [Chemistry 218]

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[0565] [Chemistry 219]

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[0567] [Chem.220]

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[0569] [Chemistry 221]

[0570]

[0571] [Chemistry 222]

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[0573] [Chemistry 223]

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[0575] [Chemistry 224]

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[0577] [Chemistry 225]

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[0579] [Chemistry 226]

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[0581] [Chemistry 227]

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[0583] [Chemistry 228]

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[0585] [Chemistry 229]

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[0587] [Chemistry 230]

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[0589] [Chemistry 231]

[0590]

[0591] [Chemistry 232]

[0592]

[0593] [Chemistry 233]

[0594]

[0595] [Chemistry 234]

[0596]

[0597] In equations (A) and (A1), Z - It is a fluoroalkyl sulfonic acid anion with a polymerizable group. The aforementioned fluoroalkyl sulfonic acid anion is preferably represented by the following formula (Z1).

[0598] [Chemistry 235]

[0599]

[0600] In formula (Z1), k can be 0, 1, 2 or 3, and should preferably be 1.

[0601] In equation (Z1), R A Each can be independently composed of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 Each can be a single bond independently, or may have substituents such as phenylene, naphthylene, or... -C(=O)-OZ 11 -. Z 11 It is an aliphatic alkylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the aliphatic alkylene group may also contain a halogen atom, a hydroxyl group, an ether bond, an ester bond, or an lactone ring. 2 It can be a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. 3 Each independently constitutes a single bond, -Z 31 -C(=O)-O-、 -C(=O)-N(H)-Z 31 -or -OZ 31 -. Z 31 It can also contain 1-20 carbon-containing hydrocarbon groups, which may also contain heteroatoms. Z 4 Each independently constitutes a single bond, -Z 41 -C(=O)-O-、 -C(=O)-N(H)-Z 41 -or -OZ 41 -. Z 41 It can also contain alkylene groups with 1 to 20 carbon atoms and heteroatoms. It represents the atomic bonds between carbon atoms in the main chain and the main chain. Indicates and Z 2 Atomic bonds. Indicates and Z 3 Atomic bonds.

[0602] Z 11 The aliphatic alkyl sub-group can be any of the following: linear, branched, or cyclic. Specific examples include: methanediyl, 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, hexane-1,6-diyl, etc.; cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, etc.; and groups obtained by combining them.

[0603] Z 31 and Z 41 The sub-hydrocarbon group represented may contain heteroatoms and can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples are listed below, but are not limited to these.

[0604] [Chemistry 236]

[0605]

[0606] In the formula, the dashed lines represent atomic bonds.

[0607] In equation (Z1), L 5 The bonds can be single bonds, ether bonds, ester bonds, carbonyl bonds, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. From a synthetic point of view, ether bonds, ester bonds, and carbonyl bonds are preferred, with ester bonds and carbonyl bonds being even more desirable.

[0608] In equation (Z1), Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among them, Rf 1 and Rf 2 To increase the acid strength of the produced acid, it is advisable that all atoms be fluorine atoms.

[0609] In equation (Z1), 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 them, Rf is used to improve solvent solubility. 3 and Rf 4 At least one of them should preferably be trifluoromethyl.

[0610] Z - The fluoroalkyl sulfonic acid anion represented by the following formula (Z2) is also preferable.

[0611] [Chemistry 237]

[0612]

[0613] In formula (Z2), m1 is 0 or 1. When m1 is 0, it is a benzene ring; when m1 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with m1 of 0 is more ideal. m2 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, m2 should preferably be 0, 1, 2, or 3, with 0, 1, or 2 being better, and 0 or 1 being even better. m3 is 0, 1, 2, or 3.

[0614] In formula (Z2), m4 is 0 or 1. When m4 is 0, it is a benzene ring; when m4 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with m4 of 0 is more ideal. m5 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, m5 should preferably be 0, 1, 2, or 3, with 0, 1, or 2 being even better. m6 is 0, 1, 2, or 3.

[0615] In formula (Z2), m7 is 0 or 1. When m7 is 0, it is a benzene ring; when m7 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with m7 of 0 is more ideal. m8 is 1, 2, 3, or 4. Considering the availability of raw materials, m8 should preferably be 1, 2, or 3, with 1 or 2 being better. m9 is 0, 1, 2, or 3.

[0616] In formula (Z2), m10 is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 1, 2 or 3, and even more preferably 1. m11 is 0 or 1. m12 is 0 or 1.

[0617] When m1 is 0, 0 ≤ m2 + m3 + m1² ≤ 4; when m1 is 1, 0 ≤ m2 + m3 + m1² ≤ 6. Also, when m4 is 0, 0 ≤ m5 + m6 ≤ 4; when m4 is 1, 0 ≤ m5 + m6 ≤ 6. Also, when m7 is 0, 0 ≤ m8 + m9 ≤ 5; when m7 is 1, 0 ≤ m8 + m9 ≤ 7. Furthermore, regarding the number of iodine atoms in the anion, a higher number of iodine atoms results in higher absorption, especially for EUV. However, there is a concern that this may lead to reduced solvent solubility and precipitation in the resist composition; therefore, 1 ≤ m2 + m5 + m8 ≤ 4 is preferable.

[0618] In equation (Z2), 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 better.

[0619] In equation (Z2), R 11The halogen atom other than iodine, nitro, cyano, hydroxyl, carboxyl, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxycarbonyl group with 2 to 20 carbon atoms containing heteroatoms. The halogen atom other than iodine is preferably a fluorine, chlorine, or bromine atom, with fluorine being more preferred. The hydrocarbon group, hydrocarbon oxy group, hydrocarbon thio group, and hydrocarbon oxycarbonyl 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, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; 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 can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. This can result in the presence of 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 m3 is 2 or 3, each R... 11 They can be the same or different.

[0620] Furthermore, when m3 is 2 or 3, there are 2 R... 11 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 ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, norbornene ring, adamantane ring, 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, and halogen atoms, and part of the -CH2- 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.

[0621] In equation (Z2), R12 The halogen atom can be any halogen group other than iodine, such as nitro, cyano, hydroxyl, or carboxyl. It can also contain a hydrocarbon group with 1 to 20 carbon atoms (containing heteroatoms), an alkyloxy group with 1 to 20 carbon atoms (containing heteroatoms), an alkylthio group with 1 to 20 carbon atoms (containing heteroatoms), or an alkyloxycarbonyl group with 2 to 20 carbon atoms (containing heteroatoms). Specific examples of halogen atoms other than iodine include fluorine, chlorine, and bromine atoms. The hydrocarbon group, alkyloxy group, alkylthio group, and alkyloxycarbonyl group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. 11 Examples of hydrocarbon groups are similar, but not limited to these. 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, and a portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. This can result in the presence of hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. When m6 is 2 or 3, each R... 12 They can be the same or different.

[0622] Also, when m6 is 2 or 3, there are 2 Rs. 12 They can also bond to each other and form rings together with the carbon atoms they are bonded to. The aforementioned rings are preferably 5- to 8-membered rings.

[0623] In equation (Z2), R 13 The halogen atom can be any halogen group other than iodine, such as nitro, cyano, hydroxyl, or carboxyl. It can also contain a hydrocarbon group with 1 to 20 carbon atoms (containing heteroatoms), an alkyloxy group with 1 to 20 carbon atoms (containing heteroatoms), an alkylthio group with 1 to 20 carbon atoms (containing heteroatoms), or an alkyloxycarbonyl group with 2 to 20 carbon atoms (containing heteroatoms). Specific examples of halogen atoms other than iodine include fluorine, chlorine, and bromine atoms. The hydrocarbon group, alkyloxy group, alkylthio group, and alkyloxycarbonyl group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. 11 Examples of hydrocarbon groups are similar, but not limited to these. 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, and a portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. This can result in the presence of hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. When m9 is 2 or 3, each R...13 They can be the same or different.

[0624] Also, when m9 is 2 or 3, there are 2 Rs. 13 They can also bond to each other and form rings together with the carbon atoms they are bonded to. The aforementioned rings are preferably 5- to 8-membered rings.

[0625] In equation (Z2), L A L B L C L D and L E These can be independently identified as single bonds, ether bonds, ester bonds, sulfonate bonds, amide bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. Among them, L... A The bonds should ideally be single bonds, ether bonds, ester bonds, or sulfonate bonds, with ether bonds, ester bonds, or sulfonate bonds being preferred. B The bonds should ideally be single bonds, ether bonds, ester bonds, amide bonds, sulfonamide bonds, or sulfonate bonds, with ester bonds or sulfonate bonds being more preferred. C The bonds should ideally be single bonds, ether bonds, ester bonds, amide bonds, or sulfonate bonds, with single bonds, ether bonds, or ester bonds being preferred. D The bonds should ideally be single bonds, ether bonds, ester bonds, amide bonds, or sulfonate bonds, with single bonds, ether bonds, or ester bonds being preferred. E It is preferable to have single bonds, ether bonds, ester bonds, or sulfonate bonds, with single bonds, ether bonds, or ester bonds being more preferred.

[0626] When m12 is 1, L A and L B Ideally, adjacent carbon atoms bonded to the aromatic ring should be present. In this case, the substituents containing the fluorosulfonic acid anion structure and the substituents containing the aromatic ring replaced by the iodine atom will be located closer in space, thus higher sensitivity can be expected.

[0627] In equation (Z2), X L1 and X L2 Each is an alkylene group consisting of 1 to 40 carbon atoms, which may be a single bond or contain heteroatoms. The aforementioned alkylene groups can be linear, branched, or cyclic; specific examples include alkyldiyl groups, cyclic saturated alkylene groups, and arylene groups. Specific examples of the aforementioned heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0628] X L1 and X L2 Specific examples of hydrocarbon groups containing 1 to 40 carbon atoms, which may also contain heteroatoms, are shown below, but are not limited to these. Additionally, in the following formula, They are respectively L A and L C or L B and L D Atomic bonds.

[0629] [Chemistry 238]

[0630]

[0631] [Chemistry 239]

[0632]

[0633] [Chemistry 240]

[0634]

[0635] [Chemistry 241]

[0636]

[0637] Among them, X is the most suitable. L -0~X L -22, X L -29~X L -34 and X L -47~X L -61.

[0638] However, in equation (Z2), m11 and m12 will not both be 0, and L A L B L C L D X L1 and X L2 It cannot be a single key at the same time.

[0639] In equation (Z2), Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. The fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms is preferably trifluoromethyl. Rf 1 and Rf 2 It would be even better if it were fluorine atoms.

[0640] In equation (Z2), Rf 3 and Rf 4 Each of the following is an independent fluorinated saturated hydrocarbon group consisting of a hydrogen atom, a fluorine atom, or 1 to 6 carbon atoms. The fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms is preferably trifluoromethyl.

[0641] In equation (Z2), -[C(Rf 3 (Rf) 4 )] m10 -C(Rf 1 (Rf) 2 )-SO3 - The specific examples of the represented partial structure should preferably be as shown below, but are not limited to these. Additionally, in the following formula, Indicates and LE Atomic bonds.

[0642] [Chemistry 242]

[0643]

[0644] Among them, Acid-1 to Acid-7 are preferred, with Acid-1 to Acid-3, Acid-6 and Acid-7 being even better.

[0645] Z - Specific examples of anions can be listed below, but are not limited to. Additionally, in the following formula, R... A and Rf 4 As mentioned above, Me is methyl. Furthermore, the bonding positions of the various substituents on the aromatic ring can be interchanged.

[0646] [Chemistry 243]

[0647]

[0648] [Chemistry 244]

[0649]

[0650] [Chemistry 245]

[0651]

[0652] [Chemistry 246]

[0653]

[0654] [Chemistry 247]

[0655]

[0656] [Chemistry 248]

[0657]

[0658] [Chemistry 249]

[0659]

[0660] [Chemistry 250]

[0661]

[0662] [Chemistry 251]

[0663]

[0664] [Chemistry 252]

[0665]

[0666] [Chemistry 253]

[0667]

[0668] [Chemistry 254]

[0669]

[0670] [Chemistry 255]

[0671]

[0672] [Chemistry 256]

[0673]

[0674] [Chemistry 257]

[0675]

[0676] [Chemistry 258]

[0677]

[0678] [Chemistry 259]

[0679]

[0680] [Chemistry 260]

[0681]

[0682] [Chemistry 261]

[0683]

[0684] [Chemistry 262]

[0685]

[0686] [Chemistry 263]

[0687]

[0688] [Chemistry 264]

[0689]

[0690] [Chemistry 265]

[0691]

[0692] [Chemistry 266]

[0693]

[0694] [Chemistry 267]

[0695]

[0696] [Chemistry 268]

[0697]

[0698] [Chemistry 269]

[0699]

[0700] [Chemistry 270]

[0701]

[0702] [Chemistry 271]

[0703]

[0704] [Chemistry 272]

[0705]

[0706] [Chemistry 273]

[0707]

[0708] [Chemistry 274]

[0709]

[0710] [Chemistry 275]

[0711]

[0712] [Chemistry 276]

[0713]

[0714] [Chemistry 277]

[0715]

[0716] [Chemistry 278]

[0717]

[0718] [Chemistry 279]

[0719]

[0720] [Chemistry 280]

[0721]

[0722] [Chemistry 281]

[0723]

[0724] [Chemistry 282]

[0725]

[0726] [Chemistry 283]

[0727]

[0728] [Chemistry 284]

[0729]

[0730] [Chemistry 285]

[0731]

[0732] [Chemistry 286]

[0733]

[0734] [Chemistry 287]

[0735]

[0736] [Chemistry 288]

[0737]

[0738] [Chemistry 289]

[0739]

[0740] [Chemistry 290]

[0741]

[0742] [Chemistry 291]

[0743]

[0744] [Chemistry 292]

[0745]

[0746] [Chemistry 293]

[0747]

[0748] [Chemistry 294]

[0749]

[0750] [Chemistry 295]

[0751]

[0752] [Chemistry 296]

[0753]

[0754] [Chemistry 297]

[0755]

[0756] [Chemistry 298]

[0757]

[0758] [Chemistry 299]

[0759]

[0760] [Chemical 300]

[0761]

[0762] [Chemical Engineering 301]

[0763]

[0764] [Chemical 302]

[0765]

[0766] [Chemical 303]

[0767]

[0768] [Chemical 304]

[0769]

[0770] [Chemical 305]

[0771]

[0772] [Chemical 306]

[0773]

[0774] [Chemical 307]

[0775]

[0776] [Chemical 308]

[0777]

[0778] [Chemical 309]

[0779]

[0780] [Chemical 310]

[0781]

[0782] [Chemistry 311]

[0783]

[0784] [Chemistry 312]

[0785]

[0786] [Chemistry 313]

[0787]

[0788] [Chemical 314]

[0789]

[0790] [Chemical 315]

[0791]

[0792] [Chemistry 316]

[0793]

[0794] [Chemistry 317]

[0795]

[0796] [Chemistry 318]

[0797]

[0798] [Chemistry 319]

[0799]

[0800] [Chemistry 320]

[0801]

[0802] [Chemistry 321]

[0803]

[0804] [Chemistry 322]

[0805]

[0806] [Chemistry 323]

[0807]

[0808] [Chemistry 324]

[0809]

[0810] [Chemistry 325]

[0811]

[0812] [Chemistry 326]

[0813]

[0814] [Chemistry 327]

[0815]

[0816] [Chemistry 328]

[0817]

[0818] [Chemistry 329]

[0819]

[0820] [Chemistry 330]

[0821]

[0822] [Chemistry 331]

[0823]

[0824] [Chemistry 332]

[0825]

[0826] [Chemistry 333]

[0827]

[0828] [Chemistry 334]

[0829]

[0830] [Chemistry 335]

[0831]

[0832] [Chemistry 336]

[0833]

[0834] [Chemistry 337]

[0835]

[0836] [Chemistry 338]

[0837]

[0838] [Chemistry 339]

[0839]

[0840] [Transformation 340]

[0841]

[0842] [Chemistry 341]

[0843]

[0844] [Chemistry 342]

[0845]

[0846] [Chemistry 343]

[0847]

[0848] [Chemistry 344]

[0849]

[0850] [Chemistry 345]

[0851]

[0852] [Chemistry 346]

[0853]

[0854] [Chemistry 347]

[0855]

[0856] [Chemistry 348]

[0857]

[0858] [Chemistry 349]

[0859]

[0860] [Chemical 350]

[0861]

[0862] [Chemistry 351]

[0863]

[0864] [Chemistry 352]

[0865]

[0866] [Chemistry 353]

[0867]

[0868] [Chemistry 354]

[0869]

[0870] [Chemistry 355]

[0871]

[0872] [Chemistry 356]

[0873]

[0874] [Chemistry 357]

[0875]

[0876] [Chemistry 358]

[0877]

[0878] [Chemistry 359]

[0879]

[0880] [Hua360]

[0881]

[0882] [Chemistry 361]

[0883]

[0884] [Chemistry 362]

[0885]

[0886] [Chem.363]

[0887]

[0888] [Chem.364]

[0889]

[0890] [Chemical Formula 365]

[0891]

[0892] [Chemical Formula 366]

[0893]

[0894] [Chemical Formula 367]

[0895]

[0896] [Chemical Formula 368]

[0897]

[0898] Z - Other specific examples of the represented anion include those described in paragraphs

[0043] to

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

[0067] to

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

[0057] to

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

[0020] to

[0023] of Japanese Laid-Open Patent Publication No. 2024-103465, paragraphs

[0067] to

[0070] of Japanese Laid-Open Patent Publication No. 2024-120703, paragraphs

[0075] to

[0084] of Japanese Patent No. 7520258, paragraphs

[0032] to

[0047] of Japanese Laid-Open Patent Publication No. 2024-043941, paragraphs

[0385] to

[0390] of Japanese Laid-Open Patent Publication No. 2025-013053, and paragraphs

[0062] to

[0064] of International Publication No. 2025 / 018169, and the like.

[0899] Specific examples of the sulfonium salt-type monomer of the present invention include any combination of the aforementioned anion and cation.

[0900] The sulfonium salt-type monomer of the present invention can be synthesized by a known method. For example, the target sulfonium salt can be obtained through a salt exchange reaction using a salt having the aforementioned sulfonium cation and a salt having the aforementioned anion, which are synthesized by a known method. The salt exchange with the corresponding anion salt can be easily carried out by a known method, and for example, reference can be made to Japanese Laid-Open Patent Publication No. 2007-145797. In addition, the aforementioned production method is merely an example, and the production method of the sulfonium salt of the present invention is not limited thereto.

[0901] The structural features of the sulfonate monomers of the present invention can be listed as follows: a fluoroalkyl sulfonic acid anion with polymerizable groups, and a triarylsulfonate cation with a cyano group and an acid-unstable group having a tertiary / secondary ether structure, a tertiary / secondary ester structure, a tertiary / secondary carbonate structure, or an acetal structure on the same aromatic ring. Because the anions of the sulfonate monomers of the present invention have polymerizable groups, the polymers of the present invention obtained using them become anionic bonded acid generators with the anionic side bonded to the polymer backbone. That is, acids bonded to the polymer backbone are generated, thus inhibiting the diffusion of the generated acids. Furthermore, polymerizable groups composed of styrene and vinylnaphthalene structures are particularly rigid than polymerizable groups such as methacrylates, and improve the glass transition temperature (Tg) of the polymer, thus being more desirable. It is believed that the aromatic rings within or between polymers will interact (π-π stacking effect), resulting in a regular arrangement of the polymer, and exhibiting resistance to pattern collapse in the developer during the formation of fine patterns. Furthermore, the etching process following the formation of the micro-pattern also exhibits excellent etching resistance due to the aromatic rings directly bonded to the main chain.

[0902] Furthermore, the sulfonium salt monomer of the present invention preferably has an iodine atom in the anion. Regarding the iodine atom, especially in EUV lithography at a wavelength of 13.5 nm, the EUV absorption of the iodine atom is very large, thus generating secondary electrons from the iodine atom during exposure. It is known that the cyano group bonded to the aromatic ring of the sulfonium cation is a strong electron-withdrawing group. It is believed that, due to this, the energy level of the lowest unoccupied molecular orbital (LUMO) in frontier molecular orbital theory is lowered. Therefore, it becomes easier to accept secondary electrons generated from the iodine atom in the anion, promoting the decomposition of the cation and efficiently generating acid. Furthermore, the nitrogen atom of the cyano group has a lone pair of electrons, so it can also be expected to interact with the protons of the generated acid and function as an acid diffusion-inhibiting group. Acid-labile groups with tertiary / secondary ether, tertiary / secondary ester, tertiary / secondary carbonate, or acetal structures on the same aromatic ring of the sulfonium cation undergo deprotection reactions due to acids generated during exposure, producing the corresponding phenols or carboxylic acids. The change in structure from lipophilic to hydrophilic improves the contrast between the exposed and unexposed areas. Furthermore, the cyano group, by bonding to the carbon atom adjacent to the carbon atom bonded to the phenolic hydroxyl or carboxyl group generated during the deprotection reaction, improves the acidity of the phenol or carboxylic acid due to the electron-withdrawing property of the cyano group. When the deprotected exposed area is developed with an alkaline developer, the improved acidity of the phenols reduces development residue due to improved solubility in the alkaline developer. Additionally, other aromatic rings in the triarylsulfonium cation preferably have fluorine atoms or substituents containing fluorine atoms. It is believed that fluorine atoms, or fluorine-containing substituents, have strong electron-withdrawing properties, which lowers the energy level of the lowest unoccupied molecular orbital in the frontier molecular orbital theory of triarylsulfonium cations. Therefore, they readily accept secondary electrons generated from iodine atoms in both cations and anions, promoting the decomposition of cations and efficiently generating acids. Utilizing these synergistic effects, high sensitivity can be achieved, resolution reduction caused by acid diffusion blurring can be prevented, and the lithography performance of LWR, CDU, and other photolithography methods can be improved. Therefore, the polymer of this invention is particularly ideal as a material for chemically amplified positive resist compositions.

[0903] [polymer]

[0904] The polymer of the present invention contains repeating units (hereinafter also referred to as repeating unit A) derived from sulfonium salt monomers represented by formula (A).

[0905] The aforementioned polymer may also contain repeating units represented by formula (a1) (hereinafter also referred to as repeating unit a1) or repeating units represented by formula (a2) (hereinafter also referred to as repeating unit a2).

[0906] [Chemistry 369]

[0907]

[0908] In equations (a1) and (a2), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0909] In equation (a1), X 1 For single bonds, phenylene, naphthylene, -C(=O)-OX 11 -or -C(=O)-N(H)-X 11 - and 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, and 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.

[0910] 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 main chain. R 21 It can be a halogen atom, cyano group, hydroxyl group, nitro group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl 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 also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms. a1 can be 0, 1, 2, 3, or 4, preferably 0 or 1. When a1 is 2, 3, or 4, each R 21 They can be the same or different.

[0911] In equations (a1) and (a2), AL 1 and AL 2 Each of these groups is an acid-indestructible group independently. Specific examples of the aforementioned acid-indestructible groups can be cited, for example, those described in Japanese Patent Application Publication No. 2013-80033 and Japanese Patent Application Publication No. 2013-83821.

[0912] For representativeness, specific examples of the aforementioned acid-instable groups can be listed as those represented by formulas (AL-3) to (AL-5).

[0913] [Transformation 370]

[0914]

[0915] In the formula, These are atomic bonds.

[0916] In equations (AL-3) and (AL-4), R L11 and R L12 Each hydrocarbon group is independently composed of 1 to 40 carbon atoms and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Preferably, the aforementioned hydrocarbon groups have 1 to 20 carbon atoms.

[0917] In formula (AL-3), a2 is an integer from 0 to 10, preferably 1, 2, 3, 4 or 5.

[0918] In equation (AL-4), R L13 and R L14 Each group is independently composed of a hydrogen atom or a hydrocarbon group having 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 atoms in the ring can also bond to each other and form a ring with 3 to 20 carbon atoms together with the carbon atoms they are bonded to, or with carbon and oxygen atoms. The aforementioned rings are preferably 4 to 16 carbon atoms, with alicyclic rings being particularly preferred.

[0919] In equation (AL-5), R L15 R L16 and R L17 Each group is an independent hydrocarbon group having 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 atoms in the ring can also 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 ring is preferably a ring with 4 to 16 carbon atoms, and an alicyclic ring is particularly preferred.

[0920] Other specific examples of the aforementioned acid-unstable groups include those described in paragraphs

[0064] to

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

[0013] to

[0014] of Japanese Patent Publication No. 7492842. These reactions are driven by the formation of conjugated olefins or acrylate derivatives after acid desorption.

[0921] Specific examples of repeated unit a1 can be listed below, but are not limited to these. Additionally, in the following formula, R... A and AL 1 Same as above.

[0922] [Chemistry 371]

[0923]

[0924] [Chemistry 372]

[0925]

[0926] [Chemistry 373]

[0927]

[0928] [Chemistry 374]

[0929]

[0930] [Chemistry 375]

[0931]

[0932] Specific examples of repeated unit a2 can be listed below, but are not limited to these. Additionally, in the following formula, R... A and AL 2 Same as above.

[0933] [Chemistry 376]

[0934]

[0935] [Chemistry 377]

[0936]

[0937] [Chemistry 378]

[0938]

[0939] The aforementioned polymer may also contain repeating units represented by the following formula (a3) ​​(hereinafter also referred to as repeating unit a3).

[0940] [Chemistry 379]

[0941]

[0942] 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 more ideal. 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 should preferably be 0, 1, 2, or 3, with 0, 1, or 2 being more preferable.

[0943] In equation (a3), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. RA It is preferable to have a hydrogen atom or a methyl group, with a hydrogen atom being better.

[0944] In equation (a3), X 3 For single bond, -C(=O)-O- or -C(=O)-N(H)-. This represents the atomic bonds between carbon atoms in the main chain and the carbon atoms in the main chain. Among these, single bonds are preferred. -C(=O)-O-, a single bond would be even better.

[0945] 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 availability of the starting materials, a single bond, a carbonyl group, or a sulfonyl group is preferable; considering the polar groups formed after the reaction, a single bond or a carbonyl group is even better.

[0946] In equation (a3), X 5 and X 6 Each can be independently an oxygen atom or a sulfur atom. However, X 4 and X 6 Adjacent carbon atoms bonded to an aromatic ring. X 5 and X 6 They can be the same or different; considering the perspective of reactivity, X 5 and X 6 All of them are ideally composed of oxygen atoms.

[0947] In equation (a3), R 22 and R 23Each hydrocarbon group consists of 1 to 20 carbon atoms, which may be hydrogen atoms or may contain heteroatoms. The aforementioned hydrocarbon groups may be saturated or unsaturated, and may 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, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; 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, and some of the -CH2- 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.

[0948] Also, R 22 and R 23 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 ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, norbornene ring, adamantane ring, 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, and halogen atoms, and part of the -CH2- 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.

[0949] In equation (a3), R 24 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 oxy group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms or -N(R) group. 24A (R) 24B R 24Aand R 24B Each halogen atom is independently 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, as well as the hydrocarbon group of the aforementioned hydrocarbon group, hydrocarbon oxygen group, hydrocarbon oxygen carbonyl group, and hydrocarbon thio group, can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. 22 and R 23 The same example applies to hydrocarbon groups. 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, and a portion of the -CH2- group in the aforementioned hydrocarbon group can also 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, sulfonate ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. When b2 is 2 or more, each R... 24 They can be the same or different.

[0950] Furthermore, when b2 is 2 or more, multiple R 24 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, and halogen atoms, and part of the -CH2- 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.

[0951] Specific examples of repeated unit a3 can be listed below, but are not limited to these. Additionally, in the following formula, R... A As mentioned above, Me is methyl. Furthermore, the bonding positions of the various substituents on the aromatic ring can be interchanged.

[0952] [Chemistry 380]

[0953]

[0954] [Chemistry 381]

[0955]

[0956] [Chemistry 382]

[0957]

[0958] [Chemistry 383]

[0959]

[0960] [Chem. 384]

[0961]

[0962] [Chem. 385]

[0963]

[0964] [Chemistry 386]

[0965]

[0966] [Chemistry 387]

[0967]

[0968] [Chem.388]

[0969]

[0970] [Chemistry 389]

[0971]

[0972] [Chemistry 390]

[0973]

[0974] [Chemistry 391]

[0975]

[0976] [Chemistry 392]

[0977]

[0978] [Chemistry 393]

[0979]

[0980] [Chem. 394]

[0981]

[0982] [Chemistry 395]

[0983]

[0984] [Chemistry 396]

[0985]

[0986] [Chemistry 397]

[0987]

[0988] [Chemistry 398]

[0989]

[0990] [Chemistry 399]

[0991]

[0992] [Chemical 400]

[0993]

[0994] [Chemical Engineering 401]

[0995]

[0996] [Chemical 402]

[0997]

[0998] [Chemical 403]

[0999]

[1000] [Chemical 404]

[1001]

[1002] [Chemical 405]

[1003]

[1004] [Chemical 406]

[1005]

[1006] [Chemical 407]

[1007]

[1008] [Chemical 408]

[1009]

[1010] [Chemical 409]

[1011]

[1012] [Chemical 410]

[1013]

[1014] [Chemistry 411]

[1015]

[1016] [Chemistry 412]

[1017]

[1018] [Chemistry 413]

[1019]

[1020] [Chemistry 414]

[1021]

[1022] [Chemical 415]

[1023]

[1024] [Chemistry 416]

[1025]

[1026] [Chemistry 417]

[1027]

[1028] [Chemistry 418]

[1029]

[1030] [Chemistry 419]

[1031]

[1032] [Chemistry 420]

[1033]

[1034] [Chemistry 421]

[1035]

[1036] [Chemistry 422]

[1037]

[1038] [Chemistry 423]

[1039]

[1040] [Chemistry 424]

[1041]

[1042] [Chemical 425]

[1043]

[1044] [Chemistry 426]

[1045]

[1046] [Chemistry 427]

[1047]

[1048] [Chemistry 428]

[1049]

[1050] [Chemistry 429]

[1051]

[1052] The aforementioned base polymer may also contain repeating units represented by formula (b1) (hereinafter also referred to as repeating unit b1) or repeating units represented by formula (b2) (hereinafter also referred to as repeating unit b2).

[1053] [Chemistry 430]

[1054]

[1055] In equations (b1) and (b2), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 For single bonds, phenylene, naphthylene, -C(=O)-OY 11 -or -C(=O)-N(H)-Y 11 - and 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 11 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. 2 For single key or -C(=O)-O-. Represents the atomic bonds between the carbon atoms in the main chain and the carbon atoms in the chain. R 31 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, carbonyl group, carboxyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulcinolone ring, and carboxylic anhydride (-C(=O)-OC(=O)-). R32 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 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 oxygen group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxygen carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When c2 is 2, 3, or 4, each R 32 They can be the same or different. c1 can be 1, 2, 3 or 4. c2 can be 0, 1, 2, 3 or 4. However, 1 ≤ c1 + c2 ≤ 5.

[1056] Specific examples of repeating unit b1 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[1057] [Chemistry 431]

[1058]

[1059] [Chemistry 432]

[1060]

[1061] [Chemistry 433]

[1062]

[1063] [Chemistry 434]

[1064]

[1065] [Chemistry 435]

[1066]

[1067] [Chemistry 436]

[1068]

[1069] [Chemistry 437]

[1070]

[1071] [Chemistry 438]

[1072]

[1073] [Chemistry 439]

[1074]

[1075] [Chemistry 440]

[1076]

[1077] [Chemistry 441]

[1078]

[1079] [Chemistry 442]

[1080]

[1081] [Chemistry 443]

[1082]

[1083] [Chemistry 444]

[1084]

[1085] [Chemistry 445]

[1086]

[1087] [Chemistry 446]

[1088]

[1089] [Chemistry 447]

[1090]

[1091] [Chemistry 448]

[1092]

[1093] [Chemistry 449]

[1094]

[1095] [Chemistry 450]

[1096]

[1097] Specific examples of repeated unit b2 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[1098] [Chemistry 451]

[1099]

[1100] [Chemistry 452]

[1101]

[1102] [Chemistry 453]

[1103]

[1104] [Chemistry 454]

[1105]

[1106] [Chemistry 455]

[1107]

[1108] Regarding repeating units b1 or b2, in ArF lithography, those with lactone rings as polar groups are particularly suitable, while in KrF lithography, EB lithography, and EUV lithography, those with phenolic sites are suitable.

[1109] The aforementioned polymer may also contain repeating units (hereinafter also referred to as repeating unit c) with a structure in which hydroxyl groups are protected by acid-instable groups. If repeating unit c has a structure with one or more hydroxyl groups protected, and the protecting groups decompose and generate hydroxyl groups due to the action of acid, there are no particular restrictions, and it is preferable to be represented by the following formula (c1).

[1110] [Chemistry 456]

[1111]

[1112] In equation (c1), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 41 It can also be a (d+1) valence hydrocarbon group with 1 to 30 carbon atoms, which may contain heteroatoms. R 42 It is an acid-labile group. d can be 1, 2, 3, or 4.

[1113] In equation (c1), R 42 The acid-unstable group indicated is one that has been deprotected by the acid, resulting in the formation of a hydroxyl group. R 42 There are no particular restrictions on the structure, and it is preferable to have an acetal structure, a ketal structure, a hydrocarbon oxy carbonyl group, or a hydrocarbon oxy methyl group represented by the following formula (c2), with a hydrocarbon oxy methyl group represented by the following formula (c2) being particularly preferred.

[1114] [Chemistry 457]

[1115]

[1116] In the formula, Represents an atomic bond. R 43 It consists of hydrocarbon groups with 1 to 15 carbon atoms.

[1117] R 42 Specific examples of the acid-unstable group, the hydroxymethyl group represented by formula (c2), and the repeating unit c can be cited as the same examples illustrated in the description of the repeating unit c described in Japanese Patent Application Publication No. 2020-111564.

[1118] The aforementioned polymer may also contain a repeating unit d derived from indene, benzofuran, benzothiophene, acenaphthene, chromone, coumarin, norbornadiene or derivatives thereof. Specific examples of the monomer that provides the repeating unit d may include those shown below, but are not limited thereto.

[1119] [Chem. 458]

[1120]

[1121] The aforementioned polymer may also contain a repeating unit e derived from indane, vinylpyridine or vinylcarbazole.

[1122] In the polymer of the present invention, the content ratios of the repeating units A, a1, a2, a3, b1, b2, c, d and e are preferably 0<A≤0.4, 0≤a1≤0.8, 0≤a2≤0.8, 0≤a3≤0.6, 0<a1+a2+a3≤0.8, 0≤b1≤0.6, 0≤b2≤0.6, 0≤c≤0.5, 0≤d≤0.3 and 0≤e≤0.3, more preferably 0<A≤0.3, 0≤a1≤0.7, 0≤a2≤0.7, 0≤a3≤0.5, 0<a1+a2+a3≤0.7, 0≤b1≤0.5, 0≤b2≤0.5, 0≤c≤0.3, 0≤d≤0.3 and 0≤e≤0.3. Provided that A+a1+a2+a3+b1+b2+c+d+e≤1.0.

[1123] The weight average molecular weight (Mw) of the aforementioned polymer is preferably 1,000 to 500,000, more preferably 3,000 to 100,000. When Mw is within this range, sufficient etching resistance can be obtained, and there is no concern about a decrease in resolution caused by failure to ensure the difference in dissolution rate before and after exposure. In the present invention, Mw is a polystyrene-equivalent measurement value determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as a solvent.

[1124] With regard to the molecular weight distribution (Mw / Mn) of the aforementioned polymer, the influence of Mw / Mn tends to increase along with the miniaturization of pattern rules, so in order to obtain a resist composition that can be ideally used for fine pattern dimensions, Mw / Mn is preferably a narrow dispersion of 1.0 to 2.0. Within the aforementioned range, there are few polymers with low molecular weight and high molecular weight, and there is no concern that foreign matter is observed on the pattern after exposure or the shape of the pattern is deteriorated.

[1125] Examples of the method for synthesizing the aforementioned polymer include a method in which a monomer that provides the aforementioned repeating unit is added with a radical polymerization initiator in an organic solvent and heated to carry out polymerization.

[1126] 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). Examples of polymerization initiators include: 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The amount of these initiators added relative to the total monomers used in polymerization should preferably be 0.01–25 mol%. The reaction temperature should preferably be 50–150 °C, preferably 60–100 °C. The reaction time should preferably be 2–24 hours, but considering production efficiency, 2–12 hours is preferred.

[1127] The aforementioned polymerization initiator can be added to the aforementioned monomer solution to supply the reactor, or an initiator solution different from the aforementioned monomer solution can be prepared and supplied to the reactor separately. Since there is a possibility that the polymerization reaction may proceed and generate ultra-high molecular weight polymers due to the generation of free radicals from the initiator during the waiting time, from a quality management perspective, the monomer solution and initiator solution should preferably be prepared separately and added dropwise. Acid-labile groups can be used directly 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 combination. In this case, the amount of these chain transfer agents added relative to the total amount of monomers used to polymerize should preferably be 0.01 to 20 mol%.

[1128] In the case of monomers containing hydroxyl groups, the hydroxyl groups can be replaced with acetal groups such as ethoxy-ethoxy, which are easily deprotected by acids, during polymerization. After polymerization, deprotection can be carried out using weak acids and water. Alternatively, acetyl groups, formyl groups, trimethylacetyl groups, etc., can be used for replacement first, and alkaline hydrolysis can be carried out after polymerization.

[1129] When copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, hydroxystyrene or hydroxyvinylnaphthalene can be copolymerized with other monomers in an organic solvent with the addition of a free radical polymerization initiator and heated. Alternatively, acetoxystyrene or acetoxyvinylnaphthalene can be used, and after polymerization, the acetoxy groups can be deprotected by alkaline hydrolysis to obtain polyhydroxystyrene or hydroxyvinylnaphthalene.

[1130] Specific examples of alkalis used in alkaline hydrolysis include ammonia and triethylamine. Furthermore, the reaction temperature should ideally be -20 to 100°C, with 0 to 60°C being more preferable. The reaction time should ideally be 0.2 to 100 hours, with 0.5 to 20 hours being more preferable.

[1131] In addition, the amount of each monomer in the aforementioned monomer solution can be appropriately set, for example, in a manner that makes it an ideal content ratio for the aforementioned repeating units.

[1132] Regarding the polymer obtained by the aforementioned manufacturing method, the reaction solution obtained by the polymerization reaction can be used as the final product, or the powder obtained by purification steps such as adding the polymer solution to a poor solvent to obtain the powder and then reprecipitating it can be used as the final product. Considering the viewpoints of work efficiency and quality stabilization, it is advisable to use the polymer solution obtained by dissolving the powder obtained by the purification step into a solvent as the final product.

[1133] Specific examples of solvents used at this time can be cited from 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, 1-ethoxy-2-propanol, and diacetone alcohol (DAA); and propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethylene glycol. Ethers such as 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; high-boiling-point alcohol solvents such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, and 1,3-butanediol; and their mixed solvents.

[1134] In the aforementioned polymer solution, the polymer concentration is preferably 0.01~30% by mass, and more preferably 0.1~20% by mass.

[1135] The aforementioned reaction solutions and polymer solutions should be filtered. Filtering removes foreign matter and gels that could cause defects, effectively stabilizing the quality.

[1136] The materials used in the aforementioned filters include: fluorocarbon, cellulose, nylon, polyester, and hydrocarbon-based materials. For filtration steps involving corrosion inhibitors, filters made of fluorocarbons such as Teflon (a registered trademark), polyethylene, polypropylene, or nylon are preferable. The pore size of the filter can be appropriately selected according to the target cleanliness level, preferably below 100 nm, and even better, below 20 nm. Furthermore, these filters can be used individually or in combination. The filtration method can involve passing the solution only once, but circulating the solution and performing multiple filtrations is preferable. The filtration steps can be performed during the polymer manufacturing process, in any order and number of times, preferably filtering the reaction solution after the polymerization reaction, the polymer solution, or both.

[1137] [Chemical amplification resist composition]

[1138] [(A) Basic Polymer]

[1139] The chemically amplified resist composition of the present invention contains a base polymer comprising the aforementioned polymer as component (A).

[1140] The aforementioned polymers may be used alone or in combination of two or more with different composition ratios, Mw and / or Mw / Mn. Furthermore, (A) the base polymer may include, in addition to the aforementioned polymers, hydrides of ring-opening metathesis polymers, for which the polymers described in Japanese Patent Application Publication No. 2003-66612 may be used.

[1141] [(B) Organic solvents]

[1142] The chemically amplified resist composition of the present invention may also contain an organic solvent as component (B). There are no particular limitations on whether the organic solvent in (B) is capable of dissolving the aforementioned components and the components described below. 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 mixtures thereof.

[1143] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, cyclohexanone, GBL, ethyl lactate, DAA, and mixtures thereof are particularly well-soluble as the base polymer of component (A).

[1144] In the chemically amplified resist composition of the present invention, the content of (B) organic solvent relative to 80 parts by mass of (A) base polymer is preferably 200-7000 parts by mass, and more preferably 400-5000 parts by mass. (B) Organic solvent may be used alone or in combination with two or more types.

[1145] [(C) Quenching agent]

[1146] The chemically amplified resist composition of the present invention may also contain a quencher as component (C). Furthermore, in the present invention, the quencher refers to a material used to prevent the diffusion of a strong acid generated from the photoacid generator in the chemically amplified resist composition towards the unexposed area and to form a desired pattern. Additionally, "strong acid" means an acid with sufficient acidity to cause a deprotection reaction of unstable acid groups.

[1147] (C) Specific examples of quenching agents can be listed as onion salts represented by formula (1) or (2).

[1148] [Chemistry 459]

[1149]

[1150] In equation (1), R q1 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain hydrogen atoms or heteroatoms, but excludes those in which the hydrogen atom at the α-position of the sulfonate group is replaced by a fluorine atom or a fluoroalkyl group. In formula (2), R q2 Hydrocarbon groups consisting of 1 to 40 carbon atoms, which may also contain heteroatoms.

[1151] R q1 The hydrocarbon groups representing carbon numbers from 1 to 40 can be specifically listed as follows: 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., alkyl groups with carbon numbers from 1 to 40; 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, and 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, these 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.]

[1152] R q2 The hydrocarbon group represented can be specifically exemplified as R. q1 In addition to the specific examples of substituents, examples include fluorinated saturated hydrocarbon groups such as trifluoromethyl and trifluoroethyl, and fluorinated aryl groups such as pentafluorophenyl and 4-trifluoromethylphenyl.

[1153] Specific examples of the anions of onium salts represented by equation (1) are listed below, but are not limited thereto.

[1154] [Chemistry 460]

[1155]

[1156] [Chemistry 461]

[1157]

[1158] [Chemistry 462]

[1159]

[1160] [Chemistry 463]

[1161]

[1162] [Chemistry 464]

[1163]

[1164] Other specific examples of the onium salt anion represented by formula (1) can be listed as follows: those described in paragraphs

[0027] to

[0029] of Japanese Patent No. 6248882, those described in paragraphs

[0029] to

[0034] of Japanese Patent No. 6648726, those described in paragraphs

[0220] to

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

[0028] to

[0029] of Japanese Patent No. 7067271. The authors recorded in 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, etc.

[1165] Specific examples of the anions of onium salts represented by equation (2) are listed below, but are not limited thereto.

[1166] [Chemistry 465]

[1167]

[1168] [Chemistry 466]

[1169]

[1170] [Chemistry 467]

[1171]

[1172] [Chemistry 468]

[1173]

[1174] [Chemistry 469]

[1175]

[1176] Other specific examples of onium salt anions represented by formula (2) can be listed as follows: paragraphs

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

[0231] ~

[0233] ,

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

[0240] ~

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

[0203] ~

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

[0282] ~

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

[0013] ~

[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 subjects described in paragraphs

[0285] to

[0290] of Japanese Patent No. 7614747 and paragraphs

[0201] to

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

[1177] In equations (1) and (2), Mq + The cation is an onium cation. Examples of the aforementioned onium cations include: sulfonium cation, monium cation, ammonium cation, etc. Specific examples of the aforementioned sulfonium cations include: examples of cations that are sulfonium salt type monomers represented by formula (A), those described in paragraphs

[0102] to

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

[0044] to

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

[0035] to

[0046] of Japanese Patent Application Publication No. 7491173, etc., but are not limited thereto.

[1178] Furthermore, the aforementioned sulfonium cation should preferably be a sulfonium cation represented by the following formula (sulfo-1).

[1179] [Chemistry 470]

[1180]

[1181] In formula (sulfo-1), e1 is 0 or 1. When e1 is 0, it is a benzene ring; when e1 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with e1 of 0 is more ideal. e2 is 0 or 1. When e2 is 0, it is a benzene ring; when e2 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with e2 of 0 is more ideal. e3 is 0 or 1. When e3 is 0, it is a benzene ring; when e3 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with e3 of 0 is more ideal.

[1182] In formula (sulfo-1), e4 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the higher the absorption of EUV, but the solvent solubility becomes more lacking and there is a concern about precipitation in the resist composition. Therefore, e4 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being better.

[1183] In formula (sulfo-1), e5 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, e5 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred. e6 is 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, e6 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred. e7 is 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, e7 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred.

[1184] In formula (sulfo-1), e8 is 0, 1, or 2. From the perspective of raw material availability, e8 is preferably 0 or 1. e9 is 0, 1, or 2. From the perspective of raw material availability, e9 is preferably 0 or 1. e10 is 0, 1, or 2. From the perspective of raw material availability, e10 is preferably 0 or 1.

[1185] In formula (sulfo-1), e11 is 0 or 1. When e11 is 0, it is a benzene ring; when e11 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with e11 of 0 is more ideal.

[1186] In formula (sulfo-1), e12 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the higher the absorption of EUV, but the solvent solubility becomes more lacking and there is a concern about precipitation in the resist composition. Therefore, e12 should preferably be 0, 1, 2, or 3, with 0, 1, or 2 being better.

[1187] In formula (sulfo-1), e13 is 0, 1, or 2. From the perspective of raw material availability, e13 is preferably 0 or 1. e14 is 0, 1, or 2. From a synthetic perspective, e14 is preferably 0 or 1.

[1188] However, when e1 is 0, 0 ≤ e6 + e9 ≤ 4; when e1 is 1, 0 ≤ e6 + e9 ≤ 6. When e2 is 0, 0 ≤ e7 + e10 ≤ 4; when e2 is 1, 0 ≤ e7 + e10 ≤ 6. When e3 is 0, 1 ≤ e4 + e5 + e8 + e14 ≤ 4; when e3 is 1, 1 ≤ e4 + e5 + e8 + e14 ≤ 6. When e11 is 0, 0 ≤ e12 + e13 ≤ 4; when e11 is 1, 0 ≤ e12 + e13 ≤ 6. Also, e4 + e12 ≥ 1.

[1189] In formula (sulfo-1), R F1 ~R F3 Each of these can be independently composed of 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 e5 is 2, 3, or 4, each R... F1 They can be the same or different. When e6 is 2, 3, 4, 5 or 6, each R... F2 They can be the same or different. When e7 is 2, 3, 4, 5 or 6, each R... F3 They can be the same or different.

[1190] In formula (sulfo-1), R q11 ~R q14The group can be a halogen atom other than iodine or fluorine, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms (which may also contain heteroatoms), a hydrocarbon oxygen group with 1 to 20 carbon atoms (which may also contain heteroatoms), or a hydrocarbon thio group with 1 to 20 carbon atoms (which may also contain heteroatoms). The hydrocarbon group, hydrocarbon oxygen group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given and illustrated in the description of formula (A) as R. 1 ~R 3 The same example applies to the hydrocarbon group. Furthermore, some or all of the hydrogen atoms in the hydrocarbon group, alkyl group, and alkyl thio group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. Also, a portion of the -CH2- group in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, the hydrocarbon group 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.

[1191] Also, when e8 is 2, there are 2 Rs. q11 They can be the same or different, and there are 2 Rs. q11 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When e9 is 2, there are 2 R atoms. q12 They can be the same or different, and there are 2 Rs. q12 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When e10 is 2, there are 2 R atoms. q13 They can be the same or different, and there are 2 Rs. q13 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When e13 is 2, there are 2 R atoms. q14 They can be the same or different, and there are 2 Rs. q14 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 ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, norbornene ring, adamantane ring, 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, and halogen atoms, and part of the -CH2- 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.

[1192] Furthermore, S is directly bonded to the sulfonium cation represented by formula (sulfo-1). + The aromatic rings can also bond with 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.

[1193] [Chemistry 471]

[1194]

[1195] In the formula, the dashed lines represent atomic bonds.

[1196] In formula (sulfo-1), L F and L G These can be independently identified as single bonds, ether bonds, ester bonds, amide bonds, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. Among them, L... F The bonds should ideally be single bonds, ether bonds, ester bonds, or sulfonate bonds, with ester bonds or sulfonate bonds being preferred. G It is preferable to have a single bond, ether bond, or ester bond, with a single bond being better.

[1197] In formula (sulfo-1), X L3 It is a single-bonded or heteroatom-containing hydrocarbon group with 1 to 40 carbon atoms. The aforementioned hydrocarbon group can be linear, branched, or cyclic; specific examples include alkyldiyl, cyclic saturated hydrocarbon groups, and arylyl groups. Specific examples of the aforementioned heteroatom include oxygen, nitrogen, and sulfur atoms. L3 Specific examples of hydrocarbon groups with 1 to 40 carbon atoms that may also contain heteroatoms can be illustrated as X in the description of formula (Z2). L1 and X L2 The example X may also contain a heteroatom-containing hydrocarbon group with 1 to 40 carbon atoms. L -0~X L -61. Among them, X L3 It is advisable to be X L -0~X L -22, X L -29~X L -34 and X L -47~X L -61.

[1198] The sulfonium cation represented by formula (sulfo-1) should preferably be represented by the following formula (sulfo-1-1).

[1199] [Chemistry 472]

[1200]

[1201] In the formula, e4~e10, e12~e14, R F1 ~R F3 R q11 ~R q14 L F LG and X L3 Same as above.

[1202] The sulfonium cation represented by formula (sulfo-1-1) should preferably be represented by formula (sulfo-1-2).

[1203] [Chemistry 473]

[1204]

[1205] In the formula, e4~e10, R F1 ~R F3 and R q11 ~R q13 Same as above.

[1206] Specific examples of sulfonium cations represented by formula (sulfo-1) are shown below, but are not limited thereto. Additionally, in the following formula, Me is a methyl group.

[1207] [Chemistry 474]

[1208]

[1209] [Chemistry 475]

[1210]

[1211] [Chemistry 476]

[1212]

[1213] [Chemistry 477]

[1214]

[1215] [Chemistry 478]

[1216]

[1217] [Chemistry 479]

[1218]

[1219] [Chemistry 480]

[1220]

[1221] [Chemistry 481]

[1222]

[1223] [Chemistry 482]

[1224]

[1225] [Chemistry 483]

[1226]

[1227] [Chemistry 484]

[1228]

[1229] [Chemistry 485]

[1230]

[1231] [Chemistry 486]

[1232]

[1233] [Chemistry 487]

[1234]

[1235] [Chemistry 488]

[1236]

[1237] [Chemistry 489]

[1238]

[1239] [Chemistry 490]

[1240]

[1241] [Chemistry 491]

[1242]

[1243] [Chemistry 492]

[1244]

[1245] [Chemistry 493]

[1246]

[1247] [Chemistry 494]

[1248]

[1249] [Chemistry 495]

[1250]

[1251] [Chemistry 496]

[1252]

[1253] [Chemistry 497]

[1254]

[1255] [Chemistry 498]

[1256]

[1257] [Chemistry 499]

[1258]

[1259] [Chemical 500]

[1260]

[1261] [Chemical 501]

[1262]

[1263] 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 thereto.

[1264] Specific examples of the aforementioned ammonium cations can be represented by the following formula (am-1).

[1265] [Chemical 502]

[1266]

[1267] In equation (am-1), R q21 ~R q24 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R q21 and R q22 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 listed and illustrated in the description of formula (A) as R. 1 ~R 3 The same example represents hydrocarbon groups.

[1268] Specific examples of ammonium cations represented by formula (am-1) are listed below, but are not limited thereto.

[1269] [Chemical 503]

[1270]

[1271] Specific examples of onium salts represented by formula (1) or (2) can be listed as any combination of the aforementioned anions and cations. Furthermore, these onium salts can be readily 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.

[1272] The onium salts represented by formula (1) or (2) function 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. Here, "weak acid" means an acidity that cannot deprotect the acid-instable groups of the units containing acid-instable groups used in the base polymer. The onium salts represented by formula (1) or (2) function as quenchers when used in combination with onium salt-type photoacid generators that have a conjugate base of a strong acid, such as sulfonic acid with fluorinated α-position, as a relative anion. That is, when onium salts that produce strong acids, such as sulfonic acid with fluorinated α-position, are mixed with onium salts that produce weak acids, such as unfluorinated sulfonic acid or carboxylic acid, if the strong acid generated from the photoacid generator due to high-energy ray irradiation collides with the unreacted onium salt with a weak acid anion, the weak acid is released through salt exchange, and an onium salt with a strong acid anion is generated. During this process, the strong acid is exchanged for a weak acid with low catalytic activity, thus appearing as acid deactivation and allowing for the control of acid diffusion.

[1273] Furthermore, (C) the quenching agent may be an onium salt having a sulfonium cation and a benzene oxide anion site within the same molecule as described in Japanese Patent No. 6848776, or an onium salt having a sulfonium cation and a carboxylate anion site within the same molecule as described in Japanese Patent No. 6583136, Japanese Patent Application Publication No. 2020-200311, or an onium salt having a monazine cation and a carboxylate anion site within the same molecule as described in Japanese Patent No. 6274755.

[1274] Here, it is believed that when the photoacid generator that produces strong acids is an onium salt, as mentioned above, the strong acid generated by high-energy ray irradiation can be exchanged for a weak acid. On the other hand, the weak acid generated by high-energy ray irradiation is not easily exchanged with the unreacted onium salt that produces strong acids. This is because onium cations more readily form ion pairs with the anions of strong acids.

[1275] When the chemically amplified resist composition of the present invention contains an onium salt represented by formula (1) or (2) as a quencher in (C), its content relative to 80 parts by mass of the base polymer in (A) is preferably 0.1 to 20 parts by mass, and more preferably 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 there is no significant reduction in sensitivity, which is ideal. The onium salt represented by formula (1) or (2) can be used alone or in combination of two or more.

[1276] The chemically amplified resist composition of the present invention may also contain a nitrogen-containing compound as a (C) quencher. Specific examples of the aforementioned nitrogen-containing compounds include primary, secondary, or tertiary 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 formed by protecting a primary or secondary amine with a carbamate group, as described in Japanese Patent Publication No. 3790649, may also be cited. In addition, compounds with a structure having any one of a lactone ring, sulfonyl lactone ring, lactam ring, or sulfonamide ring coexisting with an acid-instable group, as described in Japanese Patent Publication No. 7615989, may also be cited.

[1277] Alternatively, sulfonate sulfonates with nitrogen-containing substituents can be used as nitrogen-containing compounds. Such compounds function as quenchers in the unexposed areas, but lose their quenching ability in the exposed areas due to neutralization with the acid they generate, thus functioning 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 No. 2009-109595 and Japanese Patent Application Publication No. 2012-46501 can be referenced for photodegrading bases.

[1278] When the chemically amplified resist composition of the present invention contains a nitrogen-containing compound as a quencher (C), its content relative to 80 parts by mass of the base polymer (A) is preferably 0.001 to 12 parts by mass, 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.

[1279] [(D) Photoacid generator]

[1280] 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 being a compound that generates acid upon irradiation by high-energy rays. Ideal photoacid generators may be represented by formulas (3) or (4).

[1281] [Chemical 504]

[1282]

[1283] In equations (3) and (4), R 101 ~R 105 Each group consists independently of a 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 the aforementioned hydrocarbon groups 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 listed and illustrated in the description of formula (A) as R. 1 ~R3 The same example applies to hydrocarbon groups. 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, and some of the -CH2- 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, 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.

[1284] Specific examples of sulfonium salt cations represented by formula (3) can be listed as follows: examples of sulfonium salt type monomer cations represented by formula (A), those described in paragraphs

[0102] to

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

[0044] to

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

[0035] to

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

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

[1285] In equations (3) and (4), Xa - It is the anion of a strong acid. The anions of the aforementioned strong acids can be represented by any one of the following formulas (Xa-1) to (Xa-4).

[1286] [Chemical 505]

[1287]

[1288] In formula (Xa-1), R fa It is a hydrocarbon group with 1 to 60 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 listed and illustrated as R in the following formula (Xa-1-1). fa1 The same example represents hydrocarbon groups.

[1289] The anion represented by formula (Xa-1) should preferably be represented by the following formula (Xa-1-1).

[1290] [Chemical 506]

[1291]

[1292] In equation (Xa-1-1), Q 1 and Q 2Each of the following 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 of these is preferably trifluoromethyl. m is 0, 1, 2, 3, or 4, with 1 being particularly preferred. R fa1 The hydrocarbon group may contain heteroatoms and has 1 to 40 carbon atoms. The aforementioned heteroatoms are preferably oxygen, nitrogen, sulfur, or halogen atoms, with oxygen atoms being more preferred. Considering the high resolution achieved in the formation of fine patterns, hydrocarbon groups with 6 to 30 carbon atoms are particularly preferred.

[1293] In formula (Xa-1-1), R fa1 The hydrocarbon groups representing 1 to 40 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecanyl, eicosyl, etc., alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornel, norbornelmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, dicyclohexylmethyl, etc., cyclic groups with 3 to 40 carbon atoms. Saturated 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-bridged ethylene-9,10-dihydroanthrayl and 6,13-bridged ethylene-6,13-dihydropentaphenyl; hydrocarbon groups with 17 to 40 carbons having a steroid skeleton; and groups obtained by combining these groups.

[1294] 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, and 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, and nitrogen atoms. This can result in the presence of 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.

[1295] In equation (Xa-1-1), L a1The 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 even better.

[1296] Specific examples of anions represented by formula (Xa-1) are shown below, but are not limited to these. Additionally, in the following formula, Q... 1 As mentioned above, Ac is an acetyl group.

[1297] [Chem. 507]

[1298]

[1299] [Chem.508]

[1300]

[1301] [Chemical 509]

[1302]

[1303] [Chem.510]

[1304]

[1305] [Chem.511]

[1306]

[1307] [Chem.512]

[1308]

[1309] [Chem.513]

[1310]

[1311] [Chem.514]

[1312]

[1313] [Chem.515]

[1314]

[1315] [Chem.516]

[1316]

[1317] [Chem.517]

[1318]

[1319] [Chem.518]

[1320]

[1321] Other specific examples of anions represented by formula (Xa-1) can be listed as follows: 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, etc.

[1322] In formula (Xa-2), R fb1 and R fb2 Each hydrocarbon group consists independently of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in formula (Xa-1-1). fa1 The same example represents a hydrocarbon group. R fb1 and R fb2 It should preferably be a fluorine atom or a straight-chain fluorinated alkyl group having 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, at which point R fb1 and R fb2 The groups formed by mutual bonding should preferably be fluorinated ethylidene or fluorinated propyleneide.

[1323] In formula (Xa-3), R fc1 R fc2 and R fc3 Each hydrocarbon group consists independently of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in formula (Xa-1-1). fa1 The same example represents a hydrocarbon group. R fc1 R fc2 and R fc3 It should preferably be a fluorine atom or a straight-chain fluorinated alkyl group having 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, at which point R fc1 and R fc2 The groups formed by mutual bonding should preferably be fluorinated ethylidene or fluorinated propyleneide.

[1324] In formula (Xa-4), R fd It can be a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in formula (Xa-1-1). fa1 The same example applies to hydrocarbon groups. 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, and some of the -CH2- 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, 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.

[1325] Specific examples of anions represented by formula (Xa-4) can be listed below, but are not limited to these.

[1326] [Chem.519]

[1327]

[1328] [Chem.520]

[1329]

[1330] Other specific examples of anions represented by formula (Xa-4) can be listed, such as those described in paragraphs

[0050] to

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

[1331] Xa - Examples of anions can be further illustrated by anions having aromatic rings substituted with iodine or bromine atoms. Specific examples of such anions can be illustrated by the following formula (Xa-5).

[1332] [Chem.521]

[1333]

[1334] In equation (Xa-5), x is 1, 2, or 3. y is 1, 2, 3, 4, or 5.

[1335] z can be 0, 1, 2, or 3. However, 1 ≤ y + z ≤ 5. y should ideally be 1, 2, or 3, with 2 or 3 being better. z should ideally be 0, 1, or 2.

[1336] In equation (Xa-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.

[1337] In equation (Xa-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, and part of the -CH2- of the hydrocarbon group can also be replaced by an ether bond or an ester bond. The aforementioned saturated hydrocarbon group can be any of the following: linear, branched, or cyclic.

[1338] In equation (Xa-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.

[1339] 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: 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, etc., alkyl diyl groups with 1 to 20 carbon atoms; cyclopentanediyl, cyclohexanediyl, norcamphenediyl, adamantanediyl, 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; polycyclic hydrocarbon groups containing aromatic rings with 7-20 carbon atoms, such as 9,10-bridged ethylene-9,10-dihydroanthracenediyl and 6,13-bridged ethylene-6,13-dihydropentaphenylene; and groups obtained by combining them, etc.] 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 given by further removing one or two hydrogen atoms from the aforementioned examples of hydrocarbon groups representing 1 to 20 carbon atoms.

[1340] Furthermore, some or all of the hydrogen atoms in the aforementioned alkylene groups and (x+1) valence hydrocarbon groups can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. Also, some of the -CH2- in the aforementioned alkylene groups and (x+1) valence hydrocarbon groups can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, the groups 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.

[1341] In equation (Xa-5), L 13 It can be a single bond, ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond.

[1342] In formula (Xa-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 oxy group with 1 to 20 carbon atoms, hydrocarbon thio group with 1 to 20 carbon atoms, hydrocarbon carbonyl group with 2 to 20 carbon atoms, hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms, or hydrocarbon sulfonyl oxy 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 Furthermore, the hydrocarbon group, hydrocarbon oxy group, hydrocarbon thio group, hydrocarbon carbonyl group, hydrocarbon oxy carbonyl group, hydrocarbon carbonyl oxy group, and hydrocarbon sulfonyl oxy 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 can be 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 oxygen group having 2 to 6 carbon atoms. R feD It is an aliphatic hydrocarbon group with 1 to 16 carbon atoms, an aryl group with 6 to 12 carbon atoms, or an aralkyl group with 7 to 15 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated alkyloxy group with 1 to 6 carbon atoms, a saturated alkylcarbonyl group with 2 to 6 carbon atoms, or a saturated alkylcarbonyloxy group with 2 to 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 linear, branched, or cyclic. When x and / or z are 2 or more, each R fe They can be the same or different.

[1343] Among them, R fe It is advisable to use hydroxyl groups, -N(R) feC )-C(=O)-R feD -N(R) feC )-C(=O)-OR feD Fluorine atoms, chlorine atoms, bromine atoms, methyl groups, methoxy groups, etc.

[1344] In equation (Xa-5), Rf 11 ~Rf 14Each of these can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of them must be a fluorine atom or a trifluoromethyl group. Also, Rf 11 With Rf 12 They can also combine to form carbonyl groups. Especially Rf 13 and Rf 14 Both are ideally composed of fluorine atoms.

[1345] Specific examples of anions represented by equation (Xa-5) are shown below, but are not limited to these. Furthermore, in the following equation, X... BI Same as above.

[1346] [Chem.522]

[1347]

[1348] [Chem.523]

[1349]

[1350] [Chem.524]

[1351]

[1352] [Chem.525]

[1353]

[1354] [Chem.526]

[1355]

[1356] [Chem.527]

[1357]

[1358] [Chem.528]

[1359]

[1360] [Chem. 529]

[1361]

[1362] [Chem.530]

[1363]

[1364] [Chemistry 531]

[1365]

[1366] [Chemistry 532]

[1367]

[1368] [Chem.533]

[1369]

[1370] [Chemistry 534]

[1371]

[1372] [Chem.535]

[1373]

[1374] [Chemistry 536]

[1375]

[1376] [Chemistry 537]

[1377]

[1378] [Chem.538]

[1379]

[1380] [Chem.539]

[1381]

[1382] [Chemistry 540]

[1383]

[1384] [Chemistry 541]

[1385]

[1386] [Chemistry 542]

[1387]

[1388] [Chem.543]

[1389]

[1390] [Chemistry 544]

[1391]

[1392] [Chem.545]

[1393]

[1394] Xa -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 paragraphs

[0157] to

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

[0227] to

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

[0253] to

[0256] of Japanese Patent No. 7466597, the paragraphs

[0309] to

[0312] of Japanese Patent No. 7466782, and the paragraphs

[0042] to

[0058] of Japanese Unexamined Patent Application Publication No. 2025-023601, etc.

[1395] Xa - Other examples of anions can be further cited in 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. 60905. The fluorine-free aromatic sulfonic acid anions and alkyl sulfonic acid anions described in paragraphs

[0034] to

[0037] of Japanese Patent Application Publication No. 85, 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.

[1396] Xa - The anion may also be the disulfonic acid anion described in Japanese Patent Application Publication No. 2015-206932, the anion with sulfonic acid on one side and sulfonamide or sulfonamide on the other side as described in International Publication No. 2020 / 158366, or the anion with sulfonic acid on one side and carboxylic acid on the other side as described in Japanese Patent Application Publication No. 2015-24989.

[1397] Furthermore, the photoacid generator of component (D) should also be represented by the following formula (5).

[1398] [Chemistry 546]

[1399]

[1400] In equation (5), R 201 and R 202 Each can be independently a hydrocarbon group with 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.

[1401] 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: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 30 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornel, oxanorbornel, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms, such as decyl and adamantyl; aryl groups with 6 to 30 carbon atoms, such as phenyl, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, tert-butylnaphthyl, and anthracene; and groups obtained by combining these. 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, and some 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, groups 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.]

[1402] R 203The 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, and a portion of the -CH2- group in the aforementioned alkylene group can also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. This can result in the presence of hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. The aforementioned heteroatoms should preferably be oxygen atoms.

[1403] In equation (5), L 21 It 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 listed and illustrated as R. 203 The same example represents the subhydrocarbon group.

[1404] 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. However, X a X b X c and X d At least one of them is a fluorine atom or a trifluoromethyl group.

[1405] The photoacid generator represented by formula (5) should preferably be represented by the following formula (5').

[1406] [Chemistry 547]

[1407]

[1408] In equation (5'), L 21 Same as above. 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 listed and illustrated as R in formula (Xa-1-1). fa1 The same example represents hydrocarbon groups. p and q are independently 0, 1, 2, 3, 4 or 5, and r is 0, 1, 2, 3 or 4.

[1409] Specific examples of photoacid generators represented by formula (5) can be cited as the same examples as those exemplified in Japanese Patent Application Publication No. 2017-26980 as photoacid generators represented by formula (2).

[1410] Among the aforementioned photoacid generators, those containing anions represented by formula (Xa-1-1) or (Xa-4) exhibit low acid diffusion and excellent solvent solubility, making them particularly ideal. Furthermore, those represented by formula (5') exhibit extremely low acid diffusion, making them particularly ideal.

[1411] When the chemically amplified resist composition of the present invention contains (D) a photoacid generating agent, its content relative to 80 parts by weight of (A) the base polymer is preferably 0.1 to 40 parts by weight, and more preferably 0.5 to 20 parts by weight. If the amount of (D) photoacid generating agent added is within the aforementioned range, the resolution is good, and there is no concern about foreign matter forming in the resist film after development or during peeling, which is therefore ideal. (D) A photoacid generating agent can be used alone or in combination of two or more.

[1412] [(E) Surfactant]

[1413] The chemically amplified resist composition of the present invention may also contain a surfactant as component (E). The surfactant (E) is preferably a surfactant that is insoluble or sparingly soluble in water but soluble in alkaline developing solution, or a surfactant that is insoluble or sparingly soluble in both water and alkaline developing solution. Such surfactants can be referred to in Japanese Patent Application Publication Nos. 2010-215608 and 2011-16746.

[1414] Surfactants that are insoluble or poorly soluble in water and alkaline developing solutions, among those listed in the aforementioned announcement, are preferably FC-4430 (manufactured by 3M Corporation), SURFLON (registered trademark) S-381 (manufactured by AGC SEIMI CHEMICAL), OLFINE (registered trademark) E1004 (manufactured by Nissin Chemical Industry Co., Ltd.), KH-20, KH-30 (manufactured by AGC SEIMI CHEMICAL), and oxane ring-opening polymers represented by the following formula (surf-1).

[1415] [Chem.548]

[1416]

[1417] Here, R, Rf, A, B, C, m, and n are irrelevant to the foregoing description and apply only to formula (surf-1). R is an aliphatic group with 2 to 5 carbon atoms, valent to 2 to 4. Examples of the aforementioned aliphatic groups, for those with a valent charge, include: ethylene, 1,4-butylene, 1,2-propylene, 2,2-dimethyl-1,3-propylene, 1,5-pentane, etc.; examples of those with a valent charge or a tetravalent charge include the following.

[1418] [Chemistry 549]

[1419]

[1420] In the formula, the dashed lines represent atomic bonds, which are partial structures derived from glycerol, trimethylolethane, trimethylolpropane, and neopentyl tertrol, respectively.

[1421] Among them, 1,4-butylene, 2,2-dimethyl-1,3-propylene, etc. are preferred.

[1422] Rf is trifluoromethyl or pentafluoroethyl, preferably trifluoromethyl. m is an integer from 0 to 3, n is an integer from 1 to 4, the sum of n and m is the valence of R, and is an integer from 2 to 4. A is 1. B is an integer from 2 to 25, preferably an integer from 4 to 20. C is an integer from 0 to 10, preferably 0 or 1. Furthermore, the arrangement of the constituent units in formula (surf-1) is not specified; they can be block-bonded or randomly bonded. For details on the manufacture of surfactants in partially fluorinated oxyheterocyclic butane ring-opening polymer systems, please refer to the specification of US Patent No. 5,650,483, etc.

[1423] Surfactants that are insoluble or sparingly soluble in water but soluble in alkaline developing solutions are useful in ArF immersion lithography when no resist film is used. They reduce water penetration and leaching by aligning with the surface of the resist film. Therefore, they are useful for suppressing the leaching of water-soluble components from the resist film and reducing damage to the exposure equipment. Furthermore, they are useful for development with alkaline solutions after exposure or post-exposure baking (PEB) that dissolves in the solution and is unlikely to cause defects. Such surfactants, which are insoluble or sparingly soluble in water but soluble in alkaline developing solutions, are polymeric surfactants, also known as hydrophobic resins, and are particularly desirable for those with high water repellency and improved hydrophobic properties.

[1424] Specific examples of such polymeric surfactants may include at least one of the repeating units represented by formula (6A) (hereinafter also referred to as repeating unit 6A), the repeating unit represented by formula (6B) (hereinafter also referred to as repeating unit 6B), the repeating unit represented by formula (6C) (hereinafter also referred to as repeating unit 6C), the repeating unit represented by formula (6D) (hereinafter also referred to as repeating unit 6D), and the repeating unit represented by formula (6E) (hereinafter also referred to as repeating unit 6E).

[1425] [Chemical 550]

[1426]

[1427] In equations (6A) to (6E), R B It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. W 1 It can be -CH2-, -CH2CH2-, -O-, or two separate -H groups. R s1 Each can be independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R s2 It is a single bond, or a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms. R s3 Each can be independently a hydrogen atom, a hydrocarbon group with 1 to 15 carbon atoms, a fluorinated hydrocarbon group, or an acid-labile group. R s3 When the group is a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group can also be inserted between the carbon-carbon bonds. R s4 It is a hydrocarbon group or fluorinated hydrocarbon group with a valence of (u+1) and having 1 to 20 carbon atoms. u can be 1, 2, or 3. R s5 Each can be 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 a fluorinated hydrocarbon group with 1 to 15 carbon atoms, and an ether bond or a carbonyl group may also be inserted between its carbon-carbon bonds.

[1428] R s1The hydrocarbon group representing 1 to 10 carbon atoms should preferably be a saturated hydrocarbon group, and 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.

[1429] R s2 The alkylene group represented should preferably be a saturated alkylene group, and can be linear, branched, or cyclic. Specific examples include: methylene, ethylene, propylene, butylene, and pentylene.

[1430] 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; aliphatic unsaturated hydrocarbon groups such as alkenyl and alkynyl groups, which are preferably saturated hydrocarbon groups. Specific examples of the aforementioned saturated hydrocarbon groups can be listed as R. s1 In addition to the hydrocarbon groups indicated by R, other examples include undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl. s3 or R s6 The fluorinated hydrocarbon groups can be categorized as groups in which some or all of the hydrogen atoms of the carbon atoms bonded to the aforementioned hydrocarbon groups are replaced by fluorine atoms. As mentioned above, ether bonds or carbonyl groups may also be inserted between their carbon-carbon bonds.

[1431] R s3 Specific examples of acid-instable groups can be listed as follows: groups represented by the aforementioned formulas (AL-3) to (AL-5), trialkylsilyl groups with alkyl groups having 1 to 6 carbon atoms, and alkyl groups containing oxygen groups having 4 to 20 carbon atoms.

[1432] R s4 The (u+1) valence hydrocarbon group or fluorinated hydrocarbon group can be any of the following: straight chain, branched, or cyclic. Specific examples can be listed as groups obtained by further removing u hydrogen atoms from the aforementioned hydrocarbon group or fluorinated hydrocarbon group.

[1433] R saThe fluorinated hydrocarbon group represented is preferably a saturated one, and may be linear, branched, or cyclic. Specific examples thereof include those in which part or all of the hydrogen atoms of the aforementioned hydrocarbon group are substituted with fluorine atoms, and specific examples thereof include: 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-dodecafluoroheptyl, 2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl, 2-(perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl, and the like.

[1434] Specific examples of the repeating units 6A to 6E include those shown below, but are not limited thereto. In addition, in the following formula, R B is the same as described above.

[1435] [Chem. 551]

[1436]

[1437] [Chem. 552]

[1438]

[1439] [Chem. 553]

[1440]

[1441] [Chem. 554]

[1442]

[1443] [Chem. 555]

[1444]

[1445] [Chem. 556]

[1446]

[1447] The aforementioned polymeric surfactant may further contain other repeating units besides the repeating units 6A to 6E. Specific examples of other repeating units include repeating units derived from methacrylic acid, α-trifluoromethyl methacrylic acid derivatives and the like. In the polymeric surfactant, the content of the repeating units 6A to 6E in all the repeating units is preferably 20 mol% or more, more preferably 60 mol% or more, and still more preferably 100 mol%.

[1448] The Mw of the aforementioned polymeric surfactant is preferably 1,000 to 500,000, and more preferably 3,000 to 100,000. The Mw / Mn ratio is preferably 1.0 to 2.0, and more preferably 1.0 to 1.6.

[1449] Methods for synthesizing the aforementioned polymeric surfactants include: providing at least one monomer selected from repeating units 6A-6E, and other repeating units as needed, containing unsaturated bonds; adding a free radical initiator to an organic solvent and heating to polymerize it. Specific examples of organic solvents used in polymerization include: toluene, benzene, THF, diethyl ether, dioxane, etc. Specific examples of polymerization initiators include: AIBN, 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2-azobis(2-methylpropionic acid), benzoyl peroxide, lauroyl peroxide, etc. The reaction temperature is preferably 50-100°C. The reaction time is preferably 4-24 hours. Acid-labile groups can be directly introduced into the monomer, or they can be protected or partially protected after polymerization.

[1450] 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 number of monomers used to polymerize them should preferably be 0.01 to 10 mol%.

[1451] When the chemically amplified resist composition of the present invention contains surfactant (E), its content relative to 80 parts by weight of the base polymer (A) is preferably 0.1 to 50 parts by weight, and more preferably 0.5 to 10 parts by weight. If the content of surfactant (E) is 0.1 parts by weight or more, it will sufficiently improve the receding contact angle between the resist film surface and water; if it is 50 parts by weight or less, the dissolution rate of the resist film surface to the developer is low, and the height of the formed fine pattern is sufficiently maintained. Surfactant (E) can be used alone or in combination of two or more.

[1452] [(F) Other ingredients]

[1453] The chemically amplified resist composition of the present invention may also contain compounds that decompose due to acid and produce acid (acid-increasing compounds), organic acid derivatives, fluorinated alcohols, and compounds with a Mw of 3000 or less whose solubility in the developer changes due to acid (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, their content relative to 80 parts by mass of the base polymer in (A) is preferably 0 to 5 parts by mass, and more preferably 0 to 3 parts by mass. Excessive content may sometimes make acid diffusion control difficult, leading to 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.

[1454] [Pattern Formation Method]

[1455] 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 to high-energy radiation, and developing the aforementioned exposed resist film using a developing solution.

[1456] The aforementioned substrates may be, for example, substrates used in integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.) or substrates used in mask circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.).

[1457] The resist film can be formed by applying the aforementioned chemically amplified resist composition onto a substrate using methods such as spin coating, with a film thickness preferably of 0.05 to 2 μm, and then pre-baking it on a hot plate at a temperature preferably of 60 to 150°C for 1 to 10 minutes, more preferably at 80 to 140°C for 1 to 5 minutes.

[1458] High-energy rays used for photoresist film exposure include: KrF excimer laser, ArF excimer laser, EB, and EUV with wavelengths of 3-15 nm. When using KrF excimer laser, ArF excimer laser, or EUV for exposure, a mask for forming the desired pattern can be used, and the exposure dose should preferably be 1-200 mJ / cm². 2 And preferably, it should be 10~100mJ / cm 2 The process is carried out by irradiation. When using EB, a mask is used to form the desired pattern, or the exposure dose should be 1~300 μC / cm. 2 And preferably, it should be 10~200μC / cm 2Irradiation is performed in this manner.

[1459] In addition to the conventional exposure method, exposure can also be performed using an immersion method, 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.

[1460] The aforementioned water-insoluble protective film is used to prevent leaching from the resist film and to improve the hydrophobicity of the film surface. It is broadly classified into two types. One type is an organic solvent-stripping type, which must be stripped using an organic solvent that does not dissolve the resist film before alkaline aqueous solution development. The other type is an alkaline aqueous solution-soluble type, which is soluble in alkaline developing solution and removes the protective film while removing the soluble portion of the resist film. The latter is particularly preferred because it is based on a polymer containing 1,1,1,3,3,3-hexafluoro-2-propanol residues that is insoluble in water but soluble in alkaline developing solution, and is dissolved in alcohol solvents with 4 or more carbon atoms, ether solvents with 8 to 12 carbon atoms, or mixtures thereof. It is also possible to prepare a material by dissolving the aforementioned water-insoluble but alkaline developing solution-soluble surfactant in alcohol solvents with 4 or more carbon atoms, ether solvents with 8 to 12 carbon atoms, or mixtures thereof.

[1461] PEB can also be performed after exposure. PEB can be performed, for example, by heating on a hot plate at a temperature of 60-150°C for 1-5 minutes, preferably at 80-140°C for 1-3 minutes.

[1462] For example, a developing solution containing 0.1-5% by mass, preferably 2-3% by mass, such as tetramethylammonium hydroxide (TMAH), can be used. Common methods such as dip, immersion, and spray can be employed for 0.1-3 minutes, preferably 0.5-2 minutes. This allows the exposed areas to dissolve and form the desired pattern on the substrate.

[1463] Furthermore, after the resist film is formed, it can be rinsed with pure water to extract acid-generating agents or wash away particulate matter from the film surface. It can also be rinsed to remove water remaining on the film after exposure.

[1464] In addition, a double patterning method can also be used to form patterns. Examples of double patterning methods include: a trench method that uses a first exposure and etching to process a 1:3 trench pattern substrate, then offsets the position and uses a second exposure to form a 1:3 trench pattern, thus forming a 1:1 pattern; and a line method that uses a first exposure and etching to process a 1:3 isolated residual pattern on a first substrate, then offsets the position and uses a second exposure under the first substrate to form a 1:3 isolated residual pattern, and then processes this second substrate to form a 1:1 pattern with a pitch of half.

[1465] In the pattern forming method of the present invention, a negative tone development method can also be used, in which the aforementioned alkaline aqueous solution is replaced with an organic solvent as the developer to dissolve the unexposed portion.

[1466] In the aforementioned organic solvent development, the developing solution 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. Ethyl crotonate, 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 phenylacetate, ethyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, etc. These organic solvents can be used alone or in combination of two or more.

[1467] Example

[1468] The present invention will be specifically described below with examples of synthesis, embodiments, and comparative examples, but the present invention is not limited to the following embodiments. Furthermore, the apparatus used is described below.

[1469] MALDI TOF-MS: S3000 manufactured by Nippon Electronics Co., Ltd.

[1470] [1] Synthesis of sulfonium salt monomers

[1471] [Example 1-1] Synthesis of monomer PAG-1

[1472] (1) Synthesis of intermediate In-1

[1473] [Chem.557]

[1474]

[1475] Compounds SM-1 (71.9 g) and SM-2 (122.0 g) were dissolved in 1,2-dichloroethane (400 g) under a nitrogen atmosphere. The mixture was then heated under reflux for 15 hours. The reaction solution was cooled to 25°C, and water (100 g) was added to stop the reaction. The organic layer was then separated and washed with water, followed by concentration under reduced pressure to remove the solvent. The residue was purified by silica gel column chromatography to obtain 75.8 g of intermediate In-1 (61% yield) as a colorless oil.

[1476] (2) Synthesis of monomer PAG-1

[1477] [Chem.558]

[1478]

[1479] Under nitrogen atmosphere, intermediates In-1 (55.9 g), In-2 (76.4 g), dichloromethane (300 g), and water (150 g) were fed and stirred at room temperature for 30 minutes. The organic layer was separated and extracted, washed with water, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain 97.0 g of monomer PAG-1 (92% yield) as an oil.

[1480] The TOF-MS results for PAG-1 are shown below.

[1481] MALDI TOF-MS: POSITIVE M + 472 (equivalent to C) 26 H 22 F4NOS + )

[1482] NEGATIVE M - 699 (equivalent to C) 17 H 11 F2I2O8S2 - )

[1483] [Examples 1-2~1-9] Synthesis of monomers PAG-2~PAG-9

[1484] Using the corresponding raw materials and various organic synthesis reactions, the sulfonate-type monomers PAG-2 to PAG-9 shown below were synthesized.

[1485] [Chem.559]

[1486]

[1487] [Chem.560]

[1488]

[1489] [Comparative Examples 1-1 to 1-6] Comparison of the synthesis of monomers PAG-A to PAG-F

[1490] Using the corresponding raw materials and various organic synthesis reactions, the comparative sulfonate monomers PAG-A to PAG-F were synthesized as shown below.

[1491] [Chemistry 561]

[1492]

[1493] [2] Synthesis of basic polymers

[1494] The monomers used in the synthesis of the basic polymer, other than PAG-1 to PAG-9 and PAG-A to PAG-F, are described below.

[1495] [Chem.562]

[1496]

[1497] [Chem.563]

[1498]

[1499] [Chem.564]

[1500]

[1501] [Example 2-1] Synthesis of Polymer P-1

[1502] Under nitrogen atmosphere, monomers a1-1 (36.8 g), b1-1 (10.8 g), PAG-1 (52.6 g), V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), and 140 g of MEK were measured in a flask to prepare a monomer-polymerization initiator solution. In another flask, which had been prepared under nitrogen atmosphere, 46 g of MEK was measured, 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 maintained at 80°C with continuous stirring for 2 hours, and then cooled to room temperature. The resulting polymerization solution was added dropwise to 3000 g of vigorously stirred hexane, and the precipitated polymer was filtered and separated. 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-1 (yield 97.3 g, 97% yield). The Mw of polymer P-1 is 9300, and the Mw / Mn ratio is 1.51. Additionally, Mw is a polystyrene conversion value determined by GPC using DMF as a solvent.

[1503] [Chem.565]

[1504]

[1505] [Examples 2-2~2-26, Comparative Examples 2-1~2-18] Synthesis of polymers P-2~P-26, CP-1~CP-18

[1506] The polymers shown in Tables 1 and 2 were manufactured using the same method as in Example 2-1, except that the types and blending ratios of the monomers were changed.

[1507] [Table 1]

[1508]

[1509] [Table 2]

[1510]

[1511] [3] Preparation of chemically amplified resist composition

[1512] [Examples 3-1 to 3-26, Comparative Examples 3-1 to 3-18]

[1513] A solution was prepared by dissolving a base polymer (P-1 to P-26) containing the sulfonium salt monomers (PAG-1 to PAG-9) of the present invention, a base polymer (CP-1 to CP-18) containing the comparative sulfonium salt monomers (PAG-A to PAG-F), a photoacid generator (PAG-X to PAG-Z), and a quencher (Q-1 to Q-4) in a solvent containing 0.01% by mass of surfactant A (OMNOVA) as shown in Tables 3 and 4 below. The solution was then filtered through a 0.2 μm Teflon (registered trademark) filter to prepare chemically amplified resist compositions (R-1 to R-26, CR-1 to CR-18).

[1514] [Table 3]

[1515]

[1516] [Table 4]

[1517]

[1518] In Tables 3 and 4, the solvent, photoacid generators PAG-X, PAG-Y, PAG-Z, quenchers Q-1 to Q-4, and surfactant A are described below.

[1519] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[1520] EL (ethyl lactate)

[1521] DAA (diacetone alcohol)

[1522] Photoacid generators: PAG-X, PAG-Y, PAG-Z

[1523] [Chem.566]

[1524]

[1525] Quenching agents: Q-1~Q-4

[1526] [Chem.567]

[1527]

[1528] Surfactant A: 3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane·tetrahydrofuran·2,2-dimethyl-1,3-propanediol copolymer (manufactured by OMNOVA).

[1529] [Chem.568]

[1530]

[1531] a : (b + b') : (c + c') = 1 : 4~7 : 0.01~1 (molar ratio)

[1532] Mw=1500

[1533] [4] Evaluation of EUV lithography (1)

[1534] [Examples 4-1 to 4-26, Comparative Examples 4-1 to 4-18]

[1535] The chemically amplified resist compositions (R-1~R-26, CR-1~CR-18) shown in Tables 3 and 4 were spin-coated onto a Si substrate with a silicon-containing spin-coating hard mask SHB-A940 (silicon content 43% by mass) manufactured by Shin-Etsu Chemical Industry Co., Ltd., to a thickness of 20 nm. The substrate was pre-baked at 100°C for 60 seconds using a hot plate to obtain a resist film with a thickness of 50 nm. The aforementioned resist film was then subjected to exposure using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, dipole illumination), with variations in exposure amount and focus (exposure spacing: 1 mJ / cm). 2 An LS pattern with a size of 18 nm and a pitch of 36 nm was exposed on the wafer (focal spacing: 0.020 μm). After exposure, PEB was performed at the temperatures shown in Tables 5 and 6 for 60 seconds. Subsequently, immersion development was performed for 30 seconds with a 2.38% (w / w) TMAH aqueous solution, followed by rinsing with a surfactant-containing rinsing material and spin drying to obtain a positive pattern.

[1536] The LS patterns obtained 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. Furthermore, the development defects of the obtained LS patterns were evaluated. The results are shown in Tables 5 and 6.

[1537] [Sensitivity Evaluation]

[1538] Calculate the optimal exposure Eop (mJ / cm) for obtaining an LS pattern with a linewidth of 18nm and a pitch of 36nm. 2 ), and let it be the sensitivity. The smaller the value, the higher the sensitivity.

[1539] [EL Review]

[1540] The EL (in %) is calculated using the following formula, based on 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.

[1541] EL(%) = (|E1-E2| / Eop) × 100

[1542] E1: Provides optimal exposure for LS patterns with a linewidth of 16.2nm and a pitch of 36nm.

[1543] E2: Provides optimal exposure for LS patterns with a linewidth of 19.8nm and a pitch of 36nm.

[1544] Eop: Provides optimal exposure for LS patterns with a linewidth of 18nm and a pitch of 36nm.

[1545] [LWR Evaluation]

[1546] The dimensions at 10 points along the length of the line obtained by Eop irradiation of the LS pattern are measured, and the standard deviation (σ) is calculated as three times the value (3σ) as the LWR. The smaller this value, the more uniform the line width and roughness of the pattern can be obtained.

[1547] [DOF Rating]

[1548] For DOF evaluation, the focal depth range formed within ±10% (16.2~19.8nm) of the 18nm dimension in the aforementioned LS pattern is determined. The larger this value, the wider the focal depth.

[1549] [Collapse Limit Assessment of Line Patterns]

[1550] The line dimensions of the aforementioned LS pattern at various exposures were measured 10 times along its length for the optimal focal point. The finest line dimension obtainable without collapse was taken as the collapse limit dimension. The smaller this value, the better the collapse limit.

[1551] [Evaluation of Development Defects]

[1552] An LS pattern with a linewidth of 18nm and a pitch of 36nm, formed using the aforementioned optimal exposure, was inspected using a KLA-Tencor KLA2360 defect inspection device (trade name). The pixel size of the defect inspection device was set to 0.16μm, and the threshold was set to 20. Defects (number / cm) extracted by comparing the differences between the superposition of the image and the pixel units were detected. 2 ), and calculate the number of defects per unit area (defects / cm²). 2Subsequently, a defect inspection was conducted, and developing defects were extracted from all defects and the number of developing defects per unit area (defects / cm²) was calculated. 2 Values ​​less than 0.5 are rated A, values ​​above 0.5 but less than 1.0 are rated B, values ​​above 1.0 but less than 5.0 are rated C, and values ​​above 5.0 are rated D. Smaller values ​​indicate better performance.

[1553] [Table 5]

[1554]

[1555] [Table 6]

[1556]

[1557] As shown in Tables 5 and 6, the chemically amplified resist composition containing polymers derived from the sulfonate monomers of this invention exhibits good sensitivity, as well as excellent EL, LWR, and DOF. Furthermore, a low collapse limit value was confirmed, and pattern collapse resistance remains strong even during the formation of fine patterns. In addition, development defects were also confirmed to be suppressed. Therefore, it is demonstrated that the chemically amplified resist composition of this invention is suitable as a material for EUV lithography.

[1558] [5] Evaluation of EUV lithography (2)

[1559] [Examples 5-1 to 5-26, Comparative Examples 5-1 to 5-18]

[1560] The chemically amplified resist compositions (R-1~R-26, CR-1~CR-18) shown in Tables 3 and 4 were spin-coated onto a Si substrate with a silicon-containing spin-coating 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 obtain a resist film with a thickness of 50 nm. The resist film was exposed using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, mask with a pitch of 46 nm and a +20% deviation on the wafer). Then, PEB was performed for 60 seconds using a hot plate at the temperatures recorded in Tables 7 and 8, followed by development with a 2.38% by mass TMAH aqueous solution for 30 seconds to form a hole pattern with a size of 23 nm.

[1561] Using a Hitachi Advanced Technology Co., Ltd. critical dimension SEM (CG6300), the exposure was measured when the hole size was formed at 23nm, and this was set as the sensitivity. Furthermore, the size of 50 holes at this time was measured, and the standard deviation (σ) obtained from the results was set to three times the value (3σ) as the CDU. The results are shown in Tables 7 and 8.

[1562] [Table 7]

[1563]

[1564] [Table 8]

[1565]

[1566] The results shown in Tables 7 and 8 confirm that chemically amplified resist compositions containing repeating units of polymers derived from the sulfonate type monomers of the present invention exhibit good sensitivity and excellent CDU.

Claims

1. A sulfonium salt type monomer, represented by the following formula (A); In the formula, n1 is 0 or 1; n2 is 0, 1, or 2; n3 is 0, 1, or 2; n4 is 0, 1, or 2; however, when n1 is 0, 0 ≤ n2 + n3 + n4 ≤ 5, and when n1 is 1, 0 ≤ n2 + n3 + n4 ≤ 7; n5 is 0 or 1; n6 is 0, 1, or 2; n7 is 0, 1, or 2; n8 is 0, 1, or 2; however, when n5 is 0, 0 ≤ n6 + n7 + n8 ≤ 5. When n5 is 1, 0 ≤ n6 + n7 + n8 ≤ 7; n9 is 0 or 1; n10 is 0, 1 or 2; n11 is 0, 1 or 2; n12 is 0, 1 or 2; however, when n9 is 0, 0 ≤ n10 + n11 + n12 ≤ 5, and when n9 is 1, 0 ≤ n10 + n11 + n12 ≤ 7; also, 1 ≤ n2 + n6 + n10 ≤ 6, and 1 ≤ n3 + n7 + n11 ≤ 6; R 1 R 2 and R 3 Each R can be independently a halogen atom, nitro group, hydroxyl group, carboxyl 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, each R 1 They can be the same or different, and there are 2 Rs. 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when n8 is 2, each R 2 They can be the same or different, and there are 2 Rs. 2 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when n12 is 2, each R 3 They can be the same or different, and there are 2 Rs. 3 They can also bond to each other and form rings together with the carbon atoms they are bonded to; L 1 L 2 and L 3 Each is independently an ether bond, ester bond, or carbonate bond; when n3 is 2, each L 1 They can be the same or different; when n7 is 2, each L 2 They can be the same or different; when n11 is 2, each L 3 They can be the same or different; R AL1 R AL2 and R AL3 Each is an independent acid-labile group; when n3 is 2, each R AL1 They can be the same or different; when n7 is 2, each R AL2 They can be the same or different; when n11 is 2, each R AL3 They can be the same or different; Furthermore, the bond is to S + Two of the three aromatic rings can also bond to each other and form a ring together with the sulfur atoms they are bonded to; Z - It is a fluoroalkyl sulfonic acid anion with polymerizable groups.

2. The sulfonium salt type monomer according to claim 1, which is represented by the following formula (A1); In the formula, n2~n4, n6~n8, n10~n12, R 1 ~R 3 L 1 ~L 3 R AL1 ~R AL3 and Z - Same as above.

3. The sulfonium salt type monomer according to claim 1, wherein, The unstable group of this acid is represented by the following formula (AL-1) or (AL-2); In the formula, p1 and p2 are independently 0 or 1; q1 and q2 are independently 0, 1, 2, 3 or 4; 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 indicated hydrocarbon group may also be partially replaced by -O- or -S-, and when the hydrocarbon group contains an aromatic ring, part 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; 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, and part of the -CH2- in this ring can be replaced by -O- or -S-; however, 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; furthermore, some of the hydrogen atoms in the alicyclic rings can also be replaced by halogen atoms. 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, and part of the -CH2- of this hydrocarbon 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. 4 Together they form a heterocyclic group with 3 to 20 carbon atoms, and part of the -CH2- of the heterocyclic group can also be replaced by -O- or -S-; L 4 It can be -O- or -S-; R La ~R Ld Each is an independent hydrocarbon group consisting of a hydrogen atom or may contain heteroatoms, and may be a hydrocarbon group with 1 to 20 carbon atoms. Indicates and L 1 L 2 and L 3 Atomic bonds.

4. The sulfonium salt type monomer according to claim 1, wherein, Z - Z1 represents the anion. In the formula, k is 0, 1, 2 or 3; R A Each can be independently composed of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Z 1 Each can be a single bond independently, or may have substituents such as phenylene, naphthylene, or... -C(=O)-OZ 11 -;Z 11 It is an aliphatic alkylene group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the aliphatic alkylene group may also contain a halogen atom, hydroxyl group, ether bond, ester bond, or lactone ring; Z 2 It can be a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond; Z 3 Each independently constitutes a single bond, -Z 31 -C(=O)-O-、 -C(=O)-N(H)-Z 31 -or -OZ 31 -;Z 31 It may also contain alkylene groups with 1 to 20 carbon atoms, which are heteroatoms; Z 4 Each independently constitutes a single bond, -Z 41 -C(=O)-O-、 -C(=O)-N(H)-Z 41 -or -OZ 41 -;Z 41 It may also contain alkylene groups with 1 to 20 carbon atoms, which are heteroatoms; This represents the atomic bonds between carbon atoms in the main chain; Indicates and Z 2 atomic bonds; Indicates and Z 3 atomic bonds; L 5 It can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond; 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.

5. The sulfonium salt type monomer according to claim 1, wherein, Z - Z2 represents the anion. In the formula, m1 is 0 or 1; m2 is 0, 1, 2, 3 or 4; m3 is 0, 1, 2 or 3; m4 is 0 or 1; m5 is 0, 1, 2, 3 or 4; m6 is 0, 1, 2 or 3; m7 is 0 or 1; m8 is 1, 2, 3 or 4; m9 is 0, 1, 2 or 3; m10 is 0, 1, 2, 3 or 4; m11 is 0 or 1; m12 is 0 or 1; however, when m1 is 0, 0 ≤ m2 + m3 + m12 ≤ 4, when m1 is 1, 0 ≤ m2 + m3 + m12 ≤ 6; when m4 is 0, 0 ≤ m5 + m6 ≤ 4, when m4 is 1, 0 ≤ m5 + m6 ≤ 6; when m7 is 0, 0 ≤ m8 + m9 ≤ 5, when m7 is 1, 0 ≤ m8 + m9 ≤ 7; and 1 ≤ m2 + m5 + m8 ≤ 4. R A It consists of hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups; R 11 R 12 and R 13 Each R can be independently a halogen atom other than an iodine atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; when m3 is 2 or 3, each R 11 They can be the same or different, and there are 2 Rs. 11 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when m6 is 2 or 3, each R 12 They can be the same or different, and there are 2 Rs. 12 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when m9 is 2 or 3, each R 13 They can be the same or different, and there are 2 Rs. 13 They can also bond to each other and form rings together with the carbon atoms they are bonded to; L A L B L C L D and L E Each bond can be independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond; X L1 and X L2 Each is an independent single bond or may contain a heteroatom and be a hydrocarbon group with 1 to 40 carbon atoms; 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; However, m11 and m12 cannot both be 0, and L A L B L C L D X L1 and X L2 It cannot be a single key at the same time.

6. A monomeric photoacid generator, comprising a sulfonium salt monomer according to any one of claims 1 to 5.

7. A polymer comprising repeating units from the monomeric photoacid generator according to claim 6.

8. The polymer according to claim 7, further comprising at least one repeating unit selected from the repeating unit represented by formula (a1), the repeating unit represented by formula (a2), and the repeating unit represented by formula (a3); In the formula, R A Each can be independently composed of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; X 1 For single bonds, phenylene, naphthylene, -C(=O)-OX 11 -or -C(=O)-N(H)-X 11 - and 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 with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring; X 2 For single key or -C(=O)-O- or -C(=O)-N(H)-; This represents the atomic bonds between carbon atoms in the main chain; R 21 It can be a halogen atom, cyano group, hydroxyl group, nitro group, pentafluorothio 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 a1 is 2, 3 or 4, each R 21 They can be the same or different; AL 1 and AL 2 Each is an acid-labile group; a1 can be 0, 1, 2, 3 or 4; In the formula, b1 is 0 or 1; 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 It consists of hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups; X 3 For single bond, -C(=O)-O- or -C(=O)-N(H)-; This represents the atomic bonds between carbon atoms in the main chain; X 4 It is 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; however, X 4 and X 6 Adjacent carbon atoms bonded to the aromatic ring; R 22 and R 23 Each is an independent hydrocarbon group consisting of 1 to 20 carbon atoms, or may contain heteroatoms; also, R 22 and R 23 They can also bond to each other and form rings together with the carbon atoms they are bonded to; R 24 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 oxy group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms or -N(R) group. 24A (R) 24B ); R 24A and R 24B Each is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; when b2 is 2 or more, each R 24 They can be the same or different, and there are multiple Rs. 24 They can also bond to each other and form rings together with the carbon atoms on the aromatic rings they are bonded to.

9. The polymer according to claim 7, further comprising at least one repeating unit selected from the repeating units represented by formula (b1) and formula (b2); In the formula, R A Each can be independently composed of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Y 1 For single bonds, phenylene, naphthylene, -C(=O)-OY 11 -or -C(=O)-N(H)-Y 11 - and 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 11 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring; Y 2 For single key or -C(=O)-O-; This represents the atomic bonds between carbon atoms in the main chain; R 31 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, sulcinolone ring and carboxylic anhydride (-C(=O)-OC(=O)-); R 32 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, 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 c2 is 2, 3 or 4, each R 32 They can be the same or different; c1 can be 1, 2, 3 or 4; c2 can be 0, 1, 2, 3 or 4; however, 1≤c1+c2≤5.

10. A chemically amplified resist composition comprising (A) a base polymer comprising the polymer according to claim 7.

11. The chemically amplified resist composition according to claim 10, further comprising (B) an organic solvent.

12. The chemically amplified resist composition according to claim 10, further comprising (C) a quencher.

13. The chemically amplified resist composition according to claim 10, further comprising (D) a photoacid generator.

14. The chemically amplified resist composition according to claim 10, further comprising (E) a surfactant.

15. 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.

16. The pattern forming method according to claim 15, 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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